Hydrolytic enzymatic transformation of advanced synthetic intermediates: on the choice of the organic cosolvent

For enzymatic hydrolyses of advanced synthetic intermediates, the use of an organic cosolvent is often warranted. As a model study, the cosolvent dependence (at 10 volume%) of the key enzymatic step in our asymmetric synthesis of (−)-podophyllotoxin was examined. At high protein concentrations and rt, DMSO and the polyethereal organic cosolvents dioxane, diglyme and triglyme emerged as the best organic cosolvents, in terms of yield, % ee and catalytic efficiency (V_max/K_m). However, only in 10% triglyme was optimal efficiency maintained at both lower protein concentration and higher temperature.     

Rh-Catalyzed asymmetric hydrogenation of (Z)-ethyl 3-acetamido-2-butenoate in supercritical carbon dioxide: the effect of cosolvents

Rh-Catalyzed asymmetric hydrogenation (up to 85% ee) of (Z)-ethyl 3-acetamido-2-butenoate was carried out for the first time in supercritical CO₂ using protic cosolvents. The activity of the Rh catalyst bearing the amidophosphite ligand increases with an increase in acidity of the protic cosolvents and with hydrogen pressure.     

High-Performance Lithium Metal Batteries Enabled by a Fluorinated Cyclic Ether with a Low Reduction Potential

Electrolyte engineering is crucial for developing high-performance lithium metal batteries (LMB). Here, we synthesized two cosolvents methyl bis(fluorosulfonyl)imide (MFSI) and 3,3,4,4-tetrafluorotetrahydrofuran (TFF) with significantly different reduction potentials and add them into LiFSI-DME electrolytes. The LiFSI/TFF-DME electrolyte gave an average Li Coulombic efficiency (CE) of 99.41 % over 200 cycles, while the average Li CEs for MFSI-based electrolyte is only 98.62 %. Additionally, the TFF-based electrolytes exhibited a more reversible performance than the state-of-the-art fluorinated 1,4-dimethoxylbutane electrolyte in both Li||Cu half-cell and anode-free Cu||LiNi_0.8Mn_0.1Co_0.1O₂ full cell. More importantly, the decomposition product from bis(fluorosulfonyl)imide anion could react with ether solvent, which destroyed the SEI, thus decreasing cell performance. These key discoveries provide new insights into the rational design of electrolyte solvents and cosolvents for LMB.     

Modification of the lyotropic liquid crystalline microstructure of amphiphilic block copolymers in the presence of cosolvents

This article reviews the results of recent investigations on the macroscopic (phase behavior) and microscopic (microstructure) aspects of the role of cosolvents on the self-assembly of amphiphilic copolymers. A comprehensive account of the systematic studies performed in ternary isothermal systems consisting of a representative poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO–PPO–PEO) block copolymer (Pluronic P105, EO₃₇PO₅₈EO₃₇), water and a polar cosolvent (such as glycerol, propylene glycol or ethanol) is presented. The effect of cosolvents on the copolymer phase behavior is quantified in terms of the highest cosolvent/water ratio able to maintain the liquid crystalline structures. The effect of cosolvents on the microstructure of the lyotropic liquid crystals is quantified in terms of the degree of relative swelling per cosolvent content per copolymer content, a parameter that characterizes the given cosolvent and copolymer. The set of correlations on the cosolvent effects on the phase behavior or microstructure to the cosolvent physicochemical characteristics (such as octanol/water partition coefficient or solubility parameter) have led to the development of a hypothesis that accounts for the cosolvent effects on the self-assembly of PEO–PPO–PEO block copolymers and can be used to predict them. The rich structural diversity and the potential for a precise and convenient modification of the lyotropic liquid crystalline microstructure of the PEO–PPO–PEO block copolymers is discussed in comparison to the phase behavior of the low-molecular nonionic surfactants.     

FTIR study of hydrogen bonding of stearic acid with ethanol, dimethyl sulfoxide,and acetonitrile in supercritical CO_2

FTIR spectroscopy was used to study the hydrogen bonding of stearic acid with ethanol, dimethyl sulfoxide (DMSO),and acetonitrile in supercritical CO_2 at 318.15 K, and 12.5 and 16.5 MPa. The concentrations of the cosolvents range from 0—0.6 mol·L~(-1). The area percentage of absorption bands for hydrogen-bonded and nonhydrogen-bonded species was obtained from the IR spectra. The acid and the cosolvents can form hydrogen bond even when their concentrations are very low. At fixed solute concentration, the extent of hydrogenbonding increases with cosolvent concentration. At higher ethanol concentrations, it seems that one stearic acid molecule can hydrogen bond with more than one ethanol molecules simultaneously. It is seen that the strength of the hydrogen bond formed by the acid and the cosolvents is in the order: DMSO>ethanol>acetonitrile.     

Medium effects on the initial and the transition states upon the solvolysis of trans‐dichlorobis(N‐methyl‐ethylenediamine)cobalt(III) complex in water‐mixed solvents

The kinetics of solvolysis of trans‐dichlorobis(N‐methylethylenediamine)cobalt(III) complex have been investigated in aqua‐organic solvent media (0–60% (v/v) cosolvent) at 25 ≤ t°C ≤ 60, using n‐propanol and tert‐butyl alcohol as cosolvents. The first‐order rate constant increased nonlinearly with the reciprocal of the dielectric constant D_s^?1, and x_org, reflecting the individuality of the cosolvents and thereby suggesting that the relative stabilities of the transition state and initial state were governed by the preferential solvation effect. The thermodynamic parameters (ΔH^≠ and ΔS^≠) were sensitive to the structural changes in the bulk solvent phase. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 495–499, 2002     

Investigations of salt — Mixed solvent systems XXXVIII. Crystallization enthalpy of magnesium chloride in mixed solvent systems

The crystallization enthalpies of MgCl₂ in MgCl₂–H₂O-cosolvent systems at 25°C were determined calorimetrically as a function of the cosolvent content in the mixed solvent. Methanol, acetone, and N,N-dimethylformamide were employed as cosolvents. The results show the individual cosolvents to have very differently influences on the energy state of the salt in the saturated solution. The most pronounced changes are effected by an increase of the DMF content in the mixed solvent. The intensity of Mg²⁺-DMF interaction at a higher DMF content in the saturated solution considerably exceeds the Li⁺-DMF interaction in LiCl solutions.     

Structural features of binary mixtures of supercritical CO2 with polar entrainers by molecular dynamics simulation

Computer simulations of supercritical carbon dioxide and its mixtures with polar cosolvents: water, methanol, and ethanol (concentration, 0.125 mole fractions) at T = 318 K and ρ = 0.7 g/cm³ are performed. Atom-atom radial distribution functions are calculated by classical molecular dynamics, while the probability distributions of relative orientation of CO₂ molecules in the first and second coordination spheres describing the geometry of the nearest environment of CO₂ molecules and the trajectories of cosolvent molecules are found using Car-Parrinello molecular dynamics. Based on the latter, the conclusions regarding structure and interactions of polar entrainers in their mixtures with supercritical CO₂ are made. It is shown that the microstructure of carbon dioxide varies only slightly upon the introduction of cosolvents.     

Effects of cosolvents cetyltrimethylammonium bromide on the thresholds for nucleation of nitrogen in aqueous solutions

The decomposition of ammonium nitrite in water creates a supersaturated solution of nitrogen. The same process occurs in water-organic solvent mixtures. Acetone, dioxane, dimethylsulfoxide (DMSO) and dimethylformamide (DMF) are the cosolvents used in this study. The limits of supersaturation of nitrogen (C _SL /mol L^–1) were determined in all of these solvent mixtures by releasing the dissolved gas sonicationally and measuring the volume of released gas. C _SL was generally increased in the presence of cosolvents. The effectiveness sequence of organic solvents was found to be as DMF SL and all of the measured quantities of this study were generally affected by micelle formation.     

Effects of cosolvents on helical substituted polyacetylene particles prepared through suspension polymerization

Acetylenic monomers undergo aqueous suspension polymerization providing particles constructed by helical substituted polyacetylene. Different from suspension polymerization of vinyl monomers, a cosolvent is indispensable to dissolve Rh catalyst and solid acetylenic monomers. The cosolvent is found to play essential roles in monomers' polymerization and the particles' formation. To systemically explore the effects of cosolvents, three monomers, M1 (achiral, liquid), M2 (achiral, solid), and M3 (chiral, solid), and six cosolvents (divided into two groups by their miscibility with water) are used for performing suspension polymerization in aqueous media at 30 °C, with Rh⁺B^– (C₆H₅)₄ as catalyst and polyvinylpyrrolidone as stabilizer. FTIR spectra and gel permeation chromatography confirm the occurrence of polymerization. Raman spectra demonstrate the high cis contents of the polymer chains. Scanning electron microscope images show that the polymer particles obtained under optimal conditions are in spherical morphology. Circular dichroism and UV‐vis spectroscopy demonstrate the helical structures of the polymer chains forming the chiral particles. Dynamic light scattering characterization is carried out to characterize the nanoparticles. The type and amount of the cosolvent affect the polymerization remarkably. Cosolvents with higher polarity lead to smaller polymer particles, while lower polar cosolvents provide larger ones. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2670–2678     

Molecular interactions in polystyrene cosolvent systems

Studied here are miscible binary cosolvents for polystyrene, for which polystyrene is insoluble in either of the individual solvents. Polymer-solvent interactions in solutions of atactic polystyrene in acetone/diethyl ether and in methylcyclopentane (MCP)/acetone binary cosolvents have been investigated using nuclear magnetic resonance (NMR) spectroscopy. Polystyrene ¹³C chemical shifts were measured as a function of miscible binary solvent compositions and temperature. The NMR data were used to calculate “association constants” as a measure of specific interactions of the solvent components with all sites on the polymer. In mixtures of acetone and diethyl ether, ¹³C-NMR indicates a weak interaction between the polystyrene phenyl ring and the diethylether solvent component. In the polystyrene/MCP/acetone system, present NMR data reveal no preferential interactions. Additional NMR measurements were performed on polystyrene in mixtures of CCl₄/acetone. From these results, it is concluded that although preferential polymer-solvent interactions are present in some cosolvent systems, they are not a prerequisite for such behavior.     

Solution thermodynamics and preferential solvation of hesperidin in aqueous cosolvent mixtures of ethanol,isopropanol, propylene glycol,and n-propanol

The solubility of hesperidin in some {cosolvent (1) + water (2)} mixtures expressed in mole fraction at temperatures from 293.15 K to 333.15 K reported by Xu et al. has been used to calculate the apparent thermodynamic functions, Gibbs energy, enthalpy, and entropy, of the dissolution processes by means of the van’t Hoff and Gibbs equations. Non-linear enthalpy–entropy relationships were observed for this drug in the plots of enthalpy vs. Gibbs energy of dissolution with positive or negative slopes regarding mixtures composition and/or cosolvent. Moreover, the preferential solvation of hesperidin by the cosolvents was analysed by using the inverse Kirkwood–Buff integrals observing that this drug is preferentially solvated by water in water-rich but preferentially solvated by cosolvents in mixtures 0.20 (or 0.24) ≤ x₁° ≤ 1.00. Furthermore, a new mathematical model was proposed for correlating/predicting the solubility of hesperidin in binary solvent mixtures at various temperatures.     

Spectral studies of safranin-O in different surfactant solutions

The interaction of Safranin-O (SO), a cationic dye, with various surfactants viz., anionics; Sodiumdodecylsulfate (SDS) and Sodiumdodecylsulfonate (SDSo), nonionics; polyoxyethylenesorbitanmonolaurate (Tween 20) and polyoxyethylenedodecylether (Brij 35), cationic; Dodecyltrimethylammoniumbromide (DTAB) and zwitterionic; Laurylsulfobetaine (LSB) was studied spectrophotometrically as a function of surfactant concentration ranging from premicellar to postmicellar region in aqueous media in the absence and presence of cosolvents. The binding constants (K(b)) and fraction of bound SO to micelles (f), were calculated by means of Benesi-Hildebrand Equation. The binding tendency of SO to micelles followed the order as; Tween 20>Brij 35>SDS>SDSo>LSB. The presence of cosolvents, such as Methanol, Dimethylformamide (DMFA) and 1,4 Dioxan (DX) at various volume percentages, increased the CMC of both SDS and Tween 20 and at a certain concentration totally inhibited the micellization. The binding of SO to micelles decreased as the concentration of the cosolvents increased. This inhibitory effect of cosolvents on binding of SO to micelles followed the order as; Methanol>DMFA>DX.     

Kinetics of the solvolysis of chloropenta-amminecobalt(III) ions in mixtures of water with t-butyl alcohol or with 2-methoxyethanol

Summary As the transition state for the solvolysis of [Co(NH₃)₅Cl]²⁺ ions is known to have Cl^- ions in a situation closely similar to that in the bulk solvent, the kinetics of this solvolysis have been investigated for comparison in H₂O with added cosolvents of low and high hydrophobicities. A linear variation of log(rate constant) with the reciprocal of the dielectric constant is found with the former, but not with the latter cosolvent. Maxima in the enthalpies and entropies of activation found using the more hydrophobic cosolvent appear at solvent compositions where extrema occur in the physical properties influenced by structural changes in the solvent. The application of a free energy cycle to the solvolysis in H₂O and in the mixtures shows that the emergent solvated cobalt(III) ion in the transition state is more stabilised in the latter than [Co(NH₃)₅Cl]²⁺ with both cosolvents. The application of such a cycle to cases where the initial state is destabilised in the mixture is discussed.     

Estimation of electron transfer rate constants by static (optical and electrochemical) measurements

A kinetic study of the reduction of Co(NH₃)₅(DMSO)³⁺ (DMSO=dimethylsulfoxide) by Fe(CN)₆⁴⁻ has been carried out in several water–cosolvent mixtures at 298.2 K. The cosolvents used were ethylene glycol, acetonitrile, methanol and glucose. The free energies of activation for this thermal electron-transfer reaction have been calculated from a combination of spectroscopic and electrochemical data and compared with those obtained from the kinetic study. Quantitative agreement is found between both series of data. This shows the possibility of estimating activation free energies for electron transfer reactions from these (static) measurements.     

荧光探针技术研究共溶剂对PEO-PPO-PEO嵌段共聚物溶液胶束的形成及内部结构的影响

选择了甲醇、乙醇、正丙醇、乙二醇、乙二胺、乙醇胺及２甲氧基乙醇等七种包括单官能团和双官能团共溶剂、与水组成混合溶剂,并利用荧光探针技术研究了共溶剂对环氧乙烷环氧丙烷环氧乙烷（ＰＥＯＰＰＯＰＥＯ）共聚物水溶液胶束形成及其结构的影响,结果表明,一些共溶剂与水和共聚物ＰＰＯ段都具有较好的混溶性,使形成胶束的ＣＭＴ升高,而其它共溶剂的引入则使得形成胶束的ＣＭＴ降低．从共溶剂对所形成胶束的微结构影响看,能与共聚物链有较强作用的双官能团的共溶剂和有较小分子尺寸的共溶剂有利于使形成的胶束具有较紧密的结构,在此条件下,形成胶束的紧密程度决定了胶束内微极性的大小,而与引入共溶剂的极性大小关系不大．     

Autooxidized Polyunsaturated Oils/Oily Acids: Post-it Applications and Reactions with Fe(III) and Adhesion Properties

Soybean oil, sesame oil, linoleic acid and linolenic acid were epoxidized, peroxidized and hydroperoxidized via autooxidation under air oxygen and sunlight at room temperature to obtain novel post-it materials. Polymeric soybean oil peroxide and sesame oil peroxide were containing soluble part of 60%(w/w) together with crosslinked part of 40%(w/w) while polymeric linoleic and polymeric linolenic acids were completely soluble. The autooxidized soluble products with Mn varying between 800 and 3100 Daltons were used as post-it adhesive. The highest adhesion was observed in the case of polymeric soybean oil (3.0 Newton), while adhesion of commercial epoxidized soybean oil, polymeric linoleic and polymeric linolenic acid were 0.8, 0.5 and 0.5 Newton, respectively. Reactions of the autooxidized soluble products with Fe(NO₃)₃. 4H₂O in the presence of ethanol, glycerol and diethyleneglycol gave the hydroxy functionalized products with the same M_n values and indicating no adhesive properties. When the commercial epoxidized soybean oil was reacted with Fe(NO₃)₃. 4H₂O in the presence of the alcohols, Mn of the hydroxy functionalized polymeric oil was found to be unchanged. ¹H NMR, FT-IR, SEM and GPC techniques were used in the characterization of the products obtained.     

荧光探针技术研究共溶剂对PEO-PPO-PEO嵌段共聚物溶液胶束的形成及内部结构的影响

选择了甲醇、乙醇、正丙醇、乙二醇、乙二胺、乙醇胺及２ 甲氧基乙醇等七种包括单官能团和双官能团共溶剂、与水组成混合溶剂，并利用荧光探针技术研究了共溶剂对环氧乙烷 环氧丙烷 环氧乙烷（ＰＥＯ ＰＰＯ ＰＥＯ）共聚物水溶液胶束形成及其结构的影响，结果表明，一些共溶剂与水和共聚物ＰＰＯ段都具有较好的混溶性，使形成胶束的ＣＭＴ升高，而其它共溶剂的引入则使得形成胶束的ＣＭＴ降低．从共溶剂对所形成胶束的微结构影响看，能与共聚物链有较强作用的双官能团的共溶剂和有较小分子尺寸的共溶剂有利于使形成的胶束具有较紧密的结构，在此条件下，形成胶束的紧密程度决定了胶束内微极性的大小，而与引入共溶剂的极性大小关系不大．     

Solubilities of poly(ethylene glycol)s in the mixtures of supercritical carbon dioxide and cosolvent

The solubilities of poly(ethylene glycol) (PEG6000) (M.W.=7500) in the mixtures consisting of supercritical carbon dioxide (CO₂) and cosolvent have been measured by observing the cloud points at 313.15 K and 16 MPa. Ethanol and toluene were used as cosolvents. The solubility of PEG6000 is extremely low in either CO₂ or ethanol, but becomes about 20 wt.% in a mixture of the two. The maximum solubility is achieved at about 50 wt.% (polymer-free) ethanol. The solubilities of PEG6000 in the mixtures of supercritical CO₂ and the cosolvent have been correlated by a regular solution model using the local compositions of solvents around a solute molecule, and an expanded liquid equation of state model.     

The effect of hydrophobic-lipophilic interactions on chemical reactivity. 9. Putting the spotlight on lipophilic forces in solvent-effect studies

The hydrolytic rate constants of thep-nitrophenyl esters of acetic, octanoic, dodecanoic and hexadecanoic acids in six aquiorgano binary mixtures of graded compositions at various initial substrate concentrations were measured and discussed in terms of the hydrophobic-lipophilic interactions between the substrate molecules, and the organic cosolvents which were MeOH, Me₂SO, 1, 4-dioxane, 1,2-dimethoxyethane,n-propanol andt-butanol. The accelerating or retarding effects of the organic cosolvents on the rate constants of hydrolysis were found to be directly related to the lipophilicities of the solvents which were changed either by changing the content (ϕ) or the nature of the organic cosolvent. The classification or ordering of the six solvents on the basis of their solvent effects were found to conform to the lipophilicity order derived from Rekker's Σf values. The results support the proposition that lipophilic interactions can play an important role in solvent effects of aqueous binaries.