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121.
Dr. Vikas Tyagi Prof. Dr. Rudi Fasan 《Angewandte Chemie (International ed. in English)》2016,55(7):2512-2516
The olefination of aldehydes constitutes a most valuable and widely adopted strategy for constructing carbon–carbon double bonds in organic chemistry. While various synthetic methods have been made available for this purpose, no biocatalysts are known to mediate this transformation. Reported herein is that engineered myoglobin variants can catalyze the olefination of aldehydes in the presence of α‐diazoesters with high catalytic efficiency (up to 4,900 turnovers) and excellent E diastereoselectivity (92–99.9 % de). This transformation could be applied to the olefination of a variety of substituted benzaldehydes and heteroaromatic aldehydes, also in combination with different alkyl α‐diazoacetate reagents. This work provides a first example of biocatalytic aldehyde olefination and extends the spectrum of synthetically valuable chemical transformations accessible using metalloprotein‐based catalysts. 相似文献
122.
Simple and rapid determination of phthalates using microextraction by packed sorbent and gas chromatography with mass spectrometry quantification in cold drink and cosmetic samples
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Ramandeep Kaur Heena Ripneel Kaur Susheela Rani Ashok Kumar Malik 《Journal of separation science》2016,39(5):923-931
A simple and rapid method using microextraction by packed sorbent coupled with gas chromatography and mass spectrometry has been developed for the analysis of five phthalates, namely, diethyl phthalate, benzyl‐n‐butyl phthalate, dicyclohexyl phthalate, di‐n‐butyl phthalate, and di‐n‐propyl phthalate, in cold drink and cosmetic samples. The various parameters that influence the microextraction by packed sorbent performance such as extraction cycle (extract–discard), type and amount of solvent, washing solvent, and pH have been studied. The optimal conditions of microextraction using C18 as the packed sorbent were 15 extraction cycles with water as washing solvent and 3 × 10 μL of ethyl acetate as the eluting solvent. Chromatographic separation was also optimized for injection temperature, flow rate, ion source, interface temperature, column temperature gradient and mass spectrometry was evaluated using the scan and selected ion monitoring data acquisition mode. Satisfactory results were obtained in terms of linearity with R2 >0.9992 within the established concentration range. The limit of detection was 0.003–0.015 ng/mL, and the limit of quantification was 0.009–0.049 ng/mL. The recoveries were in the range of 92.35–98.90% for cold drink, 88.23–169.20% for perfume, and 88.90–184.40% for cream. Analysis by microextraction by packed sorbent promises to be a rapid method for the determination of these phthalates in cold drink and cosmetic samples, reducing the amount of sample, solvent, time and cost. 相似文献
123.
D.?P.?SinghEmail author Ramesh?Kumar Vandna?Malik Parikshit?Tyagi 《Transition Metal Chemistry》2007,32(8):1051-1055
A new series of complexes is synthesized by template condensation of glyoxal and oxalyldihydrazide in methanolic medium in
the presence of divalent cobalt, nickel, copper, zinc and cadmium salts forming complexes of the type: [M(C8H8N8O4)X2] where M = Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and X = Cl−1, Br−1, NO
3
−1
, OAc−1. The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic susceptibility
measurements, electronic, n.m.r., infrared and far infrared spectral studies. On the basis of these studies, a six coordinate
octahedral geometry for these complexes has been proposed. The biological activities of the metal complexes have been tested
in vitro against a number of pathogenic bacteria to assess their inhibiting potential. Most of the compounds have been found to exhibit
remarkable antibacterial activities. 相似文献
124.
Prakash Amrita Dhara Mishra R. K. Valsala T. P. Sharma V. Acharya R. Tyagi A. K. Pujari P. K. Kaushik C. P. 《Journal of Radioanalytical and Nuclear Chemistry》2021,328(2):519-526
Journal of Radioanalytical and Nuclear Chemistry - An attempt was made to increase the solubility of High Level liquid Waste (HLW), mainly Cr and Mo, by addition of P2O5 to sodium borosilicate... 相似文献
125.
Mahmoud EL-Morshedy Fahad Sameer Alshammari Abhishek Tyagi Iberahim Elbatal Yasser S. Hamed Mohamed S. Eliwa 《Entropy (Basel, Switzerland)》2021,23(4)
In this article, we have proposed a new generalization of the odd Weibull-G family by consolidating two notable families of distributions. We have derived various mathematical properties of the proposed family, including quantile function, skewness, kurtosis, moments, incomplete moments, mean deviation, Bonferroni and Lorenz curves, probability weighted moments, moments of (reversed) residual lifetime, entropy and order statistics. After producing the general class, two of the corresponding parametric statistical models are outlined. The hazard rate function of the sub-models can take a variety of shapes such as increasing, decreasing, unimodal, and Bathtub shaped, for different values of the parameters. Furthermore, the sub-models of the introduced family are also capable of modelling symmetric and skewed data. The parameter estimation of the special models are discussed by numerous methods, namely, the maximum likelihood, simple least squares, weighted least squares, Cramér-von Mises, and Bayesian estimation. Under the Bayesian framework, we have used informative and non-informative priors to obtain Bayes estimates of unknown parameters with the squared error and generalized entropy loss functions. An extensive Monte Carlo simulation is conducted to assess the effectiveness of these estimation techniques. The applicability of two sub-models of the proposed family is illustrated by means of two real data sets. 相似文献
126.
N. Kumar A. T. Kozakov S. Dash A. K. Tyagi I. N. Lin 《Physics of the Solid State》2013,55(10):2076-2087
Nanocrystalline diamond films with the properties dependent on the composition of the gaseous medium have been prepared using the microwave plasma enhanced chemical vapor deposition (MPECVD) method. A nanocrystalline film formed in the Ar/CH4 plasma is characterized by a high crystallinity factor, a small grain size, a large fraction of sp 2-amorphous carbon, and, consequently, by an increase in the hardness and elastic modulus. The low value of the friction coefficient of this film is associated with the small grain size and large fraction of the sp 2-amorphous carbon boundary phase that ensures an easy sliding. The contact angle of the film is small (hydrophilic properties) in the case when the plasma consists of an Ar/CH4 mixture. It has been shown that the wetting properties of the films are provided by a thin layer of carboxyl and hydroxyl functional groups passivating the dangling bonds at the surface that are responsible for the boundary lubrication mechanism. It has also been found that the friction coefficient of these films is inversely proportional to the contact pressure dependent on the diameter of the sliding counterbody ball. 相似文献
127.
A probability density function (PDF) based approach is employed to model multi-phase flow with interfacial mass transfer (dissolution) in porous media. The joint flow statistics is represented by a mass density function (MDF), which is transported in the physical and probability spaces via Fokker?CPlanck equation. This MDF-equation requires Lagrangian evolutions of the random flow variables; these evolutions are stochastic processes honoring the micro-scale flow physics. To demonstrate the concept, we consider an example of immiscible two-phase flow with the non-equilibrium dissolution of single component from one phase into the other-a model for solubility trapping during CO2 storage in brine aquifer. Since CO2-rich brine is denser than pure brine, density-driven countercurrent flow is set up in the brine phase. The stochastic models mimicking the physics of countercurrent flow lead to a modeled MDF-equation, which is solved using our recently developed stochastic particle method for multi-phase flow (Tyagi et al. J Comput Phys 227:6696?C6714, 2008). In addition, we derive Eulerian equations for stochastic moments (mean, variance, etc.) and show that unlike the MDF-equation the system of moment equations is not closed. In classical Darcy formulation, for example, the mean concentration equation is closed by neglecting variance. However, with several one- and two-dimensional simulations, it is demonstrated that the PDF and Darcy modeling approaches give significantly different results. While the PDF-approach properly accounts for the long correlation length scales and the concentration variance in density-driven countercurrent flow, the same phenomenon cannot be captured accurately with a standard Darcy model. 相似文献
128.
Poly(ethylene glycol) dimethacrylate (PEGDMA) and methacrylic acid (MAA) based micro and nanoparticles were prepared and evaluated as a carrier for oral delivery of insulin. PEGDMA was synthesized by esterification reaction of the PEG4000 with MAA in the presence of an acid catalyst. Particles of different size were prepared by emulsion polymerization reaction using different concentration of sodium lauryl sulphate (SLS) as an emulsifying agent. Synthesized copolymeric particle were characterized by attenuated total reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), scanning electron microscopy, and acid value. The mean particle diameter of the polymeric micro and nanoparticles at various physiologically relevant pH values was measured using dynamic light scattering. Insulin loading efficiency of the particles was found to be directly proportional to the particle size and inversely proportional to the acid value of the particles. In vitro insulin release studies from various insulin loaded particles were performed by simulating the gastrointestinal tract conditions using HPLC. At pH 2.5, the release of insulin from polymeric particles was observed in the range of 5–8% while a significant higher release (20–35%) was observed at pH 7.4 during first 15 min of in vitro release. Largest size copolymeric particles of 8.3 µm also showed the highest efficiency to reduce the blood glucose level in diabetic rabbits. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
129.
Kaushik Ghosh Pramod KumarNidhi Tyagi Udai P. SinghNidhi Goel Ajanta ChakrabortyPartha Roy Maria Camilla Baratto 《Polyhedron》2011,30(16):2667-2677
The copper complexes [Cu(Pyimpy)(H2O)](ClO4)2 (1), [Cu(Pyimpy)2](ClO4)2 (2), [Cu(Pyimpy)(Cl)2]·2H2O (3·2H2O), [Cu(Pyimpy)(N3)(ClO4)]2 (4) and [Cu(Pyimpy)(SCN)(ClO4)]2 (5) were synthesized and characterized by spectroscopic techniques, crystal structures and electrochemical studies (Pyimpy: (2-((2-phenyl-2-(pyridin-2-l)hydrazono)methyl)pyridine)). The superoxide scavenging activity of the two water soluble complexes 1 and 3 was examined. DNA interaction studies by UV-Vis absorption spectral changes during a titration experiment indicated the generation of new species. These small molecule SOD mimics exhibited excellent DNA cleavage activity in the presence of H2O2 as well as 2-mercaptoethanol. Complexes 1-5 exhibited better cytotoxicity compared to CuCl2·2H2O and the ligand Pyimpy, and showed more potency than cisplatin for MCF-7, PC-3 and HEK-293 cells. Complex 3 exhibited the highest potency for MCF-7, PC-3 and HEK-293 cells compared to the other complexes. 相似文献
130.
New hybrid materials featuring the dipolar fragment 6H-indolo[2,3-b]quinoxaline attached to the bulkier polyaromatic hydrocarbons such as fluoranthene, triphenylene, or polyphenylated benzene have been synthesized by a two-step procedure involving Sonogashira and Diels-Alder reactions. They were characterized by absorption, emission, electrochemical, thermal, and theoretical investigations. The electronic properties of the compounds were dominated by the 6H-indolo[2,3-b]quinoxaline chromophore, and the incorporation of polyaromatic hydrocarbons reduces the chances of nonradiative deactivation processes associated with the excited state and improves the emission properties. The compounds displayed cyan emission with moderate quantum efficiency when excited at the absorption maximum. All of the compounds exhibited an irreversible reduction process corresponding to the addition of electron at the quinoxaline segment. They showed moderate thermal stability and glass transition temperature greater than 100 °C. The presence of rigid 6H-indolo[2,3-b]quinoxaline and bulkier polyaromatic hydrocarbon segments enhances the thermal stability and glass transition temperature significantly. Finally, the dyes were successfully applied as an electron-transporting and emitting layer in multilayered organic light-emitting diodes comprising a N,N'-bis(l-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine hole-transporting layer. The cyan emitting devices were characterized by moderate device performance parameters. 相似文献