Polymerization of methyl methacrylate by charge-transfer mechanism with aliphatic primary amines and carbon tetrachloride

Polymerization of methyl methacrylate (MMA) with aliphatic primary amines and carbon tetrachloride has been investigated in th dimethylsulfoxide medium by employing a dilatometric technique at 60°C. The rate of polymerization (R_p) has been evaluated under the conditions, [CCl₄]/[amine] < 1 and > 1. The kinetic data indicate possible participation of the charge transfer complexes formed between the amine + CCl₄ and the amine + MMA in the polymerization of MMA. In the absence of CCl₄ or amine, no polymerization of MMA was observed under the present experimental conditions. The polymerization of MMA was inhibited by hydroquinone, indicating a free radical initiation. The energy of activation varied from 32 to 58 kJ mol^?1.     

Virtual Screening for Potential Phytobioactives as Therapeutic Leads to Inhibit NQO1 for Selective Anticancer Therapy

NAD(P)H:quinone acceptor oxidoreductase-1 (NQO1) is a ubiquitous flavin adenine dinucleotide-dependent flavoprotein that promotes obligatory two-electron reductions of quinones, quinonimines, nitroaromatics, and azo dyes. NQO1 is a multifunctional antioxidant enzyme whose expression and deletion are linked to reduced and increased oxidative stress susceptibilities. NQO1 acts as both a tumor suppressor and tumor promoter; thus, the inhibition of NQO1 results in less tumor burden. In addition, the high expression of NQO1 is associated with a shorter survival time of cancer patients. Inhibiting NQO1 also enables certain anticancer agents to evade the detoxification process. In this study, a series of phytobioactives were screened based on their chemical classes such as coumarins, flavonoids, and triterpenoids for their action on NQO1. The in silico evaluations were conducted using PyRx virtual screening tools, where the flavone compound, Orientin showed a better binding affinity score of −8.18 when compared with standard inhibitor Dicumarol with favorable ADME properties. An MD simulation study found that the Orientin binding to NQO1 away from the substrate-binding site induces a potential conformational change in the substrate-binding site, thereby inhibiting substrate accessibility towards the FAD-binding domain. Furthermore, with this computational approach we are offering a scope for validation of the new therapeutic components for their in vitro and in vivo efficacy against NQO1.     

Copper(II) complexes of acid amide derivatives of 2-aminopyridineand an exogenous ligand

The bidentate ligands, 2-[(N-acetyl)aminopyridine] (AAPH, A) and 2-[(N-benzoyl)aminopyridine] (BAPH, B) have been used to synthesize copper(II) complexes including an exogenous ligand X (X = AcO^–, HCO₂ ^–, N₃ ^– and benzimidazole). The complexes were characterized by elemental analysis, electronic and vibrational spectroscopy, magnetic and e.s.r. studies. E.s.r. parameters and visible spectra indicated that all the complexes are monomers and exist in distorted octahedral geometry except for benzimidazole. With benzimidazole as an exogenous ligand, a five coordinate complex is formed.     

An efficient diethyl ether-based soxhlet protocol to quantify faecal sterols from catchment waters

A study was conducted to evaluate the efficiency and reproducibility of a diethyl ether-based soxhlet extraction procedure for faecal sterols occurring from catchment waters. Water samples spiked with a mixture of faecal sterols were filtered and analytes were extracted using the diethyl ether-based soxhlet method and the Bligh and Dyer chloroform extraction process. For diethyl ether-based soxhlet extraction procedure, solvent extracts were saponified with 100 microL of 10% KOH in methanol (100 degrees C/120 min) and then acidified with 60 microL of 6M HCl. Lipid contents were extracted by ethanol (0.5 mL) from the saponification products. The lipid extracts were then reacted with 100 microL of bis(trimethyl)trifluoroacetamide (BSTFA) containing 1% trimethyl chlorosilane (100 degrees C/60 min) to form the trimethylsilyl (TMS) derivatives. The derivatised extracts were then analyzed by gas chromatography-mass spectrometry. For sterol concentrations ranging from 35 to 175 microg mL(-1), the soxhlet-based extraction process yielded the following recovery efficiencies for coprostanol (101%), epicoprostanol (97%), cholesterol (97%), dihydrocholesterol (97%) and 5alpha-cholestane (111%), whereas the Bligh and Dyer process yielded recoveries of 32, 41, 0, 36 and 51%, respectively. The results suggested that the diethyl ether-based soxhlet extraction method was more efficient and reproducible than the Bligh and Dyer chloroform extraction process for the analyses of trace levels of faecal sterols from water samples. Moreover, it was revealed that the diethyl ether-based soxhlet extraction method used less solvent and was logistically easier.     

Spectroscopic study of overtone and combination bands in aliphatic aldehydes

Overtone spectra of C–H stretching vibrations of formaldehyde, acetaldehyde and n-butyraldehyde have been studied in liquid phase using conventional absorption and thermal lens techniques. The overtone bands up to Δν = 4 have been monitored using the conventional IR and NIR techniques and the band involving Δν = 7 of the C–H stretching vibration with thermal lens technique. The vibrational frequencies and the anharmonicity constants for C–H stretching vibrations of the methyl as well as of the aldehyde groups for all the three molecules have been determined using these data. We have also calculated the vibrational frequencies of fundamental bands and charge distribution on carbon and hydrogen atoms using ab initio methods and the results are compared with the experimental data.     

Effect of injecting electrodes on TSD behaviour of vacuum deposited PVF films

Depolarization behaviour of vacuum deposited polyvinyl fluoride (PVF) films has been studied as a function of nature of the electrode materials used during polarization such as copper, silver, aluminium and indium using the thermally stimulated discharge current (TSD) technique. TSD spectra of these films show a single relaxation peak centered around 430 ± 1 K with activation energies of ∼ 0.65 eV. The peak current and the charge associated with the relaxation peak depend strongly on the electrode material used. This has been attributed to the electrode-polymer interface barrier controlling the injection of the charge carriers into PVF films that results into space charge effects by subsequent trapping of the injected charge carriers at macroscopic distances. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Probability distribution for the number of cycles between successive regime transitions for the Lorenz model

The Lorenz model has been widely used for exploring many real world problems. In this paper we obtain, with the help of an invariant manifold technique, the return map for the maximum value of the variable x of the model and use this return map to derive the simple, empirically obtained, regime transition rules for forecasting regime changes and length in the new regime for the model. The probability distribution for number of cycles between successive regime transitions of the Lorenz model may be of interest in many disciplines. We apply the Perron-Frobenius algorithm over the return map to estimate the probability distribution for the number of cycles between successive regime transitions. These probabilities are also estimated for the forced Lorenz model, which is a conceptual model to explore the effects of sea surface temperature on seasonal rainfall.     

Thermal stresses in an elastic sphere containing a penny-shaped crack

Zusammenfassung Es wird der Spannungszustand in einer elastischen Kugel untersucht, die im Zentrum einen münzenförmigen Riss mit konstanter Oberflächentemperatur besitzt, während die sphärische Oberfläche auf der Temperatur null gehalten wird. Dabei wird angenommen, dass an der Oberfläche a) die Schubspannung und die radiale Verschiebung, b) die Normalspannung und die Schubspannung null sind.

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This work was supported by a C.S.I.R. grant No. 3(277)/69-GAU-II.     

Structure of poly(methyl methacrylate) chains adsorbed on sapphire probed using infrared-visible sum frequency generation spectroscopy

We have studied the orientation of the train segments of a poly(methyl methacrylate) (PMMA) adsorbed layer at the CCl4-sapphire interface using surface-sensitive IR-visible sum frequency generation (SFG) spectroscopy. The SFG spectra of PMMA chains adsorbed on sapphire indicate ordered ester methyl groups. In comparison, we did not observe any significant contributions from the backbone methylene and alpha methyl groups, suggesting that these groups are disordered. No change in the structure of the adsorbed layer is observed upon cooling the solvent below the theta temperature; this is consistent with the picture of flat adsorbed chains on the surface. Interestingly, the orientation of the ester methyl groups of a spin-coated PMMA film at the PMMA-sapphire interface is similar to that of the same groups in the chains adsorbed from solution.