Two Novel Heterometallic Chains Featuring Mn-II and Na-I Ions in Trigonal-Prismatic Geometries Alternately Linked to Octahedral Mn-IV Ions: Synthesis, Structures, and Magnetic Behavior

Two new one-dimensional heterometallic complexes, Mn3Na(L)(4)(CH3CO2)(MeOH)(2)]-(ClO4)(2)center dot 3H(2)O (1), Mn3Na(L)(4)(CH3CH2CO2)-(MeOH)(2)](ClO4)(2)center dot 2MeOH center dot H2O (2) LH2 = 2-methyl-2-(2-pyridyl)propane-1,3-diol], have been synthesized and characterized by X-ray crystallography. Both complexes feature Mn-II and Na-I ions in trigonal-prismatic geometries that are linked to octahedral Mn-IV ions by alkoxy bridges. Variable-temperature direct- and alternating-current magnetic susceptibility data indicated a spin ground state of S = 11/2 for both complexes. Density functional theory calculations performed on 1 supported this conclusion.

A novel oxidative transformation of alcohols to nitriles: an efficient utility of azides as a nitrogen source

An efficient methodology to oxidize benzylic and cinnamyl alcohols to their corresponding nitriles in excellent yields has been developed. This methodology employs DDQ as an oxidant and TMSN3 as a source of nitrogen in the presence of a catalytic amount of Cu(ClO4)(2)center dot 6H(2)O.

Novel Radiation-Induced Properties of Graphene and Related Materials

Interaction of graphene, graphene oxide, and related nanocarbons with radiation gives rise to many novel properties and phenomena. Irradiation of graphene oxide in solid state or in solution by sunlight, UV radiation, or excimer laser radiation reduces it to graphene with negligible oxygen functionalities on the surface. This transformation can be exploited for nanopatterning and for large scale production of reduced graphene oxide (RGO). Laser-induced dehydrogenation of hydrogenated graphene can also be used for this purpose. All such laser-induced transformations are associated with thermal effects. RGO emits blue light on UV excitation, a feature that can be used to generate white light in combination with a yellow emitter. RGO as well as graphene nanoribbons are excellent detectors of infra-red radiation while RGO is a good UV detector.

A Novel Property of DNA - As a Bioflotation Reagent in Mineral Processing

Environmental concerns regarding the use of certain chemicals in the froth flotation of minerals have led investigators to explore biological entities as potential substitutes for the reagents in vogue. Despite the fact that several microorganisms have been used for the separation of a variety of mineral systems, a detailed characterization of the biochemical molecules involved therein has not been reported so far. In this investigation, the selective flotation of sphalerite from a sphalerite-galena mineral mixture has been achieved using the cellular components of Bacillus species. The key constituent primarily responsible for the flotation of sphalerite has been identified as DNA, which functions as a bio-collector. Furthermore, using reconstitution studies, the obligatory need for the presence of non-DNA components as bio-depressants for galena has been demonstrated. A probable model involving these entities in the selective flotation of sphalerite from the mineral mixture has been discussed.

Synthesis of benzofuran based 1,3,5-substituted pyrazole derivatives: As a new class of potent antioxidants and antimicrobials-A novel accost to amend biocompatibility

In search for a new antioxidant and antimicrobial agent with improved potency, we synthesized a series of benzofuran based 1,3,5-substituted pyrazole analogues (5a-l) in five step reaction. Initially, o-alkyl derivative of salicyaldehyde readily furnish corresponding 2-acetyl benzofuran 2 in good yield, on treatment with 1,8-diaza bicyclo5.4.0]undec-7-ene (DBU) in the presence of molecular sieves. Further, aldol condensation with vanillin, Claisen-Schmidt condensation reaction with hydrazine hydrate followed by coupling of substituted anilines afforded target compounds. The structures of newly synthesized compounds were confirmed by IR, H-1 NMR, C-13 NMR, mass, elemental analysis and further screened for their antioxidant and antimicrobial activities. Among the tested compounds 5d and 5f exhibited good antioxidant property with 50% inhibitory concentration higher than that of reference while compounds 5h and 5l exhibited good antimicrobial activity at concentration 1.0 and 0.5 mg/mL compared with standard, streptomycin and fluconazole respectively. (C) 2012 Elsevier Ltd. All rights reserved.

Novel De-Acylative Ring Opening of 3-Acetyl and 3-Bromo Acetyl Coumarins

Reaction of 3-acetyl and 3-bromoacetyl coumarins with hydrazine hydrate has resulted in the ring opening of the coumarin moiety. The reaction was attempted with a view to obtain some new pyridazinones and pyrazolones. The reaction did not proceed via the expected pathway instead led to the formation of salicyl azines, the structure of which has been confirmed by single crystal X-ray studies.

Novel Levamisole Derivative Induces Extrinsic Pathway of Apoptosis in Cancer Cells and Inhibits Tumor Progression in Mice

Background: Levamisole, an imidazo(2,1-b) thiazole derivative, has been reported to be a potential antitumor agent. In the present study, we have investigated the mechanism of action of one of the recently identified analogues, 4a (2-benzyl-6-(4'-fluorophenyl)-5-thiocyanato-imidazo2,1-b]1,3,4]thi adiazole). Materials and Methods: ROS production and expression of various apoptotic proteins were measured following 4a treatment in leukemia cell lines. Tumor animal models were used to evaluate the effect of 4a in comparison with Levamisole on progression of breast adenocarcinoma and survival. Immunohistochemistry and western blotting studies were performed to understand the mechanism of 4a action both ex vivo and in vivo. Results: We have determined the IC50 value of 4a in many leukemic and breast cancer cell lines and found CEM cells most sensitive (IC50 5 mu M). Results showed that 4a treatment leads to the accumulation of ROS. Western blot analysis showed upregulation of pro-apoptotic proteins t-BID and BAX, upon treatment with 4a. Besides, dose-dependent activation of p53 along with FAS, FAS-L, and cleavage of CASPASE-8 suggest that it induces death receptor mediated apoptotic pathway in CEM cells. More importantly, we observed a reduction in tumor growth and significant increase in survival upon oral administration of 4a (20 mg/kg, six doses) in mice. In comparison, 4a was found to be more potent than its parental analogue Levamisole based on both ex vivo and in vivo studies. Further, immunohistochemistry and western blotting studies indicate that 4a treatment led to abrogation of tumor cell proliferation and activation of apoptosis by the extrinsic pathway even in animal models. Conclusion: Thus, our results suggest that 4a could be used as a potent chemotherapeutic agent.

A Novel Fiber Bragg Grating Based Sensing Methodology for Direct Measurement of Surface Strain on Body Muscles during Physical Exercises

The present work proposes a new sensing methodology, which uses Fiber Bragg Gratings (FBGs) to measure in vivo the surface strain and strain rate on calf muscles while performing certain exercises. Two simple exercises, namely ankle dorsi-flexion and ankle plantar-flexion, have been considered and the strain induced on the medial head of the gastrocnemius muscle while performing these exercises has been monitored. The real time strain generated has been recorded and the results are compared with those obtained using a commercial Color Doppler Ultrasound (CDU) system. It is found that the proposed sensing methodology is promising for surface strain measurements in biomechanical applications.

Novel tetranuclear distorted open-cubane copper complex containing oximate bridges: Synthesis, crystal structure, DNA binding and cleavage activity

The synthesis, molecular structure, DNA binding and nuclease activity of Cu4O4 open-cubane tetranuclear copper(II) complex with 3-2-(ethyl amino)ethyl]imino]-2-butanoneoxime (HL) are reported for the first time. The neutral tetranuclear Cu4L4(ClO4)(4)] complex crystallizes in tetragonal space group P (4) over bar2(1)c with the unit cell parameters; a = 13.798(4) angstrom, b = 13.798(4) angstrom, c = 14.119(6) angstrom, V = 2688(16) angstrom(3), Z = 8, R = 0.0636. Symmetrically equivalent copper atoms exhibit a CuN3O3 elongated distorted octahedral coordination environment, with three nitrogen atoms of the L ligand and one oxime-oxygen atom of second L ligand at equatorial positions, one oxime-oxygen atom of the third L ligand and perchlorate oxygen at axial positions. The complex shows quasireversible cyclic voltammetric response at 0.805 V (Delta E-p = 277 mV) at 100 mV s (1) in DMF for the Cu(II)/Cu(I) redox couple. The binding study of the complex with calf-thymus DNA has been investigated using absorption spectrophotometry. The complex shows strong nuclease activity on stranded pBR 322 plasmid DNA in the presence of hydrogen peroxide and marginal nuclease activity in the presence of reducing agent (dithiothreitol). (C) 2012 Elsevier B. V. All rights reserved.

Crystallographic Study of Novel Transthyretin Ligands Exhibiting Negative-Cooperativity between Two Thyroxine Binding Sites

Background: Transthyretin (TTR) is a homotetrameric serum and cerebrospinal fluid protein that transports thyroxine (T4) and retinol by binding to retinol binding protein. Rate-limiting tetramer dissociation and rapid monomer misfolding and disassembly of TTR lead to amyloid fibril formation in different tissues causing various amyloid diseases. Based on the current understanding of the pathogenesis of TTR amyloidosis, it is considered that the inhibition of amyloid fibril formation by stabilization of TTR in native tetrameric form is a viable approach for the treatment of TTR amyloidosis. Methodology and Principal Findings: We have examined interactions of the wtTTR with a series of compounds containing various substitutions at biphenyl ether skeleton and a novel compound, previously evaluated for binding and inhibiting tetramer dissociation, by x-ray crystallographic approach. High resolution crystal structures of five ligands in complex with wtTTR provided snapshots of negatively cooperative binding of ligands in two T4 binding sites besides characterizing their binding orientations, conformations, and interactions with binding site residues. In all complexes, the ligand has better fit and more potent interactions in first T4 site i.e. (AC site) than the second T4 site (BD site). Together, these results suggest that AC site is a preferred ligand binding site and retention of ordered water molecules between the dimer interfaces further stabilizes the tetramer by bridging a hydrogen bond interaction between Ser117 and its symmetric copy. Conclusion: Novel biphenyl ether based compounds exhibit negative-cooperativity while binding to two T4 sites which suggests that binding of only single ligand molecule is sufficient to inhibit the TTR tetramer dissociation.

High-temperature kinetics of the reaction between CN and hydrocarbons using a novel high-enthalpy flow tube

More than 70 molecules of varied nature have been identified in the envelopes of carbon-rich stars through their spectral fingerprints in the microwave or far infrared regions. Many of them are carbon chain molecules and radicals, and a significant number are unique to the circumstellar medium. The determination of relevant laboratory kinetics data is critical to keep up with the development of the high spectral and spatial resolution observations and of the refinement of chemical models. Neutralneutral reactions of the CN radical with unsaturated hydrocarbons could be a dominant route in the formation of cyanopolyynes, even at low temperatures and deserve a detailed laboratory investigation. The approach we have developed aims to bridge the temperature gap between resistively heated flow tubes and shock tubes. The present kinetic measurements are obtained using a new reactor combining a high-enthalpy source with a flow tube and a pulsed laser photolysislaser-induced fluorescence system to probe the undergoing chemical reactions. The high-enthalpy flow tube has been used to measure the rate constant of the reaction of the CN radical with propane (C3H8), propene (C3H6), allene (C3H4), 1,3-butadiene (1,3-C4H6), and 1-butyne (C4H6) over a temperature range extending from 300 to 1200 K. All studied reactions of CN with unsaturated hydrocarbons are rapid, with rate coefficients greater than 10-10 cm3 center dot molecule-1 center dot s-1 and exhibit slight negative temperature dependence above room temperature. (c) 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 753766, 2012

Novel ATPase activity of the polyprotein intermediate, Viral Protein genome-linked-Nuclear Inclusion-a protease, of Pepper vein banding potyvirus

Potyviruses temporally regulate their protein function by polyprotein processing. Previous studies have shown that VPg (Viral Protein genome-linked) of Pepper vein banding virus interacts with the NIa-Pro (Nuclear Inclusion-a protease) domain, and modulates the kinetics of the protease. In the present study, we report for the first time that VPg harbors the Walker motifs A and B, and the presence of NIa-Pro, especially in cis (cleavage site (E191A) VPg-Pro mutant), is essential for manifestation of the ATPase activity. Mutation of Lys47 (Walker motif A) and Asp88:Glu89 (Walker motif B) to alanine in E191A VPg-Pro lead to reduced ATPase activity, confirming that this activity was inherent to VPg. We propose that potyviral VPg, established as an intrinsically disordered domain, undergoes plausible structural alterations upon interaction with globular NIa-Pro which induces the ATPase activity. (C) 2012 Elsevier Inc. All rights reserved.

Stabilization and Structural Alteration of the G-Quadruplex DNA Made from the Human Telomeric Repeat Mediated by Troger's Base Based Novel Benzimidazole Derivatives

Ligand-induced stabilization of the G-quadruplex DNA structure derived from the single-stranded 3'-overhang of the telomeric DNA is an attractive strategy for the inhibition of the telomerase activity. The agents that can induce/stabilize a DNA sequence into a G-quadruplex structure are therefore potential anticancer drugs. Herein we present the first report of the interactions of two novel bisbenzimidazoles (TBBz1 and TBBz2) based on Troger's base skeleton with the G-quadruplex DNA (G4DNA). These Troger's base molecules stabilize the G4DNA derived from a human telomeric sequence. Evidence of their strong interaction with the G4DNA has been obtained from CD spectroscopy, thermal denaturation, and UV-vis titration studies. These ligands also possess significantly higher affinity toward the G4DNA over the duplex DNA. The above results obtained are in excellent agreement with the biological activity, measured in vitro using a modified TRAP assay. Furthermore, the ligands are selectively more cytotoxic toward the cancerous cells than the corresponding noncancerous cells. Computational studies suggested that the adaptive scaffold might allow these ligands to occupy not only the G-quartet planes but also the grooves of the G4DNA.

A novel gas flow sensing application using piezoelectric ZnO thin films deposited on Phynox alloy

We report on the novel flow sensing application of piezoelectric ZnO thin film deposited on Phynox alloy sensing element. Characterization of piezoelectric ZnO films deposited on Phynox (Elgiloy) substrate at different RF powers is discussed. ZnO films deposited at RF power of 100W were found to have fine c-axis orientation, possesses excellent surface morphology with lower rms surface roughness of 1.87 nm and maximum d(31) coefficient value 4.7 pm V-1. The thin cantilever strip of Phynox alloy with ZnO film as a sensing layer for flow sensing has been tested for flow rates ranging from 2 to 18 L min(-1). A detailed theoretical analysis of the experimental set-up showing the relationship between output voltage and force at a particular flow rate has been discussed. The sensitivity of now sensing element is similar to 18 mV/(L min(-1)) and typical response time is of the order of 20 m s. The sensing element is calibrated using in-house developed testing set-up. (C) 2012 Elsevier B.V. All rights reserved.

Near-infrared light-responsive graphene oxide composite multilayer capsules: a novel route for remote controlled drug delivery

A novel and simple route for near-infrared (NIR)-light controlled release of drugs has been demonstrated using graphene oxide (GO) composite microcapsules based on the unique optical properties of GO. Upon NIR-laser irradiation, the microcapsules were ruptured in a point-wise fashion due to local heating which in turn triggers the light-controlled release of the encapsulated anticancer drug doxorubicin (Dox) from these capsules.