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Aprotic Solvents (aprotic + solvent)
Kinds of Aprotic Solvents Selected AbstractsInfluence of Aprotic Solvent on Selectivity of an Amperometric Sensor with Nafion MembraneELECTROANALYSIS, Issue 5 2006B. Chachulski Abstract This paper presents the results of investigation on selectivity of the sulfur dioxide amperometric sensor with Nafion membrane in the presence of carbon monoxide and nitrogen dioxide as the interferents. There have been compared selectivity coefficients, for the sensors containing the following internal electrolytes: solution of sulfuric acid (concentration 5,mol dm,3) in pure water (A) and solution of sulfuric acid (concentration 5,mol dm,3) in mixed solvent dimethylsulfoxide-water with an DMSO: H2O mole ratio of 1,:,2 (B). Values of the selectivity coefficients have been calculated based on the calibration curves. Analysis of both calibration curves and selectivity coefficients plays a significant role in optimization of a working point of a particular sensor. The investigated sensor operates in a three-electrode system, where the working and counter electrodes are vacuum sublimation deposited on the membrane surface. [source] Sodium Borohydride-Solid LiClO4: An Effective Reagent for Reducing Aldehydes and Ketones in Aprotic Solvent.CHEMINFORM, Issue 3 2006Azim Ziyaei Halimjani Abstract For Abstract see ChemInform Abstract in Full Text. [source] Selective and Efficient Oxidation of Sulfides and Thiols with Benzyltriphenylphosphonium Peroxymonosulfate in Aprotic Solvent.CHEMINFORM, Issue 18 2003Abdol R. Hajipour Abstract For Abstract see ChemInform Abstract in Full Text. [source] Sample preparation effects in matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry of partially depolymerised methyl celluloseRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 11 2003Dane Momcilovic Methyl cellulose (MC) was partially depolymerised and the oligomers thus obtained were studied by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS). The depolymerisation was either enzymatic or acidic. Fractions of enzymatically depolymerised MC were collected from size-exclusion chromatography and subjected to a sample preparation investigation. Several MALDI matrices and solvents were evaluated. The results showed that the solvent choice had a significant effect on the measured degree of substitution (DS). Aprotic solvents produced higher DS values, which was most likely due to poor solubility of species with low DS. The obtained signal intensity, however, did not correlate with the solubility but seemed to be more dependent on certain matrix/solvent combinations. All the matrices attempted produced mass spectra with sufficient signal intensity for accurate peak area calculation. The choice of matrix did not have any significant effect on the measured DS. Sample spots obtained from organic solvents had a more homogeneous distribution of the analyte and smaller crystals than those obtained from water. This increased both the reproducibility and peak resolution and in addition the analysis time was shorter. DS measurements were performed on two acidically depolymerised MCs with different nominal DS values. It was easy to distinguish between the two MCs, and the measured DS values agreed well with the values supplied by the manufacturers. Copyright © 2003 John Wiley & Sons, Ltd. [source] Synthesis and characterization of phthalazinone containing poly(arylene ether)s via a novel N,C coupling reactionJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2003S. J. Wang Abstract High-molecular-weight poly(phthalazinone)s with very high glass-transition temperatures (Tg's) were synthesized via a novel N,C coupling reaction. New bisphthalazinone monomers (7a,e) were synthesized from 2-(4-chlorobenzoyl) phthalic acid in two steps. Poly(phthalazinone)s, having inherent viscosities in the range of 0.34,0.91 dL/g, were prepared by the reaction of the bis(phthalazinone) monomers with an activated aryl halide in a dipolar aprotic solvent in the presence of potassium carbonate. The poly(phthalazinone)s exhibited Tg's greater than 230 °C. polymer 8b synthesized from diphenyl biphenol and bis(4-flurophenyl) sulfone demonstrated the highest Tg of 297 °C. Thermal stabilities of the poly(phthalazinone)s were determined by thermogravimetric analysis. All the poly(phthalazinone)s showed a similar pattern of decomposition with no weight loss below 450 °C in nitrogen. The temperatures of 5% weight loss were observed to be about 500 °C. The poly(phthalazinone)s containing 4,4,-isopropylidenediphenol and 4,4,-(hexafluoroisopropylidene) diphenol and diphenyl ether linkage were soluble in chlorinated solvents such as chloroform. Other poly-(phthalazinone)s were soluble in dipolar aprotic solvents such as N,N,-dimethylacetamide. The soluble poly(phthalazinone)s can be cast as flexible films from solution. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2481,2490, 2003 [source] Conformational Effects on Photophysical Characteristics of C5,C5,-linked Dihydrothymine Dimers in Solution,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 6 2000T. Ito ABSTRACT Photophysical characteristics of N-substituted C5,C5,-linked dihydrothymine dimers (1a,b[meso], meso compounds of [5R,5,S]-bi-5,6-dihydrothymines; 1a,b[rac], racemic compounds of [5R,5,R]-bi-5,6-dihydrothymines and [5S,5,S]-bi-5,6-dihydrothymines) in aqueous solution with varying contents of less-polar aprotic solvent such as tetrahydrofuran or dioxane have been investigated by UV-absorption, and steady-state and time-resolved fluorescence spectroscopies. Among the C5,C5,-linked dimers, (5R,5,S)-bi-5,6-dihydro-1-methylthymine (1a[meso]) showed a redshifted weak UV-absorption band at 270,350 nm and excimer fluorescence emission at ,max= 370 nm with a quantum yield (,F) of ,0.1 in phosphate buffer (pH < 10) at 293 K. Racemic compound of 5,6-dihydro-1-methylthymine dimer (1a[rac]), meso and racemic compounds of 5,6-dihydro-1,3-dimethylthymine dimers (1b[meso] and 1b[rac]) in phosphate buffer were nonfluorescent under similar conditions. The UV-absorption and fluorescence spectral characteristics of 1a[meso] in aqueous solution were interpreted in terms of intramolecular stacking interactions between the dihydropyrimidine chromophores leading to a preferential "closed-shell" conformation both in the ground state and the excited singlet state. In basic solutions at pH > pKa= 11.7, the fluorescence quantum yield of 1a[meso] decreased due to a dominant "open-shell" conformation resulting from the electrostatic repulsion between the deprotonated dihydrothymine chromophores of 1a[meso] in a dianion form. [source] Networks for recognition of biomolecules: molecular imprinting and micropatterning poly(ethylene glycol)- Containing films,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 10-12 2002Mark E. Byrne Abstract Engineering the molecular design of biomaterials by controlling recognition and specificity is the first step in coordinating and duplicating complex biological and physiological processes. Studies of protein binding domains reveal molecular architectures with specific chemical moieties that provide a framework for selective recognition of target biomolecules in aqueous environment. By matching functionality and positioning of chemical residues, we have been successful in designing biomimetic polymer networks that specifically bind biomolecules in aqueous environments. Our work addresses the preparation, behavior, and dynamics of the three-dimensional structure of biomimetic polymers for selective recognition via non-covalent complexation. In particular, the synthesis and characterization of recognitive gels for the macromolecular recognition of D -glucose is highlighted. Novel copolymer networks containing poly(ethylene glycol) (PEG) and functional monomers such as acrylic acid, 2-hydroxyethyl methacrylate, and acrylamide were synthesized in dimethyl sulfoxide (polar, aprotic solvent) and water (polar, protic solvent) via UV-free radical polymerization. Polymers were characterized by single and competitive equilibrium and kinetic binding studies, single and competitive fluorescent and confocal microscopy studies, dynamic network swelling studies, and ATR-FTIR. Results qualitatively and quantitatively demonstrate effective glucose-binding polymers in aqueous solvent. Owing to the presence of template, the imprinting process resulted in a more macroporous structure as exhibited by dynamic swelling experiments and confocal microscopy. Polymerization kinetic studies suggest that the template molecule has more than a dilution effect on the polymerization, and the effect of the template is related strongly to the rate of propagation. In addition, PEG containing networks were micropatterned to fabricate microstructures, which would be the basis for micro-diagnostic and tissue engineering devices. Utilizing photolithography techniques, polymer micropatterns of a variety of shapes and dimensions have been created on polymer and silicon substrates using UV free-radical polymerizations with strict spatial control. Micropatterns were characterized using optical microscopy, SEM, and profilometry. The processes and analytical techniques presented are applicable to other stimuli-sensitive and recognitive networks for biomolecules, in which hydrogen bonding, hydrophobic, or ionic contributions will direct recognition. Further developments are expected to have direct impact on applications such as analyte controlled and modulated drug and protein delivery, drug and biological elimination, drug targeting, tissue engineering, and micro- or nano-devices. This work is supported by NSF Grant DGE-99-72770. Copyright © 2003 John Wiley & Sons, Ltd. [source] Supramolecular Derivatives of 9,10-Anthraquinone.ELECTROANALYSIS, Issue 5-6 2003Complexing Properties, Electrochemistry at Regular-, Low Ionic Strength Abstract Three newly synthesized polyanthraquinone derivatives: 7,13-bis(9,10-dioxo-1-anthryl)-1,4,10-trioxa-7,13-diazacyclopentadecane, (AQ)A215C5, 7,16-bis(9,10-dioxo-1-anthryl)-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane, (AQ)A218C6, and tris[(9,10-diokso-1-antryl)-aminoethyl]amine, (AQNet)3N, were examined by cyclic and normal pulse voltammetry. All anthraquinone groups in these compounds were electroactive and formed the radicals and dianions similarly to simple anthraquinone. The differences between the voltammograms obtained in the absence and presence of supporting electrolyte are discussed, and the diffusion coefficients of the compounds and the rates of the chemical reactions following the first reduction step were evaluated. (AQNet)3N appears to be a good model compound for multi electron transfers in aprotic solvents. It offers two consecutive nearly reversible 3-electron redox systems: 0/,3 and ,3/,6. The interactions of the radicals and dianions of the above compounds with alkali metal cations were examined. [source] Utilization of tannery solid waste for protease production by Synergistes sp. in solid-state fermentation and partial protease characterizationENGINEERING IN LIFE SCIENCES (ELECTRONIC), Issue 1 2009Arumugam Ganesh Kumar Abstract Synergistes sp. DQ560074 produced a protease in submerged fermentation (SmF) at 400,420,U/mL and in solid-state fermentation (SSF) at 745,755,U/g. The protease, which belongs to the aspartic protease class, was active over a wide range of pH (5,7) and at high temperatures (25,45°C). The protease is stable and active in various polar protic solvents (50%,v/v) like ethanol, isopropanol, n,butanol, in polar aprotic solvents (50%,v/v) like acetonitrile, and in non-polar solvents (50%,v/v) such as ethylacetate and toluene, but not in hydrophilic organic solvents (methyl alcohol and acetone). As far as we know, this is the first contribution to the production of a mesophilic protease with solvent stability in SSF using a proteinaceous solid waste. [source] Novel Model Sulfur Compounds as Mechanistic Probes for Enzymatic and Biomimetic OxidationsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 1 2005Alicia B. Peñéñory Abstract To test for the intermediacy of sulfide radical cations in biomimetic and enzymatic oxidations, the sulfides PhSCH3 (1a), PhSCH2Ph (1b), PhSCHPh2 (1c), PhSCPh3 (1d), CH3SCHPh2 (2), PhSCH2CH=CH2 (3), PhSCH2CH=CHPh (4) and CH3SCH2CH=CHPh (5) were studied, and their results were compared to those obtained for the corresponding chemical electron transfer (CET) and photoinduced electron transfer (PET) oxidations. The radical cations generated from 3,5 by CET in the presence of cerium(IV) ammonium nitrate (CAN) yielded only fragmentation products from the alkyl cations and the thiyl radicals (RS·), whereas 2·+ afforded both fragmentation and mainly ,-deprotonation products. Photochemical treatment of the sulfides 1a and 1b with C(NO2)4 gave only the corresponding sulfoxides, while fragmentation was the main pathway for the photoreactions of 1c, 2 and 5, and for 1d only this latter process was observed. These results support our selection of the sulfides RSCHPh2, RSCH2CH=CHPh (R = Me, Ph) and PhSCPh3 as models for the biomimetic and enzymatic studies. As evidenced by the sulfoxides and sulfones detected as unique products both in protic and in aprotic solvents, it is proposed that the mechanism of the biomimetic sulfoxidations of sulfides 1c and 2,5 by TPPFeIIICl is direct oxygen transfer. Three enzymes , Coprinus cinereus peroxidase (CiP), horseradish peroxidase (HRP) and chloroperoxidase (CPO) , were studied in the oxidation of sulfides 1a, 2, 4 and 5. The use of a racemic alkyl hydroperoxide in the CiP enzymatic oxidation of sulfides 5 and 2 yielded the corresponding sulfoxides (23 and 29%) and the aldehyde or benzophenone (5%), respectively. These results suggest the involvement of an ET process for the CiP-catalysed oxidation. Fragmentation products were observed in the enzymatic oxidation of sulfide 4 with HRP, which confirms the previously proposed ET mechanism. On the other hand, the CPO-enzymatic oxidation of sulfide 5 yielded only the corresponding sulfoxide, as would be expected for a direct oxygen-transfer or oxene mechanism. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] One-Step Ionic-Liquid-Assisted Electrochemical Synthesis of Ionic-Liquid-Functionalized Graphene Sheets Directly from Graphite,ADVANCED FUNCTIONAL MATERIALS, Issue 10 2008Na Liu Abstract Graphite, inexpensive and available in large quantities, unfortunately does not readily exfoliate to yield individual graphene sheets. Here a mild, one-step electrochemical approach for the preparation of ionic-liquid-functionalized graphite sheets with the assistance of an ionic liquid and water is presented. These ionic-liquid-treated graphite sheets can be exfoliated into functionalized graphene nanosheets that can not only be individuated and homogeneously distributed into polar aprotic solvents, but also need not be further deoxidized. Different types of ionic liquids and different ratios of the ionic liquid to water can influence the properties of the graphene nanosheets. Graphene nanosheet/polystyrene composites synthesized by a liquid-phase blend route exhibit a percolation threshold of 0.1 vol % for room temperature electrical conductivity, and, at only 4.19 vol %, this composite has a conductivity of 13.84,S m,1, which is 3,15 times that of polystyrene composites filled with single-walled carbon nanotubes. [source] ,N-Stereogenic Quaternary Ammonium Salts' from L -Amino Acids: Synthesis, Separation, and Absolute ConfigurationHELVETICA CHIMICA ACTA, Issue 4 2009Hua-Fang Wu Abstract Diastereoisomeric linear and cyclic ,N-chiral quaternary ammonium salts' (QASs) were efficiently synthesized from corresponding L -amino acids in high yields. The diastereoisomers of each pair of ,N-chiral QASs' were successfully separated. The absolute configurations of these QASs were determined predominately by X-ray single-crystal analysis. The 1H-NMR data of ,N-chiral QASs' provided characteristic information on the configuration of the N-chiral center. ,N-Chiral QASs' exemplified by [N(R)]- 2a and [N(S)]- 2a are stable in protic and aprotic solvents within a broad pH and temperature range. [source] Synthesis of Some Novel Thioxanthenone-Fused Azacrown Ethers, and Their Use as New Catalysts in the Efficient, Mild, and Regioselective Conversion of Epoxides to , -Hydroxy Thiocyanates with Ammonium ThiocyanateHELVETICA CHIMICA ACTA, Issue 7 2007Hashem Sharghi Abstract The regioselective ring-opening reactions of some epoxides with ammonium thiocyanate in the presence of a series of new 9H -thioxanthen-9-one-fused azacrown ethers, i.e., 7,11 (Scheme,1), and also of dibenzo[18]crown-6 (12), Kryptofix®22 (13), and benzo[15]crown-5 (14) were studied (Tables 1 and 2). The epoxides were subjected to cleavage by NH4SCN in the presence of these catalysts under mild conditions in various aprotic solvents. Reagents and conditions were identified for the synthesis of individual , -hydroxy thiocyanates in high yield and with more than 90% regioselectivity. The results can be discussed in terms of a four-step mechanism (Scheme,2): 1) formation of a complex between catalyst and NH4SCN, 2) release of SCN, from the complex, 3) reaction of the released SCN, at the sterically less hindered site of the epoxide, and 4) regeneration of the catalyst. The major advantages of this method are the high regioselectivity, the simple regeneration of the catalyst, the reuse of it through several cycles without a decrease of activity, and the ease of workup of the reaction mixtures. [source] Kinetic investigation on the reactions of p -toluenesulfonyl chloride with p -substituted benzoic acid(s) in the presence of triethylamine in aprotic solventsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 5 2009Subbiah Ananthalakshmi Second-order rate constants of the reactions of p -toluenesulfonyl chloride with p -substituted benzoic acids in the presence of triethylamine in acetonitrile/acetone under equimolar and pseudo-first-order conditions have been determined by the conductometric method using the Guggenheim principle at 25, 30, 35, and 40°C. The reactions follow second order with respect to the whole and first order with respect to each of the reactants. The order of reactivity of the substituents in benzoic acid is rationalized. Activation parameters are obtained by applying the usual methods. The Hammett plot has been found nonlinear, whereas the Bronsted plot shows good correlation. This may be explained on the basis of electronic effects of substituents on the reaction center. Kinetic data and the product analyses indicate that the reaction proceeds through direct nucleophilic attack on the sulfur center. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 303,308, 2009 [source] Nucleophilic heteroaromatic substitution: Kinetics of the reactions of nitropyridines with aliphatic amines in dipolar aprotic solventsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 3 2008Chukwuemeka Isanbor Rate data are reported for the reactions of 2-chloro-5-nitropyridine 2a, 2-chloro-3-nitropyridine 2b, and the corresponding 2-phenoxy derivatives 2c with n -butylamine, pyrrolidine and piperidine and 2d with n -butylamine and pyrrolidine in dimethyl sulfoxide (DMSO) as solvent. The same reactions in acetonitrile had been reported earlier (Crampton et al., Eur J Org Chem 2007, 1378,1383). Values in these solvents are compared with those of 2,4-dinitrochlorobenzene 3a, 2,6-dinitrochlorobenzene 3b, and the corresponding nitroactivated diphenyl ethers 3c and 3d. Reactions with n -butylamine in both solvents gave values of kobs, which increase linearly with amine concentration indicating that nucleophilic attack is rate limiting. The only exception is the reactions in acetonitrile with 2c where base catalysis was observed. Values of k1, the rate constant for the nucleophilic attack, decrease in the order pyrrolidine > piperidine > n -butylamine. In acetonitrile, kinetic data show that k/k ratios are more than unity while the inverse is the case in DMSO. With the phenoxy derivatives, substitution was the only process observed. Base catalysis detected in the reactions of the 1-phenoxy derivatives is attributed to rate-limiting deprotonation of the initially formed zwitterionic intermediate. Our results shed more light on fundamental aspects of activation, hydrogen bonding, and steric effects associated with an aza or a nitro group in the molecules investigated as it affects the nucleophilic aromatic substitution (SNAr) reaction pathways. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 125,135, 2008 [source] Nonequilibrium solvent polarization in kinetics of SN2 reactionsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 2 2003J. S. JaworskiArticle first published online: 21 NOV 200 The solvent effect on the experimental activation barriers for the reactions of methyl iodide with chloride and thiocyanate ions was analyzed according to the Marcus and Shaik theories, considering SN2 mechanism in terms of a single electron shift. The linear increase in the solvent reorganization energy of the Marcus theory (after removing contributions from the specific solvation) with the solvent Pekar factor, describing the effect of the nonequilibrium solvent polarization, was observed for six aprotic solvents. The direct support of the title effect based on the Shaik theory was less evident; however, in general, the calculated activation barriers in 10 solvents change parallel with the experimental ones. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 61,66, 2003 [source] Microwave-Assisted Dieckmann Reaction: Efficient One-Step Synthesis of 2-Aroylbenzofuran-3-olsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2010Zhong-Zhen Zhou Abstract This paper describes the first efficient one-step synthesis of 2-aroylbenzofuran-3-ols from the microwave-assisted Dieckmann reaction of substituted methylsalicylates with 2-bromo-1-aroylethanones in alkaline aprotic solvents. This method features excellent yields, short reaction time (15,min) and high functional group compatibility, making it an efficient and practical approach for the synthesis of 2-aroylbenzofuran-3-ols. [source] Synthesis and characterization of new soluble polyamides from an unsymmetrical diamine bearing a bulky triaryl pyridine pendent groupJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2010Mousa Ghaemy Abstract New unsymmetrical diamine monomer containing triaryl pyridine pendent group, 2,4-diaminophenyl [4-(2, 6-diphenyl-4-pyridyl) phenyl]ether, was synthesized via aromatic substitution reaction of 1-chloro-2,4-dinitrobenzene with 4-(2,6-diphenyl-4-pyridyl) phenol, followed by Pd/C-catalyzed hydrazine reduction. Five Polyamides (PA) were prepared by the phosphorylation polycondensation of different dicarboxylic diacids with the diamine. Inherent viscosities of PAs were in the range 0.51,0.59 g/dL indicating formation of medium molecular weight polymers. The weight and number average molecular weights of a PA, (PA-d), determined by GPC were 6944 g/mol and 17,369 g/mol, respectively. PAs exhibited glass-transition temperatures (Tg) in the range 140,235°C. These polymers, essentially amorphous, were soluble in polar aprotic solvents such as DMF, NMP, DMAc, DMSO, pyridine, m -cresol, and THF. The initial decomposition temperatures (Ti) of PAs, determined by TGA in air, were in the range 300,380°C indicating their good thermal stability. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Synthesis and characterization of novel Schiff base polyurethanes,JOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2009A. V. Raghu Abstract Eight different types of novel polyurethanes (PUs) were synthesized through the polyaddition reaction of 4,4,-(ethane-1,2-diylidenedinitrilo)diphenol and 4,4,-(pentane-1,5-diylidenedinitrilo)diphenol with four different diisocyanates: 4,4,-diphenylmethane diisocyanate, toluene 2,4-diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate. The resulting PUs were soluble in polar, aprotic solvents. Structures of the diols and PUs were established with ultraviolet,visible, fluorescence, Fourier transform infrared (FTIR), 1H-NMR, and 13C-NMR spectroscopy data. FTIR and NMR spectral data indicated the disappearance of both hydroxyl and isocyanate groups in the PUs. The thermal properties were investigated with thermogravimetry and differential scanning calorimetry. The weight losses, glass transitions, onset temperatures, and crystalline melting temperatures were measured. All the PUs exhibited semicrystalline and amorphous morphologies, as indicated by X-ray diffraction. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009. [source] Convenient and efficient deuteration of functionalized aromatics with deuterium oxide: catalysis by cycloocta-1,5-dienyliridium(I) 1,3-dionatesJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 13 2003B. McAuley Abstract Aromatic compounds bearing an ortho -directing substituent may be deuterated by exchange with deuterium oxide in the presence of a range of cycloocta-1,5-dienyliridium(I)1,3-dionate catalysts. The exchange takes place in several dipolar aprotic solvents and is directly applicable to the deuteration of polar compounds. Isotope incorporation is efficient and regiospecific. The method is applicable to a wide range of ortho -directing groups some of which are only weak directors for alternative ortho -labelling approaches. In addition, the application of microwaves enables labelling within minutes even with sub-stituents which are poor directors. Copyright © 2003 John Wiley & Sons, Ltd. [source] Characterization of solvatochromic probes: simulation of merocyanine 540 absorption spectra in binary solvent mixtures and pure solvent systemsJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 3 2004S. Y. Bae Abstract An empirical extension of the continuum model was used to reproduce the absorption spectrum of the optical probe merocyanine 540 in numerous solvents based on 27 probe-specific parameters in conjunction with the dielectric constant and refractive index of the solvent. The calibrated absorption spectrum of this dye allowed the accurate determination of the dielectric constant and refractive index of the bulk solvent. This study incorporates several binary solvent mixtures in addition to several pure solvents of differing functionality, including protic and aprotic solvents. A single, generally applicable, set of probe-specific parameters is presented. The accuracy of the determined solvent properties using this general set of probe parameters suggests that the influence of specific solvent,solute interactions on the absorption spectrum of this dye must be constant if not insignificant in the range of solvents studied, with the notable exception of water. Copyright © 2004 John Wiley & Sons, Ltd. [source] Looking for a contribution of the non-equilibrium solvent polarization to the activation barrier of the SN2 reactionJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 6 2002Jan S. Jaworski Abstract The solvent effect on the activation free energy of the Finkelstein reaction between methyl iodide and Cl, ions was analysed in terms of the recent Marcus theory unifying the SN2 and the electron transfer reactions. The homolytic bond dissociation energy and the related resonance energy of interaction of the states seem to be almost solvent independent. The sum of the work term wr and the solvent reorganization energy ,0/4 depends strongly on the solvent acidity parameter, e.g. ETN, describing the solvation/desolvation of anions. However, after removing the contribution of the specific solvation the linear increase of the remaining part of ,0/4 with the Pekar factor, describing the non-equilibrium solvent polarization, was observed for six aprotic solvents. Copyright © 2002 John Wiley & Sons, Ltd. [source] Synthesis and characterization of phthalazinone containing poly(arylene ether)s via a novel N,C coupling reactionJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2003S. J. Wang Abstract High-molecular-weight poly(phthalazinone)s with very high glass-transition temperatures (Tg's) were synthesized via a novel N,C coupling reaction. New bisphthalazinone monomers (7a,e) were synthesized from 2-(4-chlorobenzoyl) phthalic acid in two steps. Poly(phthalazinone)s, having inherent viscosities in the range of 0.34,0.91 dL/g, were prepared by the reaction of the bis(phthalazinone) monomers with an activated aryl halide in a dipolar aprotic solvent in the presence of potassium carbonate. The poly(phthalazinone)s exhibited Tg's greater than 230 °C. polymer 8b synthesized from diphenyl biphenol and bis(4-flurophenyl) sulfone demonstrated the highest Tg of 297 °C. Thermal stabilities of the poly(phthalazinone)s were determined by thermogravimetric analysis. All the poly(phthalazinone)s showed a similar pattern of decomposition with no weight loss below 450 °C in nitrogen. The temperatures of 5% weight loss were observed to be about 500 °C. The poly(phthalazinone)s containing 4,4,-isopropylidenediphenol and 4,4,-(hexafluoroisopropylidene) diphenol and diphenyl ether linkage were soluble in chlorinated solvents such as chloroform. Other poly-(phthalazinone)s were soluble in dipolar aprotic solvents such as N,N,-dimethylacetamide. The soluble poly(phthalazinone)s can be cast as flexible films from solution. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2481,2490, 2003 [source] Main-chain viologen polymers with triflimide counterion exhibiting lyotropic liquid-crystalline properties in polar organic solvents,JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2002Pradip K. Bhowmik Abstract The solution-phase behavior of three main-chain viologen polymers, which are composed of isomeric xylyl units and triflimide as a counterion, was studied in methanol, dimethylformamide, acetonitrile, and dimethyl sulfoxide as solvents microscopically under crossed polarizers. Each of them exhibited a lyotropic lamellar phase in both polar protic and aprotic solvents. Their C* for the formation of biphasic solutions (1,5 wt %) and concentrations (20,30 wt %) for the lyotropic solutions in methanol was much lower than those in polar aprotic solvents (20,71 and 60,81 wt %, respectively). Their high solubility, high C* for the formation of biphasic solutions, and high concentrations for the formation of lyotropic solutions in polar aprotic solvents were related to the significant reduction of strong ionic interactions between triflimide and 4,4,-bipyridinium ions in each of these viologen polymers. They were the first examples of viologen polymers that exhibited a lyotropic phase in polar aprotic solvents. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2015,2024, 2002 [source] Spectroscopic characterization of the conformational states of the bis(trifluoromethanesulfonyl)imide anion (TFSI,)JOURNAL OF RAMAN SPECTROSCOPY, Issue 8 2005M. Herstedt Abstract Ab initio calculations were combined with infrared and Raman studies to distinguish spectroscopically the two conformers of the bis(trifluoromethanesulfonyl)imide anion, (TFSI,). Spectra of crystalline LiTFSI complexes with organic ligands, where the anion adopts a known conformational state, are presented to confirm the calculated spectra. Several regions are identified where either the infrared or the Raman spectra contain separate bands for the two conformers. The conformational equilibrium between the transoid and cisoid rotamers is then illustrated from the infrared spectra of solutions of LiTFSI in aprotic solvents. The transoid form is found to be more stable than the cisoid form by about 2.2 kJ mol,1, in good agreement with the present and earlier theoretical predictions. It is also shown that the IR and Raman spectral changes coming from conformational isomerism have to be carefully distinguished from those due to ionic interactions. Copyright © 2005 John Wiley & Sons, Ltd. [source] Novel Biopolymer Structures Synthesized by Dendronization of 6-Deoxy-6-aminopropargyl celluloseMACROMOLECULAR RAPID COMMUNICATIONS, Issue 21 2008Matthias Pohl Abstract Propargyl cellulose with regioselective functionalization pattern was synthesized by nucleophilic displacement reaction of 6- O -toluenesulfonyl ester of cellulose (degree of substitution, DS 0.58) with propargyl amine. The novel 6-deoxy-6-aminopropargyl cellulose provides an excellent starting material for the selective dendronization of cellulose at position 6 via the copper-catalyzed Huisgen reaction yielding 6-deoxy-6-amino-(4-methyl-[1,2,3-triazolo]-1-propyl-polyamido amine) cellulose derivatives of first- (DS 0.33) and second (DS 0.25) generation, which are soluble in polar aprotic solvents. The novel biopolymer derivatives were characterized by elemental analysis, FT-IR spectroscopy, and one- and two dimensional NMR spectroscopy, showing no side reactions (cross-linking) or impurities and no conversion at the secondary positions. [source] Fluorescence Lifetimes Study of ,-Tocopherol and Biological Prenylquinols in Organic Solvents and Model MembranesPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 5 2006Jerzy Kruk ABSTRACT We have found that for biological prenyllipids, such as plastoquinol-9, ,-tocopherol quinol, and ,-tocopherol, the shortest fluorescence lifetimes were found in aprotic solvents (hexane, ethyl acetate) whereas the longest lifetimes were those of ubiquinonol-10 in these solvents. For all the investigated prenyllipids, fluorescence lifetime in alcohols increased along with an increase in solvent viscosity. In a concentrated hexane solution, the lifetimes of prenylquinols considerably decreased. This contrasts with methanol solutions, which is probably due to the self-association of these compounds in aprotic solvents. We have also found a correlation of the Stokes shift of prenyllipids fluorescence with the orientation polarizability of the solvents. Based on data obtained in organic solvents, measurements of the fluorescence lifetimes of prenyllipids in liposomes allowed an estimation of the relative distance of their fluorescent rings from the liposome membrane surface, and was found to be the shortest for ,-tocopherol quinol in egg yolk phosphatidyl-choline liposomes, and increased in the following order: ,-tocopherol in dipalmitoyl phosphatidylcholine liposomes < ,-tocopherol < plastoquinol-9 < ubiquinol-10 in egg-yolk phosphatidylcholine liposomes. [source] Photophysical Consequences of Coupling Bacteriochlorophyll a with Serine and its Resulting Solubility in Water,PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 2 2000I. Eichwurzel ABSTRACT We investigated the dependence on solvents of optical absorption and emission of the bacteriochlorophyll a -serine (BChl-ser), a water soluble bacteriochlorophyll (BChl) derivative. Comparison between the experimental data and those collected for BChl in nonaqueous solvents shows that only a minor interaction takes place between serine and the macrocycle's ,-electron system. Nevertheless, the coupling with serine results in a small enhancement of the nonradiative relaxation rate from the first excited singlet state S1. In buffered aqueous solution (pH = 7.4), the Stokes shift of the BChl-ser fluorescence and its nonradiative relaxation rate are enhanced compared with those in nonaqueous solutions (Scherz, A., S. Katz, Y. Vakrat, V. Brumfeld, E. Gabelmann, D. Leupold, J. R. Norris, H. Scheer and Y. Salomon (1998) Photosynthesis: Mechanisms and Effects, Vol. V (Edited by G. Garab), pp. 4207,4212. Kluwer Academic, Dordrecht.), probably as a result of a hydrogen bonding between the BChl macrocycle and the water molecules. In aprotic solvents, without hydrogen bonds, the permanent dipole moment of the first excited singlet state in both BChl and BChl-ser is increased compared with the ground state by at least 2.5 Debye. [source] Synthesis and characterization of novel aromatic poly(amide-imide)s derived from 2,2,-bis(4-trimellitimidophenoxy)biphenyl or 2,2,-bis(4-trimellitimidophenoxy)-1,1,-binaphthyl and various aromatic diaminesPOLYMER INTERNATIONAL, Issue 7 2003Ahmad Banihashemi Abstract New aromatic diimide-dicarboxylic acids having kinked and cranked structures, 2,2,-bis(4-trimellitimidophenoxy)biphenyl (2a) and 2,2,-bis(4-trimellitimidophenoxy)-1,1,-binaphthyl (2b), were synthesized by the reaction of trimellitic anhydride with 2,2,-bis(4-aminophenoxy)biphenyl (1a) and 2,2,-bis(4-aminophenoxy)-1,1,-binaphthyl (1b), respectively. Compounds 2a and 2b were characterized by FT-IR and NMR spectroscopy and elemental analyses. Then, a series of novel aromatic poly(amide-imide)s were prepared by the phosphorylation polycondensation of the synthesized monomers with various aromatic diamines. Owing to structural similarity, and a comparison of the characterization data, a model compound was synthesized by the reaction of 2b with aniline. The resulting polymers with inherent viscosities of 0.58,0.97 dl g,1 were obtained in high yield. The polymers were fully characterized by FT-IR and NMR spectroscopy. The ultraviolet ,max values of the poly(amide-imide)s were also determined. The polymers were readily soluble in polar aprotic solvents. They exhibited excellent thermal stabilities and had 10% weight loss at temperatures above 500 °C under a nitrogen atmosphere. Copyright © 2003 Society of Chemical Industry [source] Microwave-assisted synthesis and characterization of heterocyclic, and optically active poly(amide-imide)s incorporating L -amino acidsPOLYMERS FOR ADVANCED TECHNOLOGIES, Issue 12 2008Abdol R. Hajipour Abstract N,N,-Pyromelliticdiimido-di- L -alanine (1), N,N,-pyromelliticdiimido-di- L -phenylalanine (2), and N,N,-pyromelliticdiimido-di- L -leucine (3) were prepared from the reaction of pyromellitic dianhydride with corresponding L -amino acids in a mixture of glacial acetic acid and pyridine solution (3/2 ratio) under refluxing conditions. The microwave-assisted polycondensation of the corresponding diimide-diacyl chloride monomers (5,7) with 4-phenyl-2,6-bis(4-aminophenyl) pyridine (10) or 4-(p -methylthiophenyl)-2,6-bis(4-aminophenyl) pyridine (12) were carried out in a laboratory microwave oven. The resulting poly(amide-imide)s were obtained in quantitative yields, and they showed admirable inherent viscosities (0.12,0.55 dlg,1), were soluble in polar aprotic solvents, showed good thermal stability and high optical purity. The synthetic compounds were characterized by IR, MS, 1H NMR, and 13C NMR spectroscopy, elemental analysis, and specific rotation. Copyright © 2008 John Wiley & Sons, Ltd. [source] | ||||||||||||||||||||||||||||