Design and analysis of UPQC in a microgrid using model reference adaptive control ensemble with back-stepping controller.

In recent years, the power sector has shifted to decentralized power generation, exemplified by microgrids that combine renewable and traditional power sources. With the introduction of renewable energy resources and distributed generators, novel strategies are required to improve reliability and quality of power (PQ). In our proposed system, a model consisting of photovoltaics, wind energy, and fuel cells has been designed to share a network, bolstered by the integration of UPQC to rectify PQ issues. Notably, our model introduces a Back-stepping controller method featuring Model Reference Adaptive Control (MRAC) with online parameter tuning, offering superior adaptability and responsiveness. This approach not only ensures optimal grid management but also enhances efficiency and stability. Furthermore, the proposed model demands minimal additional infrastructure, leveraging existing resources to streamline implementation and maintenance, thereby promoting sustainability and cost-effectiveness. The research culminates in a comparative analysis between the MRAC-Back-stepping controller, Adaptive Neuro-Fuzzy Inference System (ANFIS), and Fuzzy controller, highlighting the efficacy and versatility of our proposed model in microgrid operations. A Matlab model has been designed along with a hardware setup to demonstrate the robustness of the model.

The non-canonically organized members of MIR395 gene family in Brassica juncea are associated with developmentally regulated, sulfate-stress responsive bidirectional promoters that exhibit orientation-dependent differential transcriptional activity.

Several MICRORNA genes belonging to same family or different families are often found in homologous or non-homologous clusters. Among the various classes, head-to-head arranged genes form one of the largest categories of non-canonically organized genes. Such head-to-head arranged, non-canonically organized genes possibly share cis-regulatory region with the intergenic sequence having the potential to function as bi-directional promoter (BDP). The transcriptional regulation of head-to-head arranged genes, especially with bidirectional promoters, remains an enigma. In the past, bidirectional promoters have been characterized for a small set of protein-coding gene pairs in plants; however, to the best of our knowledge, no such study has been carried so far for MICRORNA genes. The present study thus functionally characterizes bidirectional promoters associated with members of MIR395 family, which is evolutionary conserved and is most frequently occurring cluster across plant kingdom. In Arabidopsis thaliana, the MIR395 gene family contains six members with two head-to-head arranged gene pairs- MIR395A-B and MIR395E-F. This organization was found to be conserved at seven loci for MIR395A-B, and eleven loci for MIR395E-F in five Brassica sps. Sequence analysis of the putative bidirectional promoters revealed variation in length, GC content and distribution of strict TATA-box. Comparatively higher level of conservation at both the ends of the bidirectional promoters, corresponding to ca. 250 bp upstream of 5'end of the respective MIRNA precursor, was observed. These conserved regions harbour several abiotic stress (nutrient, salt, drought) and hormone (ABA, ethylene) responsive cis-motifs. Functional characterization of putative bidirectional promoters associated with MIR395A-B and MIR395E-F from Arabidopsis and their respective orthologs from Brassica juncea (Bj_A08 MIR395A-B, Bj_B03 MIR395A-B, Bj_A07.1 MIR395E-F and Bj_A07.2 MIR395E-F) was carried out using a dual-reporter vector with ß-glucuronidase (GUS) and Green Fluorescent Protein (GFP). Analysis of transcriptional regulation of the two reporter genes - GUS and GFP during developmental stages confirmed their bidirectional nature. Orientation-dependent differential reporter activity indicated asymmetric nature of the promoters. Comparison of the reporter activity amongst orthologs, paralogs and homeologs revealed regulatory diversification, an outcome expected in polyploid genomes. Interestingly, reporter gene activities driven by selected bidirectional promoters were also observed in anther and siliques apart vegetative tissues indicating role of miR395 in anther and fruit development. Finally, we evaluated the activity of reporter genes driven under transcriptional regulation of bidirectional promoters under normal and sulfate-deprived conditions which revealed asymmetric inducibility under sulfate-starvation, in agreement with the known role of miR395 in sulfate homeostasis.

Vibrational, optical, and photocatalytic properties of ZnO/layered carbon nanocomposite synthesized by ball milling.

ZnO/layered carbon nanocomposites with varied sizes of ZnO nanoparticles (NPs) were synthesized by mechanical milling of mixture of ZnO NPs and carbon NPs. The NP size of ZnO was controlled with average particle sizes about 19.33, 21.87, 24.21, and 27.89 nm by varying the concentrations of carbon NPs viz 0, 2, 5, and 10 weight percent, respectively, in the mixture. Presence of carbon with ZnO in the form of composite also resulted in the enhanced shift of the band gap of ZnO due to the optical transitions in the impurity states or presence of carbon as compared to the ZnO size change alone. Additionally, the enhancement of absorbance in the visible region with an increase in carbon content was observed. Such an increase in absorbance can enhance the photocatalytic activity of ZnO NPs. Raman bands for ZnO NPs also were found to shift faster in the presence of layered carbon. The quenching of visible photoluminescence emission of ZnO NPs with an increase in concentration of carbon NPs in the composite indicated the phenomenon associated with transfer of electrons from ZnO to layered carbon helping the separation of photo-generated electrons and holes in ZnO and can lead to enhancement of the photocatalytic activity of ZnO NPs. In the photocatalytic studies, it was observed that the degradation of methylene blue (MB) dye was significantly enhanced by the increase of content of layered carbon in the nanocomposite. The sample containing 10% carbon showed the highest adsorption in dark conditions which was up to 60% of the starting strength and this was further enhanced to 88% in the presence of UV radiation. Enhanced adsorption of MB dye and the effective separation of electron-hole pairs due to charge transfer were believed to be the main causes behind such kind of improvement in the photocatalytic effects.

Enantio- and Z-Selective δ-Hydroarylation of Aryl-Substituted 1,3-Dienes via Rh-Catalyzed Conjugate Addition.

Metal-catalyzed enantioselective conjugate arylations of electron-poor alkenes are highly selective processes for C(sp2)-C(sp3) bond formation. δ-Selective hydroarylations of electron-poor 1,3-dienes are less well developed and reactions that deliver high enantioselectivity while giving single alkene isomer products are elusive. Here we report the Rh-catalyzed δ-arylation of aryl-substituted 1,3-dienes that gives nearly exclusive Z-1,4-addition products (generally with >95 : 5 positional and geometrical selectivity). This remote functionalization provides access to chiral diarylated alkenes from readily available precursors poised for further functionalization, including in the synthesis of bioactive molecules. Mechanistic studies suggest that protonolysis of a Rh-allyl intermediate generated by diene insertion into a Rh-aryl is the turnover limiting step and occurs by an inner-sphere proton transfer pathway.

Alterations in Circadian Rhythms, Sleep, and Physical Activity in COVID-19: Mechanisms, Interventions, and Lessons for the Future.

Although the world is acquitting from the throes of COVID-19 and returning to the regularity of life, its effects on physical and mental health are prominently evident in the post-pandemic era. The pandemic subjected us to inadequate sleep and physical activities, stress, irregular eating patterns, and work hours beyond the regular rest-activity cycle. Thus, perturbing the synchrony of the regular circadian clock functions led to chronic psychiatric and neurological disorders and poor immunological response in several COVID-19 survivors. Understanding the links between the host immune system and viral replication machinery from a clock-infection biology perspective promises novel avenues of intervention. Behavioral improvements in our daily lifestyle can reduce the severity and expedite the convalescent stage of COVID-19 by maintaining consistent eating, sleep, and physical activity schedules. Including dietary supplements and nutraceuticals with prophylactic value aids in combating COVID-19, as their deficiency can lead to a higher risk of infection, vulnerability, and severity of COVID-19. Thus, besides developing therapeutic measures, perpetual healthy practices could also contribute to combating the upcoming pandemics. This review highlights the impact of the COVID-19 pandemic on biological rhythms, sleep-wake cycles, physical activities, and eating patterns and how those disruptions possibly contribute to the response, severity, and outcome of SARS-CoV-2 infection.

Exploring the carbonic anhydrase-mimetic [(PMDTA)2ZnII2(OH-)2]2+ for nitric oxide monooxygenation.

In biology, nitrite (NO2-) serves as a storage pool of nitric oxide (NO); however, the formation of NO2- from NO is still under investigation. Here, we report the NO monooxygenation (NOM) reaction of a ZnII-hydroxide complex (1), producing a ZnII-nitrito complex {2, (ZnII-NO2-)} + H2.

Genomic dataset of a multiple-drug resistant Pseudomonas sp. strain RAC1 isolated from a flacherie infected Nistari race of Bombyx mori L.

Species belonging to the genus Pseudomonas is a rod shaped Gram-negative bacteria emerged as an important silkworm pathogen with broad-level multi-drug resistance. The extensive usage of antimicrobials in sericulture farming is gradually leading to the emergence of multi-drug resistance (MDR) strains, posing a significant threat to the well-being of both Bombyx mori L. and serifarmers. Pseudomonas spp. with MDR level may gets transmitted from the infected silkworm to human handlers either via direct contact or through contaminated feces. To understand the emerging concern of antimicrobial resistance (AMR) in Pseudomonas spp. provides insights into their genomic information. Here, we present the draft genome sequence data of Pseudomonas sp. strain RAC1 isolated from a flacherie infected Nistari race of Bombyx mori L. from the silkworm rearing house of Raiganj University, India and sequenced using the Illumina NovaSeq 6000 platform. The estimated genome size of the strain was 4494347 bp with a G + C content of 63.5%. The de novo assembly of the genome generated 38 contigs with an N50 of 200 kb. Our data might help to reveal the genetic diversity, underlying mechanisms of AMR and virulence potential of Pseudomonas spp. This draft-genome shotgun project has been deposited under the NCBI GenBank accession number NZ_JAUTXS000000000.

Evaluation of non-cancer risk owing to groundwater fluoride and iron in a semi-arid region near the Indo-Bangladesh international frontier.

Groundwater quality in Hili, a semi-arid border region at Indo-Bangladesh border, was investigated in the post-monsoon season of 2021, succeeded by assessment of probabilistic health risk arising from fluoride (F-) and iron (Fe) intake, with the hypothesis that groundwater quality of the region was not satisfactory for human consumption and health, considering earlier reports on high groundwater F- and Fe in few of the neighboring districts. All water samples were found to be potable in terms of Ca2+, Mg2+, Cl-, SO42- and NO3-, , but F- and Fe exceeded prescribed safe limits for drinking water in about 48% and 7% samples. Almost all water samples were found to be good for irrigation in terms of sodium adsorption ratio (SAR), soluble sodium percentage (SSP), Kelly's index (KI), %Na and magnesium ratio (MR). The principal component analysis (PCA) identified three major factors influencing groundwater quality, explaining about 71.8% of total variance and indicated that groundwater quality was primarily influenced by geochemical factors. Carbonate and silicate weathering were mainly responsible for dissolution of minerals in groundwater. Non-carcinogenic risk due to cumulative impact of F-and Fe intake was in the order of THIChildren > THIInfant > THIAdult. As per Monte Carlo simulation run with 5000 trials to ascertain the order of probabilistic health risk, the most dominant governing factors behind non-carcinogenic risk caused by F-and Fe intake were their concentration (Ci) followed by ingestion rate (IR), and exposure duration (ED).

Comparative genomics, microsynteny, ancestral state reconstruction and selection pressure analysis across distinctive genomes and sub-genomes of Brassicaceae for analysis of evolutionary history of VQ gene family.

Any unfavorable condition that affects the metabolism, growth, or development of plants is considered plant stress. The molecular response of plants towards abiotic stresses involves signaling to cellular components, repressing transcription factors, and subsequently induced metabolic changes. Most valine-glutamine (VQ) motif-containing genes in plants encode regulatory proteins that interact with transcription factors and modulate their activity as transcription regulators. Several VQ proteins regulate plant development and stress responses. In spite of the functional importance of VQs, there is relatively little information about their evolutionary history in Brassicaceae or beyond. Brassicaceae is characterized by paleoploidy, mesopolyploidy, and neopolyploidy, offering a resource for studying evolution and diversification. In current study we performed phylogeny of the VQ gene family along with comparative genomics, microsynteny and evolutionary rates analysis across seven species of Brassicaceae. Our findings revealed the following; (1) a large segmental duplication in the shared common ancestor of the family Brassicaceae, resulted in paralogies of VQ1-VQ10, VQ15-VQ24, VQ16-VQ23, VQ17-VQ25, VQ18-VQ26, VQ22-VQ27; (2) chromosomal mapping revealed diverse distributions of the gene family; (3) duplicated segments undergo varying degrees of retention and loss; and (4) Out of the 12 paralogous members, most of the genes are under purifying selection. However, VQ23 in Brassicaceae stands out as it is under positive selection, indicating the need for further investigation. Overall, our results clearly establish that the ancestral VQ1/VQ10, VQ15/VQ24, VQ16/VQ23, VQ17/VQ25, VQ18/VQ26, VQ22/VQ27 genes duplicated in shared common ancestor of Brassicaceae. Supplementary Information: The online version contains supplementary material available at 10.1007/s12298-023-01347-z.

MIR159 regulates multiple aspects of stamen and carpel development and requires dissection and delimitation of differential downstream regulatory network for manipulating fertility traits.

Unravelling genetic networks regulating developmental programs are key to devising and implementing genomics assisted trait modification strategies. It is crucial to understand the role of small RNAs, and the basis of their ability to modify traits. MIR159 has been previously reported to cause defects in anther development in Arabidopsis; however, the complete spectrum and basis of the defects remained unclear. The present study was therefore undertaken to comprehensively investigate the role of miR159 from Brassica juncea in modulating vegetative and reproductive traits. Owing to the polyploid nature of Brassica, paralogous and homeologous copies of MIR159A, MIR159B, and, MIR159C were identified and analysis of the precursor uncovered extensive structural and sequence variation. The MIR159 locus with mature miR159 with perfect target complimentarily with MYB65, was cloned from Brassica juncea var. Varuna for functional characterization by generating constitutively over-expressing lines in Arabidopsis thaliana Col-0. Apart from statistically significant difference in multiple vegetative traits, drastic differences were observed in stamen and pistil. Over-expression of miR159a led to shortening of filament length and loss of tetradynamous condition. Anthers were apiculate, with improper lobe formation, and unsynchronized cellular growth between connective tissue and another lobe development. Analysis revealed arrested meiosis/cytokinesis in microspores, and altered lignin deposition pattern in endothecial walls thus affecting anther dehiscence. In the gynoecium, flaccid, dry stigmatic papillae, and large embryo sac in the female gametophyte was observed. Over-expression of miR159a thus severely affected pollination and seed-set. Analysis of the transcriptome data revealed components of regulatory networks of anther and carpel developmental pathway, and lignin metabolism that are affected. Expression analysis allowed us to position the miR159a-MYB65 module in the genetic network of stamen development, involved in pollen-grain maturation; in GA-mediated regulation of stamen development, and in lignin metabolism. The study, on one hand indicates role of miR159a-MYB65 in regulating multiple aspects of reproductive organ development that can be manipulated for trait modification, but also raises several unaddressed questions such as relationship between miR159a and male-meiosis, miR159a and filament elongation for future investigations. Accession numbers: KC204951-KC204960. Project number PRJNA1035268. Supplementary Information: The online version contains supplementary material available at 10.1007/s12298-023-01377-7.

Synthesis of optically active star polymers consisting of helical poly(phenylacetylene) chains by the living polymerization of phenylacetylenes and their chiroptical properties.

Star polymers consisting of three helical poly(phenylacetylene) chains with a precisely controlled molecular weight (molar mass dispersity < 1.03) were successfully synthesized by the living polymerization of phenylacetylene derivatives with a Rh-based multicomponent catalyst system comprising trifunctional initiators, which have three phenylboronates centered on a benzene ring, the Rh complex [Rh(nbd)Cl]2, diphenylacetylene, triphenylphosphine, and a base. The analysis of chiroptical properties of the optically active star polymers obtained by the living polymerization of optically active phenylacetylene derivatives revealed that the star polymers exhibited chiral amplification properties owing to their unique topology compared with the corresponding linear polymers.

Mechanistic insights into nitric oxide oxygenation (NOO) reactions of {CrNO}5 and {CoNO}8.

Here, we report the nitric oxide oxygenation (NOO) reactions of two distinct metal nitrosyls {Co-nitrosyl (S = 0) vs. Cr-nitrosyl (S = 1/2)}. In this regard, we synthesized and characterized [(BPMEN)Co(NO)]2+ ({CoNO}8, 1) to compare its NOO reaction with that of [(BPMEN)Cr(NO)(Cl-)]+ ({CrNO}5, 2), having a similar ligand framework. Kinetic measurements showed that {CrNO}5 is thermally more stable than {CoNO}8. Complexes 1 and 2, upon reaction with the superoxide anion (O2˙-), generate [(BPMEN)CoII(NO2-)2] (CoII-NO2-, 3) and [(BPMEN)CrIII(NO2-)Cl-]+ (CrIII-NO2-, 4), respectively, with O2 evolution. Furthermore, analysis of these NOO reactions and tracking of the N-atom using 15N-labeled NO (15NO) revealed that the N-atoms of 3 (CoII-15NO2-) and 4 (CrIII-15NO2-) derive from the nitrosyl (15NO) moieties of 1 and 2, respectively. This work represents a comparative study of oxidation reactions of {CoNO}8vs. {CrNO}5, showing different rates of the NOO reactions due to different thermal stability. To complete the NOM cycle, we reacted 3 and 4 with NO, and surprisingly, only 3 generated {CoNO}8 species, while 4 was unreactive towards NO. Furthermore, the phenol ring nitration test, performed using 2,4-di-tert-butylphenol (2,4-DTBP), suggested the presence of a proposed peroxynitrite (PN) intermediate in the NOO reactions of 1 and 2.

Ocular and Neuro-ophthalmic Manifestations Post COVID-19 Infection.

A 39-year-old male with a history of COVID-19 infection presented with ocular manifestations: dendritic ulcer in the left eye cornea followed by diplopia in the same eye. Extraocular motility was restricted in the levo-lateral gaze with maximum diplopia measuring 25∆ exotropia. Slit lamp biomicroscopy showed dendritic patterned lesion with diffused superficial punctate keratitis in the cornea. There are various reports associated with COVID-19 and the neuro-ophthalmic system. Although the clinicopathological aspect of COVID-19 and the neurological system is still to explicate. However, the patient showed gradual improvement with topical and systemic antiviral therapy and orthoptic exercise. This points to the need for detailed neurological and ophthalmic workup in symptomatic COVID-19 patients. Taking the risk of viral spread into serious consideration, a thorough evaluation is though mandatory. Keywords: COVID-19; dendritic ulcer; lateral rectus palsy; superficial punctate keratopathy.

Complex origin, evolution, and diversification of non-canonically organized OVATE-OFP and OVATE-Like OFP gene pair across Embryophyta.

Ovate Family Proteins (OFP) is a plant-specific gene family of negative transcriptional regulators. Till-date, a handful of in-silico studies have provided glimpses into family size, expansion patterns, and genic features across all major plant lineages. A major lacuna exists in understanding origin of organisation complexity of members such as those arranged in a head-to-head manner which may lead to transcriptional co-regulation via a common bi-directional promoter. To address this gap, we investigated the origin, organization and evolution of two head-to-head arranged gene pairs of homologs of AtOFP2-AtOFP17, and, AtOFP4-AtOFP20 across Archaeplastida. The ancestral forms of AtOFP2, AtOFP4, AtOFP17, and AtOFP20 are likely to have evolved in last common ancestors of Embryophyta (land plants) given their complete absence in Rhodophyta and Chlorophyta. The OFP gene family originated and expanded in Bryophyta, including protein variants with complete (OVATE-OFP) or partial (OVATE-Like OFP) OVATE domain; with head-to-head organization present only in Spermatophyta (gymnosperms and angiosperms). Ancestral State Reconstruction revealed the origin of head-to-head organized gene pair in gymnosperms, with both genes being OVATE-OFP (homologs of AtOFP2/4). Phylogenetic reconstruction and copy number analysis suggests the presence of a single copy of the head-to-head arranged pair of OFP2/4 (OVATE)-OFP17/20 (OVATE-Like) in all angiosperms except Brassicaceae, and a duplication event in last common ancestor of core Brassicaceae approximately 32-54 MYA leading to origin of AtOFP2-AtOFP17 and AtOFP4-AtOFP20 as paralogs. Synteny analysis of genomic regions harbouring homologs of AtOFP2-AtOFP17, AtOFP4-AtOFP20 and AtOFP2/4-AtOFP17/20 across angiosperms suggested ancestral nature of AtOFP2-AtOFP17 gene pair. The present study thus establishes the orthology and evolutionary history of two non-canonically organised gene pairs with variation in their OVATE domain. The non-canonical organisation, atleast in Brassicaceae, has the potential of generating complex transcriptional regulation mediated via a common bi-directional promoter. The study thus lays down a framework to understand evolution of gene and protein structure, transcriptional regulation and function across a phylogenetic lineage through comparative analyses.

Nitric Oxide Oxygenation Reactions of Cobalt-Peroxo and Cobalt-Nitrosyl Complexes.

Here, we report a comparative study of nitric oxide oxidation (NOO) reactions of CoIII-peroxo (CoIII-O22-) and Co-nitrosyl ({CoNO}8) complexes bearing the same N4-donor ligand (HMTETA) framework. In this regard, we prepared and characterized two new [(HMTETA)CoIII(O22-)]+ (2, S = 2) and [(HMTETA)Co(NO)]2+ (3, S = 1) complexes from [(HMTETA)CoII(CH3CN)2]2+ (1). Both complexes (2 and 3) are characterized by different spectroscopic measurements, including their DFT-optimized structures. Complex 2 produces CoII-nitrato [(HMTETA)CoII(NO3-)]+ (CoII-NO3-, 4) complex in the presence of NO. In contrast, when 3 reacted with a superoxide (O2•-) anion, it generated CoII-nitrito [(HMTETA)CoII(NO2-)]+ (CoII-NO2-, 5) with O2 evolution. Experiments performed using 18/16O-labeled superoxide (18O2•-/16O2•-) showed that O2 originated from the O2•- anion. Both the NOO reactions are believed to proceed via a presumed peroxynitrite (PN) intermediate. Although we did not get direct spectral evidence for the proposed PN species, the mechanistic investigation using 2,4-di-tert-butylphenol indirectly suggests the formation of a PN intermediate. Furthermore, tracking the source of the N-atom in the above NOO reactions using 15N-labeled nitrogen (15NO) revealed N-atoms in 4 (CoII-15NO3-) and 5 (CoII-15NO2-) derived from the 15NO moiety.

Characterizing Oscillatory and Excitability Regimes in a Protein-Free Lipid Membrane.

Observations of electric potential oscillations in artificial lipid bilayers near the order-disorder transition indicate the existence of a stable limit cycle and, therefore, the possibility of producing excitable signals close to the bifurcation. We present a theoretical investigation of membrane oscillatory and excitability regimes induced by an increase in ion permeability at the order-disorder transition. The model accounts for the coupled effects of state-dependent permeability, membrane charge density, and hydrogen ion adsorption. A bifurcation diagram shows a transition between fixed-point and limit cycle solutions, enabling both oscillatory and excitability responses at different values of the acid association parameter. Oscillations are identified in terms of the membrane state, electric potential difference, and ion concentration near the membrane. The emerging voltage and time scales agree with measurements. Excitability is demonstrated by applying an external electric current stimulus, and the emerging signals display a threshold response and the appearance of repetitive signals upon using a long-lasting stimulus. The approach highlights the important role of the order-disorder transition, enabling membrane excitability in the absence of specialized proteins.

Acid-induced nitrite reduction of nonheme iron(ii)-nitrite: mimicking biological Fe-NiR reactions.

Nitrite reductase (NiR) catalyzes nitrite (NO2 -) to nitric oxide (NO) transformation in the presence of an acid (H+ ions/pH) and serves as a critical step in NO biosynthesis. In addition to the NiR enzyme, NO synthases (NOSs) participate in NO production. The chemistry involved in the catalytic reduction of NO2 -, in the presence of H+, generates NO with a H2O molecule utilizing two H+ + one electron from cytochromes and is believed to be affected by the pH. Here, to understand the effect of H+ ions on NO2 - reduction, we report the acid-induced NO2 - reduction chemistry of a nonheme FeII-nitrito complex, [(12TMC)FeII(NO2 -)]+ (FeII-NO2 -, 2), with variable amounts of H+. FeII-NO2 - upon reaction with one-equiv. of acid (H+) generates [(12TMC)Fe(NO)]2+, {FeNO}7 (3) with H2O2 rather than H2O. However, the amount of H2O2 decreases with increasing equivalents of H+ and entirely disappears when H+ reaches ≅ two-equiv. and shows H2O formation. Furthermore, we have spectroscopically characterized and followed the formation of H2O2 (H+ = one-equiv.) and H2O (H+ ≅ two-equiv.) and explained why bio-driven NiR reactions end with NO and H2O. Mechanistic investigations, using 15N-labeled-15NO2 - and 2H-labeled-CF3SO3D (D+ source), revealed that the N atom in the {Fe14/15NO}7 is derived from the NO2 - ligand and the H atom in H2O or H2O2 is derived from the H+ source, respectively.

Exploring the nitric oxide dioxygenation (NOD) reactions of manganese-peroxo complexes.

Here, we report the nitric oxide dioxygenation (NOD) reactions of two MnIII-peroxo (MIII-O22-) complexes, [(3PYENMe)MnIII(O22-)]+ (1) and [(N3PY)MnIII(O22-)]+ (2), bearing pentadentate ligands. Complexes 1 and 2 give MnII-nitrate (MnII-NO3-) complexes (3 and 4) when reacted with nitric oxide (NO), respectively. The mechanistic study explored by using 2,4-di-tert-butylphenol (2,4-DTBP) suggested that the NOD reaction of 1 and 2 occurs via a presumed Mn-peroxynitrite ([Mn-PN]+, [Mn-ONOO-]+) intermediate. Tracking the source of N atoms using 15NO revealed that the N-atoms in MnII-NO3- (3 and 4) are derived from the 15NO moiety. Furthermore, we have explored the MIII-O22- regeneration from NOD products (3 and 4), and we have observed the formation of MIII-O22- complexes (1 and 2) upon treatment with KO2 or H2O2/triethylamine (TEA), respectively.

Transition-Metal-Catalyzed Denitrogenative Annulation to Access High-Valued N-Heterocycles.

Over the past few years, the development of efficient methods to construct high-valued N-heterocyclic molecules have received massive attention owing to their extensive application in the areas of medicinal chemistry, drug discovery, natural product synthesis and so on. To access those high-valued N-heterocycles, many methods have been developed. In this context, transition-metal-catalyzed denitrogenative annulation of 1,2,3-triazoles and 1,2,3,4-tetrazoles has appeared as a powerful synthetic tool because it offers a step- and atom-economical route for the preparation of the nitrogen-rich molecules. Compared with the denitrogenative annulation of various 1,2,3-triazole frameworks, annulation of 1,2,3,4-tetrazole remains more challenging due to the inertness of the tetrazole moiety. This Review summarizes the significant achievements made in the field of denitrogenative annulation of various 1,2,3-triazoles and 1,2,3,4-tetrazoles including some pioneering examples in this area of research. We anticipate that this denitrogenative annulation reaction will find broad applications in the pharmaceutical industry, drug discovery and other fields of medicinal chemistry.

An iron(ii)-based metalloradical system for intramolecular amination of C(sp2)-H and C(sp3)-H bonds: synthetic applications and mechanistic studies.

A catalytic system for intramolecular C(sp2)-H and C(sp3)-H amination of substituted tetrazolopyridines has been successfully developed. The amination reactions are developed using an iron-porphyrin based catalytic system. It has been demonstrated that the same iron-porphyrin based catalytic system efficiently activates both the C(sp2)-H and C(sp3)-H bonds of the tetrazole as well as azide-featuring substrates with a high level of regioselectivity. The method exhibited an excellent functional group tolerance. The method affords three different classes of high-value N-heterocyclic scaffolds. A number of important late-stage C-H aminations have been performed to access important classes of molecules. Detailed studies (experimental and computational) showed that both the C(sp2)-H and C(sp3)-H amination reactions involve a metalloradical activation mechanism, which is different from the previously reported electro-cyclization mechanism. Collectively, this study reports the discovery of a new class of metalloradical activation modes using a base metal catalyst that should find wide application in the context of medicinal chemistry, drug discovery and industrial applications.