Synthetic and Computational Studies on RhIII-Catalyzed Redox-Neutral Cascade of Carbenoid Functionalization and Dephosphonylative Annulation.

A Rh(III)-catalyzed regioselective redox-neutral cascade process of carbenoid functionalization followed by dephosphonylative annulation of benzoic acids with α-diazo-ß-keto phosphonate has been realized, which led to the direct synthesis of a privileged 3-substituted isocoumarin scaffold. To the best of our knowledge, this is the first report of a complete redox neutral method to synthesize isocoumarins using C-H functionalization strategy. In the catalytic cycle of this reaction, there are two possible pathways for the C-C coupling between ortho-positioned carbon atom of benzoic acid and the diazo carbon atom: (i) concerted 1,2-aryl shift and (ii) stepwise metal-carbene formation followed by migratory insertion. DFT study has predicted that the concerted pathway has lower activation energy as compared to the stepwise pathway by 1.5 kcal/mol.

Resolving population structure and genetic differentiation associated with RAD-SNP loci under selection in tossa jute (Corchorus olitorius L.).

The genetic basis of selection for geographic adaptation and how it has contributed to population structure are unknown in tossa jute (Corchorus olitorius), an important bast fibre crop. We performed restriction site-associated DNA (RAD) sequencing-based (1115 RAD-SNPs) population genomic analyses to investigate genetic differentiation and population structure within a collection of 221 fibre-type lines from across nine geographic regions of the world. Indian populations, with relatively higher overall diversity, were significantly differentiated (based on FST and PCA) from the African and the other Asian populations. There is strong evidence that African C. olitorius was first introduced in peninsular India that could perhaps be its secondary centre of origin. However, multiple later introductions have occurred in central, eastern and northern India. Based on four assignment tests with different statistical bases, we infer that two ancestral subpopulations (African and Indian) structure the C. olitorius populations, but not in accordance with their geographic origins and patterns of diversity. Our results advocate recent migration of C. olitorius through introduction and germplasm exchange across geographical boundaries. We argue that high intraspecific genetic admixture could be associated with increased genetic variance within Indian populations. Employing both subpopulation (FST/GST-outlier) and individual-based (PCAdapt) tests, we detected putative RAD-SNP loci under selection and demonstrated that bast fibre production was an artificial, while abiotic and biotic stresses were natural selection pressures in C. olitorius adaptation. By reinferring the population structure without outlier loci, we propose ad interim that C. olitorius was possibly domesticated as a fibre crop in the Indian subcontinent.

Synergistic effect of band edge potentials on BiFeO3/V2O5 composite: Enhanced photo catalytic activity.

The BiFeO3/V2O5 has been successfully synthesized by simple annealing of BiFeO3 nanoplates and V2O5 nanoflower. The phase, structural, optical properties and chemical state of the BiFeO3, V2O5 and different composition of BiFeO3/V2O5 samples were comparatively characterized by various spectroscopic and microscopic techniques. The prepared catalyst exhibits unique photo catalytic and post-oxidation/reduction ability for removal of various (MB, Phenol, CV, RhB) water organic pollutants. Compared to pure BiFeO3 and V2O5, the different Wt % of BiFeO3/V2O5 composition exhibited higher photo catalytic activity. The fortunate BiFeO3/V2O5 interface hybrid photo catalyst makes a significant impact in the enhancement of photo catalytic reaction. This remarkable efficiency could be ascribed to the synergistic effect between the V2O5 petals and BiFeO3 plates. The exceptional morphology, increased surface area, uniformity, less-agglomerated spreading could increase the ability of visible light response, which lead the improved electron transport ability and the higher charge separation. The enhanced rate of photo generated charge carriers separations were evinced by the EIS and PL spectrum measurements. The allowed radical trapping experiment divulge that the hole (h+), and super oxide radical (O2-) are the minimized effect in degradation, on the other hand hydroxyl radical (OH) is plays the foremost role and act as the active radicals in the catalytic organism. In relations of above investigation, a probable photo degradation mechanism of the as-synthesized photo catalyst is carefully explicated. This effort delivers an effective approach to design and fabricate the efficient photo catalyst through integrating of materials, which has a potential for industrial waste water purification.

Construction of avulsion potential zone model for Kulik River of Barind Tract, India and Bangladesh.

Avulsion is a natural fluvial process but considered it as a hazard in the populated region due to the chance of immense failure of lives and properties. So, early warning indicates that the zone of avulsion can facilitate the people living there. About 317 numbers of local and regional historical imprints of channel cutoff along river Kulik claim the need of this work. The present study tried to identify avulsion potential zone (APZ) of Kulik river of Indo-Bangladesh using multi-parametric weighted combination approach. Analytic hierarchy approach (AHP) is applied for weighting the used parameters. Avulsion potential model clearly exhibits that 9.51-km stream segment of middle and lower catchment is highly susceptible for avulsion especially during sudden high discharge and earthquake incidents. There is also high chance of channel avulsion following the existing Paleo-avulsion courses and left channels. Hard points can also be erected alongside the main channel for resisting channel avulsion propensity.

Electroactive ß-crystalline phase inclusion and photoluminescence response of a heat-controlled spin-coated PVDF/TiO2 free-standing nanocomposite film for a nanogenerator and an active nanosensor.

The electroactive ß-phase is most desirable due to its highest piezo-, pyro- and ferroelectric properties in poly(vinylidene fluoride) (PVDF). Induction of the ß-phase is successfully accomplished in titanium dioxide (TiO2) nanoparticles (NPs) doped spin-coated PVDF nanocomposite (PNC) films. The optimized yields of ß-phase and homogeneous ultra-smooth free-standing PNC film is utilized in a mechanical-energy harvesting application by fabricating a nanogenerator (NG) where the typical electrical poling step is not undertaken. Under a repeated human finger touch and release process, it delivers an open-circuit voltage of 5 V. Moreover, the physical sensing capabilities of the NG are examined through harvesting mechanical energy from mouse clicking of a laptop and wrist pulse detection, which indicates that it can also be used as a nanosensor. The blue photoluminescence centred at 444 nm, which was also observed in PNC films, makes us anticipate a new type of photonic application where the design feasibility of hybrid sensors, i.e. electromechanical and photonic combination, is also possible.

Improved dielectric constant and breakdown strength of γ-phase dominant super toughened polyvinylidene fluoride/TiO2 nanocomposite film: an excellent material for energy storage applications and piezoelectric throughput.

Titanium dioxide (TiO2) nanoparticles (NPs) embedded γ-phase containing polyvinylidene fluoride (PVDF) nanocomposite (PNC) film turns to an excellent material for energy storage application due to an increased dielectric constant (32 at 1 kHz), enhanced electric breakdown strength (400 MV m-1). It also exhibits a high energy density of 4 J cm-3 which is 25 times higher than that of virgin PVDF. 98% of the electroactive γ-phase has been acheived by the incorporation of TiO2 NPs and the resulting PNC behaves like a super-toughened material due to a dramatic improvement (more than 80%) in the tensile strength. Owing to their electroactive nature and extraordinary mechanical properties, PNC films have a strong ability to fabricate the piezoelectric nanogenerators (PNGs) that have recently been an area of focus regarding mechanical energy harvesting. The feasibility of piezoelectric voltage generation from PNGs is demostrated under the rotating fan that also promises further utility such as rotational speed (RPM) determination.

Semiconductor-Metal Nanofloret Hybrid Structures by Self-Processing Synthesis.

We present a synthetic strategy that takes advantage of the inherent asymmetry exhibited by semiconductor nanowires prepared by Au-catalyzed chemical vapor deposition (CVD). The metal-semiconductor junction is used for activating etch, deposition, and modification steps localized to the tip area using a wet-chemistry approach. The hybrid nanostructures obtained for the coinage metals Cu, Ag, and Au resemble the morphology of grass flowers, termed here Nanofloret hybrid nanostructures consisting of a high aspect ratio SiGe nanowire (NW) with a metallic nanoshell cap. The synthetic method is used to prepare hybrid nanostructures in one step by triggering a programmable cascade of events that is autonomously executed, termed self-processing synthesis. The synthesis progression was monitored by ex situ transmission electron microscopy (TEM), in situ scanning transmission electron microscopy (STEM) and inductively coupled plasma mass spectrometry (ICP-MS) analyses to study the mechanistic reaction details of the various processes taking place during the synthesis. Our results indicate that the synthesis involves distinct processing steps including localized oxide etch, metal deposition, and process termination. Control over the deposition and etching processes is demonstrated by several parameters: (i) etchant concentration (water), (ii) SiGe alloy composition, (iii) reducing agent, (iv) metal redox potential, and (v) addition of surfactants for controlling the deposited metal grain size. The NF structures exhibit broad plasmonic absorption that is utilized for demonstrating surface-enhanced Raman scattering (SERS) of thiophenol monolayer. The new type of nanostructures feature a metallic nanoshell directly coupled to the crystalline semiconductor NW showing broad plasmonic absorption.

Pathways associated with lignin biosynthesis in lignomaniac jute fibres.

We generated the bast transcriptomes of a deficient lignified phloem fibre mutant and its wild-type jute (Corchorus capsularis) using Illumina paired-end sequencing. A total of 34,163 wild-type and 29,463 mutant unigenes, with average lengths of 1442 and 1136 bp, respectively, were assembled de novo, ~77-79 % of which were functionally annotated. These annotated unigenes were assigned to COG (~37-40 %) and GO (~22-28 %) classifications and mapped to 189 KEGG pathways (~19-21 %). We discovered 38 and 43 isoforms of 16 and 10 genes of the upstream shikimate-aromatic amino acid and downstream monolignol biosynthetic pathways, respectively, rendered their sequence similarities, confirmed the identities of 22 of these candidate gene families by phylogenetic analyses and reconstructed the pathway leading to lignin biosynthesis in jute fibres. We also identified major genes and bast-related transcription factors involved in secondary cell wall (SCW) formation. The quantitative RT-PCRs revealed that phenylalanine ammonia-lyase 1 (CcPAL1) was co-down-regulated with several genes of the upstream shikimate pathway in mutant bast tissues at an early growth stage, although its expression relapsed to the normal level at the later growth stage. However, cinnamyl alcohol dehydrogenase 7 (CcCAD7) was strongly down-regulated in mutant bast tissues irrespective of growth stages. CcCAD7 disruption at an early growth stage was accompanied by co-up-regulation of SCW-specific genes cellulose synthase A7 (CcCesA7) and fasciclin-like arabinogalactan 6 (CcFLA6), which was predicted to be involved in coordinating the S-layers' deposition in the xylan-type jute fibres. Our results identified CAD as a promising target for developing low-lignin jute fibres using genomics-assisted molecular approaches.

Inorganic-organic nanofiber networks with antibacteria properties for enhanced particulate filtration: The critical role of amorphous titania.

The demand for air filter media at indoor and outdoor is increasing tremendously due to air pollution and especially for problems related to airborne particulate matter (PM). To realize that, here a class nanofiber air filter media with strong antibacterial activity, hydrophobic nature, high filtration efficiency with low pressure drop is prepared. Novel organic-inorganic nanocomposite nanofibers used in this work benefited for the multifunctional performance. Amorphous titanium dioxide (mTiO2) is utilized for air filtration application which exhibits excellent enhancement of PM2.5 filtration properties and antibacterial activity. The unique Poly (vinylpyrrolidone) (PVP)-mTiO2 nanofiber air filter media acquired hydrophobic nature with a large increase in water contact angle of 127° from 36°. The resulting free-standing nanofiber filters exhibit high PM2.5 filtration efficiency of >99.9% and low pressure drop of 39 Pa. Antibacterial activity of nanofibrous membrane has been rationally engineered by titanium oxide as the barrier to bacterial ingression. A long term of 160 h filtration test has proved PVP-mTiO2 nanofibers air filter media holds outstanding 99% filtration efficiency for PM2.5. This work takes forward a significant lead in design and production of high performance and very low pressure drop air filter media with a wide range of functional properties.

Influence of Anatase-Rutile Ratio on Band Edge Position and Defect States of TiO2 Homojunction Catalyst.

Removal of toxic air and water dissociation in the environment has become a major challenging issue throughout the world. Mixed phase rutile-anatase titanium dioxide catalysts are very effective in photocatalysis and have been studied extensively. However, the mechanism causing this effect and band alignment of the two phases are not fully understood. Pointing to the issue, we have designed one-dimensional mixed-phase TiO2 and introduced defects near the valence band. Experimental results showed that band alignment between two phases, up-shift of the band edge, and optimum anatase percentage play a key role in the enhancement of the photocatalytic activity. We predicted shifts in band edge originating from surface electric dipole layer induced by defects.

Layered Si-Ti oxide thin films with tailored electrical and optical properties by catalytic tandem MLD-ALD.

Oxides with well-controlled optical and electrical properties are key for numerous advances in nanotechnology, including energy, catalysis, sensors, and device applications. In this study we introduce layer-by-layer deposition of silicon-titanium layered oxide (Si-Ti LO) thin films using combined MLD-ALD methodology (M/ALD). The Si-Ti LO film deposition is achieved by acid-base catalysis establishing an overall catalytic tandem M/ALD super cycle (CT-M/ALD). The catalytic nature of the process allows relatively fast deposition cycles under mild conditions compared with the typical cycle time and conditions required for ALD processes with silane precursors. The Si-Ti LO thin films exhibit tuneable refractive index and electrical conductivities. The refractive index is set by the stoichiometry of Si- to Ti-oxide phases simply by selecting the MLD to ALD proportion in the CT-M/ALD super cycle, with low and high refractive index, respectively. Thermal treatment of Si-Ti LO thin films resulted in conductive thin films with both graphitic and Magnéli oxide phases. Enhanced conductivity and reduced onset temperature for Magnéli phase formation were obtained owing to the unique Si-Ti layer structure and stoichiometry attained by the CT-M/ALD process and facilitated by breaking of Si-C bonds and Red-Ox reactions between the Si sub-oxide and TiO2 phases leading to the conductive Magnéli phase. Hence, the embedded amine silane functions not only for catalysing Si-Ti LO deposition but also to further promote subsequent transformations during thermal processing. This work demonstrates the concept of embedding a meta-stable organic motif by the MLD step to facilitate transformation of an oxide phase by taking advantage of precise layer-by-layer deposition of alternating phases enabled by M/ALD.

Transcriptome profiling uncovers ß-galactosidases of diverse domain classes influencing hypocotyl development in jute (Corchorus capsularis L.).

Enzyme ß-galactosidase (EC 3.2.1.23) is known to influence vascular differentiation during early vegetative growth of plants, but its role in hypocotyl development is not yet fully understood. We generated the hypocotyl transcriptome data of a hypocotyl-defect jute (Corchorus capsularis L.) mutant (52,393 unigenes) and its wild-type (WT) cv. JRC-212 (44,720 unigenes) by paired-end RNA-seq and identified 11 isoforms of ß-galactosidase, using a combination of sequence annotation, domain identification and structural-homology modeling. Phylogenetic analysis classified the jute ß-galactosidases into six subfamilies of glycoside hydrolase-35 family, which are closely related to homologs from Malvaceous species. We also report here the expression of a ß-galactosidase of glycoside hydrolase-2 family that was earlier considered to be absent in higher plants. Comparative analysis of domain structure allowed us to propose a domain-centric evolution of the five classes of plant ß-galactosidases. Further, we observed 1.8-12.2-fold higher expression of nine ß-galactosidase isoforms in the mutant hypocotyl, which was characterized by slower growth, undulated shape and deformed cell wall. In vitro and in vivo ß-galactosidase activities were also higher in the mutant hypocotyl. Phenotypic analysis supported a significant (P ≤ 0.01) positive correlation between enzyme activity and undulated hypocotyl. Taken together, our study identifies the complete set of ß-galactosidases expressed in the jute hypocotyl, and provides compelling evidence that they may be involved in cell wall degradation during hypocotyl development.

Anionically functionalized guar gum embedded with silica nanoparticles: An efficient nanocomposite adsorbent for rapid adsorptive removal of toxic cationic dyes and metal ions.

In the present work, a novel biodegradable nanocomposite has been developed (h-GG/SiO2) based on anionically modified guar gum and in-situ deposited SiO2 NPs through sol-gel technique. Here the anionically modified guar gum stimulates the silica polymerization process and hence acts as a unique template for the development of spherical SiO2 NPs. Batch adsorption studies indicate that h-GG/SiO2 nanocomposite shows remarkable adsorption capacity for cationic dyes/metal ions (Qmax: 781.25mgg-1for malachite green (MG), 281.69mgg-1 for safranin (SF); 645.16mgg-1 for Pb2+, 709.21mgg-1 for Cd2+) as well as it efficiently and selectively removes cationic MG from mixture of dye solutions. Finally the worthy regenerative efficacy of h-GG/SiO2 facilitates the adsorbent to be economically promising for practical application in the field of wastewater management.

Patients' Preference for Integrating Homoeopathy Services within the Secondary Health Care Settings in India: The Part 3 (PPIH-3) Study.

Indian patients' preference for integrated homoeopathy services remains underresearched. Two earlier surveys revealed favorable attitude toward and satisfaction from integrated services. The objectives of this study were to examine knowledge, attitudes, and practice of homoeopathy and to evaluate preference toward its integration into secondary-level health care. A cross-sectional survey was conducted during May to October 2015 among 659 adult patients visiting randomly selected secondary-level conventional health care setups in Kolkata, Mumbai, Kottayam, and New Delhi (India) using a self-administered 24-item questionnaire in 4 local vernaculars (Bengali, Marathi, Malayalam, and Hindi). Knowledge and practice scores were compromised; attitude scores toward integration and legal regulation were high. Respondents were uncertain regarding side effects of homoeopathy and concurrent use and interactions with conventional medicines. A total of 82.40% (95% confidence interval = 79.23, 85.19) of the participants were in favor of integrating homoeopathy services. Preference was significantly higher in Delhi and lower in Kottayam. Probable strategic measures for further development of integrated models are discussed.

The draft genome of Corchorus olitorius cv. JRO-524 (Navin).

Here, we present the draft genome (377.3 Mbp) of Corchorus olitorious cv. JRO-524 (Navin), which is a leading dark jute variety developed from a cross between African (cv. Sudan Green) and indigenous (cv. JRO-632) types. We predicted from the draft genome a total of 57,087 protein-coding genes with annotated functions. We identified a large number of 1765 disease resistance-like and defense response genes in the jute genome. The annotated genes showed the highest sequence similarities with that of Theobroma cacao followed by Gossypium raimondii. Seven chromosome-scale genetically anchored pseudomolecules were constructed with a total size of 8.53 Mbp and used for synteny analyses with the cocoa and cotton genomes. Like other plant species, gypsy and copia retrotransposons were the most abundant classes of repeat elements in jute. The raw data of our study are available in SRA database of NCBI with accession number SRX1506532. The genome sequence has been deposited at DDBJ/EMBL/GenBank under the accession LLWS00000000, and the version described in this paper will be the first version (LLWS01000000).

Branch density-controlled synthesis of hierarchical TiO2 nanobelt and tunable three-step electron transfer for enhanced photocatalytic property.

The successful adjustment of phase composition and morphology of hierarchical TiO2 nanobelts, which feature homoepitaxial nanobranches, has been developed via the hydrothermal method and chemical bath deposition technique. Effects of hydrothermal reaction time, titanium butoxide treatment in chemical bath deposition, and calcination temperature are systematically investigated. For the first time, three-step ultrafast electron transfers between the band edges of the engaged phases are realized through the enhanced photocatalytic activity results. Growth mechanism related to branch density control on nanobelt surface under such soft chemical process is discussed in detail on the basis of classical nucleation theory. The current work might provide new insights into the fabrication of one-dimensional homoepitaxial branched TiO2 nanostructures as high performance photocatalysts and facilitate their application in environmental cleanup.

Tailor-made oxide architectures attained by molecularly permeable metal-oxide organic hybrid thin films.

Tailor-made metal oxide (MO) thin films with controlled compositions, electronic structures, and architectures are obtained via molecular layer deposition (MLD) and solution treatment. Step-wise formation of permeable hybrid films by MLD followed by chemical modification in solution benefits from the versatility of gas phase reactivity on surfaces while maintaining flexibility which is more common at the liquid phase.

Three dimensional Ag2O/TiO2 type-II (p-n) nanoheterojunctions for superior photocatalytic activity.

Type-II p-n junction three-dimensional Ag(2)O/TiO(2) microspheres have been fabricated by assembling p-type Ag(2)O nanoparticle on n-type TiO(2) 3D microsphere. Ag(2)O/TiO(2) microsphere nanoheterojunctions were obtained by hydrothermal synthesis of TiO(2) microspheres at 180 °C followed by photoreduction of AgNO(3). The samples were carefully characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), and energy dispersive X-ray analysis (EDX). The photocatalytic activity toward degradation of methyl orange (MO) aqueous solution under UV light was investigated. The result showed that type-II p-n nanoheterojunctions Ag(2)O/TiO(2) significantly enhanced the photocatalytic degradation compared to n-type TiO(2) microsphere. It was found that the photocatalytic degradation followed the pseudo first-order reaction model. In particular, heterostructure with molar ratio of TiO(2) and AgNO(3) of 4:1 exhibited best photocatalytic activity and the corresponding apparent first-order rate constant of 0.138 min(-1) which is 4 times than that of pure n-type microsphere.

Development of SSR markers and construction of a linkage map in jute.

Jute is an important natural fibre crop, which is only second to cotton in its importance at the global level. It is mostly grown in Indian subcontinent and has been recently used for the development of genomics resources.We recently initiated a programme to develop simple sequence repeat markers and reported a set of 2469 SSR that were developed using four SSR-enriched libraries (Mir et al. 2009). In this communication, we report an additional set of 607 novel SSR in 393 SSR containing sequences. However, primers could be designed for only 417 potentially useful SSR. Polymorphism survey was carried out for 374 primer pairs using two parental genotypes (JRO 524 and PPO4) of a mapping population developed for fibre fineness; only 66 SSR were polymorphic. Owing to a low level of polymorphism between the parental genotypes and a high degree of segregation distortion in recombinant inbred lines, genotypic data of only 53 polymorphic SSR on the mapping population consisting of 120 RIL could be used for the construction of a linkage map; 36 SSR loci were mapped on six linkage groups that covered a total genetic distance of 784.3 cM. Hopefully, this map will be enriched with more SSR loci in future and will prove useful for identification of quantitative trait loci/genes for molecular breeding involving improvement of fibre fineness and other related traits in jute.

The signal transduction pathways controlling in planta tuberization in potato: an emerging synthesis.

Tuberization is one of the multiple outputs of a single-input phytochrome B sensory system, involving several regulatory genes. Phytochrome B- and GA-mediated photoperiodic perception occurs in the leaf, and then the RNA acts as a systemic signal in the long-distance signaling pathway to initiate tuberization in the subapical region of an underground stolon. There is good evidence that flowering and tuberizing signals might be similar. Is there a cross-talk with an oxidative burst-mediated redox signaling pathway during tuberization? Is the lipoxygenase cascade involved in the formation of the perimedullary tissue in a growing tuber? Do aquaporins regulate cell division, expansion and elongation during stolon growth and tuber induction in potato? Is the adaptive diversity for tuberization under varying photoperiods a micro-evolutionary indicator of differential transduction of cell-to-cell signal molecules under spatial and temporal expression of regulatory genes encoding transcriptional activators? Taking these views into consideration, the review presents an interim synthesis of a signaling network regulating in planta tuberization in potato.