EP2609066A1 - Low molecular weight gelators for crude oil, petroleum product or chemical spill containment - Google Patents
Low molecular weight gelators for crude oil, petroleum product or chemical spill containmentInfo
- Publication number
- EP2609066A1 EP2609066A1 EP11831017.6A EP11831017A EP2609066A1 EP 2609066 A1 EP2609066 A1 EP 2609066A1 EP 11831017 A EP11831017 A EP 11831017A EP 2609066 A1 EP2609066 A1 EP 2609066A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gel
- compound
- formula
- group
- chemical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/16—Oxygen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
- C10G21/12—Organic compounds only
- C10G21/20—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
Definitions
- Low molecular weight gelators methods of making such gelators, organogels comprising such gelators, and systems and methods of using such gelators to form gels that comprise at least one of a crude oil, a petroleum product and a chemical for the containment and/or remediation of an accidental and/or intentional release of the at least one of the crude oil, the petroleum product and/or the chemical are described.
- Systems and methods, wherein gels, made from the combination of such gelators and at least one of the crude oil, the petroleum product and/or the chemical from an accidental and/or intentional release can be used to recover these oils or chemicals while allowing the gelators to be recovered and reused to clean up or contain additional crude oil, petroleum products or chemicals are also described.
- Exemplary systems and methods for containing and/or remediating a spill and/or release of at least one of a crude oil, a petroleum product and a chemical from a spill and/or release into the environment using gelators are also described.
- the gelators can be used in a variety of applications including the delivery of
- Low molecular weight gelators methods of making such gelators, organogels comprising such gelators and methods of using such organogels are described.
- Low molecular weight gelators which are capable of gelling hydrogels and organogels, methods of making such gelators, organogels comprising such gelators and methods of using such organogels are described.
- Methods of using such gelators to form gels which comprise at least one of a crude oil, a petroleum product and a chemical which has been released into the environment along, with systems for containing and/or remediating a spill and/or release of at least one of a crude oil, a petroleum product and a chemical from a spill or release into the environment using gelators have not been previously described. For at least the reasons provided below, conventional low molecular weight gelators and gels formed using the gelators are not optimal.
- This application relates to low molecular weight gelators which can be used to produce organogels, methods of making such gelators,
- organogels comprising such gelators and methods of using such organogels.
- Such materials and methods are described.
- This application also relates to low molecular weight gelators which are capable of gelling hydrogels and organogels, methods of making such gelators, organogels comprising such gelators and methods of using such organogels. Such materials and methods are described.
- This application also relates to gels and/or emulsions which comprise at least one of a crude oil, a petroleum product and a chemical which has been released into the environment and systems and methods that use gels and/or emulsions made from the contacting and/or combination of the gelators and oils or chemicals from spills, and/or other accidental or intentional releases, to recover these oils or chemicals while allowing the gelator to be recovered and reused to clean up or contain additional crude oil, petroleum products or chemicals.
- Systems for containing and/or remediating a spill and/or release of at least one of a crude oil, a petroleum product and a chemical from a spill or release into the environment using such gelators are also described.
- a gelling agent is a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen, and salts thereof, and the compound is in the (R) form, is a gelator that can be used to form
- a gelling agent is a compound of formula (II):
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms, and salts thereof, wherein the compound is in the (R) form, is a gelator that can be used to form organogels.
- a gelling agent is compound of formula (III):
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms, and salts thereof, wherein the compound is in the (R) form, is a gelator that can be used to form organogels.
- a thixotropic gel comprises an organic solvent and a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen, and salts thereof, and the compound is in the (R) form.
- a thixotropic gel comprises an organic solvent and a compound of formula (II) or formula (III):
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms, and salts thereof, and the compound of formula (II) or formula (III) is in the (R) form.
- a method of manufacturing 12-hydroxy-N- alkyloctadecanamides comprises: (a) adding a solution of 12- hydroxystearamide and triethylamine in a non-reactive solvent to a cooled solution of ethyl chloroformate in a non-reactive solvent, and (b) adding an alkyl amine to the solution of step (a).
- a method of manufacturing l-(alkylamino) octadecan-12-ols comprises the step of adding LAH to a suspension of suspension of a 12-hydroxy-N-alkyloctadecanamide in dry THF under a nitrogen atmosphere.
- a pharmaceutical composition comprises an active pharmaceutical ingredient and a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form, and a pharmaceutically acceptable carrier.
- a food composition comprises a mixture of a food and a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form.
- a cosmetic composition comprises at least one cosmetically acceptable ingredient and a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form, and a pharmaceutically acceptable carrier.
- a consumer product comprises a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form, and an acceptable medium.
- a method for containing an unintentional chemical release comprises forming a gel a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form with the chemical that was unintentionally released.
- a gelling agent is a compound of formula (IV): wherein Ri is an alkyl group of the formula C n H 2n+ i or an aryl group, n is an integer from 0 to 6, X is an anion, and at least one of B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen, and the compound is in the (R) form.
- E is a hydroxyl group.
- the gelling agent of formula (IV) is a gelator that can be used to form an organogel or a hydrogel.
- a thixotropic gel comprises an organic solvent and a compound of formula (IV):
- Ri is an alkyl group of the formula C n H 2n+ i or an aryl group
- n is an integer from 0 to 6
- X is an anion
- at least one of B, C, D, E, F, G and H is a hydroxy and the others are hydrogen, and the compound is in the (R) form.
- E is a hydroxyl group.
- a pharmaceutical composition comprises an active pharmaceutical ingredient and a compound of formula (IV):
- Ri is an alkyl group of the formula C n H 2n +i or an aryl group
- n is an integer from 0 to 6
- X is an anion
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen, and the compound is in the (R) form, and a pharmaceutically acceptable carrier.
- E is a hydroxyl group.
- a processed food composition comprises a food and a compound of formula (IV):
- n is an integer from 0 to 6
- X is an anion
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen
- E is a hydroxyl group.
- the group R 1 in the compounds of formula (IV) can be covalently attached to the nitrogen atom or can be present as the counterion of the positively charged portion of the salt.
- a cosmetic composition comprises at least one cosmetically acceptable ingredient and a compound of formula (IV):
- R is an alkyl group of the formula C n H 2n+ i or an aryl group
- n is an integer from 0 to 6
- X is an anion
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen
- the compound is in the (R) form, wherein the compound is in the (R) form, and a cosmetically acceptable carrier.
- E is a hydroxyl group.
- a consumer product comprises a compound of formula (IV): wherein is an alkyl group of the formula C n H 2n +i or an aryl group, n is an integer from 0 to 6, X is an anion, and at least one of B, C, D, E, F, G and H is a hydroxy and the others are hydrogen, and the compound is in the (R) form, wherein the compound is in the (R) form, and an acceptable medium.
- E is a hydroxyl group.
- a method for containing an unintentional chemical release comprises forming a gel a compound of formula (IV):
- n is an integer from 0 to 6
- X is an anion
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen
- the compound is in the (R) form, wherein the compound is in the (R) form, with the chemical that was unintentionally released.
- E is a hydroxyl group.
- a gel and/or emulsion composition comprises at least one of a crude oil, a petroleum product and a chemical and a compound of formula (I), (IV) or (V):
- R is an alkyl group of the formula C n H 2n+ i or an aryl group, n is an integer from 0 to 6,
- X is an anion
- A is a hydrogen or a carbonyl
- At least one of B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen,
- a method of forming a gel and/or emulsion comprising at least one of a crude oil, a petroleum product and a chemical comprises contacting and/or combining the at least one of the crude oil, the petroleum product and the chemical with a compound of formula (I), (IV) or (V):
- Ri is an alkyl group of the formula C n H 2n+ i or an aryl group, n is an integer from 0 to 6,
- X is an anion
- A is a hydrogen or a carbonyl
- At least one of B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen,
- a method of containing a release and/or spill of at least one of a crude oil, a petroleum product and a chemical comprises forming a gel and/or emulsion comprising the at least one of the crude oil, the petroleum product and the chemical and a compound of formula (I), (IV) or (V):
- Ri is an alkyl group of the formula C n H 2n +i or an aryl group, n is an integer from 0 to 6,
- X is an anion
- A is a hydrogen or a carbonyl
- At least one of B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen,
- a method of recovering at least one of a crude oil, a petroleum product and a chemical from a spill and/or release into the environment comprises: (a) forming a gel and/or emulsion comprising the at least one of the crude oil, the petroleum product and the chemical and a compound of formula (I), (IV) or (V); (b) collecting the gel and/or emulsion; and (c) converting the gel and/or emulsion to form at least a first phase comprising predominantly the at least one of the crude oil, the petroleum product and the chemical and a second phase comprising the compound of formula (I), (IV) or (V).
- a system for containing and/or remediating a spill and/or release of at least one of a crude oil, a petroleum product and a chemical from a spill and/or release into the environment comprises: (a) a compound of formula (I), (IV) or (V); and (b) a means for contacting and/or combining the compound of formula (I), (IV) or (V) with the at least one of the crude oil, the petroleum product and the chemical.
- Figure 1 shows a representation of the design of LMOGs with increasing complexity.
- Figure 2 shows the chemical structures of exemplary gelators and analogous compounds without the hydroxyl group of exemplary gelators.
- Figure 3 shows the chemical structures of exemplary gelators of formulas 1 - 12.
- Figure 4 is a plot of the melting points (T mp ) of the neat amide gelators (1-6) (0) or the Tg values of their gels with various liquids versus n, the number of carbon atoms in their N-alkyl chains.
- Figure 5 is a plot of the melting points (T mp ) of the neat amine gelators ( -12) or the Tg values of their gels with various liquids versus n, the number of carbon atoms in their N-alkyl chains.
- Figure 6 is a plot of Tg values of silicone oil gels as a function of concentration of exemplary gelling agents.
- Figure 7 is a plot of Tg values of toluene gels as a function of concentration of exemplary agents.
- Figure 8 shows polarizing optical micrographs at 24°C of 2 wt % 1 in (a, b) silicone oil and (c, d) toluene gels prepared by (a, c) fast-cooling and (b, d) slow-cooling protocols.
- Figure 9 shows polarizing optical micrographs at 24°C of gels of 2 wt % 4 in decane prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 10 shows polarizing optical micrographs at 24°C of gels of 2 wt % 4 in CCI 4 prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 1 1 shows polarizing optical micrographs (24°C) of gels of 2 wt % 4 in DMSO prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 12 shows polarizing optical micrographs (24°C) of gels of 2 wt % 4 in toluene prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 13 shows polarizing optical micrographs (24°C) of gels of 2 wt % 4 in silicone oil prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 14 shows polarizing optical micrographs (24°C) of gels of 2 wt % 6 in decane prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 15 shows polarizing optical micrographs (24°C) of gels of 2 wt % 6 in CCU prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 16 shows polarizing optical micrographs (24°C) of gels of 2 wt % 6 in DMSO prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 17 shows polarizing optical micrographs (24°C) of gels of 2 wt % 6 in silicone oil prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 18 shows polarizing optical micrographs (24°C) of gels of 2 wt % 10 in CCI 4 prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 19 shows polarizing optical micrographs (24°C) of gels of 2 wt % 10 in decane prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 20 shows polarizing optical micrographs (24°C) of gels of 2 wt % 10 in DMSO prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 21 shows polarizing optical micrographs (24°C) of gels of 2 wt % 10 in toluene prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 22 shows polarizing optical micrographs (24°C) of gels of 2 wt % 10 in silicone oil prepared by (a) fast-cooling and (b) slow-cooling.
- Figure 23 shows polarizing optical micrographs (24°C) of gels of 2 wt % 12 in silicone oil prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 24 shows polarizing optical micrographs at 24°C of gels of 0.42 wt % 6 in silicone oil prepared by (a) fast-cooling and (b) slow-cooling protocols.
- Figure 25 is SEM images of xerogels prepared from (a) 2.0 wt % 1 in CCU, (b) 0.5 wt % 1 in CCI 4 , (c) 2.0 wt % 1 in chlorobenzene, and (d) 0.5 wt % 1 in chlorobenzene.
- Figure 26 shows XRD patterns at 24°C of: (a) 4.8 wt % 1 in silicone oil gel after solvent subtraction; (b) neat 1 ; (c) 5.2 wt % 4 in silicone oil gel after solvent subtraction; (d) neat 4; (e) 5.0 wt % 6 in silicone oil gel after solvent subtraction; and (f) neat 6.
- Figure 27 shows proposed packing arrangements of gelator molecules in gel aggregates.
- Figure 28 shows X-ray d iff ractog rams of 1-(propylamino)octadecan- 12-ol (10) at 24°C: (a) 4.8 wt % gel in silicone oil (after subtracting from neat silicone oil diffractogram), (b) neat powder.
- Figure 29 shows IR spectra of (a) neat silicone oil, (b) a 5 wt % 1 in silicone oil gel.
- Figure 30 shows X-ray diffraction patterns of 1 - octadecylaminooctadecan-12-ol (12) at 24°C: (a) 5.0 wt % gel in silicone oil, and (b) neat powder.
- Figure 31 shows X-ray diffraction patterns of 1 -aminooctadecan-12- ol (7) at 24°C: (a) 5.0 wt % gel in silicone oil, and (b) neat powder.
- Figure 32 shows X-ray diffraction patterns of ammonium carbamate salt of 1 - aminooctadecan-12-ol (13) at 24°C: (a) 4.9 wt % gel in silicone oil, and (b) neat powder.
- Figure 33 shows Log-log strain sweep for a 2.0 wt % 1 in silicone oil gel at 25 and 80°C.
- Figure 34 shows Log-log frequency sweeps (0.1 % strain) for a 2.0 wt % 1 in silicone oil gel at 25, 40, 60 and 80°C.
- Figure 35 shows Log-log strain sweep (1.0 rad/sec) for a 2.0 wt % 4 in silicone oil gel at 25 and 75°C.
- Figure 36 shows Time sweep (0.1 % strain and 0.05 rad/s) at 45°C for a 2.0 wt % 12- hydroxy-N-propyloctadecanamide (4) in silicone oil gel.
- Figure 37 shows log-log frequency sweep (0.1 % strain) for a 2.0 wt % 12-hydroxy-N-propyloctadecanamide (4) in silicone oil gel at 2, 35, 45, 55, and 65°C.
- Figure 38 shows log-log strain sweep (1 .0 rad/s) at 25 (blue) and 50°C (red) for a 2.0 wt % 1 -propylaminooctadecan-12-ol (10) in silicone oil gel.
- Figure 39 shows log-log frequency sweep (0.05 % strain) for a 2.0 wt % 1- propylaminooctadecan-12-ol (10) in silicone oil gel at 25, 35, 45 and 50°C.
- Figure 40 shows G' and G" as a function of time and application of different strains and frequencies to a 2.0 wt % 1 in silicone oil gel at 25°C.
- Figure 41 shows G' and G" as a function of time and application of different strains and frequencies to a 2.0 wt % HSA in silicone oil gel at 25°C.
- Figure 42 shows G' and G" as a function of time and application of different strains and frequencies to a 2.0 wt % 2 in silicone oil gel at 25 °C.
- Figure 43 shows G' and G" as a function of time and application of different strains and frequencies to a 2.1 wt % 4 in silicone oil gel at 25 °C.
- Figure 44 shows G' and G" as a function of time and application of different strains and frequencies to a 2.1 wt % 10 in silicone oil gel at 25 °C.
- Figure 45 shows G' and G" as a function of time and application of different strains and frequencies to a 2.1 wt % 12 in silicone oil gel at 25 °C.
- Figure 46 shows a TGA plot of the weight loss of 1- aminooctadecan-12-ol (7) versus temperature.
- Figure 47 shows a TGA plot of the weight loss of 13, the
- ammonium carbamate of 1-aminooctadecan-12-ol versus temperature.
- Figure 48 shows the chemical structures of exemplary gelators of formulas 18 - 24.
- Figure 49 shows plots of the melting points (T mp ) of the neat 2-8 or the Tgel values of their 2 wt % gels with various liquids versus the number of carbon atoms in their /V-alkyl chains: in water, in CCI 4 , and in toluene.
- Figure 50 shows (I) Tg values as a function of concentration of 4 in A) toluene gels and B) hydrogels. (II) Tg values as a function of
- Figure 51 shows polarizing optical micrographs (POM) at 23°C of 4 in toluene (A, B, 4.9 wt %), 4 in water (C, D, 4.8 wt %) and 8 in octanol (E, F, 1.9 wt %) gels.
- POM polarizing optical micrographs
- Figure 52 shows offset XRD diffractograms at 22°C of A) (a) a gel consisting of 5.0 wt % 4 in toluene after empirical subtraction of solvent diffractions, (b) neat 4 and (c) a gel consisting of 5.1 wt % 4 in water after empirical subtraction of solvent diffractions. (B) (a) a gel consisting of 4.9 wt % 8 in toluene after empirical subtraction of solvent diffractions, (b) neat 8 and (c) a gel consisting of 4.9 wt % 8 in octanol after empirical subtraction of solvent diffractions.
- Figure 53 shows proposed packing arrangement of gelator molecules of (A) 4 in hydrogel aggregates, (B) 4 in toluene gel aggregates and (C) 8 in octanol gel aggregates from molecular mechanics 2 (MM2) calculations.
- Figure 54 shows log-log strain sweep (1.0 rad/sec, (A)) and log-log frequency sweep (0.1 % strain, (B)) for a 2.1 wt % hydrogel and a 2.1 wt % toluene gel of 4 at 25°C.
- Figure 55 shows water-motor oil mixtures with the addition of various gelators.
- Low molecular weight gelators which form organogels, methods of making such gelators, organogels comprising such gelators and methods of using such organogels are described.
- This application also relates to low molecular weight gelators which are capable of gelling hydrogels and organogels, methods of making such gelators, organogels comprising such gelators and methods of using such organogels. Such materials and methods are described.
- the low molecular weight gelators can be used to produce gels and/or emulsions comprising at least one of a crude oil, a petroleum product and a chemical.
- Such gelators can be used in methods and systems for containing and/or remediating the release of at least one of a crude oil, a petroleum product and a chemical.
- the release of the at least one of a crude oil, a petroleum product and a chemical can be due to either accidental releases, such as spills, shipping accidents or broken pipelines, or intentional releases.
- variable can be equal to any of the values within that range.
- the variable can be equal to any integer value of the numerical range, including the end- points of the range.
- the variable can be equal to any real value of the numerical range, including the end-points of the range.
- a variable which is described as having values between 0 and 2 can be 0, 1 or 2 for variables which are inherently discrete, and can be 0.0, 0.1 , 0.01 , 0.001 , or any other real value for variables which are inherently continuous.
- a cell includes a plurality of cells, including mixtures thereof.
- the term “about” means approximately, in the region of, roughly, or around. When the term “about” is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the numerical values set forth. In general, the term “about” or “approximately” is used herein to modify a numerical value above and below the stated value by a variance of 20%.
- aryl refers to a monovalent aromatic hydrocarbon group derived by the removal of one hydrogen atom from a single carbon atom of a parent aromatic ring system, as defined herein.
- Typical aryl groups include, but are not limited to, groups derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, coronene, fluoranthene, fluorene, hexacene,
- naphthalene octacene, octaphene, octalene, ovalene, penta-2,4-diene, pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthuene, rubicene, triphenylene,
- an aryl group comprises from 6 to 20 carbon atoms (C 6 -C 2 o aryl), more preferably from 6 to 15 carbon atoms (CQ- Ci5 aryl) and even more preferably from 6 to 10 carbon atoms (Ce-C-io aryl). More preferably the aryl group is a naphthyl group or an anthranyl group. Even more preferably, the aryl group is a napthyl group bound at the 1- or 2- position or an anthranyl group bound at the 1 -, 2- or 9- position.
- the aryl group may be substituted with one or more of the following substituents, which may be identical or different: a halogen atom, a hydroxy group, a nitro group, a cyano group, an amino group, a formyl group, a carbamoyl group, an aminosulfonyl group, a lower alkyl group, a lower alkylamino group, a hydroxy-lower alkylamino group, a di-lower alkylamino group, an imino group, a lower alkylsulfonyl group, a lower
- alkylsulfonylamino group a lower alkoxy group, which may be substituted with 1 to 3 halogen atom(s), a lower alkoxycarbonyl group, a lower alkoxycarbonylamino group, a lower alkanoyl group which may be
- lower alkyl group refers to a straight-chained or branched alkyl group having 1 to 6 carbon atom(s), and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, and the like.
- halogen atom refers to a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.
- lower alkylamino group refers to a substituent formed by N-substitution of the above “lower alkyl group” to an amino group, and examples thereof include an N-methylamino group, an N-ethylamino group, an N-propylamino group, an N-isopropylamino group, an N-butylamino group, an N-isobutylamino group, an N-tert-butylamino group, an N- pentylamino group, an N-hexylamino group, and the like.
- hydroxy-lower alkylamino group refers to a substituent formed by substitution of one or more of hydroxy group(s) to the above “lower alkyl amino group”, and examples thereof include an N- hydroxyethylamino group, an N-hydroxypropylamino group, an N- hydroxyisopropylamino group, an N-hydroxybutylamino group, an N- hydroxyisobutylamino group, an N-hydroxy-tert-butylamino group, an N- hydroxypentylamino group, an N-hydroxyhexylamino group, and the like.
- di-lower alkylamino group refers to a substituent formed by ⁇ , ⁇ -disubstitution of the above “lower alkyl group” to an amino group, and examples thereof include an ⁇ , ⁇ -dimethylamino group, an N,N- diethylamino group, an ⁇ , ⁇ -dipropylamino group, an N,N-diisopropylamino group, an ⁇ , ⁇ -dibutylamino group, an ⁇ , ⁇ -diisobutylamino group, an N,N- ditert-butylamino group, an ⁇ , ⁇ -dipentylamino group, an N,N-dihexylamino group, an N-ethyl-N-methylamino group, an N-methyl-N-propylamino group, and the like.
- lower alkylsulfonyl group refers to a substituent formed by the bonding of the above “lower alkyl group” to a sulfur atom in a sulfonyl group, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, and the like.
- lower alkylsulfonylamino group refers to a substituent formed by N-substitution of the above “lower alkylsulfonyl group” to an amino group, and examples thereof include a methylsulfonylamino group, an ethylsulfonylamino group, a butylsulfonylamino group, and the like.
- lower alkoxy group refers to a group formed by the bonding of the "lower alkyl group” to an oxygen atom, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, a neopentyloxy group, a hexyloxy group, an isohexyloxy group, and the like.
- lower alkoxycarbonyl group refers to a group formed by the bonding of the "lower alkoxy group” to a carbonyl group, and specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a
- butoxycarbonyl group an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, a
- lower alkoxycarbonylamino group refers to a group formed by N-substitution of the "lower alkoxycarbonyl group” to an amino group, and specific examples thereof include a methoxycarbonylamino group, an ethoxycarbonylamino group, a propoxycarbonylamino group, an isopropoxycarbonylamino group, a butoxycarbonylamino group, an isobutoxycarbonylamino group, a sec-butoxycarbonylamino group, a tert- butoxycarbonylamino group, a pentyloxycarbonylamino group, a
- neopentyloxycarbonylamino group a hexyloxycarbonylamino group, an isohexyloxycarbonylamino group, and the like.
- lower alkanoyl group refers to a group formed by the bonding of the "lower alkyl group” to a carbonyl group, and is preferably a group in which the alkyl group having 1 to 5 carbon atom(s) is bonded to a carbonyl group.
- an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, a pentanoyl group, and the like can be included.
- lower alkanoyloxy group refers to a group formed by bonding of the "lower alkanoyl group” to an oxygen atom, and examples thereof include an acetyloxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a vaieryioxy group, an isovaleryloxy group, a pivaloyloxy group, a pentanoyloxy group, and the like.
- lower alkylthio group refers to a substituent formed by the bonding of the "lower alkyl” to a sulfur atom, and examples thereof include a methylthio group, an ethylthio group, a butylthio group, and the like.
- LMOG means a low molecular-mass organic gelator.
- HAS refers to (R)-12-hydroxyoctadecanoic acid.
- SA refers to stearic acid, also known as octadecanoic acid.
- SAFIN refers to self-assembled fibrillar networks.
- CGC critical gelator concentration
- thixotropy refers to the property of certain gels that are thick (viscous) under normal conditions, but flow (become thin, less viscous) over time when shaken, agitated, or otherwise stressed.
- the term storage and loss modulus represents the stored energy, representing the elastic portion, and the energy dissipated as heat, representing the viscous portion measured in gels.
- the term ambidextrous means that the gelator can form hydrogels as well as organogels.
- crude oil means an unrefined complex mixture of hydrocarbons of various molecular weights, and other organic compounds, as can be found, for example, in geologic formations beneath the earth's surface.
- petroleum product means flammable, toxic, or corrosive products such as those that can be obtained from distilling and processing of crude oil, unfinished oils, natural gas liquids, blend stocks and other miscellaneous hydrocarbon compounds.
- the term "chemical” means a substance that is capable of forming a gel and/or emulsion when contacted and/or combined with an exemplary gelator described herein.
- the terms "crude oil”, “petroleum product” and “chemical” refer to substances that are capable of forming a gel and/or emulsion when contacted and/or combined with the gelator described herein. Such substances include, for example, hydrophilic substances and substances which partition into the gel and/or emulsion. Such substances generally have n-octanol/water partition coefficients of greater than about 1 ,000.
- the term "released into the environment” means that the crude oil, petroleum product or chemical has moved from an intended area to an unintended and/or undesirable area. This term includes accidental and/or intentional movement of the material.
- Accidental movement includes, but is not limited to, spills, leaks from containers including bottles, drums, pipes, and containment vessels; leaks or discharge of material from transportation vehicles, such as cars, trucks, ships and planes; and leaks from material transport systems, such as pipelines and conveyors.
- Intentional movement includes, but is not limited to, the releases described above, where the cause of the movement was intentionally performed.
- Such causes include, but are not limited to, criminal or terrorist activity and combat-related discharges, such as the release of oil from oil wells, ships, refineries and terminals during the Gulf war.
- LMOGs low molecular-mass organic gelators
- 1 D growth modes 2 to form fibers, strands, or tapes via relatively weak physical molecular interactions such as van der Waals forces, intermolecular H bonding, electrostatic forces, ⁇ - ⁇ stacking, or even London dispersion forces. How these weak physical interactions affect the formation, strength, and stability of a gel must be understood in order to design organogels with the desired properties.
- LMOGs The range of structures known to be LMOGs is extremely broad. It includes molecules as simple as n-alkanes 3"5 (a in Figure 1) and as complex as substituted steroids or salts made by the addition of two components. 1,6 Thus, London dispersion forces must play a dominant stabilizing role in networks made by the LMOG, n-hexatriacontane (C36), 4 because it lacks the functional groups that are necessary for the other favorable
- Carboxylic acids with long alkyl chains such as stearic acid (SA; i.e., octadecanoic acid), offer the possibility of additional intermolecular interactions (N.B., H bonding) within the LMOG assemblies.
- SA stearic acid
- N.B., H bonding additional intermolecular interactions
- Tg characteristic temperature
- Structure c in Figure 1 represents LMOGs with two different functional groups attached to an n-alkane.
- LMOGs with secondary amide groups are 11-(butylamido)undecanoic acid, 8 the odium salt of N-octadecyl maleamic acid (a hydrogelator), 9 and N-3- hydroxypropyldodecanamide 10 as well as a naturally occurring carboxylic acid (available from castor oil 11 ), 12- hydroxystearic acid (HSA; i.e., 12- hydroxyoctadecanoic acid ( Figure 1)), 12 which is easily obtained as its (R) enantiomer.
- Enantiopure HSA exhibits circular dichroic signals that are attributed to helical arrangements of the molecules in their fibrillar
- SAFINs self-assembled fibrillar networks
- Many LMOGs are polymorphous, and it is known that small changes in molecular structure can lead to large changes in crystal packing.
- primary amides generally form tapelike structures whereas secondary amides form chainlike structures;
- 14 urea is able to form clathrates in the presence of long n- alkanes, but ⁇ , ⁇ '-dialkylureas as small as ⁇ , ⁇ '-dimethylurea organize into fibers and SAFINs, leading to gels.
- Exemplary derivatives of HSA are amides 1-6 and amines 7-12 and the ammonium carbamate salt of 7, compound 13.
- the underlying concepts behind the choice of these molecules are that H bonding between amides can be stronger than between amines and that the N-alkyl groups and charged centers at the head groups of 13 can modify the molecular packing of the LMOGs within their fibrillar aggregates.
- SA b- and e-type gelators in Figure 1
- a gelling agent is a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form.
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms.
- R is hydrogen or an alkyl group having 1 , 2, 3, 4 or 18 carbon atoms.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- a gelling agent is a compound of formula
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms, and salts thereof, wherein the compound is in the (R) form.
- R is hydrogen or an alkyl group having 1 , 2, 3, 4 or 18 carbon atoms.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- a gelling agent is a compound of formula
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms, and salts thereof, wherein the compound is in the (R) form.
- R is hydrogen or an alkyl group having 1 , 2, 3, 4 or 18 carbon atoms.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- a thixotropic gel comprises an organic solvent and a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- at least one of B, C, D, E, F, G and H is a hydroxy and the others are hydrogen, and salts thereof, wherein the compound is in the (f?) form.
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms.
- R is hydrogen or an alkyl group having 1 , 2, 3, 4 or 18 carbon atoms.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- the gel is formed from at least one solvent is selected from the group consisting of n-hexane, n-octane, n-decane, silicone oil, methanol, 1- butanol, 1-octanol, benzyl alcohol, chlorobenzene, chloroform, carbon tetrachloride, benzene, toluene, dimethylsulfoxide, acetonitrile and
- the compound of formula (I) is present at a concentration of about 20% or less, on a weight/weight basis. In another embodiment, the compound of formula (I) is present at a concentration of about 10%, on a weight/weight basis, in the above gel. In yet another embodiment, the compound of formula (I) is present at a concentration of about 5% or less, n a weight/weight basis, in the above gel. In another embodiment, the compound of formula (I) is present at a concentration of about 2%, on a weight/weight basis, in the above gel. In yet another embodiment, the compound of formula (I) is present at a
- the compound of formula (I) is present at a concentration of about 0.5%, on a weight/weight basis, in the above gel. In yet another embodiment, the compound of formula (I) is present at a concentration of about 0.2% or less, n a weight/weight basis, in the above gel.
- the above gel recovers at least about 80% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear. In still another embodiment, the gel recovers at least about 90% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear. In a further embodiment, the gel recovers at least about 95% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear.
- the gel recovers at least about 98% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear.
- a thixotropic gel comprises at least one solvent and a compound of formula (II) or formula (III):
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms, and salts thereof, wherein the compound is in the (f?) form.
- the gel is formed from at least one solvent is selected from the group consisting of n-hexane, n-octane, n-decane, silicone oil, methanol, 1- butanol, 1-octanol, benzyl alcohol, chlorobenzene, chloroform, carbon tetrachloride, benzene, toluene, dimethylsulfoxide, acetonitrile and
- the compound of formula (II) or (III) is present at a concentration of about 20% or less, on a weight/weight basis. In another embodiment, the compound of formula (II) or (III) is present at a concentration of about 10%, on a weight/weight basis, in the above gel. In yet another embodiment, the compound of formula (II) or (III) is present at a concentration of about 5% or less, n a weight/weight basis, in the above gel. In another embodiment, the compound of formula (II) or (III) is present at a concentration of about 2%, on a weight/weight basis, in the above gel.
- the compound of formula (II) or (III) is present at a concentration of about 2% or less, on a weight/weight basis, in the above gel. In another embodiment, the compound of formula (II) or (III) is present at a concentration of about 0.5%, on a weight/weight basis, in the above gel. In yet another embodiment, the compound of formula (II) or (III) is present at a concentration of about 0.2% or less, n a weight/weight basis, in the above gel.
- the above gel recovers at least about 80% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear. In still another embodiment, the gel recovers at least about 90% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear. In a further embodiment, the gel recovers at least about 95% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear.
- the gel recovers at least about 98% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear.
- 12-hydroxy-N-alkyloctadecanamides are manufactured by (a) adding a solution of 12-hydroxystearamide and triethylamine in a dry non-reactive solvent to a solution of ethyl chloroformate in a dry non-reactive solvent while maintaining the temperature at about 0°C; and (b) adding an alkyl amine to the solution obtained in step (a).
- 1 -(alkylamino)octadecan-12-ols are manufactured by adding LAH to a suspension of suspension of a 12- hydroxy-N-alkyloctadecanamide in a dry non-reactive solvent under an inert atmosphere.
- a pharmaceutical composition comprises an active pharmaceutical ingredient and a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form, and a pharmaceutically acceptable carrier.
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms.
- R is hydrogen or an alkyl group having 1 , 2, 3, 4 or 18 carbon atoms.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- a processed food composition comprises a food and a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form.
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms.
- R is hydrogen or an alkyl group having 1 , 2, 3, 4 or 18 carbon atoms.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- a cosmetic composition comprising at least one cosmetically acceptable ingredient and a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form, and a cosmetically acceptable carrier.
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms.
- R is hydrogen or an alkyl group having 1 , 2, 3, 4 or 18 carbon atoms.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- a consumer product comprises a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form, and an acceptable medium.
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms.
- R is hydrogen or an alkyl group having 1 , 2, 3, 4 or 18 carbon atoms.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- a method for containing an unintentional chemical release comprises forming a gel a compound of formula (I):
- R is hydrogen or an alkyl group having from 1 to 36 carbon atoms
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen, and salts thereof, wherein the compound is in the (R) form with the chemical that was unintentionally released.
- R is hydrogen or an alkyl group having from 1 to 18 carbon atoms.
- R is hydrogen or an alkyl group having 1 , 2, 3, 4 or 18 carbon atoms.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- At least one compound of formula (II) or (III) is used as the compound of formula (I) in any of the above
- a gelling agent is a compound of formula (IV):
- n is an integer from 0 to 6
- X is an anion
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen
- the compound is in the (R) form, wherein the compound forms an organogel or a hydrogel upon mixing with an organic solvent or an aqueous solution.
- the anion is selected from the group consisting of chlorine, bromine, iodine, nitrate, boron trifluoride, acetate, nonanoate and oxalate.
- a thixotropic gel comprises an organic solvent and a compound of formula (IV):
- n is an integer from 0 to 6
- X is an anion
- A is a hydrogen or a carbonyl
- at least one of B, C, D, E, F, G and H is a hydroxy and the others are hydrogen
- the compound is in the (R) form.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- the anion is selected from the group consisting of chlorine, bromine, iodine, nitrate, boron trifluoride, acetate, nonanoate and oxalate.
- the at least one solvent is selected from the group consisting of n-hexane, n-octane, n-decane, silicone oil, methanol, 1-butanol, 1-octanol, benzyl alcohol, chlorobenzene, chloroform, carbon tetrachloride, n-perfluorooctane, benzene, toluene, dimethylsulfoxide, acetonitrile and water.
- the compound of formula (IV) is present at a concentration of about 20% or less, on a weight/weight basis. In another embodiment, the compound of formula (IV) is present at a concentration of about 10%, on a weight/weight basis, in the above gel. In yet another embodiment, the compound of formula (IV) is present at a concentration of about 5% or less, n a weight/weight basis, in the above gel. In another embodiment, the compound of formula (IV) is present at a concentration of about 2%, on a weight/weight basis, in the above gel. In yet another embodiment, the compound of formula (IV) is present at a
- the compound of formula (IV) is present at a concentration of about 0.5%, on a weight/weight basis, in the above gel. In yet another embodiment, the compound of formula (IV) is present at a concentration of about 0.2% or le.ss, n a weight/weight basis, in the above gel.
- the gel recovers at least about 80% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear. In still another embodiment, the gel recovers at least about 90% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear. In a further embodiment, the gel recovers at least about 95% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear.
- the gel recovers at least about 98% of its viscoelasticity within less than about one minute, preferably within less than about 30 seconds, and more preferably within less than about 15 seconds after exposure to destructive shear.
- a pharmaceutical composition comprises an active pharmaceutical ingredient and a compound of formula (IV):
- n is an integer from 0 to 6
- X is an anion
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen
- the compound is in the (R) form
- a processed food composition comprises a food and a compound of formula (IV):
- n is an integer from 0 to 6
- X is an anion
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen
- the compound is in the (R) form, wherein the compound is in the (R) form.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- a cosmetic composition comprises at least one cosmetically acceptable ingredient and a compound of formula (IV):
- n is an integer from 0 to 6
- X is an anion
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen
- the compound is in the (R) form, wherein the compound is in the (R) form, and a cosmetically acceptable carrier.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- a consumer product comprises a compound of formula (IV):
- n is an integer from 0 to 6
- X is an anion
- A is a hydrogen or a carbonyl
- B, C, D, E, F, G and H is a hydroxy and the others are hydrogen
- the compound is in the (R) form, wherein the compound is in the (R) form, and an acceptable medium.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- a method for containing an unintentional chemical release comprises forming a gel a compound of formula (IV): wherein n is an integer from 0 to 6, X is an anion, A is a hydrogen or a carbonyl, and at least one of B, C, D, E, F, G and H is a hydroxy and the others are hydrogen, and the compound is in the (R) form, wherein the compound is in the (R) form, with the chemical that was unintentionally released.
- only one of B, C, D, E, F, G and H is a hydroxy group and the others are hydrogen.
- the group R in the compounds of formula (IV) can be covalently attached to the nitrogen atom or can be present as the counterion of the positively charged portion of the salt.
- a gel and/or emulsion comprises at least one of a crude oil, a petroleum product and a chemical from an accidental and/or intentional release and a compound of formula (I), (IV) or (V):
- Ri is an alkyl group of the formula C n H 2n +i or an aryl group, n is an integer from 0 to 6, X is an anion,
- A is a hydrogen or a carbonyl
- At least one of B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen,
- E is a hydroxyl group.
- Ri is n-propyl or n-octadecyl.
- X " is a halogen ion. In yet another embodiment, X " is chlorine ion.
- a method of containing the release and/or spill of at least one of a crude oil, a petroleum product and a chemical comprises forming a gel and/or emulsion comprising the at least one of the crude oil, the petroleum product and the chemical and a compound of formula (I), (IV) or (V):
- ⁇ is an alkyl group of the formula C n H 2n +i or an aryl group, n is an integer from 0 to 6,
- X is an anion
- A is a hydrogen or a carbonyl
- at least one of B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen
- E is a hydroxyl group.
- Ri is n-propyl or n-octadecyl.
- X " is a halogen ion.
- X " is chlorine ion.
- the method further comprises collecting the gel and/or emulsion.
- the method further comprises converting the gel and/or emulsion to form at least a first phase comprising predominantly the at least one of the crude oil, the petroleum product and the chemical and a second phase comprising the compound of formula (I), (IV) or (V).
- the phase comprising the compound of formula (I), (IV) or (V) is separated from the phase comprising the at least one of the crude oil, the petroleum product and the chemical and a second phase comprising the compound of formula (I), (IV) or (V) by placing a mixture comprising the first phase and the second phase in a vessel and removing at least one of the phases from the vessel.
- the separation of the phases is enhanced by contacting the mixture with a chemically inert device, such as, for example, a screen or filter to release the first phase from the mixture.
- a chemically inert device such as, for example, a screen or filter to release the first phase from the mixture.
- the compound of formula (I), (IV) or (V) which has been separated from the first phase can be recovered and re-used in additional containment and /or remediation activities.
- a method of recovering at least one of a crude oil, a petroleum product and a chemical from a spill and/or release of the at least one of the crude oil, the petroleum product and the chemical into the environment comprises: (a) forming a gel and/or emulsion comprising the at least one of the crude oil, the petroleum product and the chemical and a compound of formula (I), (IV) or (V):
- Ri is an alkyl group of the formula C n H 2n+ i or an aryl group, n is an integer from 0 to 6,
- X is an anion
- A is a hydrogen or a carbonyl
- At least one of B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen,
- E is a hydroxyl group.
- Ri is n-propyl or n-octadecyl.
- X " is a halogen ion.
- X " is chlorine ion.
- the gel and/or emulsion further comprises water.
- the second phase in step (c) further comprises water.
- the step of collecting the gel and/or emulsion comprises physical removal of the gel and/or emulsion from the environment or removal of the gel and/or emulsion from a contained system.
- the water is a body of water or a volume of water collected from a volume of treated water comprising the spill and/or release of the at least one of the crude oil, the petroleum product and the chemical.
- the water may be a body of water, such as an ocean, gulf, bay, harbor, lake, pond, reservoir, river, bayou, stream, creek, canal, marsh, lagoon, or other type of recognized accumulations of water.
- the water may also be an accumulation of water used in emergency response, such as firefighting, as well as other accumulations of water where the water has come in contact with a crude oil, a petroleum product, and/or a chemical for which it is desirable to remove such material from the water.
- a system for containing and/or remediating a spill and/or release of at least one of a crude oil, a petroleum product and a chemical into the environment comprises: (a) compound of formula (I), (IV) or (V):
- Ri is an alkyl group of the formula C n H 2n+ i or an aryl group, n is an integer from 0 to 6,
- X is an anion
- A is a hydrogen or a carbonyl
- At least one of B, C, D, E, F, G and H is a hydroxyl group and the others are hydrogen,
- system further comprises (c) a means for collecting a gel and/or emulsion or composition formed upon contact and/or combination of the compound of formula (I), (IV) or (V) with the at least one of the crude oil, the petroleum product and the chemical.
- the system further comprises (d) a means for separating the gel and/or emulsion or composition comprising the compound of formula (I), (IV) or (V) and the at least one of the crude oil, the petroleum product and the chemical into a first phase comprising predominantly the at least one of the crude oil, the petroleum product and the chemical and a second phase comprising the compound of formula (I), (IV) or (V).
- the second phase further comprises water.
- the system further comprises a means for collecting at least one of the first phase and the second phase.
- E is a hydroxyl group.
- X " is a halogen ion. In yet another embodiment, X " is chlorine ion.
- the means for contacting and/or combining the compound of formula (I), (IV) or (V) with the at least one of the crude oil, the petroleum product and the chemical comprises applying the compound of formula (I), (IV) or (V) onto or into the spill and/or release of the at least one of the crude oil, the petroleum product and the chemical to be contained or remediated and/or onto or into water which is, or may become, in contact with the at least one of the crude oil, the petroleum product and the chemical to be contained or remediated.
- the compound of formula (I), (IV) or (V) can be contained within one or more bags or other devices which can be placed on, or into, the at least one of the crude oil, the petroleum product and the chemical to be contained or remediated and/or onto or into water which is, or may become, in contact with the at least one of the crude oil, the petroleum product and the chemical to be contained or remediated.
- the one or more bags can comprise a water-soluble material such that the bags dissolve and/or form openings upon contact with the water and/or the at least one of the crude oil, the petroleum product and the chemical to be contained or remediated, thus allowing the compound of formula (I), (IV) or (V) to come in contact with the at least one of the crude oil, the petroleum product and the chemical to be contained or remediated.
- the compound of formula (I), (IV) or (V) can be contained within containment devices, such as booms or tubes which can be placed on, or into, the at least one of the crude oil, the petroleum product and the chemical to be contained or remediated, or can be placed in water around an area containing the at least one of the crude oil, the petroleum product and chemical to be contained or
- the embodiment can, of course, employ any one these compounds alone, a combination of any two compounds, or all three, and variations thereof. It is preferable that the compound be dissolved or dispersed in a water-miscible solvent, when contacted and/or combined with the at least one of the crude oil, the petroleum product and the chemical. Exemplary solvents can be easily removed by evaporation.
- Exemplary solvents include, but are not limited, to lower alkyl alcohols, such as methanol, ethanol, and propanol; ketones, such as acetone; acetonitrile; tetrahydrofuran; and p-dioaxane, combinations thereof and the like.
- An exemplary solvent will allow the composition comprising the solvent and the compound of formula (I), (IV) or (V) to form a gel and/or emulsion when contacted and/or combined with the at least one of the crude oil, the petroleum product and the chemical.
- Exemplary solvents can also exhibit limited or almost no toxicity to
- DSC Differential scanning calorimetry
- TGA thermogravimetric analyses
- Transition temperatures from DSC (T m ) are reported at the onsets of endotherms (on heating) and exotherms (on cooling). Heating rates were 5°C/min; cooling rates were variable and depended on the difference between the cell block and ambient temperature.
- SEM Scanning electron microscopy
- Silicone oil tetramethyltetraphenylsiloxane, Dow silicone oil 704 from Dow Chemical Company, Midland, Ml
- Solvents for syntheses and other liquids for gelation studies were reagent grade or better (Aldrich).
- Anhydrous THF Acros Chemicals
- LiAIH 4 LAH, 95 %, Aldrich
- triethylamine 99.5%, Aldrich
- NH 4 OH ACS reagent, Fisher
- stearic acid Aldrich, 99 % were used as received.
- Thionyl chloride >99 %, Aldrich was distilled immediately before use.
- Dry CO 2 was prepared by passing gas formed from dry ice through an anhydrous calcium sulfate (Drierite) tube. Methylamine (2 M solution in THF, Aldrich), ethylamine (2 M solution in THF, Aldrich) and butylamine (99.5%, Aldrich) were used as received. 1-Octadecylamine (Aldrich) was purified by collecting a center fraction from two distillations under reduced pressure at 160-165°C (1 torr) and was stored under a nitrogen atmosphere at 5-6°C.
- Stearamide (8) The amide was prepared by a common recipe. Thionyl chloride (0.6 g, 6 mmol) was slowly added to stearic acid (1.0 g, 3.5 mmol) and the mixture was heated at 55°C for 2 h under a dry atmosphere. Excess thionyl chloride was removed by distillation and the remaining liquid (stearoyl chloride) was slowly added to 15 mL of an aqueous 30 %
- anhydrous ammonia gas prepared from an NH 4 OH solution (50 mL) in a hot (ca 60°C) water bath; the gas was passed through a 50 X 2 cm column filled with anhydrous Drierite and ca 20 g of activated CaO powder (prepared by heating CaCO 3 to ca 500°C for 30 min and cooling in a desiccator under a nitrogen atmosphere) was bubbled rapidly through the solution for 10 min. The mixture was kept for 12 h without stirring, during which time the temperature slowly rose to room temperature.
- anhydrous ammonia gas prepared from an NH 4 OH solution (50 mL) in a hot (ca 60°C) water bath; the gas was passed through a 50 X 2 cm column filled with anhydrous Drierite and ca 20 g of activated CaO powder (prepared by heating CaCO 3 to ca 500°C for 30 min and cooling in a desiccator under a nitrogen atmosphere) was bubbled rapidly through the solution for 10 min. The mixture was kept for 12 h without stirring, during which time
- TGA Thermal gravimetric analysis
- the ammonium carbamate salt (13) was prepared by bubbling CO2 gas through a chloroform solution of the amine 13 for 20 min.
- the salt precipitated quantitatively and was collected by filtration: mp 77.7-80.0°C on first heating; 59.2-61.2°C on second heating (corresponding to regeneration of 7).
- TGA of 13 showed a weight loss of 6.6 % between room temperature and 103°C ( Figure 47); 6.7 % is the calculated weight loss for one molecule of carbon dioxide.
- 12-Hydroxy-N-alkyloctadecanamides were prepared by the following procedure. To a cooled (at 0°C) and vigorously stirred solution of ethyl chloroformate (18.0 g, 166 mmol) in dry THF (50 mL) was added slowly a solution of HSA (10.0 g, 33 mmol) and triethylamine (2.3 g, 33 mmol) in dry THF (50 mL) while maintaining the temperature at 0°C. The mixture was stirred for an additional 20 min. An alkyl amine (33 mmol) in 50 mL dry THF was added to the solution at 0°C, and the reaction mixture was kept at room temperature for 24 h.
- 1-(Alkylamino)octadecan-12-ols were prepared by the following procedure. LAH (3.0 g, 79 mmol) was added slowly to a stirred suspension of a 12-hydroxy-N-alkyloctadecanamide (15 mmol) in dry THF (200 mL) under a nitrogen atmosphere. Then, the mixture was refluxed overnight, excess LAH was destroyed by successively adding very slowly a total of 3 mL of water in small amounts, 15 % aq NaOH solution (a total of 3 mL), and 3 mL of water. The mixture was filtered and the filter pad was washed with THF.
- Fast-cooled gels were prepared by placing weighed amounts of a liquid and gelator into a glass tube (5 mm i.d.) that was then flame-sealed. The mixture was heated to ca. 80°C in a water bath (or to 1 10°C in an oil bath with 1 ) until a solution/sol was obtained and was then placed directly into an ice-water bath for 10 min. After the sample was warmed to room temperature for 1 h, its appearance was noted. Slow-cooled gels were prepared using the protocol above except that the hot solutions/sols were kept in the water or oil bath while they returned slowly to room temperature.
- Tg Gelation temperatures
- SAFIN self-assembled fibrillar networks
- HSA organogels have been studied extensively and head-to-head contacts between carboxylic acid groups have been shown to promote the formation of multiple hydrogen-bonded sequences and aid fiber stability.
- the Tg values of 2 wt % HSA and an n-alkane with an even number of carbon atoms are slightly higher than those with odd-numbered n-alkane liquids, but all were opaque in appearance.
- the dependence of the SAFINs of the HSA gels on the liquid component is apparent when silicone oil and n-alkanes are compared: at one LMOG concentration, the silicone oil gel has a higher Tg than the n-alkane gels.
- the sodium salt of HSA has been found to gelate n-dodecane at 4 wt %, and as little as 0.5 wt % was able to gelate chloroform and carbon tetrachloride.
- the same concentration of 14 is a more efficient LMOG of higher-polarity liquids and precipitates from n-alkanes.
- Liquid 14 ( ⁇ 2) is'- * (- 2) 16' ⁇ 3) lf ( ⁇ 2)
- the Tg values for 2 wt % 14 gels are lower than those of 1 in silicone oil, benzene, and toluene but are higher in acetonitrile; in DMSO, 1 is dissolved whereas 14 forms a stable gel.
- This contrasting behavior caused by the presence or absence of a 12-hydroxyl group along the long alkyl chain, can be traced to the relative solubilities of the two
- LMOGs 14 is more soluble in less-polar liquids, and 1 is more soluble in more polar liquids.
- FIG. 4 shows the Tg values versus alkyl chain length for the gels of 1-6 in different liquids. Except for DMSO gels, the Tg values for the primary amide (1 ) were higher than those of the secondary amides with N- methyl or N-ethyl groups (2 or 3), but further increases in the N-alkyl chain length do not appreciably alter the Tg values.
- DMSO gels of 1-6 behaved differently: Tg(6) > Tg(5) > Tg(4) and 2 wt % 1 remained soluble in DMSO at room temperature. Again, this trend appears to be related to the solubilities of the amides in DMSO, and there is a precedent for such behavior in other gel systems. 22
- H-bonding between amine groups is generally weaker than between amides, and as mentioned above, the differences between amino- amino and amido-amido aggregation modes may lead to changes in the overall packing arrangements of the gelator molecules in their fibers. 1
- the importance of the stronger amide-amide interactions in the stabilization of the SAFINs is evident when the gels employing the amides (1-6) and the analogous amines (7-12) are compared.
- the primary amine (7) is a much less efficient gelator than its primary amide analogue, 1; it gelates fewer of the investigated liquids, and its gels exhibit lower Tg values.
- FIG. 7 presents a comparison of Tg values of the gels of 7-12 in DMSO and silicone oil.
- the trends in the silicone oil gels correlate with the melting temperatures of the neat gelators. This correlation and the very small temperature ranges for the gels indicate that the thermodynamic driving force for supersaturated solutions/sols in silicone oil is very large and that the gelator molecules are able to aggregate and nucleate rapidly below Tg.
- 2 wt % 7 is a viscous solution in DMSO at room temperature
- 2 wt % 8 forms an opaque gel.
- the highest Tg value of the amine LMOGs investigated was found for the N-butyl derivative (11), and 2 wt % 12 in DMSO formed a precipitate when cooled from its sol phase.
- Ammonium carbamate (13), prepared by the addition of CO2 to 1- aminooctadecan-12-ol (7), 6a is a less-efficient LMOG than any of 1-12 or HSA.
- Tg values of silicone oil gels with 2 wt % gelator increase in the order 13 (0-2°C) ⁇ 7 ⁇ HSA.
- molecules of 13 must rely principally upon electrostatic interactions of the head groups and H-bonding among 12-hydroxyl groups; London dispersion forces among methylene units along the chains contribute as well.
- Table 4 summarizes the CGCs, appearances, and stability periods of silicone oil and toluene gels of 1, 4, 6, 7,10, and 12 at room temperature. Table 4. CGCs (wt %), Appearances (AP), a and Periods of Stability (PS) b for Silicone Oil and Toluene Gels with LMOGs 1, 4, 6, 7, 10 and 12 Prepared Using the Fast-Cooling Procedure.
- the reason for this large change appears to be related to a change in the morphology of its SAFIN (vide infra).
- the silicone oil liquid aids
- ⁇ // values from the gels are normalized to 100% concentrations of the LMOG component by dividing the observed heats bv the quantities listed in footnotes b ⁇ e. "0.046. f 0.052. " ⁇ .05. ⁇ .048.
- the diffractograms of the powders of 6 and 12 may be missing key peaks at angles lower than our diffractometer can record.
- organogels from LMOGs especially those in which the SAFINs are crystalline (as is the case here) are mechanically weak and are easily destroyed when subjected to external mechanical strain. Moreover, they are only weakly thixotropic, and after the cessation of severe
- ammonium carbamate with pendant hydroxy groups (13) is an inferior gelator to the one without hydroxy groups (17) suggests that the pendant group interactions are not always beneficial to gelation.
- Two possible reasons in the present case are (1) the secondary H-bonding network from the hydroxyl groups is established and imposes restraints on molecular packing that are not conducive to fiber (and SAFIN) formation and (2) the hydroxyl groups interact with the charged centers and lead to nonfibrous packing motifs. 18
- Organo/hydro gels are thermo reversible viscoelastic materials consisting of low molecular weight gelators self assembled into complex three-dimensional structures. Different forms of molecular gels are common in everyday life for their applications ranging from personal care products (toothpaste, shampoo), foodstuffs (jellies, puddings), electronic devices, and drug delivery vehicles (gel capsules for vitamin E). Only few gelators have capability to exhibit gelation property in water and organic solvents. Less than 1 wt % of the salts described above are able to gel water and a wide variety of organic liquids with equal efficiency. (Figure 50).
- Tgel values of the 2 wt % hydrogels increase in the order of increasing their /V-alkyl chain length (that is 20 ⁇ 21 ⁇ 22 ⁇ 23, Figure 49). This trend appears to be related to the solubility of gelator molecules in water. Further increasing of V-alkyl chain from A/-pentyl to A/-hexyl increase in the hydrophobic interactions that consequence in the formation of precipitate. For the similar reason the compound having /V-octadecyl chain (8) did not gelate water.
- Figure 3 (I) show concentration versus gel melting temperatures of 4 in toluene and water gels. Concentration dependent studies of 8 in toluene gels were also studied ( Figure 50 (II). Table 10, Appearances," Tgel values (°C) , and periods of stabilit (in parentheses) of fast-cooled gels containing -2 wt % of gelator in various liquids.
- ammonium salts 9-15 were prepared. Table 10 show gelation properties of 9-15 in various liquids.
- Table 1 Appearances," Tgel values (°C) b , and periods of stability c (in parentheses) of fast- cooled gels containing ⁇ 2 wt % of gelator in various liquids.
- POM images of a 5 wt % fast- and slow-cooled transparent gel of 21 in toluene gel show a spherulitic texture ( Figure 51A and 4B). This reveals that the network structure present in the gel is crystalline in nature. More super saturation increased the effect in nucleation of crystal growth and produce larger fibers.
- the size of the objects is apparent comparing the POM image of a gel prepared by a slow-cooled protocol ( Figure 51 B) with the gel prepared by fast-cooled protocol ( Figure 51A). Larger spherulitic image is observed in the latter case.
- XRD diffractograms of neat powders and fast-cooled hydrogels with ⁇ 5 wt % 21 have been compared.
- the diffraction peaks of the networks of the gels were identified by subtracting the scattering pattern of the water from the total gel diffractogram.
- XRD reflection pattern of the hydrogel of 21 is identical with that of the neat 21 ( Figure 52A, b and Figure 52A, c) which show that same packing is present in the hydrogel networks and in neat solid gelator.
- the lattice spacings (d, A) of the hydrogel of 21 and 21 in powder state have been calculated from the Bragg relationship and are summarized in Table 12.
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US4502975A (en) * | 1981-05-26 | 1985-03-05 | New Japan Chemical Co., Ltd. | Compositions for recovering an organic material from an oily layer on a body of water |
EP0753555A1 (en) * | 1995-01-30 | 1997-01-15 | Tomoyuki Fukuda | Method of solidifying liquid oil and solidifying agent used therefor |
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US4502975A (en) * | 1981-05-26 | 1985-03-05 | New Japan Chemical Co., Ltd. | Compositions for recovering an organic material from an oily layer on a body of water |
EP0753555A1 (en) * | 1995-01-30 | 1997-01-15 | Tomoyuki Fukuda | Method of solidifying liquid oil and solidifying agent used therefor |
Non-Patent Citations (5)
Title |
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HUANG ET AL: "Molecular organogels of the sodium salt of (R)-12-hydroxystearic acid and their templated syntheses of inorganic oxides", TETRAHEDRON, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 63, no. 31, 21 June 2007 (2007-06-21) , pages 7375-7385, XP022124603, ISSN: 0040-4020, DOI: 10.1016/J.TET.2007.02.008 * |
JORGE F. TORO-VAZQUEZ ET AL: "Relationship Between Molecular Structure and Thermo-mechanical Properties of Candelilla Wax and Amides Derived from (R)-12-Hydroxystearic Acid as Gelators of Safflower Oil", FOOD BIOPHYSICS, vol. 5, no. 3, 4 May 2010 (2010-05-04), pages 193-202, XP055168789, ISSN: 1557-1858, DOI: 10.1007/s11483-010-9159-y * |
See also references of WO2012047251A1 * |
TERECH P ET AL: "LOW MOLECULAR MASS GELATORS OF ORGANIC LIQUIDS AND THE PROPERTIES OF THEIR GELS", CHEMICAL REVIEWS, AMERICAN CHEMICAL SOCIETY, US, vol. 97, 18 December 1997 (1997-12-18), pages 3133-3159, XP002127859, ISSN: 0009-2665, DOI: 10.1021/CR9700282 * |
V. AJAY MALLIA ET AL: "Robust Organogels from Nitrogen-Containing Derivatives of ( R )-12-Hydroxystearic Acid as Gelators: Comparisons with Gels from Stearic Acid Derivatives +", LANGMUIR, vol. 25, no. 15, 4 August 2009 (2009-08-04), pages 8615-8625, XP055054611, ISSN: 0743-7463, DOI: 10.1021/la8042439 * |
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