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991.
Comparison of the 1H and 13 C NMR spectra of a series of substituted 5‐benzylidene‐N,N′‐dimethylbarbituric acids (1) revealed chemical‐shift variations of different centers that correlated with the theoretical electrophilicities or with the substituent electrophilic constant σω , in an example of the usefulness of these DFT‐based indices. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
992.
Dionisia Sanz Rosa M. Claramunt Ibon Alkorta Goar Sánchez‐Sanz José Elguero 《Magnetic resonance in chemistry : MRC》2012,50(3):246-255
The structure of glibenclamide, 5‐chloro‐N‐(2‐{4‐[(cyclohexylamino)carbonyl] aminosulfonyl}phenyl) ethyl)‐2‐methoxybenzamide, an important antidiabetic drug, has been studied both in solution and in the solid state by a combination of NMR spectroscopy and theoretical calculations. The possibility that glibenclamide suffers a tautomerization under melting to afford a desmotrope was rejected. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
993.
María Yolanda Ríos M. Ángeles Ramírez‐Cisneros Ismael León‐Rivera Samuel Estrada‐Soto Gabriel Navarrete‐Vázquez A. Berenice Aguilar‐Guadarrama 《Magnetic resonance in chemistry : MRC》2012,50(4):329-331
Complete 1H and 13C NMR chemical shift assignments for 3,4‐seco‐lup‐20(29)‐en‐3‐oic acid ( 1 ) have been established by means of two‐dimensional COSY, HSQC, HMBC and NOESY spectroscopic experiments as well as by analysis of MS data. Compound 1 was isolated from Decatropis bicolor (Zucc.) Radlk. (Rutaceae) in addition to six coumarins and one alkaloid of known structure. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
994.
M. Dora Carrión Luisa C. López‐Cara Mariem Chayah Duane Choquesillo‐Lazarte Miguel A. Gallo Antonio Espinosa Antonio Entrena M. Encarnación Camacho 《Magnetic resonance in chemistry : MRC》2012,50(7):515-522
The 1H and 13C NMR resonances of twenty‐seven 2,2‐dimethyl‐5‐(2‐nitrophenyl‐5‐substituted)‐2,3‐dihydro‐1,3,4‐thiadiazoles, and twenty‐seven 3‐acyl‐5‐(2‐amino‐5‐substituted)‐2,2‐dimethyl‐2,3‐dihydro‐1,3,4‐thiadiazoles were assigned completely using the concerted application of one‐dimensional and two‐dimensional experiments (DEPT, HMQC and HMBC). NOESY experiments, X‐ray crystallography and conformational analysis confirm the preferred conformation of these compounds. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
995.
Gary E. Martin R. Thomas Williamson Kirill A. Blinov Clemens G. Anklin Wolfgang Bermel 《Magnetic resonance in chemistry : MRC》2012,50(10):691-695
1,1‐ADEQUATE and the related long‐range 1,n‐ and n,1‐ADEQUATE variants were developed to provide an unequivocal means of establishing 2JCH and the equivalent of nJCH correlations where n = 3,4. Whereas the 1,1‐ and 1,n‐ADEQUATE experiments have two simultaneous evolution periods that refocus the chemical shift and afford net single quantum evolution for the carbon spins, the n,1‐variant has a single evolution period that leaves the carbon spin to be observed at the double quantum frequency. The n,1‐ADEQUATE experiment begins with an HMBC‐type nJCH magnetization transfer, which leads to inherently lower sensitivity than the 1,1‐ and 1,n‐ADEQUATE experiments that begin with a 1JCH transfer. These attributes, in tandem, serve to render the n,1‐ADEQUATE experiment less generally applicable and more difficult to interpret than the 1,n‐ADEQUATE experiment, which can in principle afford the same structural information. Unsymmetrical and generalized indirect covariance processing methods can complement and enhance the structural information encoded in combinations of experiments e.g. HSQC‐1,1‐ or ?1,n‐ADEQUATE. Another benefit is that covariance processing methods offer the possibility of mathematically combining a higher sensitivity 2D NMR spectrum with for example 1,1‐ or 1,n‐ADEQUATE to improve access to the information content of lower sensitivity congeners. The covariance spectrum also provides a significant enhancement in the F1 digital resolution. The combination of HMBC and 1,1‐ADEQUATE spectra is shown here using strychnine as a model compound to derive structural information inherent to an n,1‐ADEQUATE spectrum with higher sensitivity and in a more convenient to interpret single quantum presentation. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
996.
Anna‐Marie Zorn Christopher Barner‐Kowollik 《Journal of polymer science. Part A, Polymer chemistry》2012,50(12):2366-2377
In the present study, n‐butyl acrylate macromonomer (BAMM) (Mn = 1900 g mol?1; PDI = 1.96) has been synthesized via a high‐temperature polymerization process. Subsequently, the olefinic termini of the BAMM have been transformed into a diol via a dihydroxylation process using KMnO4 as an oxidizing agent. The OH‐terminated macroinitiator pBA(OH)2 has subsequently been employed for the ring‐opening polymerization (ROP) of ε‐caprolactone via various catalytic systems, that is, organo‐(1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene), metal (tin(II) 2‐ethylhexanoate), and enzymatic catalysis (Novozym® 435). The obtained pBA‐b‐pCL block copolymers and the initiation efficiency of the BAMM macroinitiator have been investigated via size exclusion chromatography (SEC), electrospray ionization–mass spectrometry (ESI‐MS) hyphenated with SEC and liquid chromatography at the critical conditions of both poly(ε‐caprolactone) (pCL) and pBA. The in vitro enzyme catalysis (eROP) approach proved to be the most efficient catalysis system due to minor transesterification side reactions during the polymerization process. However, side reactions such as transesterifications occur in each catalytic system and—while they cannot be suppressed—they can be minimized. The species generated during the eROP process include the desired block copolymer pBA‐b‐pCL as main species as well as pCL homopolymer and residual macroinitiator pBA(OH)2. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
997.
Manohar Mahato Gaurav Rana Pradeep Kumar Ashwani Kumar Sharma 《Journal of polymer science. Part A, Polymer chemistry》2012,50(12):2344-2355
Highly toxic polyallylamine (PA) was reacted with a varying amount of a novel linker, 6‐(N,N,N′,N′‐tetramethylguanidinium chloride) hexanoic acid (Tmg‐HA), to prepare a series of tetramethylguanidinium‐PA (Tmg‐PA) polymers, which were used as vectors for gene transfection. The extent of attachment of the linker, Tmg‐HA, to the PA backbone was determined by 2,4,6‐trinitrobenzene sulfonic acid assay. The modified polymers (Tmg‐PAs), when complexed with pDNA, exhibited good condensation ability. The nanoparticles, so formed, were characterized by their size and zeta potential and were subsequently evaluated for their toxicity and transfection ability on various mammalian cells, viz., HeLa, CHO, and HEK 293 cells. Mobility shift assay revealed that on increasing the percent substitution of Tmg‐HA onto PA (from Tmg‐PA1 to Tmg‐PA6), relatively higher amounts of modified polymers were required to retard the mobility of a fixed amount of DNA. Besides, Tmg‐PA polymers provided sufficient protection (ca. 84–88%) to bound DNA against nucleases and one of the formulations, Tmg‐PA2 (ca. 15% substitution) displayed the highest transfection efficiency outcompeting the commercial transfection reagent, Lipofectamine? with minimal cytotoxicity. More impressively, the transfection efficiency increased despite recording a decrease in the buffering capacity of the grafted polymers suggesting that buffering capacity is not the sole parameter in determining the gene delivery efficiency of a vector system. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
998.
Julien Ramier Estelle Renard Daniel Grande 《Journal of polymer science. Part A, Polymer chemistry》2012,50(7):1445-1455
Microwave (MW)‐assisted ring‐opening polymerization (ROP) provides a rapid and straightforward method for engineering a wide array of well‐defined poly(3‐hydroxyalkanoate)‐b‐poly(D,L ‐lactide) (PHA‐b‐PLA) diblock copolymers. On MW irradiation, the bulk ROP of D,L ‐lactide (LA) could be efficiently triggered by a series of monohydroxylated PHA‐based macroinitiators previously produced via acid‐catalyzed methanolysis of corresponding native PHAs, thus affording diblock copolyesters with tunable compositions. The dependence of LA polymerization on temperature, macroinitiator structure, irradiation time, and [LA]0/[PHA]0 molar ratio was carefully investigated. It turned out that initiator efficiency values close to 1 associated with conversions ranging from 50 to 85% were obtained only after 5 min at 115 °C. A kinetic investigation of the MW‐assisted ROP of LA gave evidence of its “living”/controlled character under the experimental conditions selected. Structural analyses and thermal properties of biodegradable diblock copolyesters were also performed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
999.
1000.
《Analytical letters》2012,45(11):2055-2069
Abstract A reagentless fiber optic biosensor specific for NADH, associated with flow injection analysis and based on bacterial bioluminescence is described. Only a buffer solution as flowing stream is required for the probe which works without supply of its coreactants (FMN and N-decyl-aldehyde). These are coentrapped in a poly(vinyl)alcohol (PVA) matrix which allows their internal release in the vicinity of the immobilized enzymes. Two PVA matrices differing by the reticulation process have been tested : first, by polymerization with glutaraldehyde and secondly, by a cyclic freezing-thawing process. The self-containment working time was estimated at 1 and 1.5 h of continuous measurements, respectively. NADH was determined using flow injection analysis. The sensor gave excellent reproducibility (RSD ≤ 3%) in the linear dynamic range 5 — 500 pmol with an average cycle-time of 2.5 min. 相似文献