Insight into the MOtBu (M=Na, K)-Mediated Dehydrogenation of Dimethylamine-Borane and Transfer Hydrogenation of Nitriles to Primary Amines.

Selective synthesis of primary amines from nitriles is challenging in synthetic chemistry due to the possible en-route generation of various amines and imines. Herein, we report a practical and operationally simple MOtBu-mediated (M=Na, K) transfer hydrogenation of nitriles to the corresponding primary amines with a relatively unexplored sacrificial hydrogen source (dimethylamine borane). The strategy encompasses a broad substrate scope under transition metal-free conditions and does not require any solvent. The mechanistic investigation was performed with the aid of control experiments and spectroscopic studies. The GC analysis of the reaction mixture exhibited the evolution of the H2 gas. Additionally, detailed computational calculations were undertaken to shed light on the possible intermediates and transition states involved during the present protocol.

Cyclotrimetaphosphate-assisted ruthenium catalyst for the hydration of nitriles and oxidation of primary amines to amides under aerobic conditions in water.

Amide bonds are ubiquitous and regarded as an essential constituent of many biologically active drug molecules and fine chemicals. We report a practical and operationally simple ruthenium-based catalytic system for the hydration of nitriles and aerobic oxidation of primary amines to the corresponding amides. Both reactions proceed without any external oxidant in water under aerobic conditions and exhibit a broad substrate scope. The mechanistic investigation was executed with the aid of control experiments and kinetic and spectroscopic studies of the reaction mixture.

Biopriming for induction of disease resistance against pathogens in rice.

MAIN CONCLUSION: Rice is attacked by an armada of pathogens. Present review provides a critical evaluation of the potential of different biotic agents used to protect rice yield drop from pathogenicity and an account of unexplored areas, which might be taken into consideration to manage rice diseases. Rice (Oryza sativa L.), is the most important staple food of Asian countries. Rice production is significantly limited by a diversity of pathogens, leading to yield loss and deficit in current rice supply. Application of agrochemicals of diverse types has been considered as the only option to control pathogens and enhance rice production, thereby causing environmental concerns and making the pathogens resistant to the active ingredients. Increase in population and resistance of pathogen towards agrochemicals put pressure on the agronomists to search for safe, novel, eco-friendly alternative ways to manage rice pathogens. Inducing resistance in rice by using different biotic/abiotic agents provides an environmental friendly alternative way to effectively manage bacterial, fungal, and viral rice pathogens. In recent years, a number of protocols have been developed for inducing pathogen resistance by bio-priming of rice. However, a comprehensive evaluation of the potential of different biotic agents to protect rice crop loss from pathogens is hitherto lacking due to which the research on induction of defense against pathogens in rice is discontinuous. This review deals with the detailed analysis of the bacterial and fungal agents used to induce defense against rice pathogens, their mode of application, mechanism (physiological, biochemical, and molecular) of defense induction, and effect of defense induction on the yield of rice. It also provides an account of gaps in the research and the unexplored areas, which might be taken into consideration to effectively manage rice pathogens.

Catalytic and Mechanistic Approach to the Metal-Free N-Alkylation of 2-Aminopyridines with Diketones.

N-alkylation of amines is an important catalytic reaction in synthetic chemistry. Herein, we report a simple strategy for the N-alkylation of 2-aminopyridines with 1,2-diketones using BF3·OEt2 as a catalyst. The reaction proceeds under aerobic conditions, leading to the formation of a diverse range of substituted secondary amines in good to excellent yields. A close inspection of the mechanistic pathway using various spectroscopic techniques and the computational study revealed that the reaction proceeds through the formation of an iminium-keto intermediate with the liberation of CO2.

Transamidation of aromatic amines with formamides using cyclic dihydrogen tetrametaphosphate.

Amide fragments are found to be one of the key constituents in a wide range of natural products and pharmacologically active compounds. Herein, we report a simple and efficient procedure for transamidation with a cyclic dihydrogen tetrametaphosphate. The protocol is simple, does not require any additives, and encompasses a broad substrate scope. To comprehend the mechanism of the present methodology, detailed spectroscopic and kinetic studies were undertaken.

Interface-engineered templates for molecular spin memory devices.

The use of molecular spin state as a quantum of information for storage, sensing and computing has generated considerable interest in the context of next-generation data storage and communication devices, opening avenues for developing multifunctional molecular spintronics. Such ideas have been researched extensively, using single-molecule magnets and molecules with a metal ion or nitrogen vacancy as localized spin-carrying centres for storage and for realizing logic operations. However, the electronic coupling between the spin centres of these molecules is rather weak, which makes construction of quantum memory registers a challenging task. In this regard, delocalized carbon-based radical species with unpaired spin, such as phenalenyl, have shown promise. These phenalenyl moieties, which can be regarded as graphene fragments, are formed by the fusion of three benzene rings and belong to the class of open-shell systems. The spin structure of these molecules responds to external stimuli (such as light, and electric and magnetic fields), which provides novel schemes for performing spin memory and logic operations. Here we construct a molecular device using such molecules as templates to engineer interfacial spin transfer resulting from hybridization and magnetic exchange interaction with the surface of a ferromagnet; the device shows an unexpected interfacial magnetoresistance of more than 20 per cent near room temperature. Moreover, we successfully demonstrate the formation of a nanoscale magnetic molecule with a well-defined magnetic hysteresis on ferromagnetic surfaces. Owing to strong magnetic coupling with the ferromagnet, such independent switching of an adsorbed magnetic molecule has been unsuccessful with single-molecule magnets. Our findings suggest the use of chemically amenable phenalenyl-based molecules as a viable and scalable platform for building molecular-scale quantum spin memory and processors for technological development.

Deciphering the associated risk on soil microbes upon use of biopesticides in rice ecosystem.

Plant species, viz Cleistanthus collinus, Lantana camara, and Strychnos nux-vomica are being traditionally used for pest management in rice. However, limited investigation has been carried out to understand the toxic effect of these materials on soil microbes. Hot water extracts of these plants were evaluated for their effects on soil microbial population and enzyme activities along with neem oil and chlorpyrifos as check. Soil microbial population, viz bacteria, fungi, phosphate-solubilizing bacteria (PSB), and asymbiotic nitrogen fixers were unchanged after application of plant extracts. Maximum population of bacteria including PSB and asymbiotic nitrogen fixers were observed in control, whereas, S. nux-vomica, and C. collinus-treated soil had higher number of actinomycetes and fungal population, respectively. Soil microbial biomass did not vary differently among the plant extracts. Application of plant extracts did not alter dehydrogenase, ß-glycosidase, acid phosphatase, alkaline phosphatase, and urease content in soil. Secondary metabolites present in these plant extracts may be responsible for variable effects on soil microbes. Chlorpyrifos had a fleeting negative effect on soil microbes and enzymes in comparison to plant extracts. All the three plants did not have any negative effect on soil microbes and enzymes and can be safely recommended in rice pest management.

Genetic variability and inter species relationship between wild and cultivated yams (Dioscorea spp.) from Koraput, India based on molecular and morphological markers.

Wild yams (Dioscorea spp.) are important tuber crops used both as vegetable and medicine by the tribal people of Koraput, India. There is deficiency of documented information on genetic structure and diversity of wild yams and its genetic assessment is necessary for crop improvement program. The present study assessed the level of genetic diversity of eight wild and one cultivated yam species of Koraput by using different morphological and molecular markers. Significant variation in different yield and morphological traits was observed among the studied yam species. The major morphological traits such as branch number, stem thickness, tuber depth, tuber length, number of tubers per plant and yield showed high genetic heritability accompanied with high genetic advance and major determinants of phenotypic diversity. Molecular profiling was carried out by taking five simple sequence repeat markers. A total of 10 polymorphic bands with an average of two were detected at the loci of the five markers across the nine yam species. Genetic similarity analysis revealed that some wild yam species such as D. oppositifolia, D. hamiltonii and D. pubera showed higher genetic similarity with cultivated (D. alata) species. The knowledge of the extent of genetic variations of wild yam species is important for planning of the genetic conservation and the utilization of this resource especially for genetic improvement.

Exploring Closed-Shell Cationic Phenalenyl: From Catalysis to Spin Electronics.

The odd alternant hydrocarbon phenalenyl (PLY) can exist in three different forms, a closed-shell cation, an open-shell radical, and a closed-shell anion, using its nonbonding molecular orbital (NBMO). The chemistry of PLY-based molecules began more than five decades ago, and so far, the progress has mainly involved the open-shell neutral radical state. Over the last two decades, we have witnessed the evolution of a range of PLY-based radicals generating an array of multifunctional materials. However, it has been admitted that the practical applications of PLY radicals are greatly challenged by the low stability of the open-shell (radical) state. Recently, we took a different route to establish the utility of these PLY molecules using the closed-shell cationic state. In such a design, the closed-shell unit of PLY can readily accept free electrons, stabilizing in its NBMO upon generation of the open-shell state of the molecule. Thus, one can synthetically avoid the unstable open-shell state but still take advantage of this state by in situ generating the radical through external electron transfer or spin injection into the empty NBMO. It is worth noting that such approaches using closed-shell phenalenyl have been missing in the literature. This Account focuses on our recent developments using the closed-shell cationic state of the PLY molecule and its application in broad multidisciplinary areas spanning from catalysis to spin electronics. We describe how this concept has been utilized to develop a variety of homogeneous catalysts. For example, this concept was used in designing an iron(III) PLY-based electrocatalyst for a single-compartment H2O2 fuel cell, which delivered the best electrocatalytic activity among previously reported iron complexes, organometallic catalysts for various homogeneous organic transformations (hydroamination and polymerization), an organic Lewis acid catalyst for the ring opening of epoxides, and transition-metal-free C-H functionalization catalysts. Moreover, this concept of using the empty NBMO present in the closed-shell cationic state of the PLY moiety to capture electron(s) was further extended to an entirely different area of spin electronics to design a PLY-based spin-memory device, which worked by a spin-filtration mechanism using an organozinc compound based on a PLY backbone deposited over a ferromagnetic substrate. In this Account, we summarize our recent efforts to understand how this unexplored closed-shell state of the phenalenyl molecule, which has been known for over five decades, can be utilized in devising an array of materials that not only are important from an organometallic chemistry or organic chemistry point of view but also provide new understanding for device physics.

Lactoferrin-modified Betulinic Acid-loaded PLGA nanoparticles are strong anti-leishmanials.

Visceral Leishmaniasis (VL), caused by the protozoan parasite Leishmania donovani, is a potentially fatal disease. The only orally bioavailable drug miltefosine is toxic and the effective liposomal Amphotericin B (AmBisome) is limited by its prohibitive cost and requirement for parenteral administration. Therefore, finding a new potential drug candidate and an alternative delivery system is imperative. We report that Betulinic acid (BA), a pentacyclic triterpenoid from Betula alba bark, was loaded onto uniformly spherical PLGA nanoparticles (BANPs; diameter 187.5 ±â€¯5.60 nm) coated with Lactoferrin (Lf-BANPs). The amastigotes count in macrophages was more effectively reduced by Lf-BANP than BA and BANP. Lf-BANPs reduced the pro-parasitic, anti-inflammatory cytokine IL-10, but increased nitric oxide (NO), production in L. donovani-infected macrophages indicating that Lf-BANP possesses a significant anti-leishmanial activity.

Manganese-Catalyzed Environmentally Benign Dehydrogenative Coupling of Alcohols and Amines to Form Aldimines and H2: A Catalytic and Mechanistic Study.

The catalytic dehydrogenative coupling of alcohols and amines to form aldimines represents an environmentally benign methodology in organic chemistry. This has been accomplished in recent years mainly with precious-metal-based catalysts. We present the dehydrogenative coupling of alcohols and amines to form imines and H2 that is catalyzed, for the first time, by a complex of the earth-abundant Mn. Detailed mechanistic study was carried out with the aid of NMR spectroscopy, intermediate isolation, and X-ray analysis.

Incorporation of Bacterial Blight Resistance Genes Into Lowland Rice Cultivar Through Marker-Assisted Backcross Breeding.

Bacterial blight (BB) of rice caused by Xanthomonas oryzae pv. oryzae is a major disease of rice in many rice growing countries. Pyramided lines carrying two BB resistance gene combinations (Xa21+xa13 and Xa21+xa5) were developed in a lowland cultivar Jalmagna background through backcross breeding by integrating molecular markers. In each backcross generation, markers closely linked to the disease resistance genes were used to select plants possessing the target genes. Background selection was continued in those plants carrying resistant genes until BC(3) generation. Plants having the maximum contribution from the recurrent parent genome were selected in each generation and hybridized with the recipient parent. The BB-pyramided line having the maximum recipient parent genome recovery of 95% was selected among BC3F1 plants and selfed to isolate homozygous BC(3)F(2) plants with different combinations of BB resistance genes. Twenty pyramided lines with two resistance gene combinations exhibited high levels of tolerance against the BB pathogen. In order to confirm the resistance, the pyramided lines were inoculated with different X. oryzae pv. oryzae strains of Odisha for bioassay. The genotypes with combination of two BB resistance genes conferred high levels of resistance to the predominant X. oryzae pv. oryzae isolates prevalent in the region. The pyramided lines showed similarity with the recipient parent with respect to major agro-morphologic traits.

Selective Hydrogenation of Nitriles to Primary Amines Catalyzed by a Cobalt Pincer Complex.

The catalytic hydrogenation of nitriles to primary amines represents an atom-efficient and environmentally benign reduction methodology in organic chemistry. This has been accomplished in recent years mainly with precious-metal-based catalysts, with a single exception. Here we report the first homogeneous Co-catalyzed hydrogenation of nitriles to primary amines. Several (hetero)aromatic, benzylic, and aliphatic nitriles undergo hydrogenation to the corresponding primary amines in good to excellent yields under the reaction conditions.

Cobalt-catalyzed hydrogenation of esters to alcohols: unexpected reactivity trend indicates ester enolate intermediacy.

The atom-efficient and environmentally benign catalytic hydrogenation of carboxylic acid esters to alcohols has been accomplished in recent years mainly with precious-metal-based catalysts, with few exceptions. Presented here is the first cobalt-catalyzed hydrogenation of esters to the corresponding alcohols. Unexpectedly, the evidence indicates the unprecedented involvement of ester enolate intermediates.

Protective efficacy of ursodeoxycholic acid nanoparticles in animal model of inflammatory bowel disease.

UNLABELLED: Abstract Context: Ursodeoxycholic acid (UDCA) exerts dose-dependent chemoprevention in colonic inflammation. Polycationic UDCA nanoparticles (UNPs) are envisaged for solubility enhancement and site directed drug delivery. OBJECTIVE: The objective was to study the ameliorative efficacy of UNPs through localized delivery of the drug. METHODS: UNPs were prepared through nanoprecipitation technique. Particle size, morphology, in vitro drug release and in vivo protective efficacy in inflammatory bowel disease (IBD) of these nanoparticles were studied. RESULTS AND DISCUSSION: The average particle size was around 100 nm, and the average drug encapsulation was about 99%. In vitro drug release study shows optimal drug release in simulated colonic fluid. The lowering of tissue nitric oxide, malondialdehyde, myeloperoxidase and histology of the colon tissue supported the protective efficacy of the nanoparticles. CONCLUSION: This study presents the improved efficacy of UNPs in animal model of IBD due to complete release of drug at the desired site of action.

Transfer semi-hydrogenation of terminal alkynes with a well-defined iron complex.

The synthesis and characterization of a bis-iron(II) complex was accomplished upon treatment of a phosphine free NNN-pincer ligand (L) with FeCl2·4H2O under ambient conditions. The deep greenish colored iron(II) complex (Fe-1) was characterized by a single-crystal X-ray diffraction study along with IR spectroscopy, UV-Vis spectroscopy, mass spectrometry, and elemental analysis. The Fe-1 complex was tested for the transfer semi-hydrogenation of terminal alkynes to the corresponding alkenes through the dehydrogenation of dimethyl amine-borane. This procedure enables the conversion of various structurally different terminal alkynes to alkenes under mild conditions. Control experiments were performed to shed light on the possible intermediates generated during the present protocol.

Exploring genetic divergence and marker-trait associations for leaffolder Cnaphalocrocis medinalis (Guenee) resistance in rice landraces.

Rice production faces a significant threat from the rice leaffolder, Cnaphalocrocis medinalis. To address this challenge, growing resistant varieties stands out as a sustainable and eco-friendly pest management strategy. This necessitates identifying resistant sources and understanding their inheritance patterns through employing DNA markers for marker-assisted resistance breeding. Our study involves screening for resistant cultivars following the SES of IRRI, assessing genetic diversity among landraces using molecular markers, and identifying genomic regions associated with resistance. Screening indicated that 33.33%, 27.08%, 19.79%, and 19.80% of genotypes were resistant, moderately resistant, susceptible, and admixture, respectively. Landraces were categorized into three clusters, with clusters I and II predominantly containing moderately resistant and resistant cultivars, and cluster III mainly susceptible types. Molecular variance analysis revealed 12% variation among populations and 88% within the population. Simple linear regression identified significant marker-trait associations, with markers RM 162 and RM 284 on chromosomes 6 and 8, respectively, found highly associated with leaffolder resistance. Phenotypic variation in leaffolder damage correlated highly with the allelic effects of these markers. Further confirmation of marker linkage with resistance loci was established through independent assays on highly resistant and susceptible genotypes. The information derived from genetic diversity and marker-trait associations will be useful for future marker-assisted resistance breeding programs, enhancing the sustainability of rice production.

Engineered andrographolide nanoparticles mitigate paracetamol hepatotoxicity in mice.

PURPOSE: Paracetamol (acetaminophen, APAP) overdose is often fatal due to progressive and irreversible hepatic necrosis. The aim of this work was to design Andrographolide (AG) loaded nanoparticles to prevent similar hepatic necrosis. METHODS: Functionalized AG-loaded PLGA nanoparticles carrying different densities of heparin were prepared following a facile emulsion solvent evaporation technique. Nanoparticle morphology, loading and release kinetics were studied. Hepatic localization of the nanoparticles was investigated in both normal and APAP damaged conditions using FITC fluorescent probe. Different serum parameters and liver histopathology were further examined as indicators of hepatic condition before and after treatment. RESULT: A collection of heparin functionalized AG-loaded PLGA nanoparticles were designed. Low amount of heparin on the particle surface could rapidly localize the nanoparticles up to the liver. The new functionalized AG nanoparticles affect efficient hepatoprotection in experimental mouse APAP overdose conditions. AG nanoparticle hepatoprotection was due to the rapid regeneration of antioxidant capacity and hepatic GSH store. CONCLUSIONS: Engineered nanoparticles loaded with AG provided a fast protection in APAP induced acute liver failure.

Poly(DL-lactide-co-glycolic acid) nanoparticle design and payload prediction: a molecular descriptor based study.

Polymer nanoparticles are veritable tools for pharmacokinetic and therapeutic modifications of bioactive compounds. Nanoparticle technology development and scaling up are however often constrained due to poor payload and improper particle dissolution. This work was aimed to develop descriptor based computational models as prior art tools for optimal payload in polymeric nanoparticles. Loading optimization experiments were carried out both in vitro and in-silico. Molecular descriptors generated in three different platforms DRAGON, molecular operating environment (MOE) and VolSurf+ were used. Multiple linear regression analysis (MLR) provided computation models which were further validated based on goodness of fit statistics and correlation coefficients (DRAGON, R(2)=0.889, Q(2)=0.657, R(2)(pred)=0.616; MOE, R(2)=0.826, Q(2)=0.572, R(2)(pred)=0.601; and VolSurf+, R(2)=0.818, Q(2)=0.573, R(2)(pred)=0.653). Pharmacophore space modeling studies were carried out in order to understand the fundamental molecular interactions necessary for drug loading in poly(DL-lactide-co-glycolic acid). The space modeling study (R(2)=0.882, Q(2)=0.662, R(2)(pred)=0.725, Δ(cost)=108.931) indicated that hydrogen bond acceptors and ring aromatic features are of primary significance for nanoparticle drug loading. Results of in vitro experiments have also confirmed the fact as a viable prognosis in case of nanoparticle payload. Polymeric nanoparticles payload prediction can therefore be a useful tool for wider benefits at the preformulation stages itself.

Elicitor-induced defense responses in Solanum lycopersicum against Ralstonia solanacearum.

We investigated on important parameters of induced resistance in hydroponic tomato (Solanum lycopersicum) against Ralstonia solanacearum using the elicitors chitosan (CHT), salicylic acid (SA), and jasmonic acid (JA). The increase in total phenolic content of roots by the elicitors was significantly higher than control. Most pronounced increase in lignin synthesis was triggered by SA followed by CHT. At 24 h post-elicitation (hpe), the activity of phenylalanine ammonia lyase was 4.5 times higher than control elicited by CHT. The peroxidase activity was about 86 nkat/mg protein at 24 hpe in case of SA and 78 nkat/mg protein in case of CHT. The activity of polyphenol oxidase increased several folds by the elicitors. Cinnamyl alcohol dehydrogenase activity increased to the maximum at 48 hpe under the influence of CHT. The results indicate that the elicitors SA and CHT induced effective defense responses in tomato plants against R. solanacearum. This was evident from reduced vascular browning and wilting symptoms of tomato plants treated with SA and CHT and challenged subsequently with R. solanacearum. This reduced disease incidence in tomato by SA and CHT may be a result of cell wall strengthening through deposition of lignin and the coincident induction of defense enzymes.