Are hydrotropes distinct from surfactants?

The physicochemical properties of a homologous series of sodium p-n-alkylbenzoates have been investigated. The objective was to determine whether there is a clear transition point from hydrotropic to surfactant-like behavior with increasing alkyl chain length n, so as to shed clear light on the aggregation mechanism of so-called "hydrotropes". Electrical conductivity measurements were used for a first estimation of the critical aggregation concentrations (cac). As for classical surfactants, log(cac) depends on alkyl chain length n, but two branches of behavior were observed: one having a gradient typical of long chain fatty acid salts and the other with a more shallow dependence. Surface tension (γ) measurements of high purity aqueous solutions were used to generate limiting headgroup areas A(cac), which were in the range (40-50 ?(2)) being consistent with monolayer formation. Small-angle neutron scattering conclusively shows that the lower chain length homologues (classed as hydrotropes) exhibit sharp transitions in aggregation as a function of bulk concentration, typical of regular surfactants. As such, there is little to suggest from this study that hydrotropes differ in association behavior from regular surfactants.     

Synthesis and Mesophase Behavior of Phenylthiophene Based Amphiphilic Molecules

Novel amphiphilic molecules consisting of a rigid 2‐phenylthiophene core, with a polar flexible tri(oxylethylene) moiety attached to the phenyl ring and one or two alkyl chains attached to the thiophene ring at the other side have been synthesized by using Ni(II) and Pd(0) catalyzed coupling reaction as key steps. The tri(oxylethylene) moieties were terminated with hydroxyl group, sodium carboxylate group and lithium carboxylate group respectively. The thermotropic and solvent induced liquid crystalline behavior of these substances was investigated by polarized optical microscopy, differential scanning calorimetry and X‐ray diffraction. Thereby the influence of the terminal groups attached to the tri(oxylethylene) moities as well as the influence of the length and the number of the alkyl chains on the mesophase behavior were investigated. The single alkyl chain Na‐carboxylate termianted derivatives show smectic A phases, double alkyl chain Na‐carboxylate terminated derivatives show a thermo tropic hexagonal columnar mesophase, while columnar mesophases are found in both single and double alkyl chain Li‐carbonate terminated derivatives. The model for molecular organization in the hexagonal columnar mesophase is established.     

Copper carboxylate formation in the thermal oxidative degradation of atactic polypropylene on copper oxide films

The thermal oxidation of atactic polypropylene on CuO_0.67 surfaces in air was studied using IR reflection-absorption spectroscopy. Degradative losses of primary, secondary, and tertiary alkyl hydrogens were observed. At 60 and 73°C, carboxylic acids are the primary degradation products, while at 85 and 100°C, copper carboxylate formation predominates and CuO_0.67 is decomposed. The distinct change in the oxidative mechanisms between 73 and 85°C apparently is related to an irreversible thermal transition in the atactic polypropylene films, which may favor carboxylate production by increasing the permeability of the films to oxygen and water vapor.     

Effects of organic salt additives on the behavior of dimeric ("gemini") surfactants in aqueous solution

The effects of a series of aromatic anions, so-called hydrotropes, on characteristic solution properties of a family of ammonium gemini surfactants with dodecyl chains were explored. The stoichiometric addition of the organic salts to the geminis can result in clear solutions or in phase separation/precipitation, depending on the detailed nature of the added counterions and on the spacer group of the gemini surfactant. Many organic anions induce synergistic effects, strongly reducing the critical micellization concentration (cmc) and the surface tension at the cmc. Furthermore, a number of combinations of organic anions and geminis exhibit thickening of their aqueous solutions. The effects of the added salts are strongly enhanced for the gemini surfactants compared to the monomeric analogue N-dodecyl-N,N,N-trimethylammonium chloride. Even anions such as benzoate may be effective for thickening, and viscoelastic solutions can be obtained with salicylate despite the relatively short alkyl chains.     

Enantioselective ester synthesis in the presence of optically active polymers

Enantiomer-differentiating ester syntheses from acid salts, chlorides, and an anhydride were studied in the presence of optically active polyamines. Enantiomer selection occurred in reactions of a racemic salt with an achiral alkyl bromide and vice versa, which is good evidence of the importance of activation of the carboxylate group by complexation of the counterion and activation of alkyl bromide by the formation of a quaternary salt with polyamine under solid–liquid, phase-transfer reaction conditions. Only small optical activity was observed in the products of acid anhydride or chloride with alcohol.     

Size-controlled synthesis of monodispersed silver nanoparticles capped by long-chain alkyl carboxylates from silver carboxylate and tertiary amine

Monodispersed silver nanoparticles capped by long-chain alkyl carboxylates were prepared by the reaction of silver carboxylate with tertiary amine at 80 degrees C for 2 h. This approach is a unique, size-controlled synthetic method for the large-scale preparation of silver nanoparticles. Long-chain alkyl carboxylate derived from a precursor acts as a stabilizer to avoid the aggregation of silver nanoparticles and to control particle size. In addition, amine plays an important role both as a reagent to form a thermally unstable, amine-coordinated intermediate, bis(amine)silver(I) carboxylate, and as a mild reducing agent for the intermediate to produce nanoparticles at a low temperature. The silver core and carboxylate-capping ligand of silver nanoparticles were characterized by various techniques such as transmission electron microscopy, optical absorption spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, gas chromatograph mass spectroscopy, and thermogravimetric and differential thermal analysis. The diameter of the nanoparticles can be strongly influenced by the alkyl chain length and the structure of the carboxylate. The average diameters of the silver nanoparticles were controlled to less than 5 nm in the case of silver carboxylate with a single alkyl chain length of 13 or 17 carbon atoms. On the contrary, the average diameters of silver nanoparticles became large and polydisperse in the case of silver carboxylate with a chain length of 7 carbon atoms or a branched chain. In comparing triethylamine with trioctylamine, there was no obvious effect to regulate the size distribution of the nanoparticles because they could not function as a capping ligand of the nanoparticles due to their weak coordination to silver. In addition, the heat treatment of silver nanoparticles in solution rather than in the solid state was effective for the growth of particles while maintaining narrow size distributions.     

Critical Phenomena in the Clouding Behavior of Nonionic Surfactants Induced by Additives

Effects of anionic surfactants, hydrotropes, and electrolytes on the cloud point of Triton X-100 have been studied over six decades of additives concentrations. A comprehensive look at all the data reveals significant new learnings. While anionic surfactants and hydrotropes affect the cloud point of non-ionics at ultra low (monomeric) concentrations, electrolytes exhibit a minimum critical concentration above which they cast their effect. This suggests that the former work by modifying the surface charge of non-ionic micelles (i.e., by affecting the solute), whereas the latter work by modifying the properties of the bulk medium. Above their respective critical concentrations, salting-out electrolytes decrease the cloud point while salting-in electrolytes increase it, the trends being linear with additive concentration in either case. The magnitude of the effect of anionic surfactants and hydrotropes increases gradually with increasing concentration till their respective cmc's are reached and then there is a sharp rise in the cloud point. Copyright 1999 Academic Press.     

Facile Synthesis of Supramolecular Ionic Polymers That Combine Unique Rheological,Ionic Conductivity,and Self‐Healing Properties

A new family of supramolecular ionic polymers is synthesized by a simple method using (di‐/tri‐)carboxylic acids and (di‐/tri‐)alkyl amines. These polymers are formed by carboxylate and ammonium molecules that are weakly bonded together by a combination of ionic and hydrogen bonds, becoming solid at room temperature. The supramolecular ionic polymers show a sharp rheological transition from a viscoelastic gel to a viscous liquid between 30 and 80 °C. This sharp viscosity decrease is responsible for an unprecedented jump in ionic conductivity of four orders of magnitude in that temperature range. As a potential application, this chemistry can be used to develop polymeric materials with self‐healing properties, since it combines properties from supramolecular polymers and ionomers into the same material.     

Hydrotropic solutions

Hydrotropes are a class of amphiphilic molecules that cannot form well organized structures, such as micelles, in water but do increase the aqueous solubility of organic molecules. Often strong synergistic effects are observed when hydrotropes are added to aqueous surfactant or polymer solutions. Recent studies regarding the effects of hydrotropes on phase behavior, aggregation, surface tension, viscosity, solubility, and microstructure formation are reviewed. Novel applications of hydrotropes as molecular probes and for controlled release of pharmaceuticals are also discussed.     

Uncommon oxidative transformations of acetic and propionic acids

The oxidative decarbonylation of acetic and propionic acids with the formation of the corresponding alcohol and alkyl carboxylate is observed in the Rh^III/Cu^I,II/Cl⁻ catalytic system in the presence of O₂ and CO. The decarbonylation of propionic acid in a deuterated solvent results in the substitution of hydrogen atoms by deuterium in the alkyl part of the products to form CH₂DCOOD (CHD₂COOH) and CHD₂COOD (CD₃COOH). The subsequent decarbonylation of deuterated acetic acids affords the corresponding deuteromethanols detected as esters with propionic and deuteroacetic acids. The substitution of the hydrogen atom by deuterium in the alkyl part of molecules of the products of oxidative decarbonylation of propionic acid, when the reaction is carried out in a deuterated solvent, indicates that propionic acid behaves as saturated hydrocarbon and blocks the oxidation of poorly soluble methane. Unlike propionic acid, acetic acid enters only the oxidative decarbonylation reaction and does not block methane oxidation.     

Poly-α-ester degradation studies. VII. Thermal degradation of poly(cycloalkylidene carboxylates)

The thermal degradation of poly(cyclopentylidene carboxylate) and poly(cyclohexylidene carboxylate) has been studied over the temperature range 200–500°C by using a combination of kinetic and analytical techniques. The results obtained indicate the simultaneous operation of mechanisms previously observed with different compounds in the series. Thus kinetic studies by thermogravimetric analysis and characterization of the products formed suggest the occurrence of an essentially first-order hydrogen abstraction process with superimposed random scission reactions in the early stages. The main products are cyclopenten-1-carboxylic acid and cyclohexen-1-carboxylic acid, respectively. This corresponds to the behavior previously observed in the degradation of poly(3-pentylidene carboxylate). On the other hand, in-line pyrolysis directly linked to a gas chromatograph clearly indicates the production of cyclopentanone and cyclohexanone and, more importantly in the case of poly(cyclopentylidene carboxylate), the formation of dicyclopentyl glycollide. The appearance of these products in addition to the unsaturated acids suggests that some degradation occurs by the intramolecular ester-interchange process previously postulated for poly(methylene carboxylate) and poly(isopropylidene carboxylate). The associated thermodynamic parameters and relative quantities of the different products observed by gas-chromatographic methods indicate that the hydrogen-abstraction process predominates.     

单壁碳纳米管与卤代烷的亲电加成反应

主要考察了以路易斯酸为催化剂,几种卤代烷烃为反应试剂的单壁碳纳米管侧壁的亲电加成反应,并通过傅立叶红外光谱、热失重分析和拉曼光谱验证了实验所得产物。此反应的目的是在单壁碳纳米管的侧壁连上烷基基团以提高其溶解性和分散性,并可使其更好地与聚烯烃相结合从而提高复合材料的性能,因而具有较高的研究和应用价值。     

An In‐Depth Look at the Reactivity of Non‐Redox‐Metal Alkylperoxides

Over the past 150 years, a certain mythology has arisen around the mechanistic pathways of the oxygenation of organometallics with non‐redox‐active metal centers as well as the character of products formed. Notably, there is a widespread perception that the formation of commonly encountered metal alkoxide species results from the auto‐oxidation reaction, in which a parent metal alkyl compound is oxidized by the metal alkylperoxide via oxygen transfer reaction. Now, harnessing a well‐defined zinc ethylperoxide incorporating a β‐diketiminate ligand, the investigated alkylperoxide compounds do not react with the parent metal alkyl complex as well as Et₂Zn to form a zinc alkoxide. Upon treatment of the zinc ethylperoxide with Et₂Zn, a previously unobserved ligand exchange process is favored. Isolation of a zinc hydroxide carboxylate as a product of decomposition of the parent zinc ethylperoxide demonstrates the susceptibility of the latter to O?O bond homolysis.     

Predicting properties of new ionic liquids: density functional theory and experimental studies of tetra-alkylammonium salts of (thio)carboxylate anions, RCO2⁻, RCOS⁻ and RCS2⁻

Density functional theory calculations of alkyl-carboxylate anions and their sulfur substituted variants are presented here as an aid for the development of new ionic liquids. Electron transfer both within the anion, and between the anion and cation of an ion pair, are described using natural bond order analysis, using tetraethylammonium as a common cation. The overall stabilising effect of this electron transfer is quantified for the series of anions, and is found to correlate with clear trends in ion-pair binding energy. These and other electronic properties determine which compounds are synthesised, and experimental results validate the computational results. In combination with tetraethylammonium, a carboxylate with an unsaturated alkyl chain produces an ionic liquid at room temperature. However, computations suggest that sulfur substituted anions will produce a lower melting point and perhaps more fluid ionic liquid, but one which would be less stable against oxidation.     

Flow microcalorimetry of adsorption of anionic alkyl surfactants at the solid/liquid interface

Flow microcalorimetry was used to study the adsoption of anionic alkyl surfactants from aque--ous solutions onto silica. It is found that for alkyl sulfate systems the strength of adsorption interactionincreases with increases of the alkyl chain length and decreases as temperature rises. The adsorptiondepends only on monomer concentration of the solution even above the critical micelle concentration(cmc). The assumption is made that the adsorption involves only a transfer of monomers from bulkto surface phase. A different adsorption mechanism is operative for the alkyl carboxylate.     

Alkyl chain length-dependent viscoelastic properties in aqueous wormlike micellar solutions of anionic gemini surfactants with an azobenzene spacer

A homologue of carboxylate gemini surfactants with an azobenzene spacer and different lengths of the alkyl tails, referred to as C_m(azo)C_m, has been synthesized. All the surfactants formed wormlike micelles at relatively low concentrations without addition of salt. The reason was attributed to the long and rigid characteristic of the azobenzene spacer, which yielded the pseudo volume between the two tails and thus a columnar-like molecular geometry favorable for the formation of wormlike micelles. The results of rheology and FF-TEM measurements showed that the length of the alkyl tails strongly affected the viscoelastic properties of the wormlike micelle solution. With the increase of the alkyl tail length, the solutions evolved from a typically viscous fluid to a strong viscoelastic solution and then to a gel-like state. This was attributed to the different microstates as revealed by scaling law. These solutions behave as polyelectrolyte systems because of their additive-free nature.     

Tetrabutylammonium alkyl carboxylate surfactants in aqueous solution: self-association behavior, solution nanostructure, and comparison with tetrabutylammonium alkyl sulfate surfactants

A series of long and ultralong chain tetrabutylammonium alkyl carboxylate (TBACm, TBA = tetrabutylammonium ion; Cm = carboxylate ion C(m-1)H(2)(m-1)CO(2)(-) of total carbon number m) surfactants have been obtained by direct neutralization of the fatty acids with m = 12, 14, 18, 22, and 24 by tetrabutylammonium hydroxide. Time-resolved fluorescence quenching has been used to determine the micelle aggregation number (N) of the surfactants with m = 12, 14, and 18 in the temperature range 10-50 degrees C and of the surfactants with m = 22 and 24 in the temperature range 25-60 degrees C. In all instances the values of N were well below those that can be calculated for the maximum spherical micelle formed by surfactants with the same alkyl chain as the investigated surfactants on the basis of the oil drop model for the micelle core. The microstructure of selected solutions of TBAC22 was examined using transmission electron microscopy at cryogenic temperature and compared to the microstructure of solutions of TBA dodecyl and tetradecyl sulfates. These observations generally confirmed the findings of TRFQ. The self-association behavior of these anionic surfactants with TBA counterions is explained on the basis of the large size and the hydrophobicity of the tetrabutylammonium ions. The important differences in behavior that have been evidenced between tetrabutylammonium alkyl carboxylates and alkyl sulfates are discussed in terms of differences in distribution of the surfactant electrical charge on the headgroup and alkyl chain predicted by quantum chemical calculations (Langmuir 1999, 15, 7546).     

Solubilization in alkanes by alcohols as reverse hydrotropes or "lipotropes"

Hydrotropes in aqueous systems do not aggregate in micelles, inhibit presence of mesophases and allow significant and progressive solubilization of "insoluble" molecules in water. It was shown that n-alcohols in alkanes develop the same properties, including the power-law for maximum solubilization of "hydrophilic" molecules. The aim of this paper is to highlight properties of reverse hydrotropes or "lipotropes" by taking n-alcohol/alkane mixtures as model systems. So as to establish a clear parallel between lipotropes and hydrotropes the same methodology used to characterize hydrotropes was applied to these systems. The solubilization of solutes insoluble in alkane, i.e. water and a hydrophilic dye in dodecane, enabled by the addition of n-alcohols ( n = 2, 3, 4 and 7) was studied. In parallel, the nonmicellar aggregation state of butan-1-ol and heptan-1-ol in dodecane was investigated by small-angle X-ray scattering. By applying the Porod's treatment the specific area of the H-bond network formed by heptan-1-ol and the area occupied by hydroxyl group in this network were determined as a function of concentration. A correlation between the aggregation of alcohols in dodecane and the solubilization was made. The disrupting of concentrated mesophases by a lipotrope was illustrated by studying the effect of adding n-alcohols to water/oil/extractant ternary systems used in liquid/liquid extraction. Under some conditions the organic phase splits up into two phases: an extractant mesophase and nearly pure oil. The amount of n-alcohols required to make the extractant mesophase disappear was determined for water/alkane/malonamide extractant systems. The influence of the chain length of the n-alcohol on the efficiency as lipotrope was also experimentally studied. The trend obtained was similar to the one observed with the solubilization experiments.     

Carboxylate clays: A model study for polypropylene/clay nanocomposites

Sodium-montmorillonite was intercalated by carboxylate salts to prepare carboxylate clays. The intercalation of sodium acetate doubles the clay basal spacing and no degradation of the carboxylate clay is noticed in the extrusion temperature range. These carboxylate clays were used to synthesize polypropylene-graft-maleic anhydride (PP-g-MA)/clay nanocomposites. Nanocomposites were also produced by a one-pot process using in situ prepared carboxylate clay. The carboxylate salts within the clay layers partially neutralize the maleic anhydride groups of the PP-g-MA matrix, in situ during the melt compounding. The ionic groups of the partially neutralized polymer offer favourable interactions with the clay, hence reinforcing the interfacial bond between the polymer and the clay and improving the composite properties. The use of carboxylate clay clearly improves the clay dispersion into the PP-g-MA matrix and improves the nanocomposite’s thermal and rheological properties.