Kinetic analysis of co-pyrolysis of cellulose and polypropylene

The present research work focuses on understanding the kinetics and mechanism of co-pyrolysis of cellulose, a major constituent of biomass, and polypropylene (PP) that is abundantly present in waste plastics. Co-pyrolysis of cellulose and PP of different compositions, viz., 100:0, 80:20, 60:40, 40:60, 20:80, and 0:100 (mass%/mass%), was carried out in a thermogravimetric analyzer at various heating rates from 5 to 180 K min^?1. The kinetics of slow to medium heating rate pyrolysis was analyzed using first Kissinger and Kissinger–Akahira–Sunose techniques. Cellulose and PP decomposition occurred in two distinct temperature regimes, viz., 575–650 and 675–775 K, respectively. However, apparent activation energies of thermal decomposition of the mixtures clearly indicated the presence of interaction between cellulose and PP. The presence of cellulose in the mixture decreased the apparent activation energy of PP decomposition from 210 to 120 kJ mol^?1, while the presence of PP did not affect the apparent activation energy of cellulose decomposition (E _a = 158 ± 3 kJ mol^?1). A significant decrease in apparent activation energy was observed in the conversion regime corresponding to the completion of cellulose pyrolysis and beginning of PP pyrolysis. Differential scanning calorimetry data clearly showed the shift of exothermic char formation to higher temperatures with PP incorporation in the mixture. The presence of PP also resulted in reduction of final char content. Based on the above analyses, a new interaction step that involves a bimolecular reaction of activated PP with volatiles from cellulose pyrolysis to form interaction products and char is proposed, and the rate limiting steps for char formation are clearly identified.     

Rapid synthesis and biological evaluation of 1,4-dihydropyridine derivatives containing a benzothiazolyl moiety

A series of N-(6-methylbenzothiazolyl)-2,3,5,6-tetrasubstituted-4-(aryl)-1,4-dihydropyridines were synthesized by reaction of 2-amino-6-methylbenzothiazole, aromatic aldehyde and active methylene compound in methanol by conventional, as well as, microwave irradiation (solvent free and solid support) methods. The microwave irradiation technique gives better yield and shorter reaction time. Among solid supported microwave irradiation better yields are obtained in acidic alumina as compared to silica, neutral alumina, and basic alumina. All compounds were tested for antibacterial and antifungal activities and results have been compared with standard drugs. Entomological activities were also tested. The results showed that a change in the substitution pattern in 1,4-dihydropyridine derivatives may cause a marked effect on their antimicrobial activity.     

Detection and characterization of recombinant DNA expressing <Emphasis Type="Italic">vip3A</Emphasis>-type insecticidal gene in GMOs—standard single,multiplex and construct-specific PCR assays

Vegetative insecticidal protein (Vip), a unique class of insecticidal protein, is now part of transgenic plants for conferring resistance against lepidopteron pests. In order to address the imminent regulatory need for detection and labeling of vip3A carrying genetically modified (GM) products, we have developed a standard single PCR and a multiplex PCR assay. As far as we are aware, this is the first report on PCR-based detection of a vip3A-type gene (vip-s) in transgenic cotton and tobacco. Our assay involves amplification of a 284-bp region of the vip-s gene. This assay can possibly detect as many as 20 natural wild-type isolates bearing a vip3A-like gene and two synthetic genes of vip3A in transgenic plants. The limit of detection as established by our assay for GM trait (vip-s) is 0.1%. Spiking with nontarget DNA originating from diverse plant sources had no inhibitory effect on vip-s detection. Since autoclaving of vip-s bearing GM leaf samples showed no deterioration/interference in detection efficacy, the assay seems to be suitable for processed food products as well. The vip-s amplicon identity was reconfirmed by restriction endonuclease assay. The primer set for vip-s was equally effective in a multiplex PCR assay format (duplex, triplex and quadruplex), used in conjunction with the primer sets for the npt-II selectable marker gene, Cauliflower mosaic virus 35S promoter and nopaline synthetase terminator, enabling concurrent detection of the transgene, regulatory sequences and marker gene. Further, the entire transgene construct was amplified using the forward primer of the promoter and the reverse primer of the terminator. The resultant amplicon served as a template for nested PCR to confirm the construct integrity. The method is suitable for screening any vip3A-carrying GM plant and food. The availability of a reliable PCR assay method prior to commercial release of vip3A-based transgenic crops and food would facilitate rapid and efficient regulatory compliance. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. An application for an Indian patent (1891/DEL2006/17.08.07) comprising a substantive part of this study has been filed. ITRC communication no. 2516.     

Laser produced spectrum of Si(2) molecule in the region of 540-1010 nm

The laser produced spectrum of Si(2) molecule is recorded for the first time using laser ablation technique in the region of 540-1010 nm. About 110 bands are observed in the entire spectral region and all these bands are classified into three band systems, viz. E-X, F-X and G-X of Si(2) molecule lying in the region of 814-1010 nm, 630-900 nm and 546-710 nm, respectively. All these electronic transitions take place from ground state X(3)Sigma(g)(-) state. The molecular constants of all these states have been determined.     

pH-dependent Raman study of pyrrole and its vibrational analysis using DFT calculations

Raman spectra of pyrrole in aqueous medium at different pH values, 2.5, 5.5, 7.5 and 10.5 were recorded in the two spectral regions, 1,040-1,160 cm(-1) and 3,300-3,360 cm(-1) and pH dependence of the linewidth, peak position and intensity of the Raman bands corresponding to the ring breathing and symmetric nu(N-H) stretching modes were examined. A linear pH dependence of the peak positions for the ring breathing mode and a maximum at nearly neutral pH (7.5) for the symmetric nu(N-H) normal mode is observed, whereas the linewidth (FWHM) shows almost no variation with the change of pH. A slight decrease in the wavenumber position of the nu(N-H) mode at pH value >7.5 indicates that the influence of deprotonation is small, which results from a weak interaction between the reference molecule and the surrounding environment. The density functional theory (DFT) calculations were made primarily to obtain the optimized geometry and vibrational spectra of pyrrole in the ground electronic state using B3LYP functional and the highest level basis set 6-311++G(d,p). The assignments of the normal modes of pyrrole were made on the basis of potential energy distribution (PED). The calculations were also performed on protonated and deprotonated structures of pyrrole.     

Hydrolytic degradation of polyisobutylene and poly‐L‐lactide–based multiblock copolymers

The hydrolytic degradation of a series of poly‐L ‐lactide (PLLA)‐polyisobutylene (PIB) multiblock copolymers was studied in phosphate buffer solution (pH = 7.4) at 37 °C. The multiblock copolymers were synthesized by chain extension of PLLA‐b‐PIB‐b‐PLLA triblock copolymers, which were obtained by ring‐opening polymerization of L ‐lactide initiated by hydroxyallyl telechelic PIB. The degradation strongly depended on the PLLA segment length. At constant PIB segment length, the multiblock copolymer with the shortest PLLA segment length (DPn = 10), showed significant weight loss after 8 weeks, whereas weight loss for DPn = 36 was only observed after 24 weeks. The gel‐permeation chromatographic analysis showed a similar decrease in the number‐average molecular weight (M_n) with time further supporting the weight loss data. Dynamic mechanical analysis showed a decrease in ultimate stress and modulus with time. The crystallinity of multiblock copolymers changed significantly with degradation time as indicated from differential scanning calorimetric analysis. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3767–3774, 2010     

The Chemical Profiling of Essential Oils from Different Tissues of Cinnamomum camphora L. and Their Antimicrobial Activities

Cinnamomum camphora L. is grown as an ornamental plant, used as raw material for furniture, as a source of camphor, and its essential oil can be used as an important source for perfume as well as alternative medicine. A comparative investigation of essential oil compositions and antimicrobial activities of different tissues of C. camphora was carried out. The essential oils were extracted by hydrodistillation with a Clevenger apparatus and their compositions were evaluated through gas chromatography-mass spectrometry (GC-MS), enantiomeric composition by chiral GC-MS, and antimicrobial properties were assayed by measuring minimum inhibitory concentrations (MICs). Different plant tissues had different extraction yields, with the leaf having the highest yield. GC-MS analysis revealed the presence of 18, 75, 87, 67, 67, and 74 compounds in leaf, branch, wood, root, leaf/branch, and leaf/branch/wood, respectively. The significance of combining tissues is to enable extraction of commercial quality essential oils without the need to separate them. The oxygenated monoterpene camphor was the major component in all tissues of C. camphora except for safrole in the root. With chiral GC-MS, the enantiomeric distributions of 12, 12, 13, 14, and 14 chiral compounds in branch, wood, root, leaf/branch, and leaf/branch/wood, respectively, were determined. The variation in composition and enantiomeric distribution in the different tissues of C. camphora may be attributed to the different defense requirements of these tissues. The wood essential oil showed effective antibacterial activity against Serratia marcescens with an MIC of 39.1 μg/mL. Similarly, the mixture of leaf/branch/wood essential oils displayed good antifungal activity against Aspergillus niger and Aspergillus fumigatus while the leaf essential oil was notably active against Trichophyton rubrum. C. camphora essential oils showed variable antimicrobial activities against dermal and pulmonary-borne microbes.     

Heuristic charge assignment for deconvolution of electrospray ionization mass spectra

We propose a new algorithm for deconvolution of electrospray ionization mass spectra based on direct assignment of charge to the measured signal at each mass-to-charge ratio (m/z). We investigate two heuristics for charge assignment: the entropy-based heuristic is adapted from a deconvolution algorithm by Reinhold and Reinhold;10 the multiplicative-correlation heuristic is adapted from the multiplicative-correlation deconvolution algorithm of Hagen and Monnig.6 The entropy-based heuristic is insensitive to overestimates of z(max), the maximum ion charge. We test the deconvolution algorithm on two single-component samples: the measured spectrum of human beta-endorphin has two prominent and one very weak line whereas myoglobin has a well-developed quasi-gaussian envelope of 17 peaks. In both cases, the deconvolution algorithm gives a clean deconvoluted spectrum with one dominant peak and very few artefacts. The relative heights of the peaks due to the parent molecules in the deconvoluted spectrum of a mixture of two peptides, which are expected to ionize with equal efficiency, give an accurate measure of their relative concentration in the sample.     

Ordering in smectogenic Schiff base compound: A computational analysis based in intermolecular interactions

Russian Journal of General Chemistry - A computational analysis of ordering in N-(4-n-alkoxy benzylidene)-4′-alkyl aniline ( n O m ) with n = 7, m = 6 carbon atoms in alkyl chain has been...