Vibrational spectra and normal coordinate analysis of carbamoylazide

The Fourier transform Raman and infrared spectra of carbamoylazide and its deuterated derivative were recorded and the observed frequencies were assigned to various modes of vibration in terms of fundamentals and combinations by assuming C(s) point group symmetry. A normal coordinate analysis was also carried out using Simple valence force field. A complete vibrational analysis is presented here for these molecule and results are briefly discussed.     

Molecular sieves supported recyclable catalyst for atom transfer radical polymerization using hydration approach

Molecular Sieves (MS) were used as a recyclable support for atom transfer radical polymerization. The catalyst complex, CuBr₂/ligand was supported on hydrated MS and used for the polymerization of benzyl methacrylate at room temperature in anisole. The polymerization using CuBr₂/PMDETA (pentamethyl diethyltetraamine) catalyst that is physically held by the hydration of MS exhibited moderate control and produced catalyst free polymers (<0.1 ppm) with narrow molecular weight distribution (M_w/M_n ≤ 1.33). The polymerization occurred at the interface between the hydrated support and the solution containing initiator and monomer. The hydrated MS supported catalyst was recycled efficiently without a significant loss in activity. The polymerization proceeded in a “living”/controlled manner as was evident from first‐order time conversion plots. The split kinetics experiment affirmed that there was no propagation in the solution in the absence of the supported catalyst. The reaction order plot showed zero‐order dependence on the bulk initiator concentration in solution. The results of MS supported catalyst were compared to Na‐clay supported catalyst system and the improved results were attributed to high self‐diffusion coefficient and low diffusion activation energy of water on its surface. Published 2017.^§ J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3875–3883     

Synthesis and dilute solution properties of branched poly(benzyl methacrylate) using na-clay supported aqueous-phase catalysis

The supported aqueous-phase catalysis (SAPC) using hydrated interface has been used to synthesize branched polymers (star and graft) of benzyl methacrylate (BnMA) via atom-transfer radical polymerization (ATRP) in the presence of Na-clay supported catalyst in anisole at ambient temperature. The propagation of star poly(BnMA)s using diPENDTA-Br₆, as hexa-functional initiator is confined at the hydrated interface between the support and the liquid medium as evident from the obtained polymers that are catalyst contamination-free, and exhibited moderately narrow molecular weight distributions (M_w/M_n ≤ 1.33). The hexa-functionality of synthesized stars is verified by ¹H NMR, the measurement of their intrinsic viscosity ([η]), and radius of gyration (R_g). The polymerization was also recycled up to 5 times to produce star PBnMAs with high initiator efficiency. The star polymers prepared using hydrated Na-clay supported is compared with star prepared using covalent silica supported catalyst system. The star polymer obtained from covalently supported catalyst gave broad M_w/M_n and poor initiator efficiency. The polystyrene-graft-PBnMA (PS-g-PBnMA) copolymer is also prepared using hydrated Na-clay supported catalyst system in anisole at ambient temperature. The graft-copolymer had narrow M_w/M_n and was confirmed using ¹H NMR and atomic force microscopy. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2225–2237     

Development and validation of a reversed-phase HPLC method for determination of nitrendipine in rat plasma: application to pharmacokinetic studies

A simple and sensitive method for the determination of nitrendipine in rat plasma was developed using high-performance liquid chromatography (HPLC). The procedure involves extraction of nitrendipine in dichloromethane/sodium hydroxide, followed by reversed phase HPLC using a Waters, Spherisorb ODS2 (250 x 4.6 mm, 5 microm) column and UV detection at 238 nm. The retention times of nitrendipine and internal standard (felodipine) were 5.0 min and 7.5 min, respectively. The calibration curves were linear over the range of 5 ng/mL (lower limit of quantification, LOQ) to 200 ng/mL for nitrendipine. The intra- and inter-day coefficients of variation for all criteria of validation were less than 15% over the linearity range. The sensitivity and precision of the method were within the accepted limits (< 15%) throughout the validation period. The present method was also successfully applied for the study of plasma pharmacokinetics of nitrendipine loaded solid lipid nanoparticles (SLN) in rats.     

Thermal degradation of pentaerythritol phosphate alcohol

Intumescent material, 2,6,7-trioxa-1-phosphabicyclo-[2,2,2]-octane-4-methanol phosphate (PEPA), is synthesized and characterized using FTIR, ¹HNMR and ¹³CNMR. The degradation properties of PEPA are studied by employing TG and TG?CMS technique. The activation energies for the degradation process of PEPA are calculated by using TG curves obtained from multiple heating rates (Friedman, Kissinger?CAkahira?CSunose and Flynn?CWall?COzawa methods). The degradation that is occurring in the temperature region 307?C366?°C has the highest activation energy. Eventhough the calculated activation energies for the degradation differ depending on the approximation method employed, the trend in variation of activation energy for degradation is similar. Single ion monitoring technique proved the evolution of H₂O, CO/C₂H₄, HCHO, C₂H₅OH/HCOOH and trace amounts of C₂H₇O₃P and C₄H₉O₄P from the degrading PEPA. The thermal conductivity and stability of the char formed during the TG analysis are also discussed.     

Colossal magnetoresistance by avoiding a ferromagnetic state in the Mott system Ca3Ru2O7

Transport and magnetic studies of Ca3Ru2O7 for temperatures ranging from 0.4 to 56 K and magnetic fields B up to 45 T lead to strikingly different behavior when the field is applied along the different crystal axes. A ferromagnetic (FM) state with full spin polarization is achieved for the B//a axis, but colossal magnetoresistance is realized only for the B//b axis. For the B//c axis, Shubnikov-de Haas oscillations are observed and followed by a less resistive state than that for B//a. Hence, in contrast with standard colossal magnetoresistive materials, the FM phase is the least favorable for electron hopping. These properties together with highly unusual spin-charge-lattice coupling near the Mott transition (48 K) are driven by the orbital degrees of freedom.     

Investigation of the thermal degradation of alkyl isocyanate polymers by direct pyrolysis mass spectrometry

Thermal degradation mechanisms of alkyl isocyanate homo- and copolymers were studied using TGA and DP–MS. Both analyses showed that these polymers begin decomposing at around 190°C under inert or vacuum conditions. DP–MS analysis showed the formation of trace quantities of monomer from poly(butyl isocyanate) only and none from higher homologs. All polymers studied produced trimers as their principal decomposition product, implying that intramolecular cyclization is the dominant mechanism of decomposition.     

Grafting Efficiency of Hydroxy‐Terminated Poly(methyl methacrylate) with Multiwalled Carbon Nanotubes

Summary: Poly(methyl methacrylate)s (PMMAs) containing a terminal hydroxy group or multiple hydroxy groups as pendants were grafted to multiwalled carbon nanotubes (MWNTs) by esterification in toluene at 100 °C. The recovered polymer with a low level of MWNTs and the PMMA‐g‐MWNTs with up to 12 wt.‐% grafted polymer were characterized using spectroscopic, microscopic, and thermogravimetric analyses. The percentage of polymer present in the PMMA‐g‐MWNT samples is very low based upon the concentration of the acid groups in the tubes.

The grafting of hydroxy‐terminated PMMA to MWNTs by esterification.     

Copper Catalyzed ATRP of Methyl Methacrylate Using Aliphatic α-Bromo Ketone Initiator

The atom transfer radical polymerization (ATRP) of MMA was examined using 3-bromo-3-methyl-butanone-2 (MBB) as an initiator in the presence of CuBr as catalyst and 2,6-bis[1-(2,6-diisopropylphenylimino)ethyl]pyridine (BPIEP) as a tridentate N-donor ligand. The effect of various other N-donor ligands including a bisoxazoline ligand, namely, 2,6-bis(4,4-dimethyl-2-oxazolin-2-yl) pyridine (dmPYBOX) was studied in ATRP and reverse ATRP of MMA. The ATRP of MMA in toluene at 90 °C using MBB as initiator was relatively slow in the case of bidentate and faster in the case of tridentate N-donor ligands. The apparent rate constant, k_app, with MBB as initiator and BPIEP as ligand in toluene (50%, v/v) at 90 °C was found to be 7.15 × 10⁻⁵ s⁻¹. In addition, reverse ATRP of MMA in diphenylether at 70 °C using BPIEP/CuBr₂ as catalyst system was very effective in reducing the reaction time from several hours to 24 h for polymerization of MMA.