WO2001004234A1 - Procede de stabilisation d'une phase cristalline liquide lyotropique inverse - Google Patents

Procede de stabilisation d'une phase cristalline liquide lyotropique inverse Download PDF

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Publication number
WO2001004234A1
WO2001004234A1 PCT/GB2000/002590 GB0002590W WO0104234A1 WO 2001004234 A1 WO2001004234 A1 WO 2001004234A1 GB 0002590 W GB0002590 W GB 0002590W WO 0104234 A1 WO0104234 A1 WO 0104234A1
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Prior art keywords
liquid crystalline
inverse
crystalline phase
amphiphile
lyotropic liquid
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PCT/GB2000/002590
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English (en)
Inventor
Richard Hilary Templer
Paul David Lickiss
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Imperial College Of Science, Technology And Medicine
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Application filed by Imperial College Of Science, Technology And Medicine filed Critical Imperial College Of Science, Technology And Medicine
Priority to AU56982/00A priority Critical patent/AU5698200A/en
Priority to GB0130959A priority patent/GB2367300A/en
Publication of WO2001004234A1 publication Critical patent/WO2001004234A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials

Definitions

  • the present invention relates to a methodology for the stabilisation of inverse lyotropic liquid crystalline phases.
  • amphiphile refers to a molecule that contains a lyophilic polar head group and one or more lyophobic chains. In aqueous solutions, amphiphiles spontaneously form structures which hide the lyophobic chains but allow the polar head groups to be hydrated.
  • Lyotropic phases are characterised in the art by the amount of curvature they exhibit. For example, where an amphiphilic monolayer bends towards the water phase, the lyotropic phase is called an inverse phase. In contrast, where a monolayer bends away from the water phase, the lyotropic phase is called a normal phase.
  • Amphiphiles that have a propensity for forming inverse lyotropic crystalline phases are characterised by a desire for the area per molecule at the headgroup to shrink whilst simultaneously the cross-sectional area in the chain region wishes to expand. This means that the monolayer fluid interface formed by such molecules in water will wish to have interfacial curvature. It has recently been shown that for known amphiphile/ water systems the monolayer interface wishes to exist in the form of spherical, cylindrical and hyperbolic geometries, each being increasingly more energetically costly with respect to the curvature energy.
  • the monolayer is to form a spherical interface in an amphiphile/water mixture it must pay an energetic cost. This cost arises because the spheres have to have a Euclidean packing of space. If the interface remains spherical then the amphiphilic chain must be deformed to reach the peripheral edges and vertices of any chosen packing space. Alternatively the interface may deform away from its preferred geometry. Whichever choice is made, the system is energetically frustrated because of the need for the chains to pack the lyophobic region of any inverse lyotropic liquid crystalline structure. Here the energetic cost of the packing frustration is greatest for packings of spherical interfaces and least for hyperbolic interfaces.
  • WO 98/30318 relates to inverse hexagonal phase-forming lyotropic liquid crystalline monomers in which a polymerisable group is attached to each of the hydrophobic lipid tail groups.
  • the resulting composite may further comprise a matrix component and a filler component.
  • the present invention seeks to provide an improved method of stabilising inverse lyotropic liquid crystalline phases.
  • the present method provides stable inverse lyotropic liquid crystalline phases in which the amphiphiles remain fluid, i.e. the amphiphiles are free to diffuse along the amphiphile/solvent interface.
  • the present invention relates to a method of stabilising an inverse lyotropic liquid crystalline phase, i.e. a phase bending towards the aqueous phase.
  • liquid crystalline phase refers to a phase having fluid properties similar to that ⁇ of a viscous liquid and a degree of molecular disorder similar to a crystalline solid.
  • the invention provides a method of stabilising an inverse lyotropic liquid crystalline phase, said method comprising the steps of:
  • lyophobic refers to a species having a low affinity for the continuous phase, i.e. "solvent-hating”.
  • lyophilic refers to a species having a high affinity for the continuous phase, i.e. "solvent-loving”.
  • the polar medium is water.
  • the stabilisation method of the present invention makes use of the balance between the desire for uniform monolayer, interfacial curvature and the need to uniformly pack the lyophobic regions of inverse phases.
  • By allowing larger volume fractions of such a lyophobic molecule to partition into the stressed regions of the phase one eventually scans through all the available phase geometries, i.e. lamellar, inverse bicontinuous cubic, inverse hexagonal, inverse micellar cubic and finally inverse micellar. This has been demonstrated previously with alkanes and alkenes for a range of different systems.
  • the polymerisation step, (b) is induced by a polymerisation initiator.
  • Suitable polymerisation initiators include those which are radiation sensitive, thermally sensitive, anaerobic sensitive or aerobic sensitive.
  • the term "radiation" in relation to the polymerisation initiator covers any suitable polymerisation initiator that is activated by a suitable radiation source, such as any one or more of UV, visible, IR, ⁇ , ⁇ or ⁇ radiation.
  • a suitable radiation source such as any one or more of UV, visible, IR, ⁇ , ⁇ or ⁇ radiation.
  • it includes photosensitive polymerisation initiators.
  • it is preferably a UV polymerisation initiator.
  • the photoinitiator may be of the free radical type, for example, those sold under the trade name IRGACURE: for example, either 2,2-dimethoxy-l,2-diphenylethane-l-one (Irgacure
  • radical photoinitiators include 2-hydroxy-2-methylpropiophenone, 2,2-dimethyl-2-2- phenylacetophenone, 4-4'-dihydroxy benzophenone.
  • anaerobic in relation to the polymerisation initiator covers any suitable polymerisation initiator that enhances or activates the polymerisation of monomers in the substantial absence of oxygen.
  • anobic in relation to the polymerisation initiator covers any suitable polymerisation initiator that enhances or activates the polymerisation of monomers in the presence of oxygen.
  • thermal in relation to the polymerisation initiator covers any suitable polymerisation initiator that is activated by the application or exposure to heat - which can come from or be generated by any suitable source.
  • Suitable initiators which are heat sensitive include essentially any organic peroxide or azo compound, for example, benzoyl peroxide, azobis(isobutyronitrile) (AIBN), and t-butylperoxide.
  • the initiator is AIBN.
  • the lyotropic liquid crystalline phase of the invention is an inverse fluid lamellar phase.
  • Lamellar phases are the simplest and most common of all the lyotropic crystalline phases and consist of a one-dimensional stack of fluid bilayers having a typical thickness of 30-
  • the lyotropic liquid crystalline phase of the invention is an inverse bicontinuous cubic phase.
  • Bicontinuous phases are non-lamellar phases which exhibit the least degree of curvature and appear to be based on mathematical surfaces known as infinitely periodic minimal surfaces.
  • Typical examples of bicontinuous cubic phases include the double diamond phase (based on D minimal surface and with water channels that connect at 4-fold junctions), the gyroid phase (with helical channels of opposite chirality and water channels that connect at 3-fold junctions), and phases with cubic symmetry (based on P minimal surface and with water channels that connect a 6-fold junctions).
  • the lyotropic liquid crystalline phase of the invention is an inverse hexagonal phase.
  • inverse hexagonal phase refers to a matrix geometry of tubular channels in which the lyophilic head groups of the amphiphile are orientated towards the centre of the cylindrical axis and the lyophobic tail portions extend outwards. Confirmation of the inverse hexagonal geometry can be made by polarised light spectroscopy or low angle X- ray diffraction.
  • the lyotropic liquid crystalline phase of the invention is an inverse micellar phase.
  • mice phase refers to discrete discontinuous aggregates of amphiphiles. More particularly, the term “inverse micellar phase” refers to discrete discontinuous aggregates of amphiphiles wherein the lyophobic groups are on the outside in contact with the polar medium and the lyophilic polar head groups are on the inside of the micelle.
  • amphiphile of the present invention is a glycolipid or a phospholipid, each of which may be derived from a glyceride.
  • glycolide refers to fatty acid esters of glycerol which may be esterified at one, two or all three hydroxyl groups to give mono-, di- and triglycerides respectively.
  • the glyceride is an ester of glycerol, and a C 4 to C 24 fatty acid. More preferably, the glyceride is selected from glycerides having a fatty acid chain length of no greater than 14 carbons, glycerides having a fatty acid chain length of from 4 to 14 carbons, glycerides having a fatty acid chain length of from 6 to 14 carbons, glycerides having a fatty acid chain length of from 8 to 14 carbons, glycerides having a fatty acid chain length of from 10 to 14 carbons, glycerides having a fatty acid chain length of 12 carbons, glycerides having a fatty acid chain length of from 16 to 24 carbons, glycerides having a fatty acid chain length of from 16 to 22 carbons, glycerides having a fatty acid chain length of from 18 to 22 carbons, glycerides having a fatty acid chain length of from 18 to 20 carbons, mixtures and
  • Typical phospholipids suitable for use in the present invention include any of the above- mentioned glycerides wherein at least one of the hydroxy groups is esterified with a phosphate group.
  • Typical glycolipids suitable for use in the present invention include any of the above-mentioned glycerides wherein at least one of the hydroxy groups is esterified with a sugar.
  • the amphiphile is selected from 1-monoolein, dioleoylphosphatidylcholine and dioleoylphosphatidyl-ethanolamine, or a mixture thereof.
  • the stabilisation method of the present invention uses a polymerisable lyophobic component.
  • lyophobic material refers to a compound which is lyophobic or a compound which has a lyophobic group attached thereto.
  • the polymerisable lyophobic component is hydrophobic.
  • suitable polymerisable lyophobic components include one of: (alkyl and cycloalkyl) acrylates or diacrylates; (alkyl and cycloalkyl) methacrylates or dimethacrylates; free-radical polymerisable olefinic acids, including alkoxy-, alkylphenoxy-, alkylphenoxy-(polyethyleneoxide)-, vinyl ester-, amine substituted (including quaternary ammonium salts thereof), nitrile-, halo-, hydroxy-, and acid substituted (for example phospho- or sulpho-) derivatives thereof; and other suitable ethylenically unsaturated polymerisable moieties; including combinations thereof.
  • the alkyl and cycloalkyl groups contain up to 20 carbon atoms, e.g. (C1-C20 alkyl and C1-C20 cycloalkyl) acrylates or diacrylates. and (C1-C20 alkyl and C1-C20 cycloalkyl) methacrylates or dimethacrylates.
  • typical monomers include any one of methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isobornyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, iso-octyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate, eicosyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, 1,4- butanediacrylate, 1,5-pentanediacrylate, 1 ,6-hexanediacrylate, 1,7-heptanediacrylate, 1,8- octanediacrylate, 1 ,9-
  • GMAK hydroxy ethyl methacrylate
  • HEMA hydroxy ethyl methacrylate
  • alkyl methacrylates or dimethacrylates such as Cl-20 alkyl methacrylates, more preferably Cl-15 alkyl methacrylates, more preferably Cl-10 alkyl methacrylates, more preferably Cl-5 alkyl methacrylates, such as methyl methacrylate
  • alkyl acrylates or diacrylates such as Cl-20 alkyl acrylates, more preferably Cl-15 alkyl acrylates, more preferably Cl-10 alkyl acrylates, more preferably Cl-5 alkyl acrylates, such as methyl acrylate
  • the polymerisable lyophobic component may be crosslinking or non-crosslinking.
  • the polymerisable lyophobic component is non-crosslinking, preferably it is contacted with a crosslinking agent on polymerisation.
  • the polymerisable lyophobic component is an acrylate-containing component.
  • the polymerisable lyophobic component of the invention is 1 ,9-nonanebisacrylate.
  • said polymerisable lyophobic component is 1 ,9- nonanebisacrylate
  • said initiator is AIBN
  • said polar medium is water
  • said amphiphile is selected from 1-monoolein, dioleoylphosphatidylcholine and dioleoylphosphatidylethanol-amine, or a mixture thereof.
  • each amphiphile is free to diffuse along the amphiphile/polar medium interface.
  • fluid amphiphilic interfaces have been stabilised by the direct polymerisation of one amphiphile to its neighbours or by solidifying the aqueous regions. The essential difference in the outcome of the present method is that the interface remains fluid, i.e. the amphiphiles remain free to diffuse along the interface.
  • the inverse lyotropic liquid crystalline phase is stabilised with respect to changes in temperature and/or pH.
  • changes in temperature and/or pH do not destabilise the supramolecular structure to such an extent as to cause it to rearrange into an alternative, lower energy conformation.
  • the present invention also provides inverse lyotropic liquid crystalline phases that are stabilised by the method of the invention.
  • the invention provides a composition comprising:
  • a polymer comprising a polymerised lyophobic component, wherein the lyophobic component is in addition to the amphiphile, and disposed in the lyophobic region of said inverse liquid crystalline phase.
  • each amphiphile is free to diffuse along the amphiphile/polar medium interface.
  • the amphiphiles are free to diffuse along the interface between the polar medium (usually water) and the polar head groups of the amphiphiles.
  • a third aspect of the invention provides a process for preparing a stable inverse lyotropic liquid crystalline phase, said process comprising the steps of:
  • a fourth aspect of the invention provides a method of stabilising an inverse lyotropic liquid crystalline phase, said method comprising the steps of:
  • the present invention thus provides a simple generic approach for stabilising self assembled inverse lyotropic structures.
  • Specific volume fractions of lyophobic polymer precursor and initiator are brought into contact with an amphiphile and a polar medium to induce the full range of inverse lyotropic liquid crystalline phases: fluid lamellar, inverse bicontinuous cubic, inverse hexagonal and inverse micellar.
  • the polymer precursor resides in the lyophobic region of these phases so as to release the packing frustration.
  • Subsequent polymerisation produces a highly interconnected polymer network in the lyophobic regions of these phases.
  • the amphiphilic interface remains fluid, but the phase structure is now stable to thermodynamic changes.
  • the stabilised inverse lyotropic liquid crystalline phases of the invention may be useful in the preparation of molecular sieves.
  • the teachings of the present invention enable the diameter of the water channels in the resulting material to be fine-tuned in accordance with the desired properties of the particular type of molecular sieve.
  • the method, process and compositions of the invention may also have applications in the field of slow release drug products. To date, it has often proved difficult to deliver small non-polar hydrophobic drugs in therapeutically effective amounts to the desired target within the body. As a consequence, such species usually have to be administered in extremely high amounts in order to compensate for poor delivery mechanisms.
  • compositions of the present invention have the potential to encapsulate small hydrophobic drug molecules in their hydrophobic regions, thereby allowing the drugs to be transported within the body and released gradually over a period of time.
  • the compositions of the present invention should enable such species to be delivered more efficiently, thereby allowing the administration of lower concentrations.
  • the method, process and compositions of the present invention may also have potential applications in the field of catalysis, more specifically enzymatic catalysis.
  • the lyophilic regions of the compositions of the invention may be used to encapsulate small reactant molecules, such as peptides, which require solvation.
  • the resulting material may then be processed (for example, by grinding) and subsequently used as a "high concentration" reaction medium to speed up reactions which would otherwise have to be carried out at high dilution.
  • the method, process and compositions of the present invention may also be useful for templating the formation of nanostructures. More specifically, by carrying out reactions within the channels of the compositions, it should be possible to influence the geometry of the product obtained. One such possibility would be to induce the formation of rod- like inorganic materials by allowing the synthesis to take place within the channels of the composition.
  • the present invention has been successfully demonstrated using lyotropic phases made up of a variety of mixtures of 1-monoolein, dioleoylphosphatidylcholine and dioleoylphosphatidylethanolarnine in water, and using the polymer precursor, 1, 9 - nonanebisacrylate with AIBN as the initiator. To date, this is believed to be the first example of the stabilisation of self assembled, fluid, supra-molecular structures. The methodology of the present invention has been tested in a variety of amphiphilic systems.
  • One such example is the induction and stabilisation of the Pn3m, inverse bicontinuous cubic phase and the inverse hexagonal phase in a mixture of 1-monoolein and dioleoylphosphatidylcholine using 1,9-nonanebisacrylate as the polymer precursor and AIBN as the initiator.
  • 1,9-nonanebisacrylate the system was shown to exhibit a fluid lamellar structure.
  • contacting a small volume fraction of the polymer precursor with the amphiphile and polar medium induced the inverse bicontinuous cubic phase.
  • polymerisation takes place and once completed, the Pn3m phase is stabilised as a hydrated plastic.
  • the wide angle X-ray scattering patterns demonstrates that the amphiphilic chains are still fluid, whereas the low angle pattern confirms that the self assembled lyotropic structure is stabilised.
  • the stability of these structures has been tested and it has been revealed that changes in temperature of up to 80 °C do not change the lattice parameter of the structures or the polymerised phases. This observation is in stark contrast to the phase and structural behaviour observed before polymerisation.
  • test sample was placed in a sealed jar containing degassed water and placed in a water bath at 60°C for 18h. Upon removal from the water bath the sample was immediately cooled to 4°C.
  • the polymerisation yields a waxy white solid that exhibits birefringence on viewing through crossed polarisers.
  • the birefringent texture of both the polymeric sample and control is typical of a two dimensional hexagonal structure.
  • the polymeric sample does not deform under pressure, in contrast with control sample which is fluid.
  • Small angle X- ray diffraction of both samples shows Bragg reflections with spacings indexed in the ratio Vl, V3, 4 and 7, indicative of two dimensional hexagonal symmetry.
  • the lattice parameters of the samples are 70.43 A and 54.11 A, for the polymeric and control samples respectively.
  • Wide angle X-ray diffraction of the polymeric sample shows a diffuse peak centred at 4.6A due to fluid motion of the lipid chains.
  • the bulk sample was formed as a white solid in contrast to the control sample which appears with a clear gel-like texture.
  • Small angle X-ray diffraction of the polymeric sample showed Bragg reflections indexed with the ratio 2, V3, 4, V ⁇ , and V ⁇ , consistent with a bicontinuous cubic phase of Pn3m symmetry. This symmetry was observed over the temperature range 10-60°C Wide angle diffraction exhibits a peak centred at 4.6A again indicating the presence of fluid lipid chains.
  • the polymeric sample appears as a waxy white solid having granulated birefringence characteristic of a lamelar array, when viewed through crossed polars.
  • the polymeric sample exhibits Bragg reflections indexed as Vl, 4, and 9 in the small angle region with a diffuse peak at 4.6A in the wide angle region, indicative of two dimensional periodic stacking.
  • the lattice parameter is constant at 61.5A ⁇ lA over the temperature range 10-60°C.
  • the small angle diffraction pattern of the control sample shows reflections indexed as 1, 2, and 3 in the temperature range 10-35°C, and Vl, 3, 4 and 7 reflections in the temperature range 35-60°C. This change from lamellar to hexagonal symmetry is observed under crossed polarisers as a change from a granulated birefringence to a fan-like birefringence in the range 32-35°C.

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  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne un procédé de stabilisation d'une phase cristalline liquide lyotropique inverse, consistant à (a) mettre en contact un amphiphile, un milieu polaire et au moins une matière lyophobe polymérisable, l'amphiphile et le milieu polaire constituant une phase cristalline liquide lyotropique, et (b) polymériser au moins une matière lyophobe polymérisable pour former un polymère dans la région lyophobe de ladite phase cristalline liquide lyotropique. Un second aspect de cette invention concerne une composition contenant (a) une phase cristalline liquide lyotropique renfermant un amphiphile et un milieu polaire, et (b) un polymère contenant une matière lyophobe polymérisée, en plus de l'amphiphile, et situé dans la région lyophobe de ladite phase cristalline liquide lyotropique inverse. Un autre aspect de cette invention concerne un procédé de préparation d'une phase cristalline liquide lyotropique inverse.
PCT/GB2000/002590 1999-07-07 2000-07-06 Procede de stabilisation d'une phase cristalline liquide lyotropique inverse WO2001004234A1 (fr)

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Application Number Priority Date Filing Date Title
AU56982/00A AU5698200A (en) 1999-07-07 2000-07-06 Method of stabilising an inverse lyotropic liquid crystalline phase
GB0130959A GB2367300A (en) 1999-07-07 2000-07-06 Method of stabilising an inverse lyotropic liquid crystalline phase

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GB9915936.0 1999-07-07
GBGB9915936.0A GB9915936D0 (en) 1999-07-07 1999-07-07 Method

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019226086A1 (fr) * 2018-05-25 2019-11-28 Amferia Ab Élastomère mésoporeux

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2729670A1 (fr) * 1995-01-24 1996-07-26 Thomson Csf Procede d'obtention de materiau composite a base de cristal liquide disperse dans du polymere
WO1998030318A2 (fr) * 1997-01-08 1998-07-16 The Regents Of The University Of California Nanocomposites, membranes et catalyseurs polymeres nanoporeux

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2729670A1 (fr) * 1995-01-24 1996-07-26 Thomson Csf Procede d'obtention de materiau composite a base de cristal liquide disperse dans du polymere
WO1998030318A2 (fr) * 1997-01-08 1998-07-16 The Regents Of The University Of California Nanocomposites, membranes et catalyseurs polymeres nanoporeux

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE INSPEC THE INSTITUTION OF ELECTRICAL ENGINEERS, STEVENAGE, GB; 1 December 1997 (1997-12-01), SMITH R C ET AL: "Controlling materials architecture on the nanometer-scale: PPV nanocomposites via polymerisable lyotropic liquid crystals", XP002151691 *
IV. SYMPOSIUM, ELECTRICAL, OPTICAL AND MAGNETIC PROPERTIES OF ORGANIC SOLID-STATE MATERIALS, 1 December 1997 (1997-12-01) - 5 December 1997 (1997-12-05), Boston, MA, USA *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019226086A1 (fr) * 2018-05-25 2019-11-28 Amferia Ab Élastomère mésoporeux

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GB9915936D0 (en) 1999-09-08
GB0130959D0 (en) 2002-02-13
GB2367300A (en) 2002-04-03
AU5698200A (en) 2001-01-30

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