Synthesis,spectroscopic and structural characterization of the mer isomer of ammonium bis(phenylpyruvic acid thiosemicarbazone)-cobalt(III) hemihydrate

Summary Phenyl pyruvate thiosemicarbazone (H₂PPVATSC) coordinates in its binegative thiolate form to cobalt(III) in the complex isolated from basic medium. An X-ray structure determination of the resulting meridional isomer was found to contain mutually cis sulphur, trans nitrogen, and trans oxygen donor atoms, respectively. The two five-membered rings formed by each ligand are puckered towards each other, resulting in a distortion from regular octahedral geometry about the cobalt atom. The complex was found to exhibit only a metal-based one electron reversible reduction at -0.97 V, while the parent ligand yields a c.v. profile consisting of two irreversible reduction peaks at -0.75 and -1.05V respectively, the latter corresponding to the reduction of the azomethine group.     

An enantiospecific synthesis of (+)-isoparvifolinone and (−)-parvifoline

An enantiospecific synthesis of (+)-isoparvifolinone and (−)-parvifoline, from naturally occurring (R)-(+)-citronellal, employing intramolecular Friedel-Crafts acylation as the key step, is described.     

EGFRisopred: a machine learning-based classification model for identifying isoform-specific inhibitors against EGFR and HER2

The EGFR kinase pathway is one of the most frequently activated signaling pathways in human cancers. EGFR and HER2 are the two significant members of this pathway, which are attractive drug targets of clinical relevance in lung and breast cancer. Therefore, identifying EGFR- and HER2-specific inhibitors is one of the important challenges in cancer drug discovery. To address this issue, a dataset of 519 compounds having inhibitory activity against both the isoforms, i.e., EGFR and HER2, was collected from the literature and developed a knowledge-based computational classification model for predicting the specificity of a molecule for an isoform (EGFR/HER2) with precision. A total of seventy-two classification models using nine fingerprint types, four classifiers (IBK, NB, SMO and RF) and two different datasets (EGFR and HER2 isoform specific) were developed. It was observed that the models developed using random forest and IBK performed better for EGFR- and HER2-specific datasets, respectively. Scaffold and functional group analysis led to the identification of prevalent core and fragments in each of the datasets. The accuracy of the selected best performing models was also evaluated using the decoy dataset. We have also developed an application EGFRisopred, which integrates the best performing models and permits the user to predict the specificity of a compound as an EGFR-/HER2-specific anticancer agent. It is expected that the tool’s availability as a free utility will allow researchers to identify new inhibitors against these targets important in cancer.

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Comparative Enrichment Capabilities of Some Carbonaceous and Macroreticular Resins Using Selected Radioactive Model Compounds in Fortified Aqueous Samples

Abstract

The concentration efficiency of synthetic macroreticular resins, XAD-2 and XAD-7 and carbonaceous resins, XE-340, XE-347 and XE-348 was evaluated and compared using trace levels of eight radioactive model environmental contaminants present in aqueous medium. Influences of chemical functionalities of the solvents, physical characteristics of the sorbents, and pH of the aqueous medium on sorption of the model compounds were investigated under frontal dynamic chromatographic conditions. The elution behavior of these sorbates and desorption properties of the polymer adsorbents with respect to solvents of different polarities were studied.     

Metal-Stabilized [B8H8]2− Derivatives with Dodecahedral Structure in the Solid and Solution States: [(Cp2MBH3)2B8H6] (Cp=η5-C5H5; M=Zr (1-Zr) and Hf (1-Hf)).

Despite the synthesis and structural characterization of closo-hydroborate dianions, [B_nH_n]²⁻ (n=6–12) more than 50 years ago, some ambiguity remains about the structure of [B₈H₈]²⁻. Although the solid-state structure of [B₈H₈]²⁻ was established by single-crystal X-ray studies in 1969, fast rearrangements in solution at accessible temperatures prevented its detailed characterization. We therefore stabilized a derivative of [B₈H₈]²⁻ by using Cp₂MBH₃ and structurally characterized two new octaborane analogues, [(Cp₂MBH₃)₂B₈H₆] (Cp=η⁵-C₅H₅; M=Zr ( 1-Zr ) and Hf ( 1-Hf )), so that the dynamics of the B₈ skeleton were arrested. The solid-state structures of both 1-Zr and 1-Hf comprise a dodecahedron core protected by {Cp₂MBH₃} moieties on both sides of the cluster. Spectroscopic characterization (¹¹B NMR) validates the intactness of the B₈ dodecahedron core in solution as well. Theoretical calculations establish that the two exo-{Cp₂MBH₃} fragments provide structural and electronic structural stability to the B₈ core and its intact dodecahedral dianionic nature. Furthermore, we propose isodesmic equations for the formation of higher analogues of the B_n core (n>8) guarded by different group 4 transition metals. Our analysis suggests that, as we move to higher polyhedra (n>10), the formation becomes unfavourable irrespective of metal.     

Chemoenzymatic Synthesis of (R) - and (S) - Atenolol and Propranolol employing Lipase Catalyzed Enantioselective Esterification and Hydrolysis

Chemoenzymatic synthesis of (R) - and (S) - atenolol and propranolol employing lipase catalyzed enantioselective esterification and hydrolysis is described     

Heat transfer in a visco-elastic fluid past a stretching sheet with viscous dissipation and internal heat generation

This paper deals with the study of heat transfer characteristics in the laminar boundary layer flow of a visco-elastic fluid over a linearly stretching continuous surface with variable wall temperature subjected to suction or blowing. The study considers the effects of frictional heating (viscous dissipation) and internal heat generation or absorption. An analysis has been carried out for two different cases of heating processes namely: (i) Prescribed surface temperature (PST) and (ii) Prescribed wall heat flux (PHF) to get the effect of visco-elastic parameter for various situations. Further increase of visco-elastic parameter is to decrease the skin friction on the sheet. The solutions for the temperature and the heat transfer characteristics are obtained in terms of Kummers function. Received: June 16, 2004; revised: February 8, 2005     

Formal synthesis of (±)-camptothecin via tricyclic lactone as key synthon

Formal synthesis of (±)-camptothecin via CDE tricyclic lactone employing tandem Michael addition, Dieckmann condensation and addition-elimination reaction as key steps starting from glycinate is described.     

Colossal magnetoresistance in La0.7Ca0.3−xHgxMnO3 (0⩽x⩽0.2) system over wide temperature range

The divalent substitutions in rare-earth manganites create quenched disorders; those are responsible for the modification of magnetoelectronic properties through competition of two phases. In this regards, the substitution of divalent Hg is rarely studied. Here, we present the results on effect of Hg²⁺ substitution in LCMO manganites. We have synthesized polycrystalline samples with nominal compositions La_0.7Ca_0.3?xHg_xMnO₃ (0?x?0.2) by the standard solid-state reaction method. The X-ray diffraction data revealed monophasic nature without a signature of Hg related or any other impurity phase. The ac susceptibility measurement showed variation in the magnetic transition temperature as well as the transition width. The electrical resistivity measurement showed variation in metal-insulator transition temperature. The magnetoresistance (MR) measurements were carried out at 5 T magnetic field. The samples show varying magnitude of magnetoresistance as high as 74.48%. The distinct feature seen with Hg substitution is the increase in the magnitude of MR and temperature range over which MR value is sustained. It also improves the microstructure of the samples.