Organic Solvent Composition Research Articles

Investigating the self-assembly and shape transformation of poly(ethylene glycol)-b-poly(d,l-lactide) (PEG-PDLLA) polymersomes by tailoring solvent-polymer interactions

Different ratios between THF and dioxane were used to study the effect of organic solvent composition on the self-assembly and subsequent shape-change of poly(ethylene glycol)-b-poly(d,l-lactide) (PEG-PDLLA) polymersomes.

Improving the Performance of PVDF/PVDF-g-PEGMA Ultrafiltration Membranes by Partial Solvent Substitution with Green Solvent Dimethyl Sulfoxide during Fabrication.

Traditional organic solvents used in membrane manufacturing, such as dimethylformamide and tetrahydrofuran, are generally very hazardous and harmful to the environment and human health. Their total or partial substitution with green solvent dimethyl sulfoxide (DMSO) is proposed to fabricate membranes composed of poly(vinylidene fluoride) (PVDF) blended with PVDF-graft-poly(ethylene glycol) methyl ether methacrylate (PEGMA), with the purpose to accomplish a greener chemical process and enhance the membrane performance. Various organic solvent compositions were first investigated using the Hansen solubility theory, and the best mixture was thus applied experimentally. The membrane prepared by a ratio of N,N-dimethylacetamide/DMSO = 7:3 outperformed the membranes prepared by other solvent mixtures. This membrane showed high wetting behavior with the water contact angle declining from 71 to 7° in 18 s and a pure water flux reaching values larger than 700 L m–2 h–1 under 0.07 MPa applied hydraulic pressure. The membrane rejected sodium alginate at a rate of 87%, and nearly complete flux recovery was achieved following fouling and physical cleaning. The introduction of green chemistry concepts to PVDF/PVDF-g-PEGMA blended membranes is a step forward in the goal to increase the sustainability of membrane production.

Process intensification applied to spent nuclear fuel reprocessing: An alternative flowsheet using small channels

Commercial plants for spent nuclear fuel reprocessing rely on the Plutonium Uranium Extraction (PUREX) process, based on traditional liquid–liquid extraction technologies. In this paper, an alternative flowsheet for spent nuclear fuel reprocessing is proposed, based on small-scale extractors to overcome some of the issues related to the conventional technologies, such as solvent degradation, size and nuclear criticality control. The main goal of the process is to preclude the risk of nuclear proliferation, hence a mixed uranium/plutonium oxide is produced instead of pure plutonium.A superstructure optimisation based framework has been used to identify a process with several benefits over the conventional process. Novel flow configurations and organic solvent composition have been investigated. A large number of components and chemical reactions are included in the framework. The resulting model is a mixed integer nonlinear optimisation problem, implemented in the General Algebraic Modeling System (GAMS).The most promising flowsheet identified is more cost effective than the conventional one. Furthermore, advantages in terms of safety and separation efficiency have been achieved. It was found that increasing the inner diameter of the small channels up to 2.5 mm, as well as increasing the tributyl phosphate fraction in the organic solvent, are advantageous.

The Performance Investigation of Bimodal Cation Exchange/Hydrophilic Interaction Liquid Chromatography–Electrospray Ionization Mass Spectrometry by Modifying Mobile Phase Composition in Amino Acid Separation

Owing to its unique selectivity, mixed‐mode chromatography (MMC) has been extended to the analysis of biological fluids. Among various MMC applications, ion exchange/hydrophilic interaction liquid chromatography (IEX/HILIC) is particularly beneficial for the analysis of polar compounds without derivatization or ion pairing. Nevertheless, no practical information about the retention behavior is discussed. In this study, the chromatographic behavior of amino acids in a CEX/hydrophilic interaction mixed‐mode column via the modification of the mobile phase was investigated. A low buffer salt concentration led to increased retention; particularly, positively charged amino acids were not eluted by excessive interactions with the negatively charged stationary phase at a moderate salt concentration (<20 mM). An acid modifier of formic acid or acetic acid exhibited a similar effect on the separation, and a low acid concentration (<0.5%) led to peak broadening by additional ion exchange with a silanol group at high pH. With respect to the composition of organic solvents, aprotic solvents such as tetrahydrofuran or acetonitrile afforded appropriate retention. However, protic solvents led to the considerably reduced retention except positively charged amino acids. Novel, practical information for the optimization or development of applications with a CEX/HILIC column for polar analytes such as amino acids was obtained.

Determination and Correlation of the Solubility of l-Fucose in Four Binary Solvent Systems at the Temperature Range from 288.15 to 308.15 K

Experimental solubility data of l-fucose in methanol + water, ethanol + water, 2-propanol + water, and acetone + water systems were measured at temperatures ranging from 288.15 to 308.15 K under atmosphere pressure (P = 0.1 MPa), using the gravimetric method. The experimental results indicate that the solubility of l-fucose increases with increasing temperature and water content, as well as decreasing with the composition of organic solvents used in this work. According to the data measured in this experiment, methanol is less effective than ethanol, 2-propanol, and acetone in the antisolvent crystallization process of l-fucose. By means of our research, the solubility of l-fucose in the pure solvents was affected by polarity and hydrogen bond. The modified Apelblat model, CNIBS/R-K model, and Apelblat–Jouyban–Acree model were used to correlate the solubility data, and all three of the thermodynamic models were found to agree well with the measured experimental solubility data.

Effect of Binary Organic Solvents Together with Emulsifier on Particle Size and In vitro Behavior of Paclitaxel-Encapsulated Polymeric Lipid Nanoparticles.

Biodegradable nanoparticles with diameters between 100 nm and 500 nm are of great interest in the contexts of targeted delivery. The present work provides a review concerning the effect of binary organic solvents together with emulsifier on particle size as well as the influence of particle size on the in vitro drug release and uptake behavior. The polymeric lipid nanoparticles (PLNs) with different particle sizes were prepared by using binary solvent dispersion method. Various formulation parameters such as binary organic solvent composition and emulsifier types were evaluated on the basis of their effects on particle size and size distribution. PLNs had a strong dependency on the surface tension, intrinsic viscosity and volatilization rate of binary organic solvents and the hydrophilicity/hydrophobicity of emulsifiers. Acetone-methanol system together with pluronic F68 as emulsifier was proved to obtain the smallest particle size. Then the PLNs with different particle sizes were used to investigate how particle size at nanoscale affects interacted with tumor cells. As particle size got smaller, cellular uptake increased in tumor cells and PLNs with particle size of ~120 nm had the highest cellular uptake and fastest release rate. The paclitaxel (PTX)-loaded PLNs showed a size-dependent inhibition of tumor cell growth, which was commonly influenced by cellular uptake and PTX release. The PLNs would provide a useful means to further elucidate roles of particle size on delivery system of hydrophobic drugs.

A multi-detector chromatographic approach for characterization and quantitation of botanical constituents to enable in silico safety assessments

An approach has been developed to characterize the individual chemical constituents of botanicals. The challenge was to identify and quantitate the significant analytes in these complex mixtures, largely in the absence of authentic standards. The data-rich information content generated by this three-detector configuration was specifically intended to be used to conduct safety and/or quality evaluations for complex botanical mixtures, on a chemical constituent basis. The approach utilized a broad gradient UHPLC chromatographic separation. Following the chromatographic separation and UV detection, the eluent was split and sent into a charged aerosol detector (CAD), for quantitation, and a quadrupole/time-of-flight high-resolution mass spectrometer for component identification. The known bias of the otherwise universal CAD response, for organic solvent composition of the mobile phase, was compensated by the addition of an inverse gradient make-up stream. This approach and the orthogonal information content from the chromatography and three different detectors was specifically designed to enable in-silico safety assessments. These guide, minimize, or even eliminate the need for in vivo and in vitro safety assessments. The methodology was developed and demonstrated using standardized extracts of Ginkgo biloba. Results from the development of this novel approach and the characterization example reported here demonstrate the suitability of this instrumental configuration for enabling in-silico safety assessments and proving general quality assessments of botanicals.

Lithium-Ion Conductivity of Polymers Based on Sulfonated Polystyrene and Polymethylpentene Intercalated by Organic Solvents

Ion-exchange membranes based on polymethylpentene and sulfonated polystyrene with different grafting degrees were obtained. Solvation and mobility of lithium ions depending on the composition of initial organic solvents were studied. The highest ionic conductivity at room temperature (30°C) are obtained for the membranes containing dimethylsulfoxide (σ = 1.31 × 10–4 S/cm for membrane with GD = 78%). Membranes containing dimethylformamide are characterized by a constant phase composition in a broad temperature range and the highest ionic conductivity at low temperature (σ = 9 × 10–6 S/cm at–20°C for a polymer with GD = 78%).

Self‐Assembly of Rod‐Coil Block Copolymers on Carbon Nanotubes: A Route toward Diverse Surface Nanostructures

In this work, it is reported that poly(γ-benzyl-l-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) rod-coil block copolymers (BCPs) can disperse carbon nanotubes (CNTs) in solution and form various surface nanostructures on the CNTs via solution self-assembly. In an organic solvent that dissolves the BCPs, the PBLG rod blocks adsorb on CNT surfaces, and the BCPs form conformal coatings. Then, by the introduction of water, a selective solvent for PEG blocks, the BCPs in the coatings further self-assemble into diverse surface nanostructures, such as helices (left-handed or right-handed), gyros, spheres, and rings. The morphology of the surface nanostructure can be tailored by initial organic solvent composition, preparation temperature, feeding ratio of BCPs to CNTs, degree of polymerization of PBLG blocks, and diameter of the CNTs.

Conductivity of Nafion-117 membranes intercalated by polar aprotonic solvents

The Nafion-117 membranes in the Li+ form with pore-intercalated aprotonic organic solvents were prepared. The prepared materials were characterized by IR, impedance, and 7Li NMR spectroscopy. The solvent uptake of the membranes is shown to be controlled by the composition of organic solvents and their mixtures as well as by the conditions of the preliminary treatment of the initial membranes. For the Nafion-117 membrane, the degree of solvation can be improved by the preliminary treatment with alcohols, especially by the thermal treatment in methanol. Conductivity of the membranes is shown to increase with increasing content of the sorbed solvents. The best conductivity at 25 °C (2.5 × 10−3 and 1.6 × 10−3 S cm−1) was attained for the electrolytes based on the Nafion-117 membrane in lithium form with sorbed ethylene carbonate-propylene carbonate and ethylene carbonate-dimethoxyethane mixtures, respectively.

Thin Layer Chromatographic Resolution of Some β-adrenolytics and a β2-Agonist Using Bovine Serum Albumin as Chiral Additive in Stationary Phase

Direct enantiomeric resolution of commonly used five racemic β-adrenolytics, namely, bisoprolol, atenolol, propranolol, salbutamol and carvedilol has been achieved by thin layer chromatography using bovine serum albumin (BSA) as chiral additive in stationary phase. Successful resolution of the enantiomers of all racemic β-adrenolytics was achieved by use of different composition of simple organic solvents having no buffer or inorganic ions. The effect of variation in pH, temperature, amount of BSA as the additive, and composition of mobile phase on resolution was systematically studied. Spots were visualized in iodine vapors. Native enantiomers for each of the five analytes were isolated and identified and their elution order was determined. The limit of detection was found to be 0.7, 1.2, 0.84, 1.6 and 0.9 μg (per spot) for each enantiomer of bisoprolol, atenolol, propranolol, salbutamol and carvedilol, respectively.

Role of ammonium in the ionization of phosphatidylcholines during electrospray mass spectrometry.

Electrospray mass spectrometry methods for the analysis of phosphatidylcholines (PCs) routinely include ammonium acetate or ammonium formate in the mobile phase. In an effort to justify and optimize the use of these additives, we investigated possible functions of ammonium compounds in the ionization of PCs. Because PCs contain a quaternary amine, the role of ammonium in neutralizing the negatively charged phosphate group was investigated by using deuterated ammonium acetate, adjusting the pH, varying the organic solvent composition, and by comparing the additives ammonium acetate, ammonium formate and ammonium bicarbonate. Seven PC standards were measured ranging from lyso 1-palmitoyl-sn-glycero-3-phosphocholine to 1,2-dieicosapentaenoyl-sn-glycero-3-phosphocholine as well as a mixture of PCs in a krill oil dietary supplement. Under all conditions tested, aqueous acetonitrile provided more abundant formation of protonated PCs than did aqueous methanol. Regardless of the mobile phase composition and electrospray ion source parameters, no [M+NH4 ]+ ions were detected. Adding deuterated ammonium acetate to the mobile phase failed to form deuterated PCs, indicating that ammonium is not the source of the proton that neutralizes the phosphate negative charge. Instead, water was the source of the proton as deuterated water resulted in the formation of [M+D]+ ions. Addition of organic acids, ammonium formate, ammonium acetate, or ammonium bicarbonate to the mobile phase did not enhance and in most cases suppressed PC ionization. Ammonium compounds and organic acids can suppress ionization of PCs when using an aqueous acetonitrile mobile phase during electrospray. Copyright © 2016 John Wiley & Sons, Ltd.

Preparation of the Sm3+-Doped Magnetic Nanoparticles via Microwave-Assisted Polyol Synthesis

Sm3+-doped magnetic nanoparticles (NPs) were prepared via microwave-assisted polyol synthesis in ethylene glycol, poly(ethylene glycol) and mixed ethylene glycol—poly(ethylene glycol) solutions. In present work, the effects of organic solvent composition on particle size, particle size distribution, extent of agglomeration, and samarium content in prepared NPs were studied. The synthesized NPs were characterized by several techniques as follows: X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetry (TGA) and X-Ray fluorescence (XRF) analysis. XRD and TEM results showed formation of ~6.0–17.9 nm NPs having different microstructure characteristics (average particle size, particle size distribution, and agglomeration). The TGA analysis indicated the presence of organic components on the surface of NPs. Cytotoxic activity of the prepared magnetic NPs towards HeLa cells was evaluated by using standard live/dead assay in comparison to a control solution. It was shown that prepared magnetic NPs are characterized by low toxicity that makes possible their use for biomedical applications.

A Rotating Ring Disk Electrode Study of the Stability in Different Electrolytes for Lithium-Oxygen Batteries

The electrolyte formula (especially, the composition of organic solvent) is well-known to influence the electrochemical performance of Li-O2 batteries. The electrolyte instability in the battery can be attributed to its reaction with the superoxide radical (O2 • −) produced at the battery’s cathode during discharge. In this work, we have employed the rotating ring disk electrode (RRDE) technique to study the stability of various organic solvents against O2 • − by the quantification of the electrolyte decomposition rate constant (k) for the reaction between various electrolytes and O2 • −. Moreover, RRDE transients are also applied to estimate O2 solubility and diffusion rates of O2 and O2 • − coefficients ( and ) at different electrolytes.

Influence of mobile phase, source parameters and source type on electrospray ionization efficiency in negative ion mode

Electrospray ionization (ESI) efficiency is known to be affected by the properties of the analytes, source design and source parameters. In this study, the ionization efficiency of 17 acidic compounds at various conditions in ESI negative ion mode was evaluated. Namely, the influence of organic solvent content in the mobile phase, ionization source parameters, ionization source geometry and functionality (conventional ESI, ESI with thermal focussing and with additional internal nebulizer gas) was studied. It was observed that the ionization efficiency in thermal focussing ESI is only marginally affected by the organic solvent composition, while for conventional ESI and ESI with internal nebulizer gas, the ionization efficiency increases significantly with increasing organic modifier content. For all ionization sources and mobile phase compositions, the ionization efficiency values between different setups showed good correlation. Copyright © 2016 John Wiley & Sons, Ltd.

The influence of water–organic solvent composition on the morphology and luminescent properties of CdS nanoparticles obtained by chemical precipitation

Cadmium sulfide (CdS) nanoparticles have been obtained by chemical precipitation onto the surface of single-crystalline silicon from an aqueous solution of ammonia, cadmium chloride (CdCl2), and thiourea, as well as from water–DMSO and water–DMF mixtures with the same concentrations of the reagents. According to data of atomic force microscopy, the samples obtained from the aqueous solution consist of individual nanoparticles and agglomerates thereof with sizes of no larger than 1 µm. Materials obtained from the water–organic mixtures are distinguished by the aggregation of CdS nanoparticles into threadlike chains. The length of the formed curved chains and the size of CdS nanoparticles composing them depend on the nature and amount of an organic component of a mixture. Atomic force microscopy, transmission electron microscopy, and photoluminescence spectroscopy data have shown that the average size of CdS nanoparticles is 2–2.5 nm depending on solvent composition.

Superhelices with Designed Helical Structures and Temperature-Stimulated Chirality Transitions

The synthesis of multicomponent superhelices with determined chirality has been realized. By adding water to polymer solution in organic solvents (tetrahydrofuran/N,N′-dimethylformamide, THF/DMF), poly(γ-benzyl l-glutamate)-block-poly(ethylene glycol) (PBLG-b-PEG) are able to pack orderly around the surface of PBLG homopolymer bundles with designed helical structures, e.g., right-handed and left-handed, depending on THF/DMF ratio and temperature. A systematic investigation leads to the construction of a temperature–organic solvent composition phase diagram. Before the organic solvents were totally removed, the chirality of the assemblies can be reversibly switched using temperature stimulus. This temperature-stimulated chirality transition of polypeptide superhelices is unprecedented. Circular dichroism (CD) experiments indicated that the packing mode of pending phenyl groups from PBLG chain is responsible for the determination of the helical morphologies.

A thermodynamic study of reactions of amino acids with crown ethers in nonaqueous media as examples of guest—host molecular complex formation

Our findings and the literature data on the effect of binary aqueous organic solvents on the enthalpy and entropy of molecular complexation reactions of 18-crown-6 with glycine, D, L-alanine, and L-phenylalanine and on the stability of the resulting complexes were reviewed. The relationships between the thermodynamic parameters of the complexation reactions and the reactant solvation were analyzed to reveal the key factors that are crucial for the stability of the complexes and the increasing exothermicity of the processes under study in water—ethanol, water—DMSO, and water—acetone. The changes in the stability of 18-crown-6 complexes with amino acids were assumed to be predicted from the Gibbs energy changes in the transsolvation of the amino acids. This criterion was proposed as a basic thermodynamic parameter for estimating the changes in the stability of 18-crown-6 complexes with peptides and ammoniumtype cations (structurally related to amino acids) when the composition of the binary aqueous organic solvent is varied.

Development and validation of a method for the quantification of extractable perfluoroalkyl acids (PFAAs) and perfluorooctane sulfonamide (FOSA) in textiles

In textiles, like outdoor clothing, per- and polyfluoroalkyl substances (PFASs) are often used for durable water repellency (DWR) of the final products. The analytical performance to determine the concentration of these chemicals available for exposure to humans and to the environment need to be established. Here a method for the extraction and analysis of one class of PFASs, namely perfluoroalkyl acids (PFAAs), in outdoor clothing was developed and validated. The PFAAs which were validated, included perfluoroalkyl carboxylic acids (PFCAs) (C4–C14), and perfluoroalkane sulfonic acids (PFSAs) (C4, C6, C7, C8). In addition, perfluorooctane sulfonamide (FOSA) was included in this study. The method was based on an organic solvent extraction and analysis by high-performance liquid chromatography–tandem mass spectrometry (LC–MS/MS). No further cleaning was needed. Two commonly used organic solvent compositions were evaluated for the optimal extraction, i.e. methanol and acetone/acetonitrile (80:20, v/v), and the number and duration of the sequential extractions were optimized. Results showed that two sequential extractions with 5mL methanol and an extraction time of 30min gave an optimal performance with an extraction efficiency of >90%. The influence of matrix on the quantification of PFAAs was studied. This indicated ion suppression due to different matrix effects or sorption behavior to specific textile samples. Validation of the entire method showed overall recoveries of>80% and relative standard deviations (RSDs) of<9% (n=3) for repeatability and <20% (n=3) for reproducibility. This is the first validation of an analytical method for the analysis of extractable PFCAs, PFSAs and FOSA associated to textiles, which is of high importance due to the regulation of PFAAs in textile.

Solvent dependence of protonation equilibria for gallic acid in water and different acetonitrile–water cosolvent systems

The stoichiometric dissociation constants (pK) of gallic acid were determined in water and several mixed solvents comprising 10–90% (v/v) acetonitrile in water at a temperature of 24.0±0.5°C and an ionic strength of 0.10moldm−3 KCl medium. In this study, the protonation equilibrium values were calculated from potentiometric measurements and the influence of organic solvent composition on the equilibria was correlated with Born electrostatic model and the Kamlet, Abboud and Taft (KAT) solvatochromic parameters of acetonitrile–water mixtures. The pK values obtained increase when the amount of acetonitrile solvent increases in system investigated. The KAT single and multiple correlation analysis suggest that the specific and non-specific solvent interactions including hydrogen-bond donor ability (α), hydrogen-bond acceptor ability (β) and dipolarity/polarizability (π*) are dominating factors which control the protonation equilibria in system under study.