Flame retardant polyphosphate esters: 1. Condensation polymers of bisphenols with aryl phosphorodichloridates: synthesis, characterization and thermal studies

Polyphosphate esters were synthesized by the solution polycondensation of bisphenols with aryl phosphorodichloridates. The polymers were characterized by i.r. and 1H, 13C and 31P n.m.r. spectroscopy. The molecular weights were determined by end group analysis using 1H and 31P n.m.r. spectral data. The thermal stability of the polymers was analysed by thermogravimetry.

Identification and characterization of a library of microheterogeneous cyclohexa-depsipeptides from the fungus

Ten new cyclic hexadepsipeptides, six isariins and four isaridins, from the fungus Isaria have been identified and characterized by high-performance liquid chromatography, coupled to tandem electrospray ionization mass spectrometry (LC-ESIMS/MS). The isariins possess a beta-hydroxy acid residue and five alpha-amino acids, while isaridins contain a beta-amino acid, an alpha-hydroxy acid, and four alpha-amino acids. One- and two-dimensional NMR spectroscopy confirmed the chemical identity of some of the isariin fractions. Mass spectral fragmentation patterns of [M + H](+) ions reveal clear diagnostic fragment ions for the isariins and isaridins. Previously described cyclic depsipeptides, isarfelins from Isaria felina (Guo, Y. X.; Liu, Q. H.; Ng, T. B.; Wang H. X. Peptides 2005, 26, 2384), are now reassigned as members of the isaridin family. Examination of isaridin sequences revealed significant similarities with cyclic hexadepsipeptides such as destruxins and roseotoxins. The structure of an isariin (isariin A) investigated by NMR spectroscopy indicated the presence of a hybrid alpha beta C-11 turn, formed by the beta-hydroxy acid and glycine residues and a (D)Leu-(L)Ala type II' beta-turn. Additionally, the inhibitory effect of isariins and an isaridin on the intra-erythrocytic growth of Plasmodium falciparum is presented.

Synthesis, characterization, and fire retardancy of ferrocene containing polyphosphate esters

Polyphosphate esters containing ferrocene structures were synthesized from 1,1′-bis (p-hydroxyphenylamido) ferrocene and 1,1′-bis (p-hydroxyphenoxycarbonyl) ferrocene with aryl phosphorodichloridates by interfacial polycondensation using a phase transfer catalyst. The polymers were characterized by infrared, 1H-, 13C-, and 31-NMR spectroscopy. The molecular weights were determined by end group analysis using 31P-NMR spectral data. The thermal stability and fire retardancy were respectively determined by thermogravimetry and limiting oxygen index (LOI) measurements. The polyamide-phosphate esters showed better thermal stability and higher LOI values than the polyester-phosphate esters.

Synthesis and characterization of photo-crosslinkable main-chain liquid-crystalline polymers containing bis(benzylidene)cycloalkanone units

A series of new photo-crosslinkable main-chain liquid-crystalline polymers containing bis(benzylidene)cycloalkanone units have been studied. These units in the polymers function as mesogens as well as photoactive centres. Polyesters with three different bis(4-hydroxybenzylidene)cycloalkanones corresponding to three cycloalkanones, namely cyclopentanone, cyclohexanone and cycloheptanone, have been prepared. Three dicarboxylic acids with ether linkages, which were derived from oligoethylene oxides, namely triethylene glycol, tetraethylene glycol and pentaethylene glycol, have been used as spacers in these polymers. Polymerization was carried out by both solution and interfacial polycondensation; the latter method gave high-molecular-weight polymers. Structural characterizations were done by ultra-violet, infra-red and H-1 nuclear magnetic resonance spectroscopy. Liquid-crystalline properties were studied by differential scanning calorimetry and polarized-light optical microscopy. These polymers show a nematic mesophase. Liquid-crystalline transition temperatures were correlated with polymer structure. The decrease in transition temperature with increase in cycloalkanone ring size was explained in terms of the change in geometrical anisotropy of bis(benzylidene)cycloalkanone units. MNDO (modified neglect of differential overlap) calculations were performed on the model compounds, bis(4-acetyloxybenzylidene)cycloalkanone to elucidate the geometrical variation of the mesogenic units with cycloalkanone ring size. Studies of photolysis reveal the two kinds of photoreactions that proceed in these polymer systems, namely photoisomerization and photo-crosslinking. The former reaction disrupts the parallel stacking of the chromophores and is reflected as an increase in the ultra-violet spectral intensity. The favourability of these two reactions depends on the mobility of the polymer chains. When the photolysis was done below T-g, photo-crosslinking dominates over photoisomerization. Above T-g, photoisomerization is followed by photo-crosslinking. The photosensitivity of the polymers decreases with increase in size of the cycloalkanone ring.

Synthesis and characterization of N,N'-aliphatic dicarboxylbis(hydrazones)

N,N'-Malonylbis-,N,N'-adipinylbis- and N,N'-sebacoylbis-(hydrazones) 1 of various aldehydes and ketones have been prepared and characterized by elemental analyses, melting points, and H-1 NMR and IR spectral data.

Synthesis and characterization of some new dimesogenic compounds

We have synthesized four different types of dimesogenic compounds involving the cholesteryl moiety as one of the mesogenic constituents, and have investigated their liquid crystalline properties. The molecular structures of these dimesogens have been confirmed by spectral analyses; they exhibit a rich polymorphism, as revealed by optical microscopic and differential scanning calorimetric observations. The studies show that the mesomorphic behaviour is sensitive to the nature of the terminal alkyl chains, and to the structure of the 'second mesogen' that is attached to the cholesteryl unit through a polymethylene spacer.

Synthesis, structural characterization, thermal studies and chain dynamics of poly(methacrylonitrile peroxide) by NMR spectroscopy

Poly(methacrylonitrile peroxide) (PMNP) has been synthesized from methacrylonitrile by free radical initiated oxidative polymerization and characterized by different spectroscopic methods. NMR spectroscopy confirmed the alternating copolymer structure with labile peroxy bonds in the main chain. The extreme instability of PMNP was noted from FTIR spectroscopy. Thermal degradation studies by using differential scanning calorimetry and thermogravimetry have revealed that PMNP degrades highly exothermically and the heat of degradation, 42.5 kcal mol−1, is of the same order as that reported for other vinyl polyperoxides. Mass spectral fragmentation pattern under electron impact (EI) condition has also been investigated. The mechanism of the primary exothermic degradation has been substantiated by thermochemical calculations. The chain dynamics of the polyperoxide chain has been studied by means of 13C spin–lattice relaxation times (T1) of the main chain as well as the side chain carbons. The temperature dependence of the spin–lattice relaxation times shows that the PMNP is more flexible compared to the analogous poly(styrene peroxide).

Synthesis of electrically conducting copolymers of o-/m-toluidines and o-/m-amino benzoic acid in an organic peroxide system and their characterization

Copolymers of o-lm-toluidine with o-lm-amino benzoic acid have been synthesized by chemical polymerization using inverse emulsion pathway and characterized by a number of techniques including UV-Vis, FT-IR, FT Raman, EPR and NMR spectroscopies, thermal analysis and conductivity. The solubility of the copolymers in organic solvents increases with increase in the amount of amino benzoic acid in the feed. The copolymers synthesized at room temperature show relatively higher conductivity and are obtained in higher yield compared to those synthesized at 0 and 60 degreesC. The spectral studies have revealed restricted conjugation along the polymer chain. The effect of -COOH substituent on the copolymer structure is discussed. (C) 2003 Elsevier Science B.V All rights reserved.

Site Characterization of Bangalore using Geophysical Method

A number of geophysical methods have been proposed for near-surface site characterization and measurement of shear wave velocity by using a great variety of testing configurations, processing techniques,and inversion algorithms. In particular, two widely-used techniques are SASW (Spectral Analysis of SurfaceWaves) and MASW (Multichannel Analysis of SurfaceWaves). MASW is increasingly being applied to earthquake geotechnical engineering for the local site characterization, microzonation and site response studies.A MASW is a geophysical method, which generates a shear-wave velocity (Vs) profile (i.e., Vs versus depth)by analyzing Raleigh-type surface waves on a multichannel record. MASW system consisting of 24 channels Geode seismograph with 24 geophones of 4.5 Hz frequency have been used in this investigation. For the site characterization program, the MASW field experiments consisting of 58 one-dimensional shear wave velocity tests and 20 two-dimensional shear wave tests have been carried out. The survey points have been selected in such a way that the results supposedly represent the whole metropolitan Bangalore having an area of 220 km2.The average shear wave velocity of Bangalore soils have been evaluated for depths of 5m, 10m, 15m, 20m, 25m and 30 m. The subsoil site classification has been made for seismic local site effect evaluation based on average shear wave velocity of 30m depth (Vs30) of sites using National Earthquake Hazards Reduction Program (NEHRP) and International Building Code (IBC) classification. Soil average shearwave velocity estimated based on overburden thickness from the borehole information is also presented. Mapping clearly indicates that the depth of soil obtained from MASW is closely matching with the soil layers in bore logs. Among total 55 locations of MASW survey carried out, 34 locations were very close to the SPT borehole locations and these are used to generate correlation between Vs and corrected “N” values. The SPT field “N” values are corrected by applying the NEHRP recommended corrections.

Phase Characterization and Study of Molecular Order of a Three-Ring Mesogen by (13)C NMR in Smectic C and Nematic Phases

Molecules exhibiting a thermotropic liquid-crystalline property have acquired significant importance due to their sensitivity to external stimuli such as temperature, mechanical forces, and electric and magnetic fields. As a result, several novel mesogens have been synthesized by the introduction of various functional groups in the vicinity of the aromatic core as well as in the side chains and their properties have been studied. In the present study, we report three-ring mesogens with hydroxyl groups at one terminal. These mesogens were synthesized by a multistep route, and structural characterization was accomplished by spectral techniques. The mesophase properties were studied by hot-stage optical polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. An enantiotropic nematic phase was noticed for lower homologues, while an additional smectic C phase was found for higher homologues. Solid-state high-resolution natural abundance (13)C NMR studies of a typical mesogen in the solid phase and in the mesophases have been carried out. The (13)C NMR spectrum of the mesogen in the smectic C and nematic phases indicated spontaneous alignment of the molecule in the magnetic field. By utilizing the two-dimensional separated local field (SLF) NMR experiment known as SAMPI4, (13)C-(1)H dipolar couplings have been obtained, which were utilized to determine the orientational order parameters of the mesogen.

Characterization of Major Zinc Containing Myonecrotic and Procoagulant Metalloprotease `Malabarin' from Non Lethal Trimeresurus malabaricus Snake Venom with Thrombin Like Activity: Its Neutralization by Chelating Agents

A major myonecrotic zinc containing metalloprotease `malabarin' with thrombin like activity was purified by the combination of gel permeation and anion exchange chromatography from T. malabaricus snake venom. MALDI-TOF analysis of malabarin indicated a molecular mass of 45.76 kDa and its N-terminal sequence was found to be Ile-Ile-Leu-Pro(Leu)-Ile-Gly-Val-Ile-Leu(Glu)-Thr-Thr. Atomic absorption spectral analysis of malabarin raveled the association of zinc metal ion. Malabarin is not lethal when injected i.p. or i.m. but causes extensive hemorrhage and degradation of muscle tissue within 24 hours. Sections of muscle tissue under light microscope revealed hemorrhage and congestion of blood vessel during initial stage followed by extensive muscle fiber necrosis with elevated levels of serum creatine kinase and lactate dehydrogenase activity. Malabarin also exhibited strong procoagulant action and its procoagulant action is due to thrombin like activity; it hydrolyzes fibrinogen to form fibrin clot. The enzyme preferentially hydrolyzes A alpha followed by B beta subunits of fibrinogen from the N-terminal region and the released products were identified as fibrinopeptide A and fibrinopeptide B by MALDI. The myonecrotic, fibrinogenolytic and subsequent procoagulant activities of malabarin was neutralized by specific metalloprotease inhibitors such as EDTA, EGTA and 1, 10-phenanthroline but not by PMSF a specific serine protease inhibitor. Since there is no antivenom available to neutralize local toxicity caused by T. malabaricus snakebite, EDTA chelation therapy may have more clinical relevance over conventional treatment.

Spectroscopic Characterization and Modeling of Quadrupolar Charge-Transfer Dyes with Bulky Substituents

Joint experimental and theoretical work is presented on two quadrupolar D-pi-A-pi-D chromophores characterized by the same bulky donor (D) group and two different central cores. The first chromophore, a newly synthesized species with a malononitrile-based acceptor (A) group, has a V-shaped structure that makes its absorption spectrum very broad, covering most of the visible region. The second chromophore has a squaraine-based core and therefore a linear structure, as also evinced from its absorption spectra. Both chromophores show an anomalous red shift of the absorption band upon increasing solvent polarity, a feature that is ascribed to the large, bulky structure of the moleCules. For these molecules, the basic description of polar solvation in terms of a uniform reaction field fails. Indeed, a simple extension of the model to account for two independent reaction fields associated with the two molecular arms quantitatively reproduces the observed linear absorption and fluorescence as well as fluorescence anisotropy spectra, fully rationalizing their nontrivial dependence on solvent polarity. The model derived from the analysis of linear spectra is adopted to predict nonlinear spectra and specifically hyper-Rayleigh scattering and two-photon absorption spectra. In polar solvents, the V-shaped chromophore is predicted to have a large HRS response in a wide spectral region (approximately 600-1300 nm). Anomalously large and largely solvent-dependent HRS responses for the linear chromophores are ascribed to symmetry lowering induced by polar solvation and amplified in this bulky system by the presence of two reaction fields.

Synthesis and Electrochemical Characterization of LiNi0.8Co0.2O2 as Cathode Material for Aqueous Rechargeable Lithium Batteries

LiNi0.8Co0.2O2 cathode material for lithium ion batteries is synthesized by reaction under autogenic pressure at elevated temperature (RAPET) method. The simple synthesis procedure is time and energy saving, and thus is promising for commercial application. The structure and stability of the material have been characterized by means of XRD and TG-DTA. The electrochemical properties of the LiNi0.8Co0.2O2 cathode are investigated in 2 M Li2SO4 aqueous electrolyte and they are compared to that in an organic electrolyte. A battery cell consisting of LiNi0.8Co0.2O2 as cathode in 2 M Li2SO4 solution is constructed in combination with LiTi2 (PO4)(3) as anode. The cell retained almost constant discharge capacity over hundred cycles. The electrochemical impedance spectral ( EIS) studies in aqueous and nonaqueous electrolytes revealed that the mechanism of lithium ion intercalation and deintercalation processes in LiNi0.8Co0.2O2 electrode follow almost similar mechanism in both aqueous and nonaqueous electrolytes. The chemical diffusion coefficient was calculated from slow scan rate cyclic voltammetry and EIS. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.075205jes] All rights reserved.

Ultrasonic Guided Wave Characterization and Damage Detection in Foam-core Sandwich Panel using PWAS and LDV

Lamb wave type guided wave propagation in foam core sandwich structures and detectability of damages using spectral analysis method are reported in this paper. An experimental study supported by theoretical evaluation of the guided wave characteristics is presented here that shows the applicability of Lamb wave type guided ultrasonic wave for detection of damage in foam core sandwich structures. Sandwich beam specimens were fabricated with 10 mm thick foam core and 0.3 mm thick aluminum face sheets. Thin piezoelectric patch actuators and sensors are used to excite and sense guided wave. Group velocity dispersion curves and frequency response of sensed signal are obtained experimentally. The nature of damping present in the sandwich panel is monitored by measuring the sensor signal amplitude at various different distances measured from the center of the linear phased array. Delaminations of increasing width are created and detected experimentally by pitch-catch interrogation with guided waves and wavelet transform of the sensed signal. Signal amplitudes are analyzed for various different sizes of damages to differentiate the damage size/severity. A sandwich panel is also fabricated with a planer dimension of 600 mm x 400 mm. Release film delamination is introduced during fabrication. Non-contact Laser Doppler Vibrometer (LDV) is used to scan the panel while exciting with a surface bonded piezoelectric actuator. Presence of damage is confirmed by the reflected wave fringe pattern obtained from the LDV scan. With this approach it is possible to locate and monitor the damages by tracking the wave packets scattered from the damages.

Synthesis and Characterization of a Fluorescent Analogue of Cyclic di-GMP

Cyclic di-GMP (c-di-GMP), a ubiquitous bacterial second messenger, has emerged as a key controller of several biological processes. Numbers of reports that deal with the mechanistic aspects of this second messenger have appeared in the literature. However, the lack of a reporter tag attached to the c-di-GMP at times limits the understanding of further details. In this study, we have chemically coupled N-methylisatoic anhydride (MANT) with c-di-GMP, giving rise to Mant-(c-di-GMP) or MANT-CDG. We have characterized the chemical and physical properties and spectral behavior of MANT-CDG. The fluorescence of MANT-CDG is sensitive to changes in the microenvironment, which helped us study its interaction with three different c-di-GMP binding proteins (a diguanylate cyclase, a phosphodiesterase, and a PilZ domain-containing protein). In addition, we have shown here that MANT-CDG can inhibit diguanylate cyclase activity; however, it is hydrolyzed by c-di-GMP specific phosphodiesterase. Taken together, our data suggest that MANT-CDG behaves like native c-di-GMP, and this study raises the possibility that MANT-CDG will be a valuable research tool for the in vitro characterization of c-di-GMP signaling factors.