DMSO), N,N-dimethylacetamide Research Articles

Solid-Liquid Equilibrium Behavior and Solvent Effect of Gliclazide in Mono- and Binary Solvents.

The solubility data of gliclazide in 10 mono-solvents (1,2-dichloroethane, 1,4-dioxane, 2-methoxyethanol, n-propyl acetate, isopropyl acetate, n-butyl acetate, pentyl acetate, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMA), and 2-butanone) and one kind of binary solvent (DMA + water) were measured between 278.15 and 323.15 K under atmospheric pressure by the gravimetric method. The Hansen solubility parameters and the KAT-LSER equation were used to investigate the solubility order and the influence of solvent effects on solubility. The experimental data were correlated by six thermodynamic models (the λh model, the Yaws model, the Apelblat model, the Jouyban model, the modified Jouyban–Acree model, and the Sun model). The results show that all of these models can correlate the experimental data well. Among them, the Apelblat model is the most suitable for correlating the solubility data of gliclazide in mono-solvents and binary solvents.

Effect of aprotic solvent on characteristics of Al2O3 ceramic hollow fiber substrates prepared by phase inversion for hydrogen permeation applications

ABSTRACT The phase inversion procedure was used to prepare Al2O3 ceramic hollow fiber substrates (AlCHFS) utilizing the dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAC), and 1-methyl-2-pyrrolidone (NMP) aprotic solvents. Different aprotic solvent and non-solvent (water) interactions were used to calibrate different ceramic oxide substrates. AlCHFS with an asymmetrical structure consisting of a finger-like structure on the lumen side and a pore structure on the shell side was obtained using an aprotic solvent/non-solvent pair with a high total Hildebrand solubility (δt). As the aprotic strength was reduced, the finger-like structure on the shell sides became more prominent. Hydrogen permeation studies conducted between 350°C and 450°C reveal that the Pd-coated AlCHFS produced from DMAC aprotic solvent has the maximum hydrogen flux (~0.24 mol m−2 s−1). The activation energy for the thermally activated hydrogen transport process through the Pd-coated AlCHFSs is determined to be around 11.06–14.61 kJ mol−1 in the temperature range of 350°C to 450°C, and it increases linearly with increasing surface porosity of ceramic oxide substrate.

Spirocyclizative Remote Arylcarboxylation of Nonactivated Arenes with CO 2 via Visible-Light-Induced Reductive Dearomatization

Spirocyclizative Remote Arylcarboxylation of Nonactivated Arenes with CO ₂ via Visible-Light-Induced Reductive Dearomatization

Solubility modelling and solvent effect for domperidone in twelve green solvents

Solid solubility is a significant physical property for a drug development and design. In the present work, the domperidone solubility, which has less study in the near-term, was reported, which was determined by the shake-flask method in twelve green solvents e.g. methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, acetonitrile, N,N-dimethylformamide (DMF), water, dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMA), ethylene glycol (EG) at the temperatures from 278.15 to 318.15K under atmospheric pressure (p=101.2kPa). The domperidone solubility in the twelve solvents increased with the increasing temperature. At a desired temperature, they obeyed the following order from high to low in these solvents: DMA>DMSO>DMF>butanol>n-propanol>(isobutanol, EG)>ethanol>isopropanol>methanol>acetonitrile>water. The experimental solubility was described mathematically with the Buchowski–Książczak λh equation, Apelblat equation Wilson model and NRTL model. The largest percentage of relative average deviation was 3.28×10−2, and the maximum value of root-mean-square deviation was 3.16×10−5. On the basis of the Wilson model, the mixing properties, e.g. mixing Gibbs energy, mixing enthalpy, mixing entropy, activity coefficient at infinitesimal concentration and reduced excess enthalpy were computed. Moreover, the solvent effect was studied by using the concept of Kamlet-Taft Linear Solvation Energy Relationship. The type and extent and direction of solvent-solvent and solute-solvent interactions were identified.

Cobalt(ii) liquid metal salts for high current density electrodeposition of cobalt.

Cobalt(ii)-containing ionic liquids were synthesized using N,N-dimethylformamide, N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), N,N-dimethylacetamide (DMAc), pyridine-N-oxide (py-O), 1,10-phenanthroline (phen), ethylenediamine (en) and dimethylimidazolidinone (DMI) as ligands. The weakly coordinating bis(trifluoromethylsulfonyl)imide (Tf2N-) was used as a counter anion. Several compounds had a melting temperature below 100 °C, and the compound [Co(DMAc)6][Tf2N]2 was liquid at room temperature, with a viscosity of only 18 mPa s at 80 °C. Several compounds were recrystallized to give high quality single crystals and their crystal structures were determined. EXAFS measurements were performed on [Co(DMAc)6][Tf2N]2 at different temperatures and it was observed that the [Co(DMAc)6]2+ ion partially dissociated at higher temperatures, which explains the temperature-dependent color change (thermochromism). The electrochemical properties of the compounds with the lowest melting points were also investigated. Adherent, crack-free metallic cobalt layers could be electrodeposited from [Co(DMAc)6][Tf2N]2, [Co(DMI)6][Tf2N]2 and [Co(NMP)6][Tf2N]2. From the first two, black deposits consisting of micrometer-sized needles were obtained, whereas the latter resulted in a dull grey cobalt layer consisting of micrometer-sized cobalt spheres. The Co(iii)/Co(ii) redox couple was not found to occur in any compound with an O-donor ligand, but the Co(iii)/Co(ii) redox couple was found to be quasi-reversible for [Co(phen)3][Tf2N]2 dissolved in [BMP][Tf2N].

Carbon Nanotube Dispersion in Solvents and Polymer Solutions: Mechanisms, Assembly, and Preferences.

Debundling and dispersion of carbon nanotubes (CNTs) in polymer solutions play a major role in the preparation of carbon nanofibers due to early effects on interfacial ordering and mechanical properties. A roadblock toward ultrastrong fibers is the difficulty to achieve homogeneous dispersions of CNTs in polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA) precursor solutions in solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF). In this contribution, molecular dynamics simulations with accurate interatomic potentials for graphitic materials that include virtual π electrons are reported to analyze the interaction of pristine single wall CNTs with the solvents and polymer solutions at 25 °C. The results explain the barriers toward dispersion of SWCNTs and quantify CNT-solvent, polymer-solvent, as well as CNT-polymer interactions in atomic detail. Debundling of CNTs is overall endothermic and unfavorable with dispersion energies of +20 to +30 mJ/m2 in the pure solvents, + 20 to +40 mJ/m2 in PAN solutions, and +20 to +60 mJ/m2 in PMMA solutions. Differences arise due to molecular geometry, polar, van der Waals, and CH-π interactions. Among the pure solvents, DMF restricts CNT dispersion less due to the planar geometry and stronger van der Waals interactions. PAN and PMMA interact favorably with the pure solvents with dissolution energies of -0.7 to -1.1 kcal per mole monomer and -1.5 to -2.2 kcal per mole monomer, respectively. Adsorption of PMMA onto CNTs is stronger than that of PAN in all solvents as the molecular geometry enables more van der Waals contacts between alkyl groups and the CNT surface. Polar side groups in both polymers prefer interactions with the polar solvents. Higher polymer concentrations in solution lead to polymer aggregation via alkyl groups and reduce adsorption onto CNTs. PAN and PMMA solutions in DMSO and dilute solutions in DMF support CNT dispersion more than other combinations whereby the polymers significantly adsorb onto CNTs in DMSO solution. The observations by molecular simulations are consistent with available experimental data and solubility parameters and aid in the design of carbon nanofibers. The methods can be applied to other multiphase graphitic materials.

Full evaporation headspace gas chromatography for sensitive determination of high boiling point volatile organic compounds in low boiling matrices

Determination of volatile organic components (VOC's) is often done by static headspace gas chromatography as this technique is very robust and combines easy sample preparation with good selectivity and low detection limits. This technique is used nowadays in different applications which have in common that they have a dirty matrix which would be problematic in direct injection approaches. Headspace by nature favors the most volatile compounds, avoiding the less volatile to reach the injector and column. As a consequence, determination of a high boiling solvent in a lower boiling matrix becomes challenging. Determination of VOCs like: xylenes, cumene, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMA), N-methyl-2-pyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), benzyl alcohol (BA) and anisole in water or water soluble products are an interesting example of the arising problems. In this work, a headspace variant called full evaporation technique is worked out and validated for the mentioned solvents. Detection limits below 0.1μg/vial are reached with RSD values below 10%. Mean recovery values ranged from 92.5 to 110%. The optimized method was applied to determine residual DMSO in a water based cell culture and DMSO and DMA in tetracycline hydrochloride (a water soluble sample).

Effect of solvent on the volumetric behavior of N,N′-salicylidenephenyl diamine (Salophen) Schiff base at different temperatures (288.15–318.15) K

Densities of binary mixtures containing N,N′-salicylidenephenyl diamine (Salophen)+organic solvents {dimethylsulfoxide (DMSO), N,N-dimethylacetamide (DMA), 1,4-dioxacyclohexane (1,4-dioxane), and oxolane (THF)} have been measured at 10K intervals from 288.15K to 318.15K. Using these data, apparent molar volumes (Vϕ), standard partial molar volumes (Vϕ0), standard partial molar isobaric expansivity (Eϕ0), Hepler's constant (∂2Vϕ0/∂T2)p, and isobaric thermal expansion coefficient (α) have been calculated for all the mixtures. The values of interaction volumes (Vint), and cavity volumes (Vcav) have also been estimated using the scaled particle theory [20]. The results show that Salophen in the studied organic solvents predominantly acts as a structure-breaker.

Synthesis and characterization of novel aromatic polyamides via Yamazaki–Higashi phosphorylation method

AbstractWe synthesized four aromatic diacids: 1,3‐bis(3‐carboxyphenoxy)benzene, 1,4‐bis(4‐carboxyphenoxy)benzene, 1,4‐bis(3‐carboxyphenoxy) benzene, and 1,3‐bis(4‐carboxyphenoxy)benzene, following a procedure of a previously reported synthesis (Ueda and Komatsu, J Polym Sci Part A: Polym Chem 1989, 27, 1017). These diacids were condensed directly with aromatic diamines 4,4′‐oxydianiline (ODA), via the Yamazaki–Higashi phosphorylation method in the presence of triphenylphosphite (TPP), pyridine (Py) and halide salts to give high molecular aromatic polyamides (PAs). The synthesized PAs were obtained in quantitative yields with inherent viscosities between 0.5 and 1.0 dL g−1. The structures and properties of the obtained PAs were characterized by Fourier transform infrared (FTIR) spectra, nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), polarizing optical microscope (POM). Four PAs all showed good solubility in polar solvents, such as dimethylsulfoxide (DMSO), N,N‐dimethylacetamide (DMAc), N‐dimethylformamide (DMF), 1‐methylpyrrolidone (NMP), and so on. The obtained polymers showed high thermal stability with decomposition temperature around 400°C. The polyamide membranes manifest excellent mechanical properties, with Young's modulus of 2.5–5.5 GPa. Interestingly, the film of PA‐1, PA‐2, and PA‐3 is completely transparent in the visible range, while PA‐4 film is opaque. Crystallization was observed in PA‐4 film, although the molecular structure of PA‐4 is not as symmetrical as PA‐2. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Testis-mediated gene transfer in mice: comparison of transfection reagents regarding transgene transmission and testicular damage.

Testis-mediated gene transfer (TMGT) has been used as in vivo gene transfer technology to introduce foreign DNA directly into testes, allowing mass gene transfer to offspring via mating. In this study, we used plasmid DNA (pEGFP-N1) mixed with dimethylsulfoxide (DMSO), N,N-dimethylacetamide (DMA) or liposome (Lipofectin) in an attempt to improve TMGT. Males receiving consecutive DNA complex injections were mated to normal females to obtain F0 progeny. In vivo evaluation of EGFP expression, RT-PCR and PCR were used to detect the expression and the presence of exogenous DNA in the progeny. We also evaluated possible testicular damage by histological procedures. PC R and RT-PCR analyses revealed that liposome and DMSO increased the rate of TMGT. Histological analyses demonstrated that repeated (4 times) injections of DNA complexes can affect spermatogenesis. DMSO was the most deleterious among the reagents tested. In this study, we detected the presence of transgene in the progeny, and its expression in blood cells. Consecutive injections of DNA complexes were associated with impaired spermatogenesis, suggesting requirement of optimal conditions for DNA delivery through TMGT.

Flexible, low-colored and transparent thin films prepared from new thermo-stable and organo-soluble poly(amide-imide)s

An imide ring-containing diacid, 2,2′-diphenyl-4,4′-bis(N-trimellitoyl)diphenyl ether (PTPE) was synthesized through a three-step pathway starting from 2,2′-diiodo-4,4′-dinitrodiphenyl ether. A series of novel aromatic poly(amide-imide)s having bulky phenyl pendant groups at 2,2′-disubstituted positions were then prepared via a direct phosphorylation polycondensation between PTPE and various aromatic diamines. Chemical structure of the new monomer as well as the resulted polymers was thoroughly confirmed by IR and NMR spectroscopic methods. Intrinsic viscosities [ η] of the polymer solutions at 25 °C were measured by the extrapolation of their viscosity numbers till zero concentration. M w ¯ and M n ¯ values of the resulting polymers were determined using gel-permeation chromatography (GPC). The polymers showed a good film-forming ability, and some characteristics of their thin films including color and flexibility were investigated qualitatively. In addition, the absorption edge values ( λ 0) obtained from their UV curves were determined, and all the resulting poly(amide-imide)s films exhibited high optical transparency. Thermal stability of the polymers using their TGA thermograms was investigated. The T g values of the poly(amide-imide)s obtained from their DSC plots were also quantified. Crystallinity amount of the prepared macromolecules was evaluated using wide-angle X-ray diffraction (XRD). Furthermore, solubility of the samples in a variety of organic solvents including dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), pyridine, tetrahydrofuran (THF), and toluene was tested.

Testis-mediated gene transfer in mice: comparison of transfection reagents regarding transgene transmission and testicular damage

Testis-mediated gene transfer (TMGT) has been used as in vivo gene transfer technology to introduce foreign DNA directly into testes, allowing mass gene transfer to offspring via mating. In this study, we used plasmid DNA (pEGFP-N1) mixed with dimethylsulfoxide (DMSO), N,N-dimethylacetamide (DMA) or liposome (Lipofectin) in an attempt to improve TMGT. Males receiving consecutive DNA complex injections were mated to normal females to obtain F0 progeny. In vivo evaluation of EGFP expression, RT-PCR and PCR were used to detect the expression and the presence of exogenous DNA in the progeny. We also evaluated possible testicular damage by histological procedures. PC R and RT-PCR analyses revealed that liposome and DMSO increased the rate of TMGT. Histological analyses demonstrated that repeated (4 times) injections of DNA complexes can affect spermatogenesis. DMSO was the most deleterious among the reagents tested. In this study, we detected the presence of transgene in the progeny, and its expression in blood cells. Consecutive injections of DNA complexes were associated with impaired spermatogenesis, suggesting requirement of optimal conditions for DNA delivery through TMGT.

Polycarbazole Copolymers from 3-(4-Fluorobenzoyl)carbazole and 4,4′-Biphenol via Combined C-N and C-O Coupling Reactions with Activated Difluorides

3-(4-Fluorobenzoyl)carbazole was synthesized by a Friedel-Crafts reaction of carbazole with 4-fluorobenzoylchloride. 1H-NMR and MALDI-TOF MS confirmed the structure and the purity. Copolymers of these NH/OH-containing monomers were prepared with 4, 4′-biphenol and bis(4-fluorophenyl)sulfone as comonomers by combined C-O and C-N coupling reactions with activated difluorides. These copolymers were soluble in N-methylpyrrolidinone (NMP), dimethylsulfoxide (DMSO), N,N-dimethylacetamide (DMAc) and dimethylformamide (DMF). The inherent viscosities of the copolymers in NMP solutions at 30°C were all around 0.8 dL/g. They could be easily cast into tough films from NMP solutions. The copolymers exhibited Tgs ranging from 238°C to 282°C. Thermal stabilities by TGA showed no weight loss below 400°C and the temperatures of 5% weight loss ranged from 535°C to 558°C. The homopolymer of 3-(4-fluorobenzoyl)carbazole was insoluble in common solvents and had a Tg of 332°C, and temperature of 5% weight loss of 560°C. UV-VIS absorption and fluorescence of the polymers are also presented.

Using modified poly(3,4-ethylene dioxythiophene): Poly(styrene sulfonate) film as a counter electrode in dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs), assembling with nano-crystalline TiO 2 adsorbed cis-Ru(dcb) 2(NCS) 2 dye (known as N3) using polar solvent-treated poly(3,4-ethylene dioxythiophene): poly(styrene sulfonate) (PEDOT:PSS) coating on a conductive glass (fluorine-doped tin oxide, FTO) as a counter electrode, were studied. The conductivity of a bare PEDOT:PSS film was only 2±0.05 S/cm. However, the conductivities of PEDOT:PSS films treated with dimethyl sulfoxide (DMSO), N, N-dimethyl acetamide (DMAc), N, N-dimethyl formamide (DMF), and dichloromethane (DMC) reached 85±15, 45±10, 36±7, and 20±6 S/cm, respectively. In addition, carbon blacks (0.02, 0.1, 0.5, 1.0, 2.0 wt% with respect to PEDOT:PSS aqueous solution) were added into the DMSO-treated PEDOT:PSS solution (denoted as DMSO-PEDOT:PSS) to enhance the conductivity. Atomic force microscopy (AFM) images of PEDOT:PSS and various DMSO-PEDOT:PSS films coated on the FTO glasses were examined. The topographical images reveal that the increased surface roughness is responsible for the enhanced electrochemical property of the DMSO-PEDOT:PSS films. AC impedance technique was also employed to analyze the kinetics at the electrolyte/counter electrode interface. The DSSC using carbon black (0.1 wt%)-modified DMSO-PEDOT:PSS conductive coating as a counter electrode reached a cell efficiency of 5.81% under 100 mW/cm 2. This efficiency is higher than a DSSC using Pt as a counter electrode (5.66%).

Solvent effects in the interaction of methyl-β-cyclodextrin with solvatochromic merocyanine dyes

The UV-vis spectroscopic behavior of dyes: 2,6-diphenyl-4-(2,4,6-triphenylpyridinium-1-yl)phenolate (1) and 4-[(1-methyl-4(1H)-pyridinylidene)-ethylidene]-2,5-cyclohexadien-1-one (2) was investigated in solutions of methyl- beta-cyclodextrin (methyl-beta-CyD), using water, methanol, ethanol, propan-2-ol, butan-1-ol, acetone, acetonitrile, N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMA), chloroform and dichloromethane as solvents. In aqueous solutions of dye (2) the addition of M-beta-CD leads to a bathochromic shift (of the maximum absorption), showing that the probe was transferred to a microenvironment of lower polarity and suggesting the formation of a 1 : 1 dye (2) : CyD inclusion complex, with a binding constant of 128.5 +/- 3.5 dm(3) mol(-1). Data for dye 2 in alcohols showed hypsochromic shifts, which increased in the following order: methanol < ethanol < propan-2-ol < butan-1-ol. These observations appear to reflect dye-solvent interactions through hydrogen bonding. If dye-solvent interactions are strong, the CyD-dye interactions are consequently weak, but the latter increase in importance when the dye-solvent interaction becomes weaker. With hydrogen-bond accepting solvents, data for both dyes showed clearly increasing hypsochromic shifts following the order: DMSO < DMA < DMF < acetone < acetonitrile. This order is exactly the inverse of the increasing order of basicity of the medium. This indicates that the dominant factor for the observed effects in these solvents is the solvent-CyD interaction through hydrogen bonding involving the hydroxyl groups of the CyD and the basic groups of the solvents. These interactions diminish in intensity if the basic character of the medium is reduced, increasing the capability of the dye to interact with the CyD using its phenoxide donor moiety. The largest hypsochromic shifts were obtained in chloroform (66.0 nm) and dichloromethane (67.5 nm) with dye after addition of methyl-beta-CyD. In these specific situations, solvents display weak basic and acid properties, that enhanced CyD-dye interactions to such an extent that association complexes formed through hydrogen bonding could be detected (K11) values of 24.8 +/- 4.9 dm3 mol(-1) in dichloromethane and 66.1 +/- 8.0 dm3 mol(-1) in chloroform).

Refrigerated storage and cryopreservation of black drum ( [formula omitted]) spermatozoa

Procedures were developed for the collection, refrigerated storage and cryopreservation of black drum spermatozoa. Sperm samples were collected by removing and slicing the testis, and suspending the spermatozoa in Hanks' balanced salt solution (HBSS) at 200 mOsm/kg. Threshold activation (10%) of black drum spermatozoa occurred at 370 mOsm/kg, and complete activation occurred at 580 mOsm/kg in HBSS. Sperm cells activated in artificial seawater had higher motility than those activated in HBSS at osmolalities from 350 to 500 mOsm/kg. Spermatozoa stored at 4 °C in HBSS or artificial seawater at osmolalities from 202 to 290 mOsm/kg retained motility longer than did those stored at other osmolalities Dilution rate had no effect on sperm storage time at 4 °C. Four chemicals were evaluated as cryoprotectants: dimethyl sulfoxide (DMSO), n,n-dimethyl acetamide (DMA), methanol, and glycerol. Glycerol and DMA at concentrations of 10% significantly reduced motility within 52 min. Spermatozoa were cryopreserved at 3 freezing rates (−27, −30, or −45 °C/min) in a nitrogen vapor shipping dewar or a computer-controlled freezer. Spermatozoa frozen using 10% DMSO had the highest post-thaw motility at a freezing rate of −27 or −30 °C/min. Spermatozoa frozen using 5% glycerol, 5% DMSO, or 10% DMSO had the highest post-thaw motility at a freezing rate of −45 °C/min.

Synthesis and thermal properties of poly(enaminonitriles) containing flexible ether units

AbstractPoly(enaminonitriles) containing flexible alkyl ether units were prepared by reacting p‐bis(1‐chloro‐2,2‐dicyanovinyl)benzene with various α,ω‐bis(4‐aminophenoxy)alkanes in N‐methyl‐2‐pyrrolidone (NMP). All the polymers are soluble in polar aprotic solvents such as N,N‐dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N,N‐dimethylacetamide (DMAc) and NMP as well as in common organic solvents such as tetrahydrofuran and acetone. High molecular weight polymers possessing inherent viscosities in the range of 0.82–1.20 dL/g were obtained and tough films were cast from a DMF solution. They showed a large exotherm around 340°C attributable to the chemical changes of the dicyanovinyl group. Thermogravimetric analyses exhibited a good thermal stability with a 10% weight loss around 450°C and 73–88% residual weight at 500°C under nitrogen.