Keith JOHNSON
Oil-Water Nanocluster Emulsion
Oil-Water Nanocluster Emulsion
Related:
COTTELL : Ultrasonic Fuel-Water Burner
MUNSON : Water Fuel Rx
STREY : Microemulsion Fuel
GUNNERMAN : Water-Fuel Emulsion
GLOBUS : Water-Gasoline Emulsion
LO / GANN : Cluster Water
JENKINS : Water-Fuel Emulsion
https://www.newscientist.com/article/mg16121775-100-just-add-water/
13 March 1999
Just add water
By Bennett Davis
By Bennett Davis
IF YOU believe that oil and water don’t mix, it’s time to meet Keith Johnson. Recently retired as a professor of materials physics at MIT, Johnson has succeeded where many have failed — by combining diesel fuel with tap water to form a mixture that cuts pollution, maintains engine efficiency and works in existing engines.
His fuel is as simple to make as instant coffee, yet it is stable for years. If he can make it cheaply enough, it could improve the lives of millions of people who live in cities packed with old, diesel-powered buses and cars. Their clapped-out engines belch soot and nitrogen oxides (NOX) that damage the environment and cause lung disease. Clean up vehicle exhausts, and these cities should become cleaner and healthier places to live.
The reason that his fuel is so stable and green, says Johnson, is that he has found a family of detergent-like surfactants that chemically bond molecules of water to molecules of the diesel, nudging the water molecules into stable 20-molecule clusters resembling “buckyballs”. Johnson calculates that these clusters pulsate with vibrations, an effect that endows them with remarkable chemical properties. He has licensed his discovery to Quantum Energy Technologies (QET), based in Cambridge, Massachusetts, which plans to make and market his watery fuel worldwide...
US5997590
Stabilized water nanocluster-fuel emulsions designed through quantum chemistry
Stabilized water nanocluster-fuel emulsions designed through quantum chemistry
The present invention provides combustible compositions utilizing water clusters characterized by high oxygen reactivity due to protruding, delocalized p pi orbitals. In preferred embodiments, the compositions include one or more surfactants having molecular orbitals that interact with and participate in the delocalized p pi orbitals. The invention also provides methods of designing, producing, and using the compositions.
BACKGROUND OF THE INVENTION
Due to its critical importance in processes ranging from heat transfer to solvation and biological reactions, water has been extensively studied. However, the microscopic structure of water is still poorly understood. Only recently have systematic studies been undertaken to evaluate complex water structures (see, for example, Pugliano et al., Science 257:1937, 1992). None of the studies performed to date, all of which focus on hydrogen bonding capabilities, has provided a full picture of the structure and properties of water. Accordingly, there remains a need for development of a more accurate understanding of water structure and characteristics. Moreover, mechanisms for harnessing water's extraordinary properties for practical applications are required.
One particular application for which water use has been explored is in the area of fuel combustion. In the past, water has been dispersed in fuels in order to i) decrease fuel flammability; ii) decrease the temperature of combustion; iii) reduce particulate emissions resulting from combustion; and/or iv) reduce levels of NOx emissions resulting from combustion (see, for example Donnelly et al., DOE/CS/50286-4, published September 1985; Compere et al., ORNL TM-9603, published March 1985 by A. L. Compere et al.; Griffith et al., U.S. DOE ORNL TM-11248 DE89 017779). However, no stable, combustible water/fuel dispersion has made it to market. Several problems that have been encountered in the preparation of such compositions. There remains a need for a stable, inexpensive water/fuel composition that has improved combustion properties.
SUMMARY OF THE INVENTION
The present invention provides an analysis of water structure that reveals unexpected characteristics of certain molecular arrangements. While most prior investigations have focused on the role of hydrogen bonding in water, the present invention encompasses the discovery that second-nearest neighbor interactions between oxygen atoms in adjacent water molecules help determine the long-range properties of water.
The present invention provides the discovery that oxygens on neighboring water molecules can interact with one another through overlap of oxygen p orbitals. This overlap produces degenerate, delocalized p.pi. orbitals that mediate long-range interactions among water molecules in liquid water. The present invention provides the further discovery that, in clusters of small numbers of water molecules, interactions among the water molecules can produce structures in which these degenerate, delocalized orbitals protrude from the structure surface in a manner that renders them available for reaction with other atoms or molecules. The invention therefore provides water clusters containing reactive oxygens. These oxygens can contribute to fuel combustion.
Preferred water clusters of the present invention have high symmetry, preferably at least pentagonal symmetry. Also, it is preferred that oxygen-oxygen vibrational modes in the clusters are induced, either through application of an external electromagnetic or accoustical field or through intrinsic action of the dynamical Jahn-Teller (DJT) effect. As is known, the Jahn-Teller (JT) effect causes highly symmetrical structures to distort or deform along symmetry-determined vibronic coordinates (Bersuker et al., "Vibronic Interactions in Molecules and Crystals" Springer-Verlag, 1989). Potential energy minima corresponding to the broken-symmetry forms then arise, and the structure can either settle into one of these minima (static Jahn-Teller effect) or can oscillate between or among such minima by vibrating along the relevant vibrational coordinates (dynamical Jahn-Teller effect).
The present invention provides the recognition that DJT-induced vibronic oscillations in certain water clusters can significantly lower the energy barrier for chemical reactions involving such clusters. Specifically, the present invention teaches that water clusters (or aggregates thereof) having a ground-state electronic structure characterized by a manifold of fully occupied molecular orbitals (HOMO) separated from a manifold of unoccupied molecular orbitals (LUMO) by an energy gap can be made to have enhanced reactivity characteristics if a degeneracy (or near degeneracy) is induced between the HOMO and LUMO states, leading to a prescribed distortive symmetry breaking and DJT-induced vibronic oscillations.
In one particular embodiment, the present invention provides useful compositions including these reactive water clusters. Preferred compositions of the present invention are combustible compositions in which the water clusters are dispersed in, for example, a fuel. Certain preferred combustible compositions involve water clusters dispersed within a fuel and stabilized by one or more surfactants selected for an ability to contribute to the desirable electronic structure of the water cluster. Preferred surfactants donate one or more electrons to the delocalized p.pi. orbitals. In most cases, these preferred surfactants will be oxygen-rich compounds. Particularly preferred surfactants additionally have one or more of the following characteristics: i) they have appropriate density and miscibility attributes so that they mix readily with the water and fuel and the water/fuel/surfactant emulsion is stable for more than about one year; ii) they introduce no new toxicities into the composition (or into the environment upon combustion of the composition); and iii) they are inexpensive. The invention further provides methods of designing, making, and using such combustible compositions.
DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a representation of the molecular orbitals of water.
FIG. 2 depicts the preferred relative orientation of adjacent water molecules.
FIG. 2A shows the relative orientations of the atoms in neighboring molecules;
FIG. 2B shows the relative orientations of molecular orbitals.
FIG. 3 presents p.pi. orbitals produced through interaction of three water molecules.
FIG. 4 presents p.pi. orbitals produced through interaction of four water molecules.
FIG. 5 shows various characteristics of pentagonal dodecahedral water structures: FIG. 5A shows the molecular orbital energy levels; FIG. 5B displays the computed vibrational modes; FIG. 5C depicts "squashing" and "twisting" vibrational modes associated with oxygen-oxygen interactions in the structures.
FIG. 6 shows potential energy wells for Jahn-Teller disterted water clusters and the resulting reduction in the energy barrier for reaction of these water clusters.
FIG. 7 shows a reaction path for A.fwdarw.B.
FIG. 8 depicts a pentagonal, 5-molecule water cluster.
FIG. 9 shows one of the delocalized p.pi. orbitals of the 5-molecule water cluster shown in FIG. 8.
FIG. 10 depicts a 10-molecule water cluster having partial pentagonal symmetry.
FIG. 11 shows one of the delocalized p.pi. orbitals of the 10-molecule water cluster shown in FIG. 10.
FIG. 12 shows a 20-molecule pentagonal dodecahedral water cluster.
FIG. 13, Panels A-E, show different delocalized p.pi. orbitals associated with the 20-molecule pentagonal dodecahedral water cluster of FIG. 12.
FIG. 14 shows an s-like LUMO molecular orbital of a pentagonal dodecahedral water cluster.
FIG. 15 shows a p-like LUMO molecular orbital of a pentagonal dodecahedral water cluster.
FIG. 16 shows a d-like LUMO molecular orbital of a pentagonal dodecahedral water cluster.
FIG. 17 shows the interaction of water cluster p.pi. orbitals with the carbon p.pi. orbitals of an aromatic soot precursor.
FIG. 18 shows the interaction of water cluster p.pi. orbitals with the carbon p.pi. orbitals of a cetane (diesel) fuel molecule.
FIG. 19 shows a water cluster interacting with a typical fatty acid surfactant by sharing molecular orbitals.
FIG. 20 shows the effect of including neutralizing agent in the water cluster/surfactant system shown in FIG. 19.
FIG. 21 presents emission data from combustion of water cluster/fuel emulsions of the present invention.
FIG. 22 presents an H2 O/H2 O@18 difference Raman spectrum for a water cluster/fuel emulsion of the present invention.
FIG. 23 shows that decreasing micelle size correlates with increasing weight percent of water.
FIG. 24 shows that increasing wieght percent water (which correlates with decreasing micelle size) correlates with decreasing NOx emissions.
FIG. 25 shows that decreasing micelle size correlates with increasing combustion efficiency.
FIG. 26 shows that decreasing micelle size correlates with increasing CO emissions (Panel A), and confirms that increasing CO emissions correlates with increasing weight percent of water (Panel B) and decreasing NOx emissions (Panel C).
FIG. 27 depicts a new engine designed for combustion of water cluster/fuel compositions of the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
As discussed above, the present invention encompasses a new theory of interactions between and among water molecules. In order to facilitate the understanding of the invention, we begin with a basic discussion of what is known about water structure.
FIG. 1 depicts the molecular orbital structure of a single water molecule. As can be seen, this structure can be effectively modeled as an interaction between an oxygen atom (left side) and a hydrogen (H2) molecule (right side). Oxygen has three p orbitals (px, py, and pz) available for interaction with the hydrogen molecule's .sigma. (bonding) and .sigma.* (antibonding) orbitals. Interaction between the oxygen and the hydrogen molecule produces three bonding orbitals: one that represents a bonding interaction between the oxygen Px orbital and the hydrogen .sigma. orbital; one that represents interaction of the oxygen py orbital with the antibonding hydrogen .sigma.* orbital; and one that represents the oxygen pz orbital. In FIG. 1, these orbitals are labelled with their symmetry designations, 1a1, 1b2, and b1, respectively.
The oxygen/hydrogen molecule interaction also produces two antibonding orbitals: one that represents an antibonding interaction between the oxygen py orbital and the hydrogen .sigma.* orbital; and one that represents an antibonding interaction between the oxygen px orbital and the hydrogen .sigma. orbital. These orbitals are also given their symmetry designations, 2b2 and 2a1, respectively, in FIG. 1. For simplicity, the orbitals depicted in FIG. 1 will hereinafter be referred to by their symmetry designations. For example, the oxygen p@z orbital present in the water molecule will be referred to as the water b1 orbital.
The present invention provides the discovery that, when water molecules are positioned near each other in appropriate configurations, the b1 orbital on a first water oxygen will interact with the 1b2 orbital on an adjacent, second water molecule, which in turn will interact with the b1 orbital of a third adjacent water molecule, etc. As shown in FIG. 2, when successive water molecules are oriented perpendicular to one another (FIG. 2A), the b1 and 1b2 orbitals on alternating molecules can interact (see FIG. 2B) to form delocalized p.pi.-type orbitals that extend along any number of adjacent waters.
Those of ordinary skill in the art will readily appreciate that the larger the number of water molecules that are interacting with one another, the more different combinations of b1 and 1b2 orbitals will be created, each producing a p.pi. orbital with a particular extent of bonding or antibonding character. For example, FIG. 3 presents possible orbitals produced by combinations of b1 and 1b2 orbitals on three water molecules; FIG. 4 present possible p.pi. orbitals produced by combinations of b1 and 1b2 orbitals on four water molecules. As can be seen, the larger the number of interacting water molecules, the larger the manifold of possible p.pi. orbitals.
It will be appreciated that both the b1 and 1b2 orbitals in water are occupied. Accordingly, the oxygen-oxygen interactions described by the present invention involve interactions of filled orbitals. Traditional molecular orbital theory teaches that interactions between such filled orbitals typically do not occur because, due to repulsion between the electron pairs, the antibonding orbitals produced by the interaction are more destabilized than the bonding orbitals are stabilized. However, in the case of interacting oxygen atoms on adjacent water molecules, the interacting atoms are farther apart (about 2.8 .ANG., on average) than they would be if they were covalently bonded to one another. Thus, the electron-pair repulsion is weaker than it would otherwise be and such asymmetrical orbital splitting is not expected to occur. In fact, some "bonding" and "antibonding" orbital combinations can have substantially identical energies. The highest occupied molecular orbital (HOMO) in water is, therefore, a manifold of substantially degenerate p.pi. orbitals with varying bonding and antibonding character; the lowest unoccupied molecular orbital (LUMO) in water represents a manifold of states corresponding to interactions involving 2b2 orbitals an adjacent water molecules.
As described above, one aspect of the invention is the discovery that oxygen-oxygen interactions can occur among neighboring water molecules through overlap of b1 and 1b2 orbitals on adjacent oxygens that produces degenerate, delocalized p.pi. orbitals. A further aspect of the invention is the recognition that such p.pi. orbitals can protrude from the surface of a water structure and can impart high reactivity to oxygens within that structure. The inventors draw an analogy between the presently described water oxygen p.pi. orbitals and dwr orbitals known to impart reactivity to certain chemical catalysts (see, for example Johnson, in The New World of Quantum Chemistry, ed. by Pullman et al., Reidel Publishing Co., Dorderecht-Holland, pp. 317-356, 1976). According to the present invention, water oxygens can be made to catalyze their own oxidative addition to other molecules by incorporating them into water structures in which p.pi. delocalized orbitals associated with oxygen-oxygen interactions protrude from the structure surface.
A further aspect of the invention provides the recognition that reactivity of water oxygens within structures having protruding p.pi. orbitals can be enhanced through amplification of certain oxygen-oxygen vibrational modes. It is known that the rate limiting step associated with oxidative addition of an oxygen atom from O2 is the dissociation of the oxygen atom from the O2 molecule. Thus, in general, oxygen reactivity can be enhanced by increasing the ease with which the oxygen can be removed from the molecule with which it is originally associated. The present inventors have recognized that enhancement of oxygen-oxygen vibrational modes in water clusters increases the probability that a particular oxygen atom will be located a distance from the rest of the structure. Where the oxygen is participating in interactions that create a protruding p.pi. orbital, displacement of the oxygen away from the structure increases the probability that the p.pi. orbital will have the opportunity to overlap with orbitals of a potential reaction partner, and therefore increases the reactivity of the oxygen atom. Essentially, the vibrations create an orbital steering effect.
The present invention therefore provides "water clusters" that are characterized by high oxygen reactivity as a result of their orbital and vibrational characteristics. A "water cluster", as that term is used herein, describes any arrangement of water molecules that has sufficient "surface reactivity" due to protruding p.pi. orbitals that the reactivity of cluster oxygens with other reactants is enhanced relative to the reactivity of oxygens in liquid water. Accordingly, so long as a sufficient number of p.pi. orbitals protrude from the cluster of water molecules in a way that allows increased interaction with nearby reactants, the requirements of the present invention are satisfied.
Preferred water clusters of the present invention have symmetry characteristics. Symmetry increases the degeneracy of the p.pi. orbitals, and also produces more delocalized orbitals, thereby increasing the "surface reactivity" of the cluster. Symmetry also allows collective vibration of oxygen-oxygen interactions within the clusters, so that the likelihood that a protruding p.pi. orbital will have an opportunity to overlap with a potential reactant orbital is increased. Particularly preferred water clusters comprise pentagonal arrays of water molecules, and preferably comprise pentagonal arrays with maximum icosahedral symmetry. Most preferred clusters comprise pentagonal dodecahedral arrays of water molecules.
Water clusters comprising pentagonal arrays of water molecules are preferred at least in part because the vibrational modes that can contribute to enhanced oxygen reactivity are associated with the oxygen-oxygen "squashing" and "twisting" modes (depicted for a pentagonal dodecahedral water structure in FIG. 5). These modes have calculated vibrational frequencies that lie between the far infrared and microwave regions of the electromagnetic spectrum, within the range of approximately 250 cm@-1 to 5 cm@-1. Induction of such modes may be accomplished resonantly, for example through application of electrical, electromagnetic, and/or ultrasonic fields, or may be accomplished intrinsically through the dynamical Jahn-Teller effect.
As discussed above, the DJT effect refers to a symmetry-breaking phenomenon in which molecular vibrations of appropriate frequency couple with certain degenerate energy states available to a molecule, so that those states are split away from the other states with which they used to be degenerate (for review, see Bersuker et al., Vibronic Interactions in Molecules and Crystals, Springer Verlag, N.Y., 1990). Essentially, the Jahn-Teller effect (or the pseudo-Jahn-Teller effect) produces instability in high-symmetry structures that are in orbitally degenerate (or nearly degenerate) electronic states, causing the structures to distort or deform along symmetry-determined vibronic coordinates (Qs). The distorted structures have reduced-energy potential energy wells (A' in FIG. 6); the DJT effect can induce the large amplitude vibrations along vibronic coordinates that represent oscillations between these structures. These Jahn-Teller-induced potential minima, and the rapid dynamical-Jahn-Teller vibrations between them, can significantly lower the energy barrier for a chemical reaction (indicated as A.fwdarw.B in FIG. 7) involving the water structures. The reduction in energy barrier is qualitatively similar to that produced by a catalyst, but in this case the reaction pathway from the reactants A to the products B is predictably determined from symmetry by the DJT vibronic coordinates (Qs). Thus, natural coupling between the oxygen-oxygen vibrations and the degenerate p.pi. molecular orbitals of water clusters of the present invention can enhance oxygen reactivity.
Water clusters having pentagonal symmetry are particularly preferred for use in the practice of the present invention because adjacent pentagonal clusters repel each other, imparting kinetic energy to the clusters that can contribute to their increased reactivity.
It will be appreciated that not all of the molecules in the water clusters of the present invention need be water molecules per se. For example, molecules (such as alcohols, amines, etc.) that represent a substitution of a water hydrogen can be incorporated into water clusters of the invention without disrupting the oxygen-oxygen interactions. Methonal, ethanol, or any other substantially saturated alcohol is suitable in this regard. Other atoms, ions, or molecules (e.g., metal ions such as Cu and Ag) can additionally or alternatively be included in the structure so long as they don't interfere with formation of the reactive p.pi. orbital(s). Preferred atoms, ions, or molecules participate in and/or enhance the formation of the p.pi. orbitals. The water structures themselves may also be protonated or ionized. Given that not all of the molecules in the cluster need be water molecules, we herein describe certain desirable characteristics of inventive water clusters with reference to the number of oxygens in the cluster.
Preferred water clusters of the present invention are "nanodroplets", preferably smaller than about 20 .ANG. in their longest dimension, and preferably comprising between about 5 and 300 oxygens. Particularly preferred clusters include between about 20 and 100 oxygens. Most preferred water clusters contain approximately 20 oxygens and have pentagonal dodecahedral symmetry.
Particular embodiments of preferred inventive water clusters for use in the practice of the present invention are presented in FIGS. 8-14 FIG. 8 shows a 5-molecule water cluster with pentagonal symmetry, FIG. 9 shows one of the p.pi. orbitals associated with this cluster. Solid lines represent the positive phase of the orbital wave function; dashed lines represent the negative phase. As can be seen with reference to FIG. 9, a delocalized p.pi. orbital forms that protrudes from the surface of the cluster. This orbital (and others) is available for interaction with orbitals of neighboring reaction partners. Overlap with an orbital lobe of the same phase as the protruding p.pi. orbital lobe will create a bonding interaction between the relevant cluster oxygen and the reaction partner.
FIG. 10 shows a 10-molecule water cluster with partial pentagonal symmetry; FIG. 11 shows one of its delocalized p.pi. orbitals. As can be seen, the orbital delocalization (and protrusion) is primarily associated with the water molecules in the pentagonal arrangement. Thus, FIG. 11 demonstrates one of the advantages of high symmetry in the water clusters of the present invention: the p.pi. orbital associated with the pentagonally-arranged water molecules is more highly delocalized and protrudes more effectively from the surface. The orbital therefore creates surface reactivity not found with the oxygens in water molecules that are not part of the pentagonal array.
FIG. 12 shows a 20-molecule water cluster with pentagonal dodecahedral symmetry; FIG. 13, Panels A-E show various of its p.pi. orbitals. Once again, extensive orbital delocalization and surface protrusion is observed in this highly symmetrical structure. For comparison, the normally unoccupied culster molecular orbitals associated with the same structure are depicted in FIGS. 14-16. More delocalization is observed over the cluster surface, implying greater reactivity when these orbitals become occupied (e.g., through Jahn-Teller symmetry breaking or through electronic charge addition.
Water clusters comprising more than approximately 20 water molecules are not specifically depicted in Figures presented herein, but are nonetheless useful in the practice of the present invention. For example, clusters comprising approximately 80 molecules can assume an ellipsoidal configuration with protruding p.pi. orbitals at the curved ends. When clusters comprise more than approximately 300 water molecules, however, the cluster tends to behave more like liquid water, which shows low "surface reactivity." Of course, if the cluster were to comprise a large number (>300) of water molecules all arranged in stable symmetrical structures (e.g., several stable pentagonal dodecahedral), these problems would not be encountered. Such "aggregates" of the inventive water clusters are therefore within the scope of the present invention.
As has been mentioned, water clusters comprising pentagonal dodecahedral molecular arrangements are particularly preferred for use in the practice of the present invention. Accordingly, pentagonal dodecahedral water structures are discussed in more detail below. Those of ordinary skill in the art will appreciate, however, that the following discussion is not intended to limit the scope of the present invention, and that any and all embodiments encompassed by the above broad description fall within the scope of the claims.
Pentagonal Dodecahedral Water Clusters
Pentagonal dodecahedral water structures (such as, for example, (H2 O)20, (H2 O)20@++, (H2 O)20 H@+, (H2 O)21 H@+,and (H2 O)20@-, as well as analogous structures including alcohol molecules) are particularly preferred for use in the practice of the present invention because, as shown in FIG. 13, delocalized p.pi. orbitals protrude from the dodecahedron vertices, so that all 20 oxygens in the structure are predicted to have enhanced reactivity. Furthermore, Coulomb repulsion between like-charged dodecahedra can render pentagonal dodecahedral structures kinetically energetic. Also, the symmetry of the structure produces degenerate molecular orbitals that can couple with oxygen-oxygen vibrational modes in the far infrared to microwave regions, resulting in increased reactivity of the structure oxygens. As discussed above, these modes can be induced through application of appropriate fields, or through the dynamical Jahn-Teller effect.
Quantum mechanics computations reveal that the Jahn-Teller-active molecular orbitals of a pentagonal dodecahedral water cluster have protruding lobes available for overlap with orbitals of potential reaction partners (see FIGS. 13-16); certain of the orbitals have the shapes of large "s", "p", and "d" atomic-like orbitals (see FIGS. 14-16) that are spatially delocalized around the surface oxygen atoms of the cluster. It is the availability of these orbitals, particularly the "p-like" and "d-like" ones, that allows the clusters to "catalyze" and/or provide their oxygens to various chemical reactions. The rate constant for reactions is given by the equation:
.kappa.=Ae@-E barrier/RT
The pre-exponential term, A, in this equation increases with the frequency of collision (orbital overlap) between water clusters and their potential reaction partners. This collision frequency, in turn, increases with the effective collisional cross-sectional areas of the reactants, which is proportional to the square of the reactant molecular-orbital diameter, d. Pentagonal dodecahedral water clusters have a relatively large molecular orbital diameter (.about.8 .ANG.). Furthermore, this diameter is effectively increased through the action of the Jahn-Teller-induced low frequency vibrational modes (see, e.g. FIG. 5). Thus, when Ebarrier is low pentagonal dodecahedral waters are likely to be significantly more reactive than liquid waters. As described above, Ebarrier is lowered by coupling with the DJT-induced symmetry-breaking low frequency vibrational modes. Furthermore, the coupling of electrons and DJT-induced cluster vibrations can lead to the conversion of electronic energy to vibronic energy, so that the potential energy of the cluster is increased by .DELTA.Evib (see FIG. 6), resulting a further effective lowering of the energy barrier separating reactants and products.
It should be noted that pentagonal dodecahedral water structures had been produced and analyzed well before the development of the present invention. As early as 1973, researchers were reporting unexpected stabilities of water clusters of the form H@+ (H2 O)20 and H@+ (H2 O)21 (see, for example, Lin, Rev. Sci. Instrum. 44:516, 1973; Searcy et al., J. Chem. Phys. 61:5282, 1974; Holland et al., J. Chem. Phys. 72:11, 1980; Yang et al., J. Am. Chem. Soc. 111:6845, 1989; Wei et al., J. Chem. Phys. 94:3268, 1991). However, prior art analyses of these structures centered around discussions of hydrogen bond interactions, and struggled to explain their structure and energetics (see, for example, Laasonen et al., J. Phys. Chem. 98:10079, 1994). No prior art reference discussed the oxygen-oxygen interactions described herein, and none recognized the increased reactivity of cluster oxygens. Moreover, no prior art reference recognized the desirability of inducing particular vibrational modes in these clusters in order to increase oxygen reactivity.
On the other hand, certain elements of the data collected in prior art studies are consistent with and can be explained by the theory presented herein. For example, the present invention predicts that low-frequency vibrations attributable to oxygen-oxygen bonds at the vertices of pentagonal dodecahedral structures should be observable by Raman scattering. Several groups have reported low frequency Raman scattering in water (see, for example, Rousset et al., J. Chem. Phys. 92:2150, 1990; Majolino et al., Phys. Rev. E47:2669, 1993; Mizoguchi et al., J. Chem. Phys. 97:1961, 1992), but each has offered its own explanation for the effect, none of which involves vibrations of oxygen-oxygen bonds at the vertices of pentagonal dodecahedral structures. In fact, Sokolov et al. recently, summarized the state of understanding of the observed low frequency vibrations by saying "the description of the spectrum and its relation with the critical behavior of other properties are still not clear" (Sokolov et al., Phys. Rev. B 51:12865, 1995). The present invention solves this problem.
The analysis of water structure provided by the present invention explains several observations about water properties that cannot be understood through studies of hydrogen bond interactions. For example, Seete et al. (Phys. Rev. Lett 75:850, 1995) have reported propagation of "fast sound" through liquid water is not dependent on the hydrogen isotope employed. Accordingly, fast sound cannot be propagating only on the hydrogen network.
According to the present invention, preferred pentagonal dodecahedral water structures include (H2 O)20, (H2 O)20@++, (H2 O)20 H@+, (H2 O)21 H@+, and (H2 O)20. Also preferred are structures including one or more alcohol molecules, or other molecules (e.g., surfactants) that can contribute to the desirable delocalized electronic structure, substituted for water. Preferred structures may also include clathrated (or otherwise bonded) ions, atoms, molecules or other complex organic or metallo-organic ligands. In fact, clathration can act to stabilize pentagonal dodecahedral water structures. Preferred clathration structures include (H2 O)21 H@+ structures in which an H3 O@+ molecule is clathrated within a pentagonal dodecahedral shell. Other preferred clathrated structures include those in which a metal ion is clathrated by pentagonal dodecahedral water. Negatively charged structures are particularly preferred; such structures contain one or more electrons in the above-described normally unoccupied orbital and are even more reactive than the neutral and positively charged species. Any water structure in which an electron has been introduced into the above-mentioned orbital is a "negatively charged" structure according to the present invention.
Water clusters containing stable pentagonal dodecahedral water structures may be produced in accordance with the present invention by any of a variety of methods. In liquid water, pentagonal dodecahedral structures probably form transiently, but are not stable. In fact, liquid water can be modeled as a collection of pentagonal dodecahedra in which inter-structure interactions are approximately as strong as, or stronger than, intra-structure interactions. Accordingly, in order to produce stable pentagonal dodecahedral water structures from liquid water, the long-range inter-structure interactions present in liquid water must be disrupted in favor of the intra-structure association. Any of a variety of methods, including physical, chemical, electrical, and electromagnetic methods, can be used to accomplish this. For example, perhaps the most straightforward method of isolating pentagonal dodecahedral water structures is simply to isolate 20 or 21 water molecules in a single nanodroplet. Preferred water clusters of the present invention comprise 20 to 21 water molecules.
Other methods of producing pentagonal dodecahedral water structures include passing water vapor through a hypersonic nozzle, as is known in the art (see, for example Lin, Rev. Sci. Instrum. 44:516, 1973; Searcy et al., J. Chem. Phys. 61:5282, 1974). All known methods of hypersonic nozzling are useful in accordance with the present invention. The present invention, however, also provides an improved hypersonic nozzling method for preparing pentagonal dodecahedral water structures. Specifically, in a preferred embodiment of the present invention, the hypersonic nozzle comprises a catalytic material such as nickel or a nickel alloy positioned and arranged so that, as water passes through the nozzle, it comes in contact with reacting orbitals on the catalytic material. Under such conditions, the catalytic material is expected to disrupt inter-cluster bonding, by sending electrons into anti-bonding orbitals, without interfering with intra-cluster bonding interactions.
Chemical methods for producing water clusters comprising pentagonal dodecahedral structures include the use of surfactants and/or clathrating agents. Electrical methods include inducing electrical breakdown of inter-cluster interactions by providing an electrical spark of sufficient voltage and appropriate frequency. Electromagnetic methods include application of microwaves of appropriate frequency to interact with the "squashing" vibrational modes of inter-cluster oxygen-oxygen interactions. Also, since it is known that ultrasound waves can cavitate (produce bubbles in) water, it is expected that inter-cluster associations can be disrupted ultrasonically without interfering with intra-cluster interactions. Finally, various other methods have been reported for the production of pentagonal dodecahedral water structures as can be employed in the practice of the present invention. Such methods include ion bombardment of ice surfaces (Haberland, in Electronic and Atomic Collisions, ed. by Eichler et al., Elsevier, Ansterdam, pp. 597-604, 1984), electron impact ionization (Lin, Rev. Sci. Instrum. 44:516, 1973; Hermann et al., J. Chem. Phys. 72:185, 1982; Dreyfuss et al., J. Chem. Phys. 76:2031, 1982; Stace et al., Chem. Phys. Lett. 96:80, 1983; Echt et al., Chem. Phys. Lett. 108:401, 1989), and near-threshold vacuum-UV photoionization of neutral clusters (Shinohara et al., Chem. Phys. 83:4183, 1985; Nagashima et al., J. Chem. Phys. 84:209, 1986)].
However the pentagonal dodecahedral water structures are initially produced, it may be desirable to ionize them (e.g., by passing them through an electrical potential after they are formed) in order to increase their kinetic energy, and therefore their reactivity, through coulombic repulsion.
As mentioned above, negatively charged structures are particularly useful in the preactice of the present invention. Such negatively charged structures may be produced, for example, chemically (e.g., by selecting a surfactant or additive that contributes one or more electrons to the LUMO), by direct addition of one or more electrons to the LUMO (e.g., by means of an electronic injector), or, if the energy gap between the HOMO and the LUMO is of the appropriate size, photoelectrically (e.g., using uv light to excite an electron into the LUMO). Of course, any other available method that successfully introduces one of more electrons into the LUMO may latematively be used.
Applications
As described above, the present invention provides reactive water clusters reactive oxygens. The invention also provides methods of using such clusters, particularly in "oxidative" reactions (i.e., in reactions that involve transfer of an oxygen from one molecule to another). The clusters can be employed in any oxidative reaction, in combination with any appropriate reaction partner.
One particularly useful application of the water structures of the present invention is in combustion. According to the present invention, the reactive water oxygens can efficiently combine with carbon in a fuel so that the specific energy of the combustion reaction is increased.
In order to model the reactivity of water structure oxygens with neighboring carbons, the inventors have analyzed pentagonal dodecahedral water clusters ionteracting with aromatic molecular soot precursors and C16 H34 (cetane-diesel) fuel molecules. FIGS. 17 and 18, respectively, present calculated highest occupied p.pi. orbitals for these structures. As can be seen with both structures, electron density between the carbon and oxygen is high.
The structures depicted in FIGS. 17 and 18 model systems in which an isolated pentagonal dodecahedral water cluster is surrounded with hydrocarbon molecules. The high electron density between the cluster oxygen and adjacent carbon indicate that the likelihood that the oxygen will be oxidatively added to the carbon is increased. Thus, the present invention teaches that dispersions of water clusters in fuel should have enhanced specific energy of fuel combustion as compared with fuel alone. Also, the invention teaches that the dispersed water molecules promote combuistion of soot molecules, thereby reducing particular matter emmissions. Accordingly, one aspect of the present invention comprises combustible compositions comprising water clusters dispersed in fuel. The compositions are designed to include water structures with reactive oxygens and to maximize interaction of the fuel with those oxygens.
Fuels that can usefully be employed in the water cluster/fuel compositions of the present invention include any hydrocarbon source capable of interaction with reactive oxygens in water clusters of the present invention. Preferred fuels include gasoline and diesel. Diesel fuel is particularly preferred.
Water cluster/fuel compositions of the present invention may be prepared by any means that allows formation of water clusters with reactive oxygens and exposes a sufficient number of such reactive oxygens to the fuel so that the specific energy of combustion is enhanced as compared to the specific energy observed when pure fuel is combusted under the same conditions.
For example, in one preferred embodiment of the invention, the compositions are prepared by combining fuel and water together under supercritical conditions. Water has a critical temperature of 374 DEG C. Above this temperature, no amount of hydrostatic pressure will initiate a phase change back to the liquid state. The minimum pressure required to reliquify water just below its critical temperature, known as the critical pressure, is 221 atmospheres. Provisional application entitled "Supercritical Fuel and Water Compositions", filed on even date herewith and incorporated herein by reference, discloses that single-phase fuel/water compositions can be prepared under supercritical conditions. Without wishing to be bound by any particular theory, we propose that such single-phase compositions represent water clusters of the present invention dispersed within the fuel. Accordingly, desirable water cluster/fuel compositions of the present invention may be prepared through supercritical processing as described in the above-mentioned, incorporated provisional application.
In an alternative preferred embodiment of the present invention, the inventive water cluster fuel compositions are prepared by a process in which stable water structures that contain reactive oxygens are prepared prior to introduction of the water into the water cluster/fuel compositions. Surfactants may be employed to stabilize the water cluster/fuel compositions if desired.
When utilized, surfactants should be selected to participate in the desired electronic and vibrational characteristics of the water clusters. Preferred surfactants also donate one or more electrons to the water cluster LUMO. Particularly preferred surfactants are characterized by one or more of the following additional features: i) low cost; ii) high density as compared with fuel; iii) viscosity approximating that of the fuel (so that the composition flows freely through a standard diesel engine); iv) ready miscibility with other fuel components; v) absence of new toxicities (so that the inventive composition is no more toxic than the fuel alone); vi) stability to exposure to temperatures as low as -30 DEG C. and as high as 120 DEG C.; and vii) ability to form an emulsion composition with the fuel and water that is stable for at least about one year.
Preferred inventive surfactant-containing combustible compositions utilize surfactants with relatively oxygen-rich hydrophilic ends. For example, preferred surfactants have carboxyl (COOH), ethoxyl (CH2 --O), CO3, and/or NO3 groups. Preferably, the surfactant also has at least one long (preferably 6-20 carbons) linear or branched hydrophobic tail that is soluble in the fuel. Compositions containing carboxylate surfactants preferably also contain a neutralizing base such as ammonia (NH4 OH) or methyl amine (MEA). Typically, the secondary surfactant is relatively less polar than the primary surfactant (e.g., is an alcohol) and interacts less strongly with the water phase, but has a hydrocarbon tail that orients and controls the primary surfactant, for example through van der Waals interactions. Preferred primary surfactants for use in accordance with the present invention include fatty acids having a carboxylate polar group. For example, oleic acid, linoleic acid, and stearic acid are preferred primary surfactants.
FIG. 19 depicts a water cluster interacting with a typical fatty acid by sharing molecular orbitals, according to the present invention. As can be seen with reference to FIG. 19, surfactant molecular orbitals effectively donates an electron to and participate in the delocalized p.pi. water cluster orbital.
Other components may also be included in the inventive combustible compositions. For example, as discussed above, it is sometimes desirable to add one or more neutralizing agents. Particularly where the surfactant is an organic acid such as, for example, a fatty acid (e.g., see FIG. 19), such neutralizing agents are likely to be desirable. Examples of preferred neutralizing agents include, but are not limited to methyl amine and ammonia. Addition of such a neutralizing agent has the effect of placing a nitrogen atom at the center of the water cluster, thereby promoting electron delocalization to the cluster periphery, for example as shown in FIG. 20.
It is important to note that the present invention is not the first description of the use of surfactants in combustible water/fuel compositions. However, the prior art does not include identification of the desirable water clusters as described herein, nor of the appropriate surfactants selected for interaction with the water cluster molecular orbitals.
In order that the fuel in the water cluster/fuel compositions of the present invention be exposed to the maximum number of reactive oxygens, it is desirable to minimize the size of the water clusters in the water cluster/fuel compositions, therefore increasing the combustion efficiency. Preferably, the water clusters have an average diameter of no more than about 20 .ANG. along their longest dimension. More preferably, each cluster comprises fewer than about 300 water molecules. In particularly preferred embodiments, the water cluster/fuel composition comprises individual pentagonal dodecahedral water clusters dispersed within the fuel.
It will be appreciated that the extent of interaction between the hydrocarbon fuel and reactive oxygens in the water will depend not only on the size (and surface reactivity) of the water clusters in the composition, but also on the number of water clusters dispersed within the fuel. Preferred water cluster/fuel compositions contain between about 1% and 20% water, preferably between about 3% and 15% water, and most preferably between about 5% and 12% water. Particularly preferred water cluster/fuel compositions contain at least about 50% water.
As mentioned above, the water cluster/fuel compositions of the present invention are preferably prepared so that the specific energy of combustion is as close as possible to that of pure fuel. Preferably, the specific energy is at least about 85%, more preferably at least about 90%, and yet more preferably at least about 95-99% that of pure fuel. In some particularly preferred embodiments, the specific energy of combustion of inventive compositions is higher than that of pure fuel. Preferably, the specific energy is increased at least about 1-2%, more preferably at least about 10%, still more preferably at least about 15-20%, and most preferably at least about 50%.
As described in the Examples, we have prepared various water cluster/fuel compositions and have tested their combustive properties in a standard diesel engine, under normal operating conditions. As can be seen, emission data compiled from combustion of these emulsions, and reveals that NOx and particulate emissions are reduced upon combustion of the inventive emulsions; CO levels are increased.
The water phase of the inventive emulsions described in Example 1 had a particle size of about 4-7 .ANG.. Moreover, the phase was shown to include inventive water clusters, characterized by oxygen-oxygen vibrational modes. Specifically, an isotope effect was observed in the region of about 100-150 cm@-1 of the Raman spectra of emulsions containing H2 O@18 (see FIG. 22). This effect reveals that vibrations including oxygens are responsible for the spectral lines observed in that region.
The emulsion analyses described in Example 2 showed that decreasing water cluster size (micelle size) correlated with i) increases in the weight percent of water in the composition; ii) decreases in NOx emission; iii) increases in CO emission; and iv) increases in combustion efficiency. Interestingly, previous reports had reported that NOx emissions could be reduced in prior art combustible composition by decreasing the combustion temperature. Since reductions in combustion temperature are expected to restrict the extent of combustion, these reports would suggest that CO levels would decrease in parallel with NOx levels. We observe the opposite, presumably because the inventive compositions increase, rather than decrease, the extent of combustion by providing appropriate electronic configurations. Thus, combustion of inventive emulsions results in lower NOx emission but higher CO emission than combustion of diesel alone.
The results presented in the Examples were achieved by combusting diesel or water cluster/diesel emulsions in a standard diesel engine. The present invention can therefore readily be implemented with existing technology. However, an additional aspect of the invention involves altering the design of engines used in combustion of water cluster/fuel compositions of the present invention.
One embodiment of an altered engine for use in the practice of the present invention is a derivative of standard diesel engine, altered so as not to have a functional air intake valve. Given that the oxygen used in combustion of the inventive water cluster/fuel compositions can come from the water instead of from air, air intake should not be required.
More dramatic changes in engine design are also envisioned. For example, FIG. 23 presents one embodiment of a new engine for combusting water cluster/fuel compositions of the present invention. As shown, water clusters 100 are injected into a chamber 200, into which fuel 300 is also injected. The water clusters may be prepared by any of the means described above, but preferably are prepared by ejection from a hypersonic nozzle. In preferred embodiments, the nozzle comprises a catalytic material. In some embodiments, the clusters are also ionized by passage through a potential.
As has been discussed herein, it is desirable to expose the fuel to the water clusters in a way that maximizes interaction between fuel carbons and water oxygens. Because pentagonal dodecahedral water structures have high surface reactivity particularly preferred embodiments of the invention inject individual pentagonal dodecahedral water structures into the chamber. One additional advantage of injecting water clusters into a chamber, and particularly of injecting individual pentagonal dodecahedral water structures, is that it allows the Coulombic repulsion between individual water clusters to be harnessed as kinetic energy, thereby increasing the energy available for conversion during combustion.
Once inside the chamber, the water cluster/fuel composition is ignited according to standard procedures. As mentioned above, air intake is not required.
Those of ordinary skill in the art will appreciate that many of the known variations to engine structure and combustion conditions may be incorporated into the present invention. For example, various additives may be included in the water cluster/fuel composition in order to improve combustibility, stability, lubricity, corrosion-resistance or other desirable characteristics.
EXAMPLES
Example 1
Preparation and Analysis of Combustible Water Cluster/Fuel Emulsions
Water cluster/fuel emulsions were prepared according to the following method:
The water can be distilled water or tap water, or a mixture of water and a short chain alcohol such as methanol. Surfactant I has the structure Cx H20 (OCH2 CH2)y OH, where x=8-10 and y=4-10. Surfactant II is a polyglyceril-oleate or cocoate. Surfactant III is a short chain, (C2-8) linear alcohol.
The emulsions were prepared by mixing the Diesel with Surfactant I and II. Water and surfactant III were then added simultaneously. The water nanodroplets in the emulsion had a grain size of about 4-7 .ANG.. Two particular formulations were prepared that had the following components:
Raman spectra of Formulation 2, were taken using laser excitation at both 406.7 nm and 647.1 nm. The spectra at 406.7 nm were highly fluorescent and only anti-stokes scattering/emission was carefully examined. The results at 647.1 nm did not have these problems. Isotope shift experiments were performed by introducing H2 O@18 into the emulsions. The H2 O/H2 O@18 difference spectrum is presented as FIG. 22. As can be seen, a peak was observed around 100-150 cm@-1, in the region associated with oxygen-oxygen squashing vibrational modes. Accordingly, it was concluded that the Formulation 2 emulsion contained water clusters having at least pentagonal symmetry.
The water cluster/fuel emulsions were weighed and then were pumped into a small YANMAR diesel engine. Energy output, injection timing, and engine operation were monitored according to standard techniques. Exhaust samples were taken and emissions were analyzed also according to standard techniques.
FIG. 21 presents the results of emissions analysis of two water cluster/fuel emulsions, Formulation 1 and Formulation 2. As can be seen, NOx and particulate levels are reduced, and CO levels may be increased.
Example 2
Preparation and Analysis of Combustible Water Cluster/Fuel Emulsions:
Water cluster/fuel emulsions were prepared according to the following method:
The fatty acid based microemulsion fuels were made by mixing of diesel fuel, partially neutralized fatty acid surfactant, water, and an alcohol co-surfactant. The fuel is Philips D-2 Diesel or the equivalent. The water is distilled water or tap water. Alcohol co-surfactants utilized include t-butyl alcohol (TBA), n-butyl alcohol (NBA), methyl benzyl alcohol (MBA) and methanol (MeOH), isopropyl alcohol (IPA), and t-amyl alcohol (TAA). Fatty acids include tall oil fatty acids (TOFA) and Emersol 315 (E-315) refined vegetable fatty acid. Specifically, the fatty acid should be only partially neutralized, with the optimum degree of neutralization depending on the specific alkanolamine used. MEA (monoethanolamine) was preferably used to neutralize the fatty acid by gradual addition to the fatty acid during mixing.
When a (macro)emulsion is first made from diesel, surfactant and water (without the alcohol), the mixture converts to a microemulsion within seconds of addition and mild mixing of the alcohol co-surfactant. When mixing the components sequentially, the order of addition affects the ease of mixing. It is more difficult to disperse water when it is added last due to the formation of localized streamers of waxy precipitates, which require more intense mixing to disperse and form the final microemulsion.
Additionally, "microemulsifier concentrates", consisting of all the ingredients needed to form a microemulsion except the base fuel itself, can be mixed without difficulty to form low viscosity, single phase mixtures (i.e. no gels). The concentrates can then be blended directly with diesel fuel with moderate mixing, to form water-in-oil microemulsion fuels.
The particular formulations that were prepared are shown in Appendix A.
The water cluster/fuel emulsions were weighed and then were pumped into a small YANMAR diesel engine. Energy output, injection timing, and engine operation were monitored according to standard techniques. Exhaust samples were taken and emissions were analyzed also according to standard techniques.
FIGS. 23-26 present the results of emissions analysis of several water cluster/fuel emulsions.
OTHER EMBODIMENTS
Those of ordinary skill in the art will recognize that the foregoing has provided a detailed description of certain preferred embodiments of the invention. Various changes and modifications can be made to the particular embodiments described above without departing from the spirit and scope of the invention. All such changes and modifications are incorporated within the scope of the following claims.
US5800576
Water clusters and uses therefor
Water clusters and uses therefor
The present invention provides water cluster compositions characterized by high oxygen reactivity due to protruding, delocalized p pi orbitals. The invention also provides methods of producing the structures. The invention further provides methods of using the water clusters, for example in combustion, and compositions associated therewith.
BACKGROUND OF THE INVENTION
Due to its critical importance in processes ranging from heat transfer to solvation and biological reactions, water has been extensively studied. However, the microscopic structure of water is still poorly understood. Only recently have systematic studies been undertaken to evaluate complex water structures (see, for example, Pugliano et al., Science 257:1937, 1992). None of the studies performed to date, all of which focus on hydrogen bonding capabilities, has provided a full picture of the structure and properties of water. Accordingly, there remains a need for development of a more accurate understanding of water structure and characteristics. Moreover, mechanisms for harnessing water's extraordinary properties for practical applications are required.
SUMMARY OF THE INVENTION
The present invention provides an analysis of water structure that reveals unexpected characteristics of certain molecular arrangements. While most prior investigations have focussed on the role of hydrogen bonding in water, the present invention encompasses the discovery that second-nearest neighbor interactions between oxygen atoms in adjacent water molecules help determine the long-range properties of water.
The present invention provides the discovery that oxygens on neighboring water molecules can interact with one another through overlap of oxygen p orbitals. This overlap produces degenerate, delocalized p.pi. orbitals that mediate long-range interactions among water molecules in liquid water. The present invention provides the further discovery that, in clusters of small numbers of water molecules, interactions among the water molecules can produce structures in which p.pi. orbitals protrude from the structure surface in a manner that renders them available for reaction with other atoms or molecules. The invention therefore provides water clusters containing reactive oxygens. Preferred clusters have at least pentagonal symmetry. Also, it is preferred that oxygen-oxygen vibrational modes in the clusters are induced, either through application of an external field or through intrinsic action of the dynamical Jahn-Teller (DJT) effect.
DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a representation of the molecular orbitals of water.
FIG. 2 depicts the preferred relative orientation of adjacent water molecules. FIG. 2A shows the relative orientations of the atoms in neighboring molecules; FIG. 2B shows the relative orientations of molecular orbitals.
FIG. 3 presents p.pi. orbitals produced through interaction of three water molecules.
FIG. 4 presents p.pi. orbitals produced through interaction of four water molecules.
FIG. 5 depicts "squashing" and "twisting" vibrational modes associated with oxygen-oxygen interactions in pentagonal dodecahedral water structures.
FIG. 6 depicts a pentagonal, 5-molecule water cluster.
FIG. 7 shows one of the delocalized p.pi. orbitals of the 5-molecule water cluster shown in FIG. 6.
FIG. 8 depicts a 10-molecule water cluster having partial pentagonal symmetry.
FIG. 9 shows one of the delocalized p.pi. orbitals of the 10-molecule water cluster shown in FIG. 8.
FIG. 10 shows a 20-molecule pentagonal dodecahedral water cluster.
FIG. 11, Panels A-E, show different delocalized p.pi. orbitals associated with the 20-molecule pentagonal dodecahedral water cluster of FIG. 10.
FIG. 12 shows an unoccupied antibonding p.pi.* orbital associated with the 20-molecule petagonal dodecahedral water cluster of FIG. 10.
FIG. 13 shows a p.pi. orbital in a pentagonal dodecahedral water/methanol structure.
FIG. 14 shows a p.pi. orbital in a pentagonal dodecahedral water/ethanol structure.
FIG. 15 presents an H2 O/H2 O@18 difference Raman spectrum for a water cluster/fuel emulsion of the present invention.
FIG. 16 presents emission data from combustion of water cluster/fuel emulsions of the present invention.
FIG. 17 depicts a new engine designed for combustion of water cluster/fuel compositions of the present invention.
DESCRIPTION OF PREFERRED EMBODIMENTS
As discussed above, the present invention encompasses a new theory of interactions between and among water molecules. In order to facilitate the understanding of the invention, we begin with a basic discussion of what is known about water structure.
FIG. 1 depicts the molecular orbital structure of a single water molecule. As can be seen, this structure can be effectively modeled as an interaction between an oxygen atom (left side) and a hydrogen (H2) molecule (right side). Oxygen has three p orbitals (px, py, and pz) available for interaction with the hydrogen molecule's .sigma. (bonding) and .sigma.* (antibonding) orbitals. Interaction between the oxygen and the hydrogen molecule produces three bonding orbitals: one that represents a bonding interaction between the oxygen px orbital and the hydrogen .sigma. orbital; one that represents interaction of the oxygen py orbital with the antibonding hydrogen .sigma.* orbital; and one that represents the oxygen pz orbital. In FIG. 1, these orbitals are labelled with their symmetry designations, 1a1, 1b2, and b1, respectively.
The oxygen-hydrogen molecule interaction also produces two antibonding orbitals: one that represents an antibonding interaction between the oxygen py orbital and the hydrogen .sigma.* orbital; and one that represents an antibonding interaction between the oxygen px orbital and the hydrogen .sigma. orbital. These orbitals are also given their symmetry designations, 2b2 and 2a1, respectively, in FIG. 1. For simplicity, the orbitals depicted in FIG. 1 will hereinafter be referred to by their symmetry designations. For example, the oxygen pz orbital present in the water molecule will be referred to as the water b1 orbital.
The present invention provides the discovery that, when water molecules are positioned near each other in appropriate configurations, the b1 orbital on a first water oxygen will interact with the 1b2 orbital on an adjacent, second water molecule, which in turn will interact with the b1 orbital of a third adjacent water molecule, etc. As shown in FIG. 2, when successive water molecules are oriented perpendicular to one another (FIG. 2A), the b1 and 1b2 orbitals on alternating molecules can interact (see FIG. 2B) to form delocalized p.pi.-type orbitals that extend along any number of adjacent waters.
Those of ordinary skill in the art will readily appreciate that the larger the number of water molecules that are interacting with one another, the more different combinations of b1 and 1b2 orbitals will be created, each producing a p.pi. orbital with a particular extent of bonding or antibonding character. For example, FIG. 3 presents possible p.pi. orbitals produced by combinations of b1 and 1b2 orbitals on three water molecules; FIG. 4 present possible p.pi. orbitals produced by combinations of b1 and 1b2 orbitals on four water molecules. As can be seen, the larger the number of interacting water molecules, the larger the manifold of possible p.pi. orbitals.
It will be appreciated that both the b1 and 1b2 orbitals in water are occupied. Accordingly, the oxygen-oxygen interactions described by the present invention involve interactions of filled orbitals. Traditional molecular orbital theory teaches that interactions between such filled orbitals typically do not occur because, due to repulsion between the electron pairs, the antibonding orbitals produced by the interaction are more destabilized than the bonding orbitals are stabilized. However, in the case of interacting oxygen atoms on adjacent water molecules, the interacting atoms are farther apart (about 2.8 .ANG., on average) than they would be if they were covalently bonded to one another. Thus, the electron-pair repulsion is weaker than it would otherwise be and such asymmetrical orbital splitting is not expected to occur. In fact, some "bonding" and "antibonding" orbital combinations can have substantially identical energies. The highest occupied molecular orbital (HOMO) in water is, therefore, a manifold of substantially degenerate p.pi. orbitals with varying bonding and antibonding character; the lowest unoccupied molecular orbital (LUMO) in water represents a manifold of states corresponding to interactions involving 2b2 orbitals an adjacent water molecules.
As described above, one aspect of the invention is the discovery that oxygen-oxygen interactions can occur among neighboring water molecules through overlap of b1 and 1b2 orbitals on adjacent oxygens that produces degenerate, delocalized p.pi. orbitals. A further aspect of the invention is the recognition that such p.pi. orbitals, if made to protrude from the surface of a water structure, can impart high reactivity to oxygens within that structure. The inventors draw an analogy between the presently described water oxygen p.pi. orbitals and d.pi. orbitals known to impart reactivity to certain chemical catalysts (see, for example Johnson, in The New World of Quantum Chemistry, ed. by Pullman et al., Reidel Publishing Co., Dorderecht-Holland, pp. 317-356, 1976. According to the present invention, water oxygens can be made to catalyze their own oxidative addition to other molecules by incorporating them into water structures in which p.pi. orbitals associated with oxygen-oxygen interactions protrude from the structure surface.
A further aspect of the invention provides the recognition that reactivity of water oxygens within structures having protruding p.pi. orbitals can be enhanced through amplification of certain oxygen-oxygen vibrational modes. It is known that the rate limiting step associated with oxidative addition of an oxygen atom from O2 is the dissociation of the oxygen atom from the O2 molecule. Thus, in general, oxygen reactivity can be enhanced by increasing the ease with which the oxygen can be removed from the molecule with which it is originally associated. The present inventors have recognized that enhancement of oxygen-oxygen vibrational modes in water clusters increases the probability that a particular oxygen atom will be located a distance from the rest of the structure. Where the oxygen is participating in interactions that create a protruding p.pi. orbital, displacement of the oxygen away from the structure increases the probability that the p.pi. orbital will have the opportunity to overlap with orbitals of a potential reaction partner, and therefore increases the reactivity of the oxygen atom. Essentially, the vibrations create an orbital steering effect.
The present invention therefore provides "water clusters" that are characterized by high oxygen reactivity as a result of their orbital and vibrational characteristics. A "water cluster", as that term is used herein, describes any arrangement of water molecules that has sufficient "surface reactivity" due to protruding p.pi. orbitals that the reactivity of cluster oxygens with other reactants is enhanced relative to the reactivity of oxygens in liquid water. Accordingly, so long as a sufficient number of p.pi. orbitals protrude from the cluster of water molecules in a way that allows increased interaction with nearby reactants, the requirements of the present invention are satisfied.
Preferred water clusters of the present invention have symmetry characteristics. Symmetry increases the degeneracy of the p.pi. orbitals and also produces more delocalized orbitals, thereby increasing the "surface reactivity" of the cluster. Symmetry also allows collective vibration of oxygen-oxygen interactions within the clusters, so that the likelihood that a protruding p.pi. orbital will have an opportunity to overlap with a potential reactant orbital is increased. Particularly preferred water clusters comprise pentagonal arrays of water molecules, and preferably comprise pentagonal arrays with maximum icosahedral symmetry. Most preferred clusters comprise pentagonal dodecahedral arrays of water molecules.
Water clusters comprising pentagonal arrays of water molecules are preferred at least in part because of their vibrational modes that can contribute to enhanced oxygen reactivity are associated with the oxygen-oxygen "squashing" and "twisting" modes (depicted for a pentagonal dodecahedral water structure in FIG. 5). These modes have calculated vibrational frequencies that i.e. between the far infrared and microwave regions of the electromagnetic spectrum, within the range of approximately 250 cm@-1 to 5 cm@-1. Induction of such modes may be accomplished resonantly, for example through application of electrical, electromagnetic, and/or ultrasonic fields, or may be accomplished intrinsically through the dynamical Jahn-Teller effect.
The DJT effect refers to a symmetry-breaking phenomenon in which molecular vibrations of appropriate frequency couple with certain degenerate energy states available to a molecule, so that those states are split away from the other states with which they used to be degenerate (for review, see Bersuker et al., Vibronic Interactions in Molecules and Crystals, Springer Verlag, N.Y., 1990). Thus, natural coupling between the oxygen-oxygen vibrations and the degenerate p.pi. molecular orbitals of water clusters of the present invention can enhance oxygen reactivity.
Water clusters having pentagonal symmetry are particularly preferred because adjacent pentagonal clusters repel each other, importing kinetic energy to the clusters that can contribute to their increased reactivity.
It will be appreciated that not all of the molecules in the water clusters of the present invention need be water molecules per se. For example, molecules (such as alcohols, amines, etc.) that represent a substitution of a water hydrogen can be incorporated into water clusters of the invention without disrupting the oxygen-oxygen interactions. Methonal, ethanol, or any other substantially saturated alcohol is suitable in this regard. Other atoms, ions, or molecules can additionally or alternatively be included in the structure so long as they don't interfere with protrusion of the interactive p.pi. orbital(s). The structures themselves may also be protonated or ionized. Given that not all of the molecules in the cluster need be water molecules, we herein describe certain desirable characteristics of inventive water clusters with reference to the number of oxygens in the cluster.
Preferred water clusters of the present invention are "nanodroplets", preferably smaller than about 20 .ANG. in their longest dimension, and preferably comprising between about 5 and 300 oxygens. Particularly preferred clusters include between about 20 and 100 oxygens. Most preferred water clusters contain approximately 20 oxygens and have pentagonal dodecahedral symmetry.
Particular embodiments of preferred inventive water clusters for use in the practice of the present invention are presented in FIGS. 6-12. FIG. 6 shows a 5-molecule water cluster with pentagonal symmetry, FIG. 7 shows one of the p.pi. orbitals associated with this cluster. Solid lines represent the positive phase of the orbital wave function; dashed lines represent the negative phase. As can be seen with reference to FIG. 7, a delocalized p.pi. orbital forms that protrudes from the surface of the cluster. This orbital (and others) is available for interaction with orbitals of neighboring reaction partners. Overlap with an orbital lobe of the same phase as the protruding p.pi. orbital lobe will create a bonding interaction between the relevant cluster oxygen and the reaction partner.
FIG. 8 shows a 10-molecule water cluster with partial pentagonal symmetry; FIG. 9 shows one of its delocalized p.pi. orbitals. As can be seen, the orbital delocalization (and protrusion) is primarily associated with the water molecules in the pentagonal arrangement. Thus, FIG. 9 demonstrates one of the advantages of high symmetry in the water clusters of the present invention: the p.pi. orbital associated with the pentagonally-arranged water molecules is more highly delocalized and protrudes more effectively from the surface. The orbital therefore creates surface reactivity not found with the oxygens in water molecules that are not part of the pentagonal array.
FIG. 10 shows a 20-molecule water cluster with pentagonal dodecahedral symmetry; FIG. 11, Panels A-E show various of its p.pi. orbitals. Once again, extensive orbital delocalization and surface protrusion is observed in this highly symmetrical structure. For comparison, an unoccupied antibonding orbital associated with the same structure is depicted in FIG. 12. Much less delocalization is observed.
Water clusters comprising more than approximately 20 water molecules are not specifically depicted in Figures presented herein, but are nonetheless useful in the practice of the present invention. For example, clusters comprising approximately 80 molecules can assume an ellipsoidal configuration with protruding p.pi. orbitals at the curved ends. When clusters comprise more than approximately 300 water molecules, however, the cluster tends to behave more like liquid water, which shows low "surface reactivity." Of course, if the cluster were to comprise a large number (>300) of water molecules all arranged in stable symmetrical structures (e.g., several stable pentagonal dodecahedral), these problems would not be encountered. Such large clusters are therefore within the scope of the present invention.
As has been mentioned, water clusters comprising pentagonal dodecahedral molecular arrangements are particularly preferred for use in the practice of the present invention. Accordingly, pentagonal dodecahedral water structures are discussed in more detail below. Those of ordinary skill in the art will appreciate, however, that the following discussion is not intended to limit the scope of the present invention, and that any and all embodiments encompassed by the prior broad description fall within the scope of the claims.
Pentagonal Dodecahedral Water Clusters
Pentagonal dodecahedral water structures (such as, for example, (H2 O)20, (H2 O)20@++, (H2 O)20 H@+, and (H2 O)21 H@+, and analogous structures including alcohol molecules) are particularly preferred for use in the practice of the present invention because, as shown in FIG. 11, delocalized p.pi. orbitals protrude from the dodecahedron vertices, so that all 20 oxygens in the structure are predicted to have enhanced reactivity. Furthermore, Coulomb repulsion between like-charged dodecahedra can render pentagonal dodecahedral structures kinetically energetic. Also, the symmetry of the structure produces degenerate molecular orbitals that can couple with oxygen-oxygen vibrational modes in the far infrared to microwave regions, resulting in increased reactivity of the structure oxygens. As discussed above, these modes can be induced through application of appropriate fields, or through the dynamical Jahn-Teller effect.
It should be noted that pentagonal dodecahedral water structures had been produced and analyzed well before the development of the present invention. As early as 1973, researchers were reporting unexpected stabilities of water clusters of the form H@+ (H2 O)20 and H@+ (H2 O)21 (see, for example, Lin, Rev. Sci. Instrum. 44:516, 1973; Searcy et al., J. Chem. Phys. 61:5282, 1974; Holland et al., J. Chem. Phys. 72:11, 1980; Yang et al., J. Am. Chem. Soc. 111:6845, 1989; Wei et al., J. Chem. Phys. 94:3268, 1991). However, prior art analyses of these structures centered around discussions of hydrogen bond interactions, and struggled to explain their structure and energetics (see, for example, Laasonen et al., J. Phys. Chem. 98:10079, 1994). No prior art reference discussed the oxygen-oxygen interactions described herein, and none recognized the increased reactivity of cluster oxygens. Moreover, no prior art reference recognized the desirability of inducing particular vibrational modes in these clusters in order to increase oxygen reactivity.
On the other hand, certain elements of the data collected in prior art studies are consistent with and can be explained by the theory presented herein. For example, the present invention predicts that low-frequency vibrations attributable to oxygen-oxygen bonds at the vertices of pentagonal dodecahedral structures should be observable by Raman scattering. Several groups have reported low frequency Raman scattering in water (see, for example, Rousset et al., J. Chem. Phys. 92:2150, 1990; Majolino et al., Phys. Rev. E47:2669, 1993; Mizoguchi et al., J. Chem. Phys. 97:1961, 1992), but each has offered its own explanation for the effect, none of which involves vibrations of oxygen-oxygen bonds at the vertices of pentagonal dodecahedral structures. In fact, Sokolov et al. recently, summarized the state of understanding of the observed low frequency vibrations by saying "the description of the spectrum and its relation with the critical behavior of other properties are still not clear" (Sokolov et al., Phys. Rev. B 51:12865, 1995). The present invention solves this problem.
The analysis of water structure provided by the present invention explains several observations about water properties that cannot be understood through studies of hydrogen bond interactions. For example, Seete et al. (Phys. Rev. Lett 75:850, 1995) have reported propagation of "fast sound" through liquid water is not dependent on the hydrogen isotope employed. Accordingly, fast sound cannot be propagating only on the hydrogen network.
According to the present invention, preferred pentagonal dodecahedral water structures include (H2 O)20, (H2 O)20@++, (H2 O)20 H@+, and (H2 O)21 H@+. Also preferred are structures including one or more alcohol molecules substituted for water. Preferred structures may also include clathrated (or otherwise bonded) ions, atoms, molecules or other complex organic or metallo-organic ligands. In fact, clathration can act to stabilize pentagonal dodecahedral water structures. Preferred clathration structures include (H2 O)21 H@+ structures in which an H3 O@+ molecule is clathrated within a pentagonal dodecahedral shell. Other preferred clathrated structures include those in which a metal ion is clathrated by pentagonal dodecahedral water.
Water clusters containing stable pentagonal dodecahedral water structures may be produced in accordance with the present invention by any of a variety of methods. In liquid water, pentagonal dodecahedral structures probably form transiently, but are not stable. In fact, liquid water can be modeled as a collection of pentagonal dodecahedra in which inter-structure interactions are approximately as strong as, or stronger than, intra-structure interactions. Accordingly, in order to produce stable pentagonal dodecahedral water structures from liquid water, the long-range inter-structure interactions present in liquid water must be disrupted in favor of the intra-structure association. Any of a variety of methods, including physical, chemical, electrical, and electromagnetic methods, can be used to accomplish this. For example, perhaps the most straightforward method of isolating pentagonal dodecahedral water structures is simply to isolate 20 or 21 water molecules in a single nanodroplet. Preferred water clusters of the present invention comprise 20 to 21 water molecules.
Other methods of producing pentagonal dodecahedral water structures include passing water vapor through a hypersonic nozzle, as is known in the art (see, for example Lin, Rev. Sci. Instrum. 44:516, 1973; Searcy et al., J. Chem. Phys. 61:5282, 1974). All known methods of hypersonic nozzling are useful in accordance with the present invention. The present invention, however, also provides an improved hypersonic nozzling method for preparing pentagonal dodecahedral water structures. Specifically, in a preferred embodiment of the present invention, the hypersonic nozzle comprises a catalytic material such as nickel or a nickel alloy positioned and arranged so that, as water passes through the nozzle, it comes in contact with reacting orbitals on the catalytic material. Under such conditions, the catalytic material is expected to disrupt inter-cluster bonding, by sending electrons into anti-bonding orbitals, without interfering with intra-cluster bonding interactions.
Chemical methods for producing water clusters comprising pentagonal dodecahedral structures include the use of surfactants and/or clathrating agents. Electrical methods include inducing electrical breakdown of inter-cluster interactions by providing an electrical spark of sufficient voltage and appropriate frequency. Electromagnetic methods include application of microwaves of appropriate frequency to interact with the "squashing" vibrational modes of inter-cluster oxygen-oxygen interactions. Also, since it is known that ultrasound waves can cavitate (produce bubbles in) water, it is expected that inter-cluster associations can be disrupted ultrasonically without interfering with intra-cluster interactions. Finally, various other methods have been reported for the production of pentagonal dodecahedral water structures as can be employed in the practice of the present invention. Such methods include ion bombardment of ice surfaces (Haberland, in Electronic and Atomic Collisions, ed. by Eichler et al., Elsevier, Ansterdam, pp. 597-604, 1984), electron impact ionization (Lin, Rev. Sci. Instrum. 44:516, 1973; Hermann et al., J. Chem. Phys. 72:185, 1982; Dreyfuss et al., J. Chem. Phys. 76:2031, 1982; Stace et al., Chem. Phys. Lett. 96:80, 1983; Echt et al., Chem. Phys. Lett. 108:401, 1989), and near-threshold vacuum-UV photoionization of neutral clusters (Shinohara et al., Chem. Phys. 83:4183, 1985; Nagashima et al., J. Chem. Phys. 84:209, 1986)??].
However the pentagonal dodecahedral water structures are initially produced, it may be desirable to ionize them (e.g., by passing them through an electrical potential after they are formed) in order to increase their kinetic energy, and therefore their reactivity, through coulombic repulsion.
Applications
As described above, the present invention provides water clusters that include reactive oxygens. The invention also provides methods of using such clusters, particularly in "oxidative" reactions (i.e., in reactions that involve transfer of an oxygen from one molecule to another). The clusters can be employed in any oxidative reaction, in combination with any appropriate reaction partner.
One particularly useful application of the water structures of the present invention is in combustion. According to the present invention, the reactive water oxygens can efficiently combine with carbon in a fuel so that the specific energy of the combustion reaction is increased.
In order to model the reactivity of water structure oxygens with neighboring carbons, the inventors have analyzed pentagonal dodecahedral clusters in water cluster/methanol and water cluster/ethanol mixtures. FIGS. 13 and 14 present calculated p.pi. orbitals for these structures. As can be seen with both structures, the depicted orbital has the same phase with respect to the carbon and its adjacent oxygen. By contrast, the orbital phase often shifts between the oxygen and neighboring hydrogens. Electron density between the carbon and oxygen is high.
The structures depicted in FIGS. 3 and 14 model systems in which an isolated pentagonal dodecahedral water cluster is surrounded with hydrocarbon molecules. The high electron density between the cluster oxygen and adjacent carbon indicate that the likelihood that the oxygen will be oxidatively added to the carbon is increased. Thus, the present invention teaches that dispersions of water droplets in fuel should have enhanced specific energy of combustion as compared with fuel alone. Accordingly, one aspect of the present invention comprises combustible compositions comprising clusters dispersed in fuel. The compositions are designed to include water structures with reactive oxygens and to maximize interaction of the fuel with those oxygens.
Fuels that can usefully be employed in the water cluster/fuel compositions of the present invention include any hydrocarbon source capable of interaction with reactive oxygens in water clusters of the present invention. Preferred fuels include gasoline and diesel. Diesel fuel is particularly preferred.
Water cluster/fuel compositions of the present invention may be prepared by any means that allows formation of water clusters with reactive oxygens and exposes a sufficient number of such reactive oxygens to the fuel so that the specific energy of combustion is enhanced as compared to the specific energy observed when pure fuel is combusted under the same conditions. Preferably, stable water structures that contain reactive oxygens are prepared prior to introduction of the water into the water cluster/fuel compositions. Surfactants may be employed to stabilize the water cluster/fuel compositions if desired.
In order that the fuel in the water cluster/fuel compositions of the present invention be exposed to the maximum number of reactive oxygens, it is desirable to minimize the size of the water clusters in the water cluster/fuel compositions. Preferably, the water clusters have an average diameter of no more than about 20 .ANG. along their longest dimension. More preferably, each droplet comprises less than about 300 water molecules. In particularly preferred embodiments, the water/cluster fuel composition comprises individual pentagonal dodecahedral water clusters are dispersed within the fuel.
It will be appreciated that the extent of interaction between the hydrocarbon fuel and reactive oxygens in the water will depend not only on the size (and surface reactivity) of the water clusters in the composition, but also on the number of water clusters dispersed within the fuel. Preferred water cluster/fuel compositions contain at least about 5% water, preferably at least about 20-30%. Particularly preferred water cluster/fuel compositions contain at least about 50% water.
As mentioned above, the water cluster/fuel compositions of the present invention are preferably prepared so that the specific energy of combustion is higher than that of pure fuel. Preferably, the specific energy is increased at least about 1-2%, more preferably at least about 10%, still more preferably at least about 15-20%, and most preferably at least about 50%.
As described in Example 1, we have prepared various water cluster/fuel emulsions and have tested their combustive properties in a standard diesel engine, under normal operating conditions. FIG. 16 presents emission data compiled from combustion of these emulsions, and reveals that NOx and particulate emissions are reduced upon combustion of the inventive emulsions; CO levels may be increased.
The water phase of the inventive emulsions described in Example 1 had a particle size of about 4-7 .ANG.. Moreover, the phase was shown to include inventive water clusters, characterized by oxygen-oxygen vibrational modes. Specifically, an isotope effect was observed in the region of about 100-150 cm@-1 of the Raman spectra of emulsions containing H2 O@18 (see FIG. 15). This effect reveals that vibrations including oxygens are responsible for the spectral lines observed in that region.
The results presented in FIG. 16 were achieved by combusting diesel or water cluster/diesel emulsions in a standard diesel engine. The present invention can therefore readily be implemented with existing technology. However, an additional aspect of the invention involves altering the design of engines used in combustion of water cluster/fuel compositions of the present invention.
One embodiment of an altered engine for use in the practice of the present invention is a derivative of standard diesel engine, altered so as not to have a functional air intake valve. Given that the oxygen used in combustion of the inventive water cluster/fuel compositions can come from the water instead of from air, air intake should not be required.
More dramatic changes in engine design are also envisioned. For example, FIG. 17 presents one embodiment of a new engine for combusting water cluster/fuel compositions of the present invention. As shown, water clusters 100 are injected into a chamber 200, into which fuel 300 is also injected. The water clusters may be prepared by any of the means described above, but preferably are prepared by ejection from a hypersonic nozzle. In preferred embodiments, the nozzle comprises a catalytic material. In some embodiments, the clusters are also ionized by passage through a potential.
As has been discussed herein, it is desirable to expose the fuel to the water clusters in a way that maximizes interaction between fuel carbons and water oxygens. Because pentagonal dodecahedral water structures have high surface reactivity particularly preferred embodiments of the invention inject individual pentagonal dodecahedral water structures into the chamber. One additional advantage of injecting water clusters into a chamber, and particularly of injecting individual pentagonal dodecahedral water structures, is that it allows the Coulombic repulsion between individual water clusters to be harnessed as kinetic energy, thereby increasing the energy available for conversion during combustion.
Once inside the chamber, the water cluster/fuel composition is ignited according to standard procedures. As mentioned above, air intake is not required.
Those of ordinary skill in the art will appreciate that many of the known variations to engine structure and combustion conditions may be incorporated into the present invention. For example, various additives may be included in the water cluster/fuel composition in order to improve combustibility, stability, lubricity or other desirable characteristics.
EXAMPLES
Example 1
Preparation and Analysis of Combustible Water Cluster/Fuel Emulsions
Water cluster/fuel emulsions were prepared according to the following method:
COMPONENT AMNT/GALLON EMULSION
Diesel 0.55 Gal
Water 0.22 Gal
Surfactant I
1.07 lb
Surfactant II
0.27 lb
Surfactant III
0.10 Gal
The water can be distilled water or tap water, or a mixture of water and a short chain alcohol such as methanol. Surfactant I has the structure Cx H20 (OCH2 CH2)y OH, where x=8-10 and y=4-10. Surfactant II is a polyglyceril-oleate or cocoate. Surfactant III is a short chain, (C2-8) linear alcohol.
The emulsions were prepared by mixing the Diesel with Surfactant I and II. Water and surfactant III were then added simultaneously. The water nanodroplets in the emulsion had a grain size of about 4-7 .ANG.. Two particular formulations were prepared that had the following components:
Component Amount (g)
Formulation 1
hexaethoxyoctanol
155.5
polyglyceril-oleate
25.9
diesel 592.5
water 148.4
pentanol 77.7
Formulation 2
hexaethoxyoctanol
148.7
polyglyceril-oleate
37.2
diesel 504.8
water 216.3
40:60 butanol:hexanol
9.29
Raman spectra of Formulation 2, were taken using laser excitation at both 406.7 nm and 647.1 nm. The spectra at 406.7 nm were highly fluorescent and only anti-stokes scattering/emission was carefully examined. The results at 647.1 nm did not have these problems. Isotope shift experiments were performed by introducing H2 O@18 into the emulsions. The H2 O/H2 O@18 difference spectrum is presented as FIG. 15. As can be seen, a peak was observed around 100-150 cm@-1, in the region associated with oxygen-oxygen squashing vibrational modes. Accordingly, it was concluded that the Formulation 2 emulsion contained water clusters having at least pentagonal symmetry.
The water cluster/fuel emulsions were weighed and then were pumped into a small YANMAR diesel engine. Energy output, injection timing, and engine operation were monitored according to standard techniques. Exhaust samples were taken and emissions were analyzed also according to standard techniques.
FIG. 16 presents the results of emissions analysis of two water cluster/fuel emulsions, Formulation 1 and Formulation 2. As can be seen, NOx and particulate levels are reduced, and CO levels may be increased.
Other Embodiments
Those of ordinary skill in the art will recognize that the foregoing has provided a detailed description of certain preferred embodiments of the invention. Various changes and modifications can be made to the particular embodiments described above without departing from the spirit and scope of the invention. All such changes and modifications are incorporated within the scope of the following claims.
US2006110418
Water-in-oil emulsions and methods
Water-in-oil emulsions and methods
BACKGROUND OF THE INVENTION
[0001] Much of the cosmetic industry has been and continues to be focused on the development of effective skin moisturizers to help overcome the skin hydration barrier. However, the typical cosmetic moisturizing formulation uses oil formulations to deliver various active ingredients, with water present as a non-active ingredient carrier, which typically evaporates from the skin surface
[0002] The pharmaceutical industry has likewise devoted a significant part of its resources toward the development of drugs that can be delivered transdermally for the treatment of afflictions ranging from skin disorders to bodily disease. Transdermal drug delivery systems provide for the controlled release of drugs directly into the bloodstream through intact skin. Transdermal drug delivery is an attractive alternative that can be used often when oral drug treatment is not possible or desirable. In particular, with transdermal administration long duration of action and controlled activity is achieved.
[0003] Industry is continually seeking to develop more effective applications of beneficial formulations to the skin.
BRIEF SUMMARY OF THE INVENTION
[0004] The present invention provides water nanocluster/oil (W/O) formulations and methods for delivering water nanoclusters to the skin. In one aspect, the invention provides a process for the delivery of water nanoclusters through the outermost layer of human skin by preparing a water nanocluster composition comprising water nanoclusters having a least one dimension between about 0.5 and 10.0 nanometers (about 5-100 Angstroms) and an oil formulation as a W/O emulsion, and applying said water nanocluster composition onto the outermost layer of human skin.
[0005] The present invention also provides a water nanocluster/oil W/O emulsion composition comprised of (1) about 5 to 50% by weight water containing water nanoclusters having at least one dimension between about 0.5 and 10.0 nanometers (about 5-100 Angstroms), and preferably less than about 1.0 nanometer, (2) about 5 to 50% by weight of one or more surfactants selected from the group consisting of fatty acids, ethoxylates and alcohols, and (3) about 10 to 90% by weight being oils, including other beneficial ingredients.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] FIG. 1 depicts a pentagonal 5-molecule water nanocluster
[0007] FIG. 2 depicts a 20-molecule pentagonal dodecahedral water nanocluster
[0008] FIG. 3 depicts a 20-molecule pentagonal dodecahedral water nanocluster interacting with a typical fatty acid surfactant, oleic acid. The red spheres represent oxygen atoms, the blue spheres represent carbon atoms, and the white spheres represent hydrogen atoms.
[0009] FIG. 4 depicts the ability of the cage structure of the water nanocluster to engulf and clathrate the hydrophobic lipid molecule to counteract the hydrophobic effects of the lipid hydrophobes.
[0010] FIG. 5 depicts the ability of the outermost electronic structure of the water nanocluster to give up an electron and function as an antioxidant.
[0011] FIG. 6 depicts the ability of the outermost electronic structure of Vitamin E to give up an electron and function as an antioxidant.
[0012] FIG. 7 depicts a needle-like array of five pentagonal dodecahedral water clusters sharing a pentagonal face between neighboring dodecahedra.
[0013] FIG. 8 depicts an "end-on" view of the needle-like array of water clusters shown in the above FIG. 7. Note the cavity that runs down the length of the needle.
[0014] FIG. 9 depicts the ability of the outermost electronic structure of the needle-like array of water clusters shown in FIG. 7 to give up an electron and function as antioxidant. (Cf. FIG. 5).
[0015] FIG. 10 depicts the stabilization of the needle-like array of water clusters shown in FIGS. 7 by a single fatty-acid surfactant such as oleic acid.
DETAILED DESCRIPTION OF THE INVENTION
[0016] Water clusters of the type used in the present invention are described in U.S. Pat. Nos. 5,800,576 and 5,997,590, both of which are incorporated herein by reference. The specific formulations described therein are waterclusters/fuel emulsions, but the teaching of the form of the water cluster components (e.g., see columns 1-14 and FIGS. 1-10 of U.S. Pat. No. 5,997,590) are the same as those water clusters useful in this invention. The water clusters are preferably concatenated pentagonal water clusters like that shown in FIG. 12 of U.S. Pat. No. 5,800,576 and are comprised of twenty-one or fewer water molecules and having at least one dimension of 8A (0.8 nm) or less. For example, individual water clusters in dodecahedral form are essentially spherical in shape and have a diameter of about 0.8 nanometer (see FIG. 2); those in pentagonal form are puckered rings and have a diameter of about 0.5 nanometer (see FIG. 1).
[0017] The water clusters can be present as individual water cluster units and/or as an array of aggregated water cluster units. The pentagonal water cluster shown FIG. 2 and the dodecahedral water cluster shown in FIG. 1 are examples of individual water clusters. FIG. 7 shows an array of five dodecahedral water clusters in a needle-like array. One dimension of the array of water clusters is less than about one nanometer (10 Angstroms), with the length of the array being about 3 nanometers (about 30 Angstroms) (see FIG. 7).
[0018] The type and size of the individual water clusters, as well as the degree and type of aggregation thereof, will and may vary in a given water cluster formulation of this invention. For example, a given composition of this invention may contain individual pentagonal and pentagonal dodecahedral water clusters, some of which may be in the form of multi-cluster arrays, e.g., needle-like arrays like that shown in FIG. 7. Regardless of the water cluster type, size and degree of aggregation, one dimension of the water cluster or array thereof, about 10.0 nanometers (100 Angstroms), preferably less than about one nanometer (10 Angstroms), most preferably less than or equal to about 0.8 nanometer (8 Angstroms).
[0019] All of the water which is present need not be in the form of water clusters. Some of the water may be present in traditional bulk water form (i.e., in the form of globules larger than 10 nanometers or 100 Angstroms in diameter, which exhibit all the physical characteristics of bulk water). Since the benefits of the present invention are attributed to the presence of the water clusters, it is preferred that a substantial (most preferably greater than 50%) portion of the water present be in the water cluster form.
[0020] The water nanoclusters of the present invention can be produced by a variety of means as taught in the aforesaid referenced patents (e.g., see columns 9-10 of U.S. Pat. No. 5,997,590). However, for purposes of this invention, use of surfactants to produce the desired nanoemulsion (as described below) is most preferred.
[0021] The oil formulations useful herein include for cosmetic applications: cosmetic industry oils such as soybean, peanut, olive, sesame and paraffin. Suitable cosmetic oil formulation may also include any of a variety of additives useful or non-deleterious in a cosmetic product, such as oil soluble vitamins and other cosmetic nutrients (e.g., Vitamin E), fragrances and other active (e.g., sunscreens) or inert additives, which are preferably soluble in the oil.
[0022] The preferred oil formulation for pharmaceutical applications is light mineral oil. This oil is used to produce pharmaceutical formulations useful herein, which include pharmaceutical ingredients, such as FDA-approved dermatological drugs and vitamin supplements of all types, which are soluble at to a reasonable degree in the oil and/or water nanoclusters. Preferred examples of pharmaceutical ingredients that made be included in the inventive compositions and processes include the topical delivery of Vitamins C and E, which may be for example used to prevent or reverse skin damage due to sun exposure or aging. Vitamin C, soluble (clathrated) in the water nanoclusters, stimulates the production of collagen in the skin and functions as an antioxidant along with the antioxidant property of the water nanoclusters. Vitamin E, soluble in the oil, functions along with the water nanoclusters as antioxidant scavenger of cell-damaging free radicals, and the present invention provides for effective delivery thereof to the skin. Additional or alternative preferred pharmaceutical ingredients include FDA-approved transdermally deliverable "classic" drugs such as hormonally active testosterone, progesterone, and estradiol, glycyril trinitrate (e.g., for treatment of angina), hyoscine (e.g., for seasickness), nicotine (e.g., for smoking cessation); prostaglandin E1 (e.g., for treatment of erectile dysfunction); proteins and peptides; DNA and oligonucleotides (e.g., for gene therapy; DNA vaccines).
[0023] The types of suitable surfactants include fatty acids, ethoxylates and long chain alcohols. Short chain alcohols are also used as cosurfactants. A preferred surfactant has a polar end (typically a carboxyl COOH group) which attaches. itself to a water cluster. Preferably, the surfactant also has at least one long (preferably 6-20 carbons) linear or branched hydrophobic "tail" that is soluble in the cosmetic oil. The surfactants are preferably present in the up to 50% by weight range.
[0024] Preferred fatty acids include hydrolysis products of edible oils, e.g., soybean or Canola oil. These materials consist mainly of oleic and linoleic acid. Purified cuts of these containing larger amounts of these acids can also be used. Fatty acids are examples of anionic surfactants. Anionic surfactants are known to penetrate and interact strongly with skin (P. Morganti et al., J. Appl. Cosmetol. 8, 23, 1990; 12, 25-30, 1994). Most anionic surfactants can induce swelling of the stratum corneum and the viable epidermis (P. Morganti et al., Int. J. Cosmet. Sci. 5, 7, 1983; M. Chvapil and Z. Eckmayer, Int. J. Cosmet. Sci. 7,41-49, 1985). It has been suggested that in conventional cosmetics, the hydrophobic interaction of the alkyl chains with the substrate leaves the negative end group of the surfactant exposed, creating additional anionic sites of the skin membrane (P. Morganti et al., Int. J. Cosmet. Sci. 5, 7, 1983). However, our preferred water clusters in cosmetic formulations bind the negative end group of the surfactant, reducing or eliminating any skin-irritating effects while actually increasing the hydration level of the tissue.
[0025] Some cationic surfactants in skin formulations are more irritating to the skin than the anionics and generally would be less suitable for stabilizing water-cluster nanoemulsions.
[0026] Nonionic surfactants have the smallest potential for producing skin irritation. In conventional cosmetic microemulsions, they seem to have the ability to partition into the intercellular lipid phases of the stratum corneum, leading to increased "fluidity" in this region. Water-cluster cosmetic nanoemulsions stabilized by nonionic surfactants or a mixture of nonionics and anionics are the preferred compositions.
[0027] Ionic surfactants generally have an advantage over nonionic surfactants in being more effective in stabilizing a given amount of water. In addition, they are far more resistant to emulsion breaking at elevated temperature than nonionics. Nonionics maintain themselves at the interface because the polar groups (e. g., -OH) hydrogen bond with water. However, the hydrogen bond is a weak bond (e.g., about 5 Kcal/mol) and becomes less effective as temperature rises above ambient.
[0028] Fatty acids are effective detergents but only when at least partially neutralized. Frequently ammonia or organic bases are used to neutralize fatty acids. Ammonia can be an effective neutralizing agent, but is a very weak base and will serve to neutralize only a fraction of the carboxylate, which is also a weak acid.
[0029] Amines are effective organic bases. Common amines are the lower alkanol amines, such as monoethanol amine (MEA), isopropanol amine and 2-butanol amine. Also common are the lower alkyl amines. There is a degree of neutralization significantly less than 100% for carboxylic acid surfactants which is optimum for solubilizing the maximum ratio of water to surfactant.
[0030] A common nonionic surfactant class useful herein is ethoxylates. Theses are formed by reacting a mole of alcohol or amine with a number of moles of ethylene oxide (EO). The alcohol or amine generally contains a significant sized hydrocarbon group, for example, an akylated phenol or a long chain (C10-C20) alkyl group. Alcohols frequently used are nonyl phenol and lauryl alcohol. The hydrocarbon group serves as the nonpolar section of the molecule. The alcohol can be a can have more than one -OH group and the amine more than one -H, so several ethoxy chains can be present on one molecule. However these multichain ethoxy compounds don't usually function well as surfactants because they do not easily orient at the interface and pack poorly. The balance between hydrophobicity and hydrophylicity is obtained by choosing the hydrocarbon group and the average number of ethylene oxides added. Commonly 3-5 moles of EO are added per mole alcohol or amine.
[0031] Another common class of nonionic surfactants useful herein is long chain (C10-C20) alcohols. These are frequently derived from hydrogenation of fatty acids, e.g., myristyl alcohol from myristic acid. Another source is ethylene oligomerization.
[0032] Microemulsions may include a "cosurfactant" (e.g., n-pentanol), which is not in itself a surfactant (i.e., a material that can not be used as the sole surfactant, but which may be included to improve the functioning of the material which per se can be used herein as a surfactant). Use of co-solvents is theorized to lower the interfacial tension and reduce dramatically the surfactant requirement. Other co-solvents included n-butanol, n-hexanol, 2 methyl 1-pentanol, 2 methyl 1-hexanol and 2 ethyl 1-hexanol.
[0033] One skilled in the art would readily be able to select the amount and type of surfactant to form the desired water clusters, while taking account other considerations (e.g., skin irritation potential) which may be associated with a particular surfactant(s).
[0034] The water cluster/surfactant(s) will be present in the oil as a water-in-oil (W/O) emulsion. The W/O emulsions will be comprise of the water clusters (individual or arrays thereof in the forms, shapes and dimensions described above) with surfactants molecules attached thereto. As shown in FIGS. 2 & 3, the single dodecahredral water cluster with fatty-acid surfactant would exist as a W/O emulsion in the cosmetic oil. The water cluster itself is spherical and has a diameter of about 0.8 nanometer (8 Angstroms), with the surfactant molecule extending from the cluster, resulting in a W/O reverse micelle of about 3 nanometers (30 Angstroms) in diameter. As shown in FIGS. 7 & 8, a five-dodecahedral water cluster needle-like array with fatty-acid surfactant would also exist as a W/O emulsion in the cosmetic oil. The water cluster array itself is needle-like and has one dimension of about 0.8 nanometer an a length of about 3 nanometers, with the surfactant molecule linearly clathrated in the needle cavity, resulting in a cylindrically symmetric W/O micelle of about 4 nanometers. (40 Angstroms) in its largest dimension and about 0.8 nanometers (8 Angstroms) in its smallest dimension
[0035] Preferred concentrations of water by weight are about 5-50% with the surfactant concentration (typically one surfactant molecule per water cluster) chosen to maximize the presence of water clusters between about 0.5 and 10 nanometers (about 5-100A), and preferably water clusters about 0.8 nm (about 8A) size in the formulation, to minimize separation of water and oil phases prior to application, thereby ensuring long shelf life.
[0036] Application of Water Nanoclusters to the Skin
[0037] The present invention provides a process for delivery of water nanoclusters through the outmost layer of skin. First, a water nanocluster composition comprising water nanoclusters having diameters between 0.5 and ten nanometers (5-100A) and preferably water clusters of diameter less than one nanometer (10A) and an oil formulation is prepared. The water nanocluster composition is then applied preferably to the outermost layer of human skin.
[0038] The skin as a physiological regulator plays a key role in the general metabolism of water in the body. Thus the moisture level of the outermost layer of the skin, the stratum corneum, is critical to maintaining the skin surface healthy and supple. Yet the stratum corneum is believed to be mainly responsible for the rate limiting of skin moisture permeation through the hydrophobic barrier presented by its intercellular lipids (H. Schaefer et al., in Novel Cosmetic Delivery Systems, S. Magdassi and E. Touitou, Eds., Marcel Dekker, New York, 1999, pp. 949).
[0039] First-principles quantum-chemistry computations of the electronic structure and low-frequency vibrational modes of water nanoclusters discussed herein, suggest that the permeating clusters will (1) clathrate and deactivate lipid hydrophobes responsible for the stratum corneum hydration barrier, (2) chemically scavenge free radicals that otherwise damage and age epidermal cells, (3) enhance the transdermal delivery of ingredients and (4) be subject to less water evaporation on the skin surface because of the intrinsic stability of the water nanoclusters.
[0040] The present invention provides a process and formulation which is capable of providing an effective (1) skin moisturizer, (2) anti-oxidant capable of reducing cell damage and ageing and (3) a mechanism for the delivery of beneficial cosmetic and/or pharmaceutical ingredients to the skin.
[0041] The skin moisturizer benefits are provided due to the present invention's unique capability of effectively overcoming the skin hydration barrier. First, the preferred water clusters of these this invention are less than the 10A (1 nm) size characteristic of the hydrophobic lipid intermolecular spacing and pore diameter of human skin, which enables physical penetration. Second, these water clusters have the unique capability of enclosing or "clathrating" lipid hydrophobes, which thereby counteract the hydrophobic effects of the lipid hydrophobes. This is exemplified in FIG. 3 for a pentagonal dodecahedral water cluster clathrating the end of a typical fatty acid lipid.
[0042] The antioxidant benefits include chemically scavenging free radicals that otherwise damage and age epidermal cells. These benefits are obtained from the functionality of these water clusters after the formulation containing them has been applied to the skin and effectively penetrate the to the outermost layer of human skin. After such penetration has occurred, these water clusters further serve as active antioxidants for scavenging cell-damaging free radicals. Providing anti-oxidarits, such as Vitamin E, to the human body by ingestion and dermal penetration has been a matter of considerable technical and commercial focus. Vitamin E antioxidant function is believed to be associated with its ability to donate electrons to cell-destroying free radicals via the p[pi] molecular electron orbitals located on the carbon ring moiety at one end of the molecule, as shown in FIG. 6. Without being limited to the theoretical explanation thereof, it is believed that the antioxidant functionality of the water cluster formulations of this invention is generally<1> similar to that of Vitamin E but is based upon the electron-donating power of the unique water-cluster surface p[pi] molecular electron orbitals, coupled with the low-frequency water-cluster breathing vibrational modes through the dynamic Jahn-Teller effect. As shown in FIGS. 5 & 9, the unique water-cluster surface p[pi] electron-donating molecular orbitals are qualitatively similar to the p[pi] molecular electron orbitals located on the carbon ring moiety at one end of the Vitamin E molecule shown in FIG. 6.
[0043] Individual pentagonal or needle-like arrays of pentagonal dodecahedral clusters like the ones shown in FIGS. 2 & 7 holding an extra electron donated by the surfactant (FIGS. 3 & 10) are potentially powerful antioxidants equal to or better than Vitamin E because of the effectively large reactive cross sections of the cluster surface delocalized oxygen p[pi] orbitals mapped in FIGS. 5 & 9. As shown in FIGS. 5 & 9, these water clusters can function as electron reservoirs for chemical reactions involving electron transfer to the reacting species. Thus water-cluster hydrated-electron delocalized orbitals, originating on the cluster surface oxygen atoms, can readily overlap with and scavenge cell-damaging free radicals.
[0044] Small polyhedral clusters of water molecules, especially quasiplanar and concatenated pentagonal water clusters (e.g. FIGS. 1 & 2), have been experimentally identified as being key to the hydration and stabilization of biomolecules (M. M. Teeter, Proc. Natl. Acad. Sci. 81, 6014. 1984), proteins (T. Baker et al., in Crystallography in Molecular Biology, D. Moras et al., Eds., Plenum, New York, 1985, pp 179-192), DNA (L. A. Lipscomb etal., Biochemistry 33, 3649, 1994), and DNA-drug complexes (S. Neidle, Nature 288, 129, 1980). Such examples indicate the tendency of water pentagons to form closed geometrical structures like the pentagonal dodecahedra shown in FIGS. 1 and 2. It has also been suggested that such water clusters may play a fundamental role in determining biological cell architecture (J. G. Watterson, Molec. And Cell. Biochem. 79, 101, 1988). Approximately 70 percent of the human body is water by weight. Much of that water is believed not to be ordinary bulk liquid, but instead, nanoclustered, restructured water which affects biomolecular processes ranging from protein stability to enzyme activity (J. L. Finney, Water and Aqueous Solutions, G. W. Nelson and J. E. Enderby. Eds., Adam Hilger, Bristol, 1986, pp. 227-244).
EXAMPLES
Example 1
[0045] A Water Nanocluster/Cosmetic Oil formulation is prepared by mixing the following ingredients to make 1 Kg of formulation.
Component Weight Percent
Soybean Oil 50
Water 25
Surfactant 20
Surfactant II 4
Surfactant III 1
[0046] The water is deionized. Surfactant I is an ethoxylate with the molecular structure C8H17 (OCH2CH2)6OH. Surfactant II is a polyglyceryl-oleate. Surfactant III (a cosurfactant) is n-pentanol.
[0047] The nanoemulsions are prepared by mixing the soybean oil with Surfactants I and II. Water and Surfactant III are then added simultaneously.
[0048] The resultant Water Nanocluster/Cosmetic Oil formulations is a W/O emulsion, with a significant population of stable water nanoclusters in the The water is deionized. Surfactant I is a partially (80%) neutralized (with isopropanol amine) soybean fatty acid. Surfactant II is an ethoxylate with the molecular structure C8H17 (OCH2CH2)mOH. Surfactant III (a cosurfactant) is n-pentanol.
[0049] The nanoemulsions are prepared by mixing the soybean oil with Surfactants I and II. Water and Surfactant III are then added simultaneously.
Example 4
[0050] A cosmetic oil in which the water is not in the form of nanosized micelles is made as follows:
Component Weight Percent
Soybean Oil 73
Water 25
Surfactant I 1
Surfactant II 3
[0051] The water is deionized. Surfactant I is a polyglyceryl-leate. Surfactant II (a cosurfactant) is n-pentanol. The nanoemulsion is prepared by mixing the soybean oil with Surfactant I. Water and Surfactant II are then added simultaneously.
[0052] Three grams of this formulation are placed on a watch glass and this watch glass is placed on a scale. Three grams of the formulation of Example 1 are placed on another watch glass on another scale. Weight losses for each are as follows:
Weight loss, mg.
Time, hr. Example 1 Example 4
1 28 122
2 62 226
3 83 307
Example 5
[0053] referred size range deliverable to the skin are prepared. The water nanoclusters are in the <2-10 nm nanocluster range as determined by dynamic light scattering and Raman spectroscopy to identify water clusters below 2 nm through their well defined vibrational spectra.
[0054] The resultant formulation is applied to the skin, as in any conventional cosmetic application, and penetrates the outmost layer of the skin.
Example 2
[0055] A second formulation is made as follows:
Component Weight Percent
Soybean Oil 50
Water 25
Surfactant I 12
Surfactant II 12
Surfactant III 1
[0056] The water is deionized. Surfactant I is an ethoxylate with the molecular structure C8H17(OCH2CH2)6OH. Surfactant II is a partially (50-80%) neutralized (with isopropanol amine) soybean fatty acid. Surfactant III (a cosurfactant) is n-pentanol.
[0057] The nanoemulsions are prepared by mixing the soybean oil with Surfactants I and II. Water and Surfactant III are then added simultaneously.
Example 3
[0058] Another cosmetic formulation is formed from the following ingredients:
Component Weight Percent
Soybean Oil 50
Water 25
Surfactant I 20
Surfactant II 4
Surfactant III 1
[0059] The cosmetic mixtures of Examples 1 and 4 are made up as above. Five (5) grams of each is placed on two 5 cm*5 cm samples of synthetic skin manufactured by Integra Life Sciences Company, under the trade name Integra, which has a water permeability comparable to that of human skin. Five layers of filter paper are placed under each skin sample. Periodically the filter paper samples are weighed. The percent transport of the water through each skin layer is as follows:
Time hr. Example 1 Example 4
2 7 2
5 22 8
10 41 14
Example 6
[0060] A transdermal Water Nanocluster/Vitamin C/Oil antioxidant formulation is prepared by mixing the following ingredients to make 1 Kg of formulation.
Component Weight Percent
Light mineral oil 40
Water 25
Vitamin C 10
Surfactant 20
Surfactant II 4
Surfactant III 1
[0061] The water is deionized. Surfactant I is an ethoxylate with the molecular structure C8H17 (OCH2CH2)6OH. Surfactant II is a polyglyceryl-oleate. Surfactant III (a cosurfactant) is n-pentanol.
[0062] The nanoemulsions are prepared by mixing the mineral oil with Surfactants I and II. Water, Vitamin C, and Surfactant III are then added simultaneously.
[0063] The resultant Water Nanocluster/Vitamin C/Oil formulation is a W/O nanoemulsion, with a significant population of stable water nanoclusters clathrating the Vitamin C in the preferred size range deliverable to the skin are prepared. The water nanoclusters are in the <2-10 nm nanocluster range, as determined by dynamic light scattering and Raman spectroscopy to identify water clusters below 2 nm through their well defined vibrational spectra.
[0064] The resultant formulation is applied in small amounts to the skin and penetrates the outmost layer of the skin.
Example 7
[0065] A transdermal Water Nanocluster/Oil/Vitamin E antioxidant formulation is prepared by mixing the following ingredients to make 1 Kg of formulation.
Component Weight Percent
Light mineral oil 40
Water 25
Vitamin E 10
Surfactant 20
Surfactant II 4
Surfactant III 1
[0066] The water is deionized. Surfactant I is an ethoxylate with the molecular structure C8H17 (OCH2CH2)6OH. Surfactant II is a polyglyceryl-oleate. Surfactant III (a cosurfactant) is n-pentanol.
[0067] The nanoemulsions are prepared by mixing the mineral oil with Surfactants I and II and Vitamin E. Water and Surfactant III are then added simultaneously.
[0068] The resultant Water Nanocluster/Oil/Vitamin E formulation is a W/O nanoemulsion, with a significant population of stable water nanoclusters in the preferred size range deliverable to the skin are prepared. The water nanoclusters are in the <2-10 nm nanocluster range, as determined by dynamic light scattering and Raman spectroscopy to identify water clusters below 2 nm through their well defined vibrational spectra.
[0069] The resultant formulation is applied in small amounts to the skin and penetrates the outmost layer of the skin.
Example 8
[0070] A transdermal water Nanocluster/Nano Zinc Oxide/Oil antibacterial formulation is prepared by mixing the following ingredients to make 1 Kg of formulation.
Component Weight Percent
Light mineral oil 40
Water 25
Nano Zinc Oxide 10
Surfactant 20
Surfactant II 4
Surfactant III 1
[0071] The water should be deionized. Surfactant I is an ethoxylate with the molecular structure C8H17 (OCH2CH2)6OH. Surfactant II is a polyglyceryl-oleate. Surfactant III (a cosurfactant) is n-pentanol.
[0072] Most preferably the water nanocluster compositions of this invention are stable (i.e.; they are thermodynamically stable) in the form of water-in-oil (W/O) nanocluster emulsion for extended periods, most preferably, for months or years after they are formulated). Although an oil and water emulsion can be made by various mixing techniques and/or through the use of other surfactants, such emulsions are typically either oil-in-water (O/W) emulsions (i.e.; not W/O emulsions) and/or are not stable (e.g.; significant phase separation occurs immediately or within hours or several days after preparation). In accordance with the present invention, highly stable (e.g.; which remain stable for 24-36 months) water-in-oil nanocluster emulsion for cosmetic applications are provided through the use of surfactants selected from the group consisting of fatty acid and fatty acid amides, most particularly when the cosmetic oils and the surfactant are mixed prior to the addition of the water, as shown below in Examples 9 and 10.
[0073] As discussed hereinabove, a preferred surfactant has a polar end (typically a carboxyl COOH group) which attaches itself to a water cluster and the surfactant also has at least one long (preferably 6-20 carbons) linear or branched hydrophobic "tail" that is soluble in the cosmetic oil. Fatty acid amides are most preferred including the simple fatty acid amides (having the formula R-CO-NH2), which result from the replacement of the hydroxyl of the carboxyl group with an amino group and fatty acid alkanolamides (having the formula R-CO-NH-CH2-CH2-OH), typically derived from fatty acids (e.g.; coconut oil) and alkanolamines. Among the most preferred fatty acid amides are Tallamide diethanolamine (DEA) and Cocamide DEA obtainable from McIntyre Group, Ltd., University Park, Il.60466, under the trade names Mackamide TD and Mackamide C-5, respectively. These surfactants, when used in the preparation of water nanocluster compositions of this invention, by mixing mineral (cosmetic) oil and the surfactant prior to the addition of the water, form water-in-oil nanocluster emulsion form for extended periods which remain stable essentially.
[0074] Additional materials such as PPG-3 Myristyl Ether, may also be used to enhance the mixing of the surfactant and the oil. However, the most important mixing benefit is obtained by the order of mixing (i.e.; mixing the cosmetic oil and surfactant prior to the addition of the water components).
[0075] As noted above, one skilled in the art would readily be able to select the amount and type of surfactant to form the desired water clusters, while taking account other considerations (e.g.; skin irritation potential) which may be associated with a particular surfactant(s) as well as avoiding the use of other ingredients, which may be unsuitable or limit the intended end-use. For example, although a variety of surfactants are noted in the preparation of nanoemulsions discussed in U.S. Pat. Nos. 5,800,576 and 5,997,590 and suitably form nano-emulsions with the diesel oils and other fuels oils for the combustion-related uses therein, such surfactants may not necessarily form the stable water nanocluster compositions of the cosmetic and pharmaceutical oils in the present invention (because of the inherent differences in these types of oils) and/or the hazardous properties of these oils. Further, although trimethylpentane may have been considered as a potential cosmetic in some applications, due to its hazardous properties, including skin contact hazards, such materials are not considered to cosmetic oils as the term is used herein.
Example 9
[0076] An preferred water nanocluster compositions of this invention is prepared by mixing the following ingredients in the specified approximate weight percentages:
Mineral Oil 65.8%
Tallamide DEA 11.3%
Distilled Water 22.9%
[0077] The mixing procedure involves adding the components in the order indicated above, with the oil/surfactant components premixed with a little stirring prior to the addition of the distilled water. Thick whitish tendrils are formed as the water is added drop wise into the oil/surfactant mixture. After a little stirring and a few seconds time, the final blend clarifies, indicative of the formation of a water-in-oil (W/O) nanoemulsion. The formulation at this point is a pale yellowish liquid of medium viscosity, with a very slight haze. This product is non-irritating to skin and remains a stable nanoemulsion for over 36 months.
[0078] Dynamic light-scattering measurements of the nanoemulsions indicate water-micelles between one and six nanometers (10-60 Angstroms) in diameter. Adding more water to the above mixture to a total of approximately 30% water, the mixture becomes whitish, with a tendency to thicken over time. At 40% water, a creamy white emulsion is obtained, similar to a traditional hand lotion in consistency and appearance. Continuing to add water stepwise (about 5% at a time) up to 75% water produces a lotion-like product that is stable. This procedure requires no mechanical mixing whatsoever or application of heat, as is the case for commercial production of cosmetics "pre-mixes", and therefore is a major cost-saving method of making cosmetic lotions.
Example 10
[0079] Another preferred water nanocluster compositions of this invention is prepared by the same procedure as in EXAMPLE 9, except that a mixture of Tallamide DEA and Cocamide DEA is used as the surfactants, with the percentages being 8.0 wgt % and 3.3 wgt. % respectfully, instead of using 11.30 wgt. % of Tallamide DEA alone. A water-in-oil (W/O) nanoemulsion, which is essentially identical to that of EXAPLE 9 is formed and has essentially identical properties and characteristics.
http://article.sapub.org/10.5923.j.pc.20120201.05.html
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http://article.sapub.org/10.5923.j.pc.20120201.05.html
Physical Chemistry 2012; 2(1): 21-26
doi:10.5923/j.pc.20120201.05
Water Clusters in Liquid Fuels. Their Role and
Surroundings
Kristina Zubow, Anatolij Zubow, Viktor Anatolievich Zubow
Kristina Zubow, Anatolij Zubow, Viktor Anatolievich Zubow
Abstract
The long-range order in n-hexane, gasoline, diesel and in their mixtures with/without water is investigated by the gravitational mass spectroscopy (GMS). Molecular clusters are analyzed to be present in fuels and mixtures. Using GMS subtraction spectra for water in hydrocarbons, it becomes clear what role water plays and how it interact with the surroundings. Water in fuels is concluded to appear as individual clusters, whose structure (density) depends on the nature of hydrocarbon clusters. The combustion mechanism of hydrocarbons saturated with water will be discussed. Water clusters are suggested to accelerate the diffusion processes of the combustion. Molecular clusters in liquid fuels are formed in stationary gravitational waves of white noises, penetrating the Earth.