Effect of Reaction Conditions and Alkyl Chain Lengths on the Properties of Hydroxyalkyl Starch Ethers

An efficient method of preparing hydrophobic α-hydroxy starch ethers using aqueous alkaline conditions is described. α-Hydroxy starch ethers were synthesized by addition of 1,2-epoxyalkanes to an aqueous alkaline starch gel in the presence of sodium sulfate as a co-catalyst. The reaction, carried out in a stirred autoclave at 140 °C and 3.9 bar, was optimized with respect to the concentrations of sodium hydroxide and 1,2-epoxyalkane. Optimum yields and molar substitutions (MS) were obtained at molar ratios of sodium hydroxide to anhydroglucose unit (AGU) of 0.5 to 1.0. The amount of molar substitution could be controlled by 1,2-epoxyalkane concentration. Thus, a series of α-hydroxyoctyl starch ethers with MS from 0.7 to 2.4 were synthesized in yields up to 90% by using these conditions. Starches with different amylose contents were also converted to the corresponding ethers using a threefold excess of 1,2-epoxyoctane and an equimolar ratio sodium hydroxide : AGU. The reaction is hardly effected by the origin of the starch and its amylose content. The influence of the 1,2-epoxyalkane chain length was investigated by performing the conversion with a series of terminal epoxyalkanes from 1,2-epoxyhexane to 1,2-epoxydodecane. The results indicated that the hydrophobic character of the starch ethers increased by increasing the molar substitution and alkyl chain length. All products were insoluble in water, but soluble in mixtures of methanol and methylene chloride. Furthermore the starch ethers can be converted into shaped articles by extrusion technology without the addition of plasticizers.

Colorimetric determination of the molar substitution of 2-hydroxybutyl and related starch ethers

The most currently used ionic liquids (ILs) are protic ionic liquids (PILs), subject to extensive investigation regarding their physical properties. These compounds along with their mixtures with other substances such as salts and solvents, serve as electrolytes in next generation electrochemical smart devices, and emerge as viable candidates to replace conventional Heat Transfer Fluids (HTFs) in various energy applications. Despite the extensive number of studies, important information about this kind of compounds is still unknown, such as the effect of alkyl chain length on thermal and thermophysical properties, as well as toxicity. This work, extending previous studies of our group, summarizes the liquid range, heat capacity and acute toxicity level of six ammonium ILs: specifically, n-alkyl-ammonium nitrate ILs with increasing alkyl chain length (n = 2, 3, 4, 5, 6, 8). For this study, the synthesis of the three ILs with the longest alkyl chain was performed, along with DSC, TGA and toxicity measurements. It was observed that an increase in alkyl chain length resulted in a decrease in short-term thermal stability and an increase in melting temperature, indicating a reduction in the liquid range. A compensation effect between enthalpy and entropy of melting was observed for the studied chain lengths. The isobaric specific and molar heat capacities increase with temperature for all the compounds studied here, and good correlations were obtained between molar heat capacity and the number of carbon atoms in the alkyl chain for every temperature. Finally, most of the ILs are non-toxic, although toxicity increases with alkyl chain length.

The effects of alkyl chain length in a nonionic surfactant of the solution properties of anionic-nonionic mixed surfactant systems are described. The systems studied were sodium dodecyl sulfate (SDS) -alkyl polyoxyethylene ethers (CmPOE2O, m=6, 8, 10, 12, 14, 16, and 18). The degree of ionic dissociation of mixed micelle shows a minimum with an increase in the number of alkyl chains in the nonionic surfactant. As chain length increases, the electrical conductivities of the mixed surfactant solutions decrease, in spite of decreased activation energy for conduction. The radius of mixed micelle with the electric double layer is larger for a nonionic surfactant with longer alkyl chain length than one with short chain length. Two kinds of micelles (anionic surfactant rich and nonionic rich micelles) were found to form more easily with decreasing alkyl chain length in nonionic surfactants. Of particular significance is the fact that in a mixed system consisting of SDS and C6POE20 with extremely short alkyl chains, nonionic surfactant molecules may penetrate into the palisade of an SDS micelle.

FTIR determination of the degree of molar substitution for hydroxypropyl chitosan

Colloidal properties of aqueous bivalent metal dodecylpoly(oxyethylene)sulfates and hexadecylpoly(oxyethylene)sulfates (I)

Amino acid-based anionic gemini surfactants (2C(n)diCys, where n represents an alkyl chain with a length of 10, 12, or 14 carbons and "di" and "Cys" indicate adipoyl and cysteine, respectively) were synthesized using the amino acid cysteine. Biodegradability, equilibrium surface tension, and dynamic light scattering were used to characterize the properties of gemini surfactants. Additionally, the effects of alkyl chain length, number of chains, and structure on these properties were evaluated by comparing previously reported gemini surfactants derived from cystine (2C(n)Cys) and monomeric surfactants (C(n)Cys). 2C(n)diCys shows relatively higher biodegradability than does C(n)Cys and previously reported sugar-based gemini surfactants. Both critical micelle concentration (CMC) and surface tension decrease when alkyl chain length is increased from 10 to 12, while a further increase in chain length to 14 results in increased CMC and surface tension. This indicates that long-chain gemini surfactants have a decreased aggregation tendency due to the steric hindrance of the bulky spacer as well as premicelle formation at concentrations below the CMC and are poorly packed at the air/water interface. Formation of micelles (measuring 2 to 5 nm in solution) from 2C(n)diCys shows no dependence on alkyl chain length. Further, shaking the mixtures of aqueous 2C(n)diCys surfactant solutions and squalane results in the formation of oil-in-water type emulsions. The highly stable emulsions are formed using 2C₁₂diCys or 2C₁₄diCys solution and squalane in a 1:1 or 2:1 volume ratio.

A protic ionic liquid (PIL) composed of 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU) and acetic acid can dissolve cellulose under mild conditions and catalyse its transesterification. To investigate the relationship between physicochemical properties and chemical structures, PILs composed of DBU and carboxylic acids with varying alkyl chain lengths were prepared as cellulose-dissolving solvents. The thermal behaviours of the PILs were analysed by thermogravimetry and differential scanning calorimetry, and their viscosities, ionic conductivities, and cellulose-dissolution abilities were determined. The effect of the alkyl chain length in the carboxylate ion on the physicochemical properties of the PILs was investigated. With increasing chain length, the thermal stability and ionic conductivity increased, whereas the melting point (Tm), glass-transition temperature (Tg), cellulose solubility, and viscosity decreased. The cellulose solubility increased as the difference between the pKa values of the DBU and carboxylic acid (?pKa) increased. In addition, the cellulose solubility increased with the increasing density of the PIL. It was revealed that PILs with a high ?pKa value and a carboxylate ion with a short alkyl chain are suitable for cellulose dissolution.

Influence of temperature and alkyl chain length on physicochemical properties of trihexyl- and trioctylammonium based protic ionic liquids

In this study, we have examined both the effect of alkyl chain length and anion composition on the 1-alkyl-3-methylimidazolium (C(n)mim, n = 4, 6, 8, 10, and 12) structure and orientation at the room-temperature ionic liquid (RTIL)/SiO(2) interface by sum-frequency vibrational spectroscopy (SFVS). Four different anions were investigated in this study: tetrafluoroborate (BF(4)), hexafluorophosphate (PF(6)), bis(trifluoromethylsulfonyl)imide (BMSI), and bis(pentafluoroethylsulfonyl)imide (BETI). It was found that the alkyl chain in BMSI and BETI RTILs showed a decrease in gauche defects with an increase in chain length, whereas the alkyl chains of the BF(4) and PF(6) RTILs have virtually no gauche defects regardless of chain length. The tilt of the alkyl chain lies predominantly perpendicular to the surface for all the RTILs examined. A strong correlation between the HCCH vs tilt angle and alkyl chain length was observed; as the alkyl chain is lengthened the HCCH vs lies more perpendicular to the SiO(2) surface. The results of this study suggest that the length of the alkyl chain dictates to a large degree the orientation of the imidazolium cation at the surface, regardless of anion composition. To a lesser extent, the HCCH vs tilt of the imidazolium ring of the cation also appears to be correlated to the surface charge density of the SiO(2). As the SiO(2) surface charge density becomes more negative the HCCH vs tilt angle lies more parallel to the surface.

The equilibrium adsorption behavior of two n-alkyl-beta-D-glucosides (octyl (C8G1) and decyl (C10G1)) and four n-alkyl-beta-D-maltosides (octyl (C8G2), decyl (C10G2), dodecyl (C12G2), and tetradecyl (C14G2)) from aqueous solution on a titania surface, as measured by ellipsometry, has been investigated. The main focus has been on the effect of changes in the alkyl chain length and headgroup polymerization, but a comparison with their adsorption on the silica/water and air/water interfaces is also presented. Some comparison with the corresponding adsorption of ethylene oxide surfactants, in particular C10E6 and C12E6, is given as well. For all alkyl polyglucosides, the maximum adsorbed amount on titania is reached slightly below the critical micelle concentration (cmc), where it levels off to a plateau and the amount adsorbed corresponds roughly to a bilayer. However, there is no evidence that this is the actual conformation of the surfactant assemblies on the surface, but the surfactants could also be arranged in a micellar network. On hydrophilic silica, the adsorbed amount is a magnitude lower than on titania, corresponding roughly to a layer of surfactants lying flat on the surface. A change in the alkyl chain length does not result in any change in the plateau molar adsorbed amount at equilibrium; however, the isotherm slope for the alkyl maltosides increases with increasing chain length. Headgroup polymerization on the other hand affects the adsorbed amount. The alkyl glucosides start adsorbing at lower bulk concentrations than the maltosides and equilibrate at higher adsorbed amounts above the cmc. When compared with the ethylene oxide (EO) surfactants, it is confirmed that the EO surfactants hardly adsorb on titania, since the measured changes in the ellipsometric angles are within the noise level. They do, however, adsorb strongly on silica.

We have improved the gas chromatography (GC) method with the aid of 1H NMR to determine the degree of molar substitution (MS) of hydroxypropyl cellulose (HPC). This improvement relied on our established dissolution approach for low-substituted HPC, facilitating NMR determination and subsequently expanding the working range of the MS determination from the lower limit of USP specified as 53.4% to 9.3% (MS 0.2). In this method, 2-iodopropane was produced by the reaction of hydroiodic acid with HPC at high-temperature and then measured by GC. 1H NMR was used for the correction of GC method. The MS results via the GC method (MSGC) exhibited a linear correlation with those obtained by the 1H NMR method (MSNMR), with correction equation of MSNMR=1.8026MSGC - 0.2046 (R2 = 0.9979). Method validation results showed that the average recovery and relative standard deviation (RSD) of MS are 103.5% and 0.83%, respectively. Detection limit and quantitation limit were 0.08 and 0.26, respectively. This method is accurate, sensitive with good precision, which is of great value for the production, research and development, and application of HPC, particularly the low-substituted HPC.

Molecular Structural Evolution of Near-Infrared Cationic Aggregation-Induced Emission Luminogens: Preclinical Antimicrobial Pathogens Activities and Tissues Regeneration

Effects of alkyl chain length and halide anion on hydrogen bonding, electrochemical transport properties and double layer capacitance in eutectic solvents

Effect of sodium alkyl sulfate chain length on foam stability: A molecular dynamics study