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1.
Seema Yadav Sriparna Ray Ajeet Singh Shaikh M. Mobin Tapta Kanchan Roy Chandrakanta Dash 《应用有机金属化学》2020,34(11):e5942
Dinuclear gold(I)-N-heterocyclic carbene complexes were developed for the hydrohydrazidation of terminal alkynes. The gold(I)-N-heterocyclic carbene complexes 2a-2b were synthesized in good yields from silver complexes synthesized in situ, which in turn were obtained from the corresponding imidazolium salts with Ag2O in dichloromethane as a solvent. The new air-stable gold(I)-NHC complexes, 2a - 2b, were characterized using NMR spectroscopy, elemental analysis, infrared, and mass spectroscopy studies. The gold(I) complex 2a was characterized using X-ray crystallography. Bis-N-heterocyclic carbene–based gold(I) complexes 2a - 2b exhibited excellent catalytic activities for hydrohydrazidation of terminal alkynes yielding acylhydrazone derivatives. The working catalytic system can be used in gram-scale synthesis. In addition, the catalytic reaction mechanism of the hydrohydrazidation of terminal alkynes by gold(I)-NHC complex was studied in detail using density functional theory. 相似文献
2.
ABSTRACTThe yield drop phenomenon observed in the Ti–15V-3Al–3Sn-3Cr (Ti–15–3) beta-titanium alloy and its anomalous behaviour in the boron and carbon added Ti–15–3 alloys have been studied. While the base and the carbon containing alloys exhibit yield drop, the boron containing alloy with smaller grain size than base alloy does not appear to show this phenomenon. Tensile tests were interrupted at different stress levels followed by analyses of slip lines and sub-structural characteristics using scanning and transmission electron microscopes to understand this anomalous yield point phenomenon. Infrared thermal imaging technique was used to map the strain localisation and the spatiotemporal evolution of deformation along the gauge length of the specimens during the tensile tests. Deformation in these alloys initiates only in a few grains. Pile-up of dislocations in these grains subsequently triggers the formation of dislocations in other grains and their rapid multiplications. The spreading of deformation by the generation of dislocations from pile up dislocations in one grain to neighbouring un-deformed grains and their rapid multiplication to new regions influence the yield drop phenomenon and its characteristics. It is shown in this study that microscopic instability in the grain level is a necessary, but not the sufficient condition for the manifestation of macroscopic instability during tensile deformation in polycrystalline materials. The presence of boride particles at grain boundaries restricts the slip transfer across the grains as well as the spreading of deformation to new regions, which causes the suppression of yield drop in the boron containing alloy. 相似文献
3.
Beatrice Battistella Dr. Thomas Lohmiller Dr. Beatrice Cula Prof. Dr. Peter Hildebrandt Dr. Uwe Kuhlmann Prof. Dr. Holger Dau Dr. Stefan Mebs Prof. Dr. Kallol Ray 《Angewandte Chemie (International ed. in English)》2023,62(12):e202217076
In class Ib ribonucleotide reductases (RNRs) a dimanganese(II) cluster activates superoxide (O2⋅−) rather than dioxygen (O2), to access a high valent MnIII−O2−MnIV species, responsible for the oxidation of tyrosine to tyrosyl radical. In a biomimetic approach, we report the synthesis of a thiolate-bound dimanganese complex [MnII2(BPMT)(OAc)2](ClO)4 (BPMT=(2,6-bis{[bis(2-pyridylmethyl)amino]methyl}-4-methylthiophenolate) ( 1 ) and its reaction with O2⋅− to form a [(BPMT)MnO2Mn]2+ complex 2 . Resonance Raman investigation revealed the presence of an O−O bond in 2 , while EPR analysis displayed a 16-line St=1/2 signal at g=2 typically associated with a MnIIIMnIV core, as detected in class Ib RNRs. Unlike all other previously reported Mn−O2−Mn complexes, generated by O2⋅− activation at Mn2 centers, 2 proved to be a capable electrophilic oxidant in aldehyde deformylation and phenol oxidation reactions, rendering it one of the best structural and functional models for class Ib RNRs. 相似文献
4.
Dr. Linda Iffland-Mühlhaus Dr. Beatrice Battistella Dr. Daniel Siegmund Prof. Dr. Kallol Ray Prof. Dr. Ulf-Peter Apfel 《欧洲无机化学杂志》2023,26(30):e202300418
Cobalt complexes are extensively studied as bioinspired models for non-heme oxygenases as they facilitate both the stabilization and characterization of metal-oxygen intermediates. As an analog to the well-known Co(cyclam) complex Co{N4} (cyclam=1,4,8,11-tetraazacyclotetradecane), the CoII complex Co{i-N4} with the isomeric isocyclam ligand (isocyclam=1,4,7,11-tetraazacyclotetradecane) was synthesized and characterized. Despite the identical N4 donor set of both complexes, Co{i-N4} enables the 2e−/2H+ reduction of O2 with a lower overpotential (ηeff of 385 mV vs. 540 mV for Co{N4} ), albeit with a diminished turnover frequency. Characterization of the intermediates formed upon O2 activation of Co{i-N4} reveals a structurally identified stable μ-peroxo CoIII dimer as the main product. A superoxo CoIII species is also formed as a minor product, as indicated by EPR spectroscopy. In further reactivity studies, the electrophilicity of these in situ generated Co−O2 species was demonstrated by the oxidation of the O−H bond of TEMPO−H (2,2,6,6-tetramethylpiperidin-1-ol) via a H atom abstraction process. Unlike the known Co(cyclam), Co{i-N4} can be employed in oxygen atom transfer reactions oxidizing triphenylphosphine to the corresponding phosphine oxide highlighting the impact of geometrical modifications of the ligand while preserving the ring size and donor atom set on the reactivity of biomimetic oxygen activating complexes. 相似文献
5.
Synthesis and Evaluation of GdIII‐Based Magnetic Resonance Contrast Agents for Molecular Imaging of Prostate‐Specific Membrane Antigen 下载免费PDF全文
Dr. Sangeeta Ray Banerjee Dr. Ethel J. Ngen Matthew W. Rotz Dr. Samata Kakkad Ala Lisok Richard Pracitto Mrudula Pullambhatla Dr. Zhengping Chen Dr. Tariq Shah Dr. Dmitri Artemov Dr. Thomas J. Meade Dr. Zaver M. Bhujwalla Dr. Martin G. Pomper 《Angewandte Chemie (International ed. in English)》2015,54(37):10778-10782
Magnetic resonance (MR) imaging is advantageous because it concurrently provides anatomic, functional, and molecular information. MR molecular imaging can combine the high spatial resolution of this established clinical modality with molecular profiling in vivo. However, as a result of the intrinsically low sensitivity of MR imaging, high local concentrations of biological targets are required to generate discernable MR contrast. We hypothesize that the prostate‐specific membrane antigen (PSMA), an attractive target for imaging and therapy of prostate cancer, could serve as a suitable biomarker for MR‐based molecular imaging. We have synthesized three new high‐affinity, low‐molecular‐weight GdIII‐based PSMA‐targeted contrast agents containing one to three GdIII chelates per molecule. We evaluated the relaxometric properties of these agents in solution, in prostate cancer cells, and in an in vivo experimental model to demonstrate the feasibility of PSMA‐based MR molecular imaging. 相似文献
6.
The interface between fibre and matrix of fibrous polymeric composites is most critical and decisive in maintaining sustainability, durability and also reliability of this potential material, but unfortunately a comprehensive conclusion is yet to meet the label of confidence for the engineering viability. Fiber reinforced polymer (FRP) composites are being accepted and also utilized as better and reliable alternative materials for repairing and/or replacing conventional materials, starting from tiny objects to mega structure in various engineering applications. The promise and potential of these materials are sometimes threatened in speedy replacement of conventional materials because of their inhomogeneities and inherent susceptibility to degradation due to moist and thermal environments. Environmental conditioning is traditionally believed to be a physical phenomenon but present literature has revealed that the interdiffusion between fiber and polymer matrix resin comprises of physical, chemical, mechanical, physico-chemical and mechano-chemical phenomena. The failure and fracture behavior at ambient conditions itself is a complex phenomenon till at present. The service conditions which are mostly hygrothermal in nature, along with a variation of applied loads make the mechanical behavior nearly unpredictable, far off from conclusions in evaluating the short term as well as long term durability and reliability of FRPs. It is essential to accurately simulate the initial and subsequent evolution process of this kind of damage phenomena, in order to explore the full potential of the mechanical properties of composite laminates. The present review has emphasized the need of complying scattered as well as limited literature on this front, and has focused on creating the urgency to highlight the importance of judicious uses of these materials with minimum safety factors with an aim to achieving lighter weight in enhancing specific properties. 相似文献
7.
Sisi Huang Ray T. McClain Richard Kenneth Marcus 《Journal of separation science》2022,45(9):1502-1513
Reversed phase and size-exclusion chromatography methods are commonly used for protein separations, although they are based on distinctly different principles. Reversed phase methods yield hydrophobicity-based (loosely-termed) separation of proteins on porous supports, but tend to be limited to proteins with modest molecular weights based on mass transfer limitations. Alternatively, size-exclusion provides complementary benefits in the separation of higher mass proteins based on entropic, not enthalpic, processes, but tend to yield limited peak capacities. In this study, microbore columns packed with a novel trilobal polypropylene capillary-channeled polymer fiber were used in a reversed phase modality for the separation of polypeptides and proteins of molecular weights ranging from 1.4 to 660 kDa. Chromatographic parameters including gradient times, flow rates, and trifluoroacetic acid concentrations in the mobile phase were optimized to maximize resolution and throughput. Following optimization, the performance of the trilobal fiber column was compared to two commercial-sourced columns, a superficially porous C4-derivatized silica and size exclusion, both of which are sold specifically for protein separations and operated according to the manufacturer-specified conditions. In comparison to the commercial columns, the fiber-based column yielded better separation performance across the entirety of the suite, at much lower cost and shorter separation times. 相似文献
8.
A copper catalyzed Pummerer type reaction of α-thio aryl/heteroarylacetates is described for the first time. This transformation represents a new route to synthesize α-keto esters, which are important intermediates for pharmaceuticals and organic synthesis. The reaction proceeds via in situ generation of a thionium ion that undergoes hydrolysis to furnish α-keto esters in synthetically viable yields (up to 82%). 相似文献
9.
A new method for exact solutions of variant types of time‐fractional Korteweg‐de Vries equations in shallow water waves 下载免费PDF全文
The current article devoted on the new method for finding the exact solutions of some time‐fractional Korteweg–de Vries (KdV) type equations appearing in shallow water waves. We employ the new method here for time‐fractional equations viz. time‐fractional KdV‐Burgers and KdV‐mKdV equations for finding the exact solutions. We use here the fractional complex transform accompanied by properties of local fractional calculus for reduction of fractional partial differential equations to ordinary differential equations. The obtained results are demonstrated by graphs for the new solutions. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
10.
The transport dynamics in complex systems governing by anomalous diffusion modelled with Riesz fractional partial differential equations 下载免费PDF全文
Santanu Saha Ray 《Mathematical Methods in the Applied Sciences》2017,40(5):1637-1648
In this paper, numerical solutions of fractional Fokker–Planck equations with Riesz space fractional derivatives have been developed. Here, the fractional Fokker–Planck equations have been considered in a finite domain. In order to deal with the Riesz fractional derivative operator, shifted Grünwald approximation and fractional centred difference approaches have been used. The explicit finite difference method and Crank–Nicolson implicit method have been applied to obtain the numerical solutions of fractional diffusion equation and fractional Fokker–Planck equations, respectively. Numerical results are presented to demonstrate the accuracy and effectiveness of the proposed numerical solution techniques. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献