Tale of the Breslow intermediate,a central player in N-heterocyclic carbene organocatalysis: then and now

N-Heterocyclic carbenes (NHCs) belong to the popular family of organocatalysts used in a wide range of reactions, including that for the synthesis of complex natural products and biologically active compounds. In their organocatalytic manifestation, NHCs are known to impart umpolung reactivity to aldehydes and ketones, which are then exploited in the generation of homoenolate, acyl anion, and enolate equivalents suitable for a plethora of reactions such as annulation, benzoin, Stetter, Claisen rearrangement, cycloaddition, and C–C and C–H bond functionalization reactions and so on. A common thread that runs through these NHC catalyzed reactions is the proposed involvement of an enaminol, also known as the Breslow intermediate, formed by the nucleophilic addition of an NHC to a carbonyl group of a suitable electrophile. In the emerging years of NHC catalysis, enaminol remained elusive and was largely considered a putative intermediate owing to the difficulties encountered in its isolation and characterization. However, in the last decade, synergistic efforts utilizing an array of computational and experimental techniques have helped in gaining important insights into the formation and characterization of Breslow intermediates. Computational studies have suggested that a direct 1,2-proton transfer within the initial zwitterionic intermediate, generated by the action of an NHC on the carbonyl carbon, is energetically prohibitive and hence the participation of other species capable of promoting an assisted proton transfer is more likely. The proton transfer assisted by additives (such as acids, bases, other species, or even a solvent) was found to ease the kinetics of formation of Breslow intermediates. These important details on the formation, in situ detection, isolation, and characterization of the Breslow intermediate are scattered over a series of reports spanning well over a decade, and we intend to consolidate them in this review and provide a critical assessment of these developments. Given the central role of the Breslow intermediate in organocatalytic reactions, this treatise is expected to serve as a valuable source of knowledge on the same.

Molecular insights on the formation, detection, and even isolation of the Breslow intermediate, which is the most important species in N-heterocyclic carbene (NHC) catalysis, as obtained from experimental and computational studies, are presented.     

Size dependent structural and magnetic behaviour of CaFe2O4

CaFe₂O₄ nanocrystalline powders were synthesized through sol–gel treatment in which the stoichiometric mixing of various nitrates involving calcium and iron in presence of citric acid was performed. Subsequently, the as prepared sample was annealed at various temperatures in order to obtain the fine distribution of size including the bulk counterpart. The samples were then characterized using powder X-ray diffraction followed by ⁵⁷Fe Mössbauer spectroscopy, SQUID as well as vibrating sample magnetometry. The results of spectroanalyses revealed that the samples were formed in single phase cubic spinel structure and exhibits room temperature superparamagnetism, except the bulk one, which crystallizes in characteristic orthorhombic structure of CaFe₂O₄ and displays trivial coercivity and remanent magnetization at room temperature.     

Spin and charge transport in the presence of spin-orbit interaction

We present the study of spin and charge transport in nanostructures in the presence of spin-orbit (SO) interaction. Single band tight binding Hamiltonians for Elliot-Yafet and Rashba SO interaction are derived. Using these tight binding Hamiltonians and spin resolved Landauer-Büttiker formula, spin and charge transport is studied. Specifically numerical results are presented for a new method to perform magnetic scanning tunneling microscopy with non-magnetic tip but in the presence of Elliot-Yafet SO interaction. The spin relaxation phenomena in two-dimensional electron gas in the presence of Rashba SO interaction are studied and contrary to naive expectation, it is shown that disorder helps to reduce spin relaxation.     

In-situ surface-sensitive X-ray diffraction study on the influence of iodide over the selective electrochemical etching of Cu3Au (111)

During selective etching (dealloying) surface-sensitive X-ray diffraction employing Synchrotron light has been used to in-situ monitor the potential-controlled formation of Au-rich films on the surface of Cu₃Au (111) in iodide-containing electrolytes. Similar to the case in pure sulfuric acid we observed a sequence of structural transformations starting from a well-prepared pristine surface to a porous film consisting of substrate-oriented Au ligaments. Also stacking-reversed ultrathin Au-rich films and Au islands form as intermediate steps but no passive-like behavior was observed in iodide-containing electrolytes, i.e. the surface quickly developed Au ligaments after reaching the Cu dissolution potential. At low overpotentials comparatively coarse Au islands point to a higher mobility of Au/electrolyte interfaces in iodide-containing solutions. At higher overpotentials and also with higher iodide concentrations an epitaxial Cu-iodide precipitate film showed an orientation relation of CuI (111) || CuAu (111) and two azimuthal domains of < ? 2, 2, 0 > || < ? 2, 2, 0 > and < ? 2, 2, 0 > || < 2, ? 2, 0>. This partially dissolution-inhibiting bulk CuI layer is observed to produce a bimodal pore size instead of usually obtained homogeneous porosity. The X-ray data and supporting ex-situ AFM and SEM images show marked differences in the morphology and connectivity of the forming nanoporous Au layer. Precipitation layers are thus suggested to provide means for controlling the nanoporosity for applications of dealloyed films and surfaces.     

Spaces in Which Countable Closed Sets Have Countable Character

It is proved that in a T ₃ space countable closed sets have countable character if and only if the set of limit point of the space is a countable compact set and every compact set is of countable character. Also, it is shown that spaces where countable sets have countable character are WN-spaces and are very close to M-spaces. Finally, some questions of Dai and Lia are discussed and some questions are proposed.     

Some generalizations of Lindelöf and paracompact spaces

In this paper notions ofm-Lindelöf, meta-m-Lindelöf, para-m-Lindelöf andm-closure preserving property are defined, wherem is any infinite cardinal. The main results are the following:

1. A topological space ism-Lindelöf if and only if it is meta-m-Lindelöf and it ism-Lindelöf in the sense of complete accumulation point.
2. A regular topological space is paracompact if and only if it is para-m-Lindelöf and it hasm-closure preserving property for somem.

     

Kinetics and mechanism of the oxidation of aliphatic aldehydes by hexamethylenetetramine-bromine

Oxidation of aliphatic aldehydes by hexamethylenetetramine-bromine proceeds by a mechanism involving transfer of a hydride ion from the aldehyde to the oxidantvia an intermediate complex.     

LiSn2(PO4)3-based polymer-in-ceramic composite electrolyte with high ionic conductivity for all-solid-state lithium batteries

Journal of Solid State Electrochemistry - In this work, fabrication and electrochemical behavior of polymer-in-ceramic composite electrolytes based on lithium-ion conducting triclinic LiSn2(PO4)3...     

A new substitution–diffusion based image cipher using chaotic standard and logistic maps

In this paper, we propose a new loss-less symmetric image cipher based on the widely used substitution–diffusion architecture which utilizes chaotic standard and logistic maps. It is specifically designed for the coloured images, which are 3D arrays of data streams. The initial condition, system parameter of the chaotic standard map and number of iterations together constitute the secret key of the algorithm. The first round of substitution/confusion is achieved with the help of intermediate XORing keys calculated from the secret key. Then two rounds of diffusion namely the horizontal and vertical diffusions are completed by mixing the properties of horizontally and vertically adjacent pixels, respectively. In the fourth round, a robust substitution/confusion is accomplished by generating an intermediate chaotic key stream (CKS) image in a novel manner with the help of chaotic standard and logistic maps. The security and performance of the proposed image encryption technique has been analyzed thoroughly using various statistical analysis, key sensitivity analysis, differential analysis, key space analysis, speed analysis, etc. Results of the various types of analysis are encouraging and suggest that the proposed image encryption technique is able to manage the trade offs between the security and speed and hence suitable for the real-time secure image and video communication applications.