One-pot Sonogashira coupling,hydroamination of alkyne and intramolecular CH arylation reactions toward the synthesis of indole-fused benzosultams

A one-pot Sonogashira coupling, hydroamination of alkyne and CH arylation reactions for the synthesis of indole-fused benzosultams are described. This method allows access to a variety of indole-fused seven membered benzosultams in good to excellent yields. The free indolyl nitrogen containing indole-fused benzosultams are also prepared by this method. The structures of the synthesized compounds are confirmed by single crystal XRD studies.     

Estimation of underground water radon danger in Bakreswar and Tantloi Geothermal Region,India

The main aim of the study is to present an evaluation of radon concentration in underground water of Bakreswar and Tantloi geothermal region which is mainly used for drinking purposes of the local people. Water samples were collected from tube-wells at 173 different locations. The radon (²²²Rn) concentration level was observed to fluctuate widely between 3.3 and 803.8 Bq/l with an average of 106.8 Bq/l. Nearly 42% of the samples had radon concentration above the safe limit of 100 Bq/l recommended by World Health Organisation (WHO) and European Union Commission (EU). Considering the WHO and International Commission on Radiological Protection recommended water consumption rate for adults (730 l/year) the corresponding total annual effective dose of the samples were estimated to assess the probable health risk. Total annual effective dose of the samples were varied between 16.72 and 4079.47 µSv/year with an average value of 541.92 µSv/year. About 95% samples exceed the WHO and EU Commission proposed safe limit of 100 µSv/year.     

Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods

The self‐assembled structures of atomically precise, ligand‐protected noble metal nanoclusters leading to encapsulation of plasmonic gold nanorods (GNRs) is presented. Unlike highly sophisticated DNA nanotechnology, this strategically simple hydrogen bonding‐directed self‐assembly of nanoclusters leads to octahedral nanocrystals encapsulating GNRs. Specifically, the p‐mercaptobenzoic acid (pMBA)‐protected atomically precise silver nanocluster, Na₄[Ag₄₄(pMBA)₃₀], and pMBA‐functionalized GNRs were used. High‐resolution transmission and scanning transmission electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly of silver nanoclusters via H‐bonding, leading to octahedral symmetry. The use of water‐dispersible gold nanoclusters, Au_≈250(pMBA)_n and Au₁₀₂(pMBA)₄₄, also formed layered shells encapsulating GNRs. Such cluster assemblies on colloidal particles are a new category of precision hybrids with diverse possibilities.     

Structural features and dye-sensitized solar cell performance of chemically synthesized F doped ZnO particles

Journal of Solid State Electrochemistry - In dye-sensitized solar cell (DSSC) application, the particulate morphologies of photo-anode facilitate efficient dye loading and thus lead to better...     

Assembling metals (Co II and Mn II) with pyridylcarboxylates in the presence of azide: synthesis, structural aspects and magnetic behavior of three coordination polymers

The reaction between Co(NO3)2.6H2O and substituted pyridylcarboxylic acid [nicotinic acid (Hnic) or trans-3-pyridylacrylic acid (Htpa)] in the presence of NaN3 under hydrothermal conditions yielded [Co(1.5)(nic)2 (Hnic)(N3)]n (1) and [Co(1.5)(tpa)2 (N3)(H2O)]n (2), respectively. Single crystal structure analyses reveal that both complexes are 3D complicated coordination polymers. The basic repeating units in both of the complexes are Co(3) trinuclear clusters containing syn-syn bridging carboxylate and end-on azido linker. A similar reaction using MnCl2.4H2O in presence of equimolar amounts of Htpa and NaN3 yielded a 2D corrugated sheet [Mn(tpa)2]n (3) containing no azide. Complex 3 can also be synthesized under hydrothermal conditions using Natpa in the absence of NaN3. Surprisingly, the same reaction at room temperature yielded a known mononuclear complex [Mn(tpa)2(H2O)4]. Variable temperature magnetic studies down to 2 K revealed the dominant antiferromagnetic nature of the first two complexes with a ferrimagnetic type of behavior despite the facts that they are homometallic and homospin systems. The susceptibility data in both cases were analyzed by a Co3 trinuclear model as well as considering inter-trimer interactions. Complex 3 is weakly antiferromagnetic in nature with an exchange parameter of J = -2 cm(-1) through the syn-anti bridging carboxylate pathway.     

Sequence-dependent clustering properties of nucleotides fragments in an ionic solution

The chemical nature of the DNA bases is an important factor in sequence-mediated association of DNA molecules. Nucleotides are the fundamental DNA elements and the base identity impacts the molecular properties of nucleotide fragments. It is interesting to study the fundamental nature of nucleotides in DNA, on the basis of base-specific interactions, association, and modes of standard atomic or molecular interactions. With all-atom molecular dynamics simulations of model dinucleotide and tetranucleotide systems having single-stranded dinucleotide or tetranucleotide fragments of varying sequences, we show how the base identity and interactions between the different bases as well as water may affect the clustering properties of nucleotides fragments in an ionic solution. Sequence-dependent differential interactions between the nucleotide fragments, ionic concentration, and elevated temperature are found to influence the clustering properties and dynamics of association. Well-known epigenetic modification of DNA, that is, cytosine methylation also promotes dinucleotide clustering in solution. These observations point to one possible chemical nature of the DNA bases, as well as the importance of the base pairing, base stacking, and ionic interactions in DNA structure formation, and DNA sequence-mediated association. Sequence- and the ionic environment-mediated self-association properties of the dinucleotides indicate its great potential to develop biological nanomaterials for desired applications.     

Stability and bonding of carbon(0)-iron−N2 complexes relevant to nitrogenase co-factor: EDA-NOCV analyses

The factors/structural features which are responsible for the binding, activation and reduction of N₂ to NH₃ by FeMoco of nitrogenase have not been completely understood well. Several relevant model complexes by Holland et al. and Peters et al. have been synthesized, characterized and studied by theoretical calculations. For a matter of fact, those complexes are much different than real active N₂-binding Fe-sites of FeMoco, which possesses a central C(4-) ion having an eight valence electrons as an μ₆-bridge. Here, a series of [(S₃C(0))Fe(II/I/0)-N₂]^n- complexes in different charged/spin states containing a coordinated σ- and π-donor C(0)-atom which possesses eight outer shell electrons [carbone, (Ph₃P)₂C(0); Ph₃P→C(0)←PPh₃] and three S-donor sites (i.e. ^-S-Ar), have been studied by DFT, QTAIM, and EDA-NOCV calculations. The effect of the weak field ligand on Fe-centres and the subsequent N₂-binding has been studied by EDA-NOCV analysis. The role of the oxidation state of Fe and N₂-binding in different charged and spin states of the complex have been investigated by EDA-NOCV analyses. The intrinsic interaction energies of the Fe−N₂ bond are in the range from −42/−35 to −67 kcal/mol in their corresponding ground states. The S₃C(0) donor set is argued here to be closer to the actual coordination environment of one of the six Fe-centres of nitrogenase. In comparison, the captivating model complexes reported by Holland et al. and Peter et al. possess a stronger π-acceptor C-ring (S₂C_ring donor, π-C donor) and stronger donor set like CP₃ (σ-C donor) ligands, respectively.     

Mechanistically inspired design of Fe(III)-TAML peroxide-activating catalysts

Recent broad-ranging mechanistic studies of FeIII-TAML peroxide activators enable a strategy for designing catalysts with improved (i) hydrolytic and (ii) operational stabilities, (iii) faster activation of H2O2 and other peroxides, and (iv) a pH of highest activity closer to 7. Combining all items of insight leads to [Fe{1-NO2C6H3-3,4-(NCOCMe2NCO)2CF2}(OH2)]- (1a) which exhibits the most desirable technical performance in its class.     

Three new Cu-azido polymers and their systematic interconversion: role of the amount of the blocking amine on the structural diversity and magnetic behavior

Three new coordination polymers [Cu5(N3)10(en)2]n (1), [Cu6(N3)12(en)4]n (2), and [Cu4(N3)8(en)4]n (3) have been synthesized in a controlled manner by treatment of a 1:2 mixture of Cu(NO3)2 and NaN3 with varying amount of ethylenediamine (en). Single-crystal structure analyses clearly indicated that the puckered Cu4 biscubane unit in 1 gradually opens to a slightly more open Cu4 macrocyclic unit in 2 when more en approaches to the Cu4 core. Upon addition of further en, an open Cu4 linear secondary building unit was obtained in complex 3. Complex 1 contains four different kinds of bridging modes of the azide anion and is a complicated 3D polymer. Similarly, complexes 2 and 3 are 3D and 2D polymers, respectively, containing three different kinds of bridging azides. Complex 3 contains two very rare cis end-to-end (EE) and single-end-on (EO) azido modes. Structural transformation from 1 to 3 was monitored and explained qualitatively. Variable-temperature magnetic studies in the temperature range of 300-2 K reveal the existence of dominant ferromagnetic behavior in all the three cases with a metamagnetic-type behavior in complex 1 with the critical field of transition at 0.8 T. The purity of all the complexes were established by elemental analyses, as well as by the powder XRD patterns that matched well with the expected patterns from the single-crystal structure analysis.