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.

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.

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.

Dual Role of TiO(acac)2 as a Reagent and an Activator/Catalyst: A Study on the Solvent Dependent Product Formation.

The dual operation of a chemical species in synthetic chemistry is an intriguing and relatively unexplored phenomenon. The application of such a species is expected to reduce the use of multiple reaction partners and catalysts/activators. Herein, we report a simple and easy-to-use protocol for the twin application of TiO(acac)2 , as a reagent and an activator to synthesize ß-enamino ketones with amines in acetonitrile. The same early transition metal precursor when employed in N,N-dimethylformamide with the amines, resulted in the formation of the substituted amides. Both reactions were explored with various substrates to check the viability of the present protocol. Moreover, experimental studies were conducted to understand the mechanism of both reactions.

Metal-free C-H Borylation and Hydroboration of Indoles.

The C-H borylation and hydroboration reactions have emerged as promising synthetic tools to construct organoboron compounds. Organoboron compounds of N-heterocycles, particularly indole derivatives, have found widespread application in a variety of fields. As a result, considerable advancement in the area of C-H borylation and hydroboration reactions of indoles was observed in the last few decades. Among the various synthetic methods applied, the metal-free approach has received special attention. This mini-review discusses the recent progress in the area of C-H borylation and hydroboration reactions of indoles under metal-free conditions, their scope, and brief mechanistic studies.

A Lewis Acid-Base Pair Catalyzed Dearomative Transformation of Unprotected Indoles via B-H Bond Activation.

A sustainable and metal-free protocol has been described for the reduction of unprotected indoles. The catalytic system consists of B(C6 F5 )3 and THF as a Lewis acid-base pair that can activate the B-H bond of pincolborane (HBpin). The catalytic system encompasses a broad substrate scope. Control experiments were conducted to understand the possible catalytic intermediates involved during the present protocol.

Easy Access to Tertiary Amines from Carbonyl Compounds with Substituted Amine-Boranes: A Substrate, Catalyst, and Additive-Free Approach Under Mild Conditions.

Tertiary amines are ubiquitous and play an essential role in organocatalysis, pharmaceuticals, and fine chemicals. Amongst various synthetic procedures known for their synthesis, the reductive amination of carbonyl compounds has been found to be a proficient method. Over the past few decades, different synthetic strategies for reductive amination have been developed. Most of them suffer from the use of transition metals and/or harsh reaction conditions. Herein, we present an efficient, operationally simple protocol for the chemoselective transformation of carbonyl compounds to tertiary amines under benign conditions. The strategy encompasses a broad substrate scope under the metal-free condition at room temperature and does not require any solvent. A detailed mechanistic investigation was performed with the aid of control experiments and computational study to shed light on the reaction pathway.

Synthesis of porous calcium-guar gum benzoate nano-biohybrids for sorptive removal of congo red and phosphates from water.

This work aims to develop an eco-sound nano-bio-hybrid sorbent using sustainable materials for sorptive elimination of congo red and phosphates from aquatic environment. An amphipathic biopolymer derivative, high DS guar gum benzoate (GGBN) was used for entrapment of as synthesized calcium carbonate nanoparticles using solvent diffusion nano-precipitation technique. Designer nano-biohybrids were developed upon experimenting with various materials stoichiometry. SEM, XRD and EDX studies confirmed near-uniform impregnation of rhombohedral calcium carbonate crystals throughout the biopolymer matrix. Average pore size distribution and surface area of final product Ca-GGBNC, were estimated from NDLFT and BET methods respectively. Analysis of adsorption findings acquired at study temperature 27 ± 2 °C showed that the maximum adsorption capacity of Ca-GGBNC recorded qmax, 333.33 mg/g for congo red azo dye and that for phosphate was at 500 mg/g. Adsorptive removal was noted and both components followed pseudo second order kinetics. Intra-particle diffusion kinetics investigation disclosed that the boundary layer effect was prominent and the adsorption rates were not solely directed by the diffusion stage. Activation energy, Ea was to be estimated using Arrhenius equation at 56.136 and 47.015 KJ/mol for congo red and phosphates respectively. The calculated thermodynamic parameters(ΔG°, ΔH°, and ΔS°) revealed the spontaneous, feasible and endothermic sorption process. Owing to active surface area, spherical size, functional moiety and porous network, antibacterial properties of nanobiohybrid were persistent and MIC against E. coli and S. aureus were recorded at 200 µg/mL and 350 µg/mL respectively.

The soil-borne fungal pathogen Athelia rolfsii: past, present, and future concern in legumes.

Legumes are ubiquitous, low-cost meals that are abundant in protein, vitamins, minerals, and calories. Several biotic constraints are to blame for the global output of legumes not meeting expectations. Fungi, in particular, are substantial restrictions that not only hinder production but also pose a serious health risk to both human and livestock consumption. Athelia rolfsii (Syn. Sclerotium rolfsii) is a dangerous pathogenic fungus that attacks most crops, causing massive yield losses. Legumes are no longer immune to this dreadful fungus, which can potentially result in a 100% yield loss. The initial disease symptoms based on the formation of brown color lesions at the point of infection and further development of mycelia, followed by yellowing and wilting of the whole plant. To tackle such situation, various strategies, i.e., management in cultural practices, disease-free plant growth, genetic changes, crop hybridization and in vitro culture techniques have been undertaken. This present review encapsulates the entire situation, from sclerotial dissemination through infection development and control in legume crops, with the goal of developing a tangible understanding of sustainable legume production improvements. Further study in this area might be led in an integrated manner as a result of this information, which could contribute to a better understanding of the processes of disease incidence, resistance mechanism, and its control, and fostering greater inventiveness in the production of legumes.

Chemopriming for induction of disease resistance against pathogens in rice.

Rice is an important grain crop of Asian population. Different fungal, bacterial and viral pathogens cause large reduction in rice grain production. Use of chemical pesticides, to provide protection against pathogens, has become incomplete due to pathogens resistance and is cause of environmental concerns. Therefore, induction of resistance in rice against pathogens via biopriming and chemopriming with safe and novel agents has emerged on a global level as ecofriendly alternatives that provide protection against broad spectrum of rice pathogens without any significant yield penalty. In the past three decades, a number of chemicals such as silicon, salicylic acid, vitamins, plant extract, phytohormones, nutrients etc. have been used to induce defense against bacterial, fungal and viral rice pathogens. From the detailed analysis of abiotic agents used, it has been observed that silicon and salicylic acid are two potential chemicals for inducing resistance against fungal and bacterial diseases in rice, respectively. However, an inclusive evaluation of the potential of different abiotic agents to induce resistance against rice pathogens is lacking due to which the studies on induction of defense against rice pathogens via chemopriming has become disproportionate and discontinuous. The present review deals with a comprehensive analysis of different abiotic agents used to induce defense against rice pathogens, their mode of application, mechanism of defense induction and the effect of defense induction on grain yield. It also provides an account of unexplored areas, which might be taken into attention to efficiently manage rice diseases. DATA AVAILABILITY STATEMENT: Data sharing not applicable to this article as no datasets were generated or analysed during the current study.

Chemoselective α-Alkylation of Nitriles with Primary Alcohols by Manganese(I)-Catalysis.

A sustainable and easy-to-use protocol for the alkylation of aryl nitriles with the earth-abundant manganese(I) catalyst is presented. The alkylation reaction employs readily available nitriles and naturally abundant alcohols as the coupling partners. The reaction proceeds chemoselectively and encompasses a broad substrate scope with good to excellent yields. The catalytic reaction yields selectively α-branched nitriles and water as the sole byproduct. Experimental studies were executed to understand the mechanism of the catalytic reaction.

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.

Marker-Assisted Improvement for Durable Bacterial Blight Resistance in Aromatic Rice Cultivar HUR 917 Popular in Eastern Parts of India.

Bacterial blight (BB) is a devastating disease of rice in the tropics of Indian sub-continent, where the presence of Xoo races with varying levels of genetic diversity and virulence renders disease management extremely challenging. In this context, marker-assisted improvement of plant resistance has been proven as one of the most promising approaches for the development of sustainable rice cultivars. The present study demonstrates the marker-assisted introgression of the three BB resistant genes (Xa21 + xa13 + xa5) into the background of HUR 917, a popular aromatic short grain (ASG) rice cultivar in India. The performance of the resulting improved products (near isogenic lines (NILs), HR 23-5-37-83-5, HR 23-5-37-121-10, HR 23-5-37-121-14, HR 23-65-6-191-13, HR 23-65-6-237-2, HR 23-65-6-258-10 and HR 23-65-6-258-21) establishes the utility of marker-assisted selection (MAS) approach for accelerated trait introgression in rice. The MAS-bred lines carrying three introgressed genes showed broad spectrum BB resistance (lesion length, LL of 1.06 ± 1.35 cm to 4.61 ± 0.87 cm). Besides, these improved lines showed the complete product profile of recurrent parent HUR 917 along with the enhanced level of durable BB resistance. The improved introgression lines with durable BB resistance would contribute to sustainable rice production in India, particularly in the Indo-Gangetic plane that has substantial acreage under HUR 917.

Molecular Breeding for Incorporation of Submergence Tolerance and Durable Bacterial Blight Resistance into the Popular Rice Variety 'Ranidhan'.

Ranidhan is a popular late-maturing rice variety of Odisha state, India. The farmers of the state suffer heavy loss in years with flash floods as the variety is sensitive to submergence. Bacterial blight (BB) disease is a major yield-limiting factor, and the variety is susceptible to the disease. BB resistance genes Xa21, xa13, and xa5, along with the Sub1 QTL, for submergence stress tolerance were transferred into the variety using marker-assisted backcross breeding approach. Foreground selection using direct and closely linked markers detected the progenies carrying all four target genes in the BC1F1, BC2F1, and BC3F1 generations, and the positive progenies carrying these genes with maximum similarity to the recipient parent, Ranidhan, were backcrossed into each segregating generation. Foreground selection in the BC1F1 generation progenies detected all target genes in 11 progenies. The progeny carrying all target genes and similar to the recipient parent in terms of phenotype was backcrossed, and a total of 321 BC2F1 seeds were produced. Ten progenies carried all target genes/QTL in the BC2F1 generation. Screening of the BC3F1 progenies using markers detected 12 plants carrying the target genes. A total of 1270 BC3F2 seeds were obtained from the best BC3F1 progeny. Foreground selection in the BC3F2 progenies detected four plants carrying the target genes in the homozygous condition. The bioassay of the pyramided lines conferred very high levels of resistance to the predominant isolates of bacterial blight pathogen. These BB pyramided lines were submergence-tolerant and similar to Ranidhan in 13 agro-morphologic and grain quality traits; hence, they are likely to be adopted by farmers.

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.

Mechanistic Understanding of KOt Bu-Mediated Direct Amidation of Esters with Anilines: An Experimental Study and Computational Approach.

A sustainable and cost-effective protocol has been reported for the synthesis of amide bonds from unactivated esters and non-nucleophilic amines promoted by potassium tert-butoxide under aerobic conditions. The reaction proceeds under relatively mild conditions, encompassing wide substrate scope. A combined experimental and quantum chemical study has been performed to shed light on the mechanism, which implied that a radical pathway is operating for the present protocol.

Novel Insights into Understanding the Molecular Dialogues between Bipolaroxin and the Gα and Gß Subunits of the Wheat Heterotrimeric G-Protein during Host-Pathogen Interaction.

Spot blotch disease of wheat, caused by the fungus Bipolaris sorokiniana (Sacc.) Shoem., produces several toxins which interact with the plants and thereby increase the blightening of the wheat leaves, and Bipolaroxin is one of them. There is an urgent need to decipher the molecular interaction between wheat and the toxin Bipolaroxin for in-depth understanding of host-pathogen interactions. In the present study, we have developed the three-dimensional structure of G-protein alpha subunit from Triticum aestivum. Molecular docking studies were performed using the active site of the modeled G-protein alpha and cryo-EM structure of beta subunit from T. aestivum and 'Bipolaroxin'. The study of protein-ligand interactions revealed that six H-bonds are mainly formed by Glu29, Ser30, Lys32, and Ala177 of G-alpha with Bipolaroxin. In the beta subunit, the residues of the core beta strand domain participate in the ligand interaction where Lys256, Phe306, and Leu352 formed seven H-bonds with the ligand Bipolaroxin. All-atoms molecular dynamics (MD) simulation studies were conducted for G-alpha and -beta subunit and Bipolaroxin complexes to explore the stability, conformational flexibility, and dynamic behavior of the complex system. In planta studies clearly indicated that application of Bipolaroxin significantly impacted the physio-biochemical pathways in wheat and led to the blightening of leaves in susceptible cultivars as compared to resistant ones. Further, it interacted with the Gα and Gß subunits of G-protein, phenylpropanoid, and MAPK pathways, which is clearly supported by the qPCR results. This study gives deeper insights into understanding the molecular dialogues between Bipolaroxin and the Gα and Gß subunits of the wheat heterotrimeric G-protein during host-pathogen interaction.

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.

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.

Guar gum propionate-kojic acid films for Escherichia coli biofilm disruption and simultaneous inhibition of planktonic growth.

Nosocomial bacterial infections associated with biofilms inspire to explore newer bactericidal strategy with eco-friendly biomaterials as sustainable alternatives. In this research work, we successfully developed bio-safe films from kojic acid(KA) and guar gum propionate(GGP) for Escherichia coli biofilm disruption and planktonic cell killing. High DS(degree of substitution = 1.52) GGP was synthesized from guar gum (GG)assisted by chaotropic ions at room-temperature. Biopolymers were routinely characterized in CHN analyzer, FT-IR, TGA and XRD analysis. KA loaded GGP films were prepared by cross-linking the molecules in presence of epichlorhydrin and two different percentages of KA were employed. Film physical and tensile properties were systematically evaluated and optimized. Water vapour permeability (WVP) and tensile strength of final film GGPFK10 were recorded at 0.741 ± 0.09gmm-1kPa-1h-1 and 19.23 MPa. KA release from GGP matrix followed controlled diffusion process. MIC of GGP was 130 µg/mL and zone of inhibition of GGPFK10 was confirmed at 16.1 mm. SEM experiments disclosed the absence of pili-like structures with squeezed and elongated cellular morphology in dead planktonic cells. Disruption of biofilms was experimented in detail by CV assay, fluorescent, light microscopic and SEM studies. The film showed excellent cell-viability on human adult dermal fibroblast (HADF)cell-line. Overall, the biosafe film would be a potent antibacterial device for treating infections against E.coli biofilms and planktonic cells.