Biocatalyst CAL-B catalyzed synthesis of modified nucleosides: An overview

Nucleosides are valuable biologically active compounds, which display antitumour and antiviral activities. Various types of bioactive nucleosides are designed to improve their therapeutic efficacy, However this strategy faces the difficult selectivity issues of nucleoside chemistry. Therefore, the goal of this review is to give an idea of the opportunities provided by biocatalyst CAL-B procedures in the preparation of different types of bioactive nucleoside compounds. The function of Candida Antarctica lipase-B (CAL-B) in organic synthesis is reviewed. This enzyme has been found to be a principally efficient and robust lipase catalyzing an unexpected variety of reactions including many different regio- chemo, and diastereo-selective synthesis. Moreover, the structure of Candida Antarctica lipase-B is an example of an enzyme for which its specificity has been predicted based on acylation and deacylation mechanism on substrates.     

An efficient one‐pot synthesis of 2‐benzylpyrroles and 3‐benzylindoles

One‐pot regioselective benzylation of pyrroles and indoles using zirconium tetrachloride is discussed. This has been achieved by in‐situ generation of di(1H‐pyrrol‐1‐yl)zirconium(IV) chloride and di(1H‐indol‐1‐yl)zirconium(IV) chloride. It was observed that benzylation reactions of these complexes using n‐BuLi occurred at C‐2 position for pyrrole and C‐3 for indole. Copyright © 2011 John Wiley & Sons, Ltd.     

Identification of Crucial Intermediates in the Formation of Humins from Cellulose-Derived Platform Chemicals Under Brønsted Acid Catalyzed Reaction Conditions

Humins are one of the undesirable products formed during the dehydration of sugars as well as the conversion of 5-hydroxymethylfurfural (HMF) to value-added products. Thus, reducing the formation of humins is an important strategy for improving the yield of the aforementioned reactions. Even after a plethora of studies, the mechanism of formation and the structure of humins are still elusive. In this regard, we have employed density functional theory-based mechanistic studies and microkinetic analysis to identify crucial intermediates formed from glucose, fructose, and HMF that can initiate the polymerization reactions resulting in humins under Brønsted acid-catalyzed reaction conditions. This study brings light into crucial elementary reaction steps that can be targeted for controlling humins formation. Moreover, this work provides a rationale for the experimentally observed aliphatic chains and HMF condensation products in the humins structure. Different possible polymerization routes that could contribute to the structure of humins are also suggested based on the results. Importantly, the findings of this work indicate that increasing the rate of isomerization of glucose to fructose and reducing the rate of reaction between HMF molecules could be an efficient strategy for reducing humins formation.     

Signals of leptophilic dark matter at the ILC

Adopting a model independent approach, we constrain the various effective interactions of leptophilic DM particles with the visible world from the WMAP and Planck data. The thermally averaged indirect DM annihilation cross section and the DM–electron direct-detection cross section for such a DM candidate are observed to be consistent with the respective experimental data. We study the production of cosmologically allowed leptophilic DM in association with \(Z\, (Z\rightarrow f\bar{f})\), \(f\equiv q,\,e^-,\, \mu ^-\) at the ILC. We perform the \(\chi ^2\) analysis and compute the 99% C.L. acceptance contours in the \(m_\chi \) and \(\varLambda \) plane from the two-dimensional differential distributions of various kinematic observables obtained after employing parton showering and hadronisation to the simulated data. We observe that the dominant hadronic channel provides the best kinematic reach of 2.62 TeV (\(m_\chi \) = 25 GeV), which further improves to \(\sim \)3 TeV for polarised beams at \(\sqrt{s} = 1\) TeV and an integrated luminosity of 1 ab\(^{-1}\).     

Forward and backward wave propagation in multilayer planar waveguide using metamaterials layer

In this study, an efficient method is discussed to analyze the multilayer planar waveguides with double negative guided (DNG) and double positive material as guiding film. Here, among various lossless multilayer planar waveguide structures, only three layer and five layer structures are discussed. For these structures, guided dispersion characteristic, along with electric field distribution of TM modes are numerically analyzed and compared. This analysis enables an effective comparison of guided modal properties of various modes and results in a better understanding of the multilayer planar waveguide with DNG as guiding film.     

Surface stress mediated image force and torque on an edge dislocation

The proximity of interfaces gives prominence to image forces experienced by dislocations. The presence of surface stress alters the traction-free boundary conditions existing on free-surfaces and hence is expected to alter the magnitude of the image force. In the current work, using a combined simulation of surface stress and an edge dislocation in a semi-infinite body, we evaluate the configurational effects on the system. We demonstrate that if the extra half-plane of the edge dislocation is parallel to the surface, the image force (glide) is not altered due to surface stress; however, the dislocation experiences a torque. The surface stress breaks the ‘climb image force’ symmetry, thus leading to non-equivalence between positive and negative climb. We discover an equilibrium position for the edge dislocation in the positive ‘climb geometry’, arising due to a competition between the interaction of the dislocation stress fields with the surface stress and the image dislocation. Torque in the climb configuration is not affected by surface stress (remains zero). Surface stress is computed using a recently developed two-scale model based on Shuttleworth’s idea and image forces using a finite element model developed earlier. The effect of surface stress on the image force and torque experienced by the dislocation monopole is analysed using illustrative 3D models.     

Protein extraction and cytotoxicity abilities of colloidal gold-coated silica hybrid nanoparticles

Monodisperse non-hybrid silica and hybrid colloidal silica of ≤?200 nm decorated with small Au nanoparticles (NPs) were synthesized in a simple single-step method. Non-hybrid silica NPs were synthesized in the absence and presence of different twin tail cationic surfactants, while tiny Au NPs were grown under in situ reaction conditions on non-hybrid silica synthesized previously by using cationic dextran. Bio-applicability and cytotoxicity of both hybrid as well as non-hybrid silica NPs were tested by using them for the extraction of protein fractions from complex aqueous protein solutions and treating them with blood cells, respectively. Both non-hybrid and hybrid silica NPs demonstrate excellent ability to extract proteins fractions predominantly of relatively low molecular masses, i.e., ~ 80 kDa. Extraction preferences between both kinds of silica became prominent when predominantly hydrophobic proteins such zein and rice proteins were used rather than mainly polar protein like BSA. Applicability for more complex biological fluid like serum indicated the competitive extractions among strongly versus weakly bound proteins. With significant bearing in in vivo conditions, hybrid silica was potentially toxic towards the blood cells in comparison to non-hybrid silica. It stems from the collective interactions of silica as well as nanometallic surfaces of Au NPs to interact with the blood cells causing hemolysis and hence may not be the suitable vehicles for drug release in systemic circulation.

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Ordinal indices of Small Subspaces of <Emphasis Type="Italic">L</Emphasis><Subscript><Emphasis Type="Italic">p</Emphasis></Subscript>

We calculate the ordinal L _p index defined in [3] for Rosenthal’s space X _p , \({\ell_p}\) and \({\ell_2}\). We show that an infinite-dimensional subspace of L _p \({(2 < p < \infty)}\) non-isomorphic to \({\ell_2}\) embeds in \({\ell_p}\) if and only if its ordinal index is the minimal possible. We also give a sufficient condition for a \({\mathcal{L}_p}\) subspace of \({\ell_p \oplus \ell_2}\) to be isomorphic to X _p .     

4,5-Didehydro-7-silyloxymethyl-2-oxepanone and formal total syntheses of Hagen’s gland lactones and trans-kumausynes

A concise and enantiospecific route to the 2,6-dioxabicyclo[3.3.0]octan-3-one ring system from commercially available (R)-(+)- and (S)-(−)-glycidols is described. The key features involve ring closing metathesis to construct the 7-substituted-4,5-dehydro-2-oxepanone and its base-catalyzed single-step rearrangement into the 2,6-dioxabicyclo[3.3.0]octan-3-one skeleton. Using this strategy, formal total syntheses of (7R)-cis-Hagen’s gland lactones and (+)- and (−)-trans-kumausynes have been achieved.