Optimizing the NRR activity of single and double boron atom catalysts using a suitable support: a first principles investigation.

Designing cost effective transition-metal free electrocatalysts for nitrogen fixation under ambient conditions is highly appealing from an industrial point of view. Using density functional theory calculations in combination with the computational hydrogen electrode model, we investigate the N2 activation and reduction activity of ten different model catalysts obtained by supporting single and double boron atoms on five different substrates (viz. GaN, graphene, graphyne, MoS2 and g-C3N4). Our results demonstrate that the single/double boron atom catalysts bind favourably on these substrates, leading to a considerable change in the electronic structure of these materials. The N2 binding and activation results reveal that the substrate plays an important role by promoting the charge transfer from the single/double boron atom catalysts to the antibonding orbitals of *N2 to form strong B-N bonds and subsequently activate the inert NN bond. Double boron atom catalysts supported on graphene, MoS2 and g-C3N4 reveal very high binding energies of -2.38, -2.11 and -1.71 eV respectively, whereas single boron atom catalysts supported on graphene and g-C3N4 monolayers bind N2 with very high binding energies of -1.45 and -2.38 eV, respectively. The N2 binding on these catalysts is further explained by means of orbital projected density of states plots which reflect greater overlap between the N2 and B states for the catalysts, which bind N2 strongly. The simulated reaction pathways reveal that the single and double boron atom catalysts supported on g-C3N4 exhibit excellent catalytic activity with very low limiting potentials of -0.67 and -0.36 V, respectively, while simultaneously suppressing the HER. Thus, the current work provides important insights to advance the design of transition-metal free catalysts for electrochemical nitrogen fixation from an electronic structure point of view.

Stevens-johnson Syndrome and Toxic Epidermal Necrolysis: An Overview of Diagnosis, Therapy Options and Prognosis of Patients.

Both Stevens-johnson syndrome (SJS) and Toxic-epidermal necrolysis (TEN) are generally medication-induced pathological conditions that mostly affect the epidermis and mucus membranes. Nearly 1 to 2 patients per 1,000,000 population are affected annually with SJS and TEN, and sometimes these maladies can cause serious life-threatening events. The reported death rates for SJS range from 1 to 5%, and 25 to 35% for TEN. The mortality risk may even be higher among elderly patients, especially in those who are affected by a significant amount of epidermal detachment. More than 50% of TEN patients who survive the illness may experience long-term lower quality of life and lesser life expectancy. The clinical and histopathological conditions of SJS and TEN are characterized by mucocutaneous discomfort, haemorrhagic erosions, erythema, and occasionally severe epidermal separation that can turn into ulcerative patches and dermal necrosis. The relative difference between SJS and TEN is the degree of ulcerative skin detachment, making them two extremes of a spectrum of severe cutaneous adverse drug-induced reactions (cADRs). In the majority of cases, serious drug-related hypercreativities are considered the main cause of SJS & TEN; however, herpes simplex virus and Mycoplasma pneumoniae infections may also produce similar type clinical conditions. The aetiology of a lesser number of cases and their underlying causative factors remain unknown. Among the drugs with a 'greater likelihood' of causing TEN & SJS are carbamazepine (CBZ), trimethoprim-sulfamethoxazole, phenytoin, aminopenicillins, allopurinol, cephalosporins, sulphonamides, antibiotics, quinolones, phenobarbital, and NSAIDs of the oxicam variety. There is also a strong genetic link between the occurrence of SJS and IEN in the Han Chinese population. Such genetic association is based on the human leukocyte antigen (HLA-B*1502) and the co-administration of carbamazepine. The diagnosis of SJS is made mostly on the gross observations of clinical symptoms, and confirmed by the histopathological examination of dermal biopsies of the patients. The differential diagnoses consist of the exclusion of Pemphigus vulgaris, bullous pemphigoid, linear IgA dermatosis, paraneoplastic pemphigus, disseminated fixed bullous drug eruption, acute generalized exanthematous pustulosis (AGEP), and staphylococcal scalded skin syndrome (SSSS). The management of SJS & TEN is rather difficult and complicated, and there is sometimes a high risk of mortality in seriously inflicted patients. Urgent medical attention is needed for early diagnosis, estimation of the SCORTEN prognosis, identification and discontinuation of the causative agent as well as highdose injectable Ig therapeutic interventions along with specialized supportive care. Historical aspects, aetiology, mechanisms, and incidences of SJS and TEN are discussed. An update on the genetic occurrence of these medication-related hypersensitive ailments as well as different therapy options and management of patients is also provided.

Forthcoming Developments in Models to Study the Hepatitis B Virus Replication Cycle, Pathogenesis, and Pharmacological Advancements.

Hepatitis, liver cirrhosis, and hepatocellular carcinoma are all manifestations of chronic hepatitis B. Its pathogenesis and molecular mechanism remain mysterious. As medical science progresses, different models are being used to study the disease from the physiological and molecular levels. Animal models have played an unprecedented role in achieving in-depth knowledge of the disease while posing no risk of harming humans throughout the study. The scarcity of acceptable animal models has slowed progress in hepatitis B virus (HBV) research and preclinical testing of antiviral medicines since HBV has a narrow species tropism and exclusively infects humans and higher primates. The development of human chimeric mice was supported by a better understanding of the obstacles to interspecies transmission, which has substantially opened the way for HBV research in vivo and the evaluation of possible chronic hepatitis B therapeutics. Animal models are cumbersome to handle, not accessible, and expensive. Hence, it is herculean to investigate the HBV replication cycle in animal models. Therefore, it becomes essential to build a splendid in vitro cell culture system to demonstrate the mechanisms attained by the HBV for its multiplication and sustenance. We also addressed the advantages and caveats associated with different models in examining HBV.

Potential antiviral activities of chrysin against hepatitis B virus.

BACKGROUND: Interferon and nucleos(t)ide analogues are current therapeutic treatments for chronic Hepatitis B virus (HBV) infection with the limitations of a functional cure. Chrysin (5, 7-dihydroxyflavone) is a natural flavonoid, known for its antiviral and hepatoprotective activities. However, its anti-HBV activity is unexplored. METHODS: In the present study, the anti-hepatitis B activity of chrysin was investigated using the in vitro experimental cell culture model, HepG2 cells. In silico studies were performed where chrysin and lamivudine (used here as a positive control) were docked with high mobility group box 1 protein (HMGB1). For the in vitro studies, wild type HBV genome construct (pHBV 1.3X) was transiently transfected in HepG2. In culture supernatant samples, HBV surface antigen (HBsAg) and Hepatitis B e antigen (HBeAg) were measured by enzyme-linked immunosorbent assay (ELISA). Secreted HBV DNA and intracellular covalently closed circular DNA (cccDNA) were measured by SYBR green real-time PCR. The 3D crystal structure of HMGB1 (1AAB) protein was developed and docked with the chrysin and lamivudine. In silico drug-likeness, Absorption, Distribution, Metabolism, Excretion and Toxicity (ADMET) properties of finest ligands were performed by using SwissADME and admetSAR web servers. RESULTS: Data showed that chrysin significantly decreases HBeAg, HBsAg secretion, supernatant HBV DNA and cccDNA, in a dose dependent manner. The docking studies demonstrated HMGB1 as an important target for chrysin as compared to lamivudine. Chrysin revealed high binding affinity and formed a firm kissing complex with HMGB1 (∆G = - 5.7 kcal/mol), as compared to lamivudine (∆G = - 4.3 kcal/mol), which might be responsible for its antiviral activity. CONCLUSIONS: The outcome of our study establishes chrysin as a new antiviral against HBV infection. However, using chrysin to treat chronic HBV disease needs further endorsement and optimization by in vivo studies in animal models.

Biochemical and proteomic insights revealed selenium priming induced phosphorus stress tolerance in common bean (Phaseolus vulgaris L.).

BACKGROUND: Mineral stress is one of the dominating abiotic stresses, which leads to decrease in crop production. Selenium (Se) seed priming is a recent approach to mitigate the plant's mineral deficiency stress. Although not an essential element, Se has beneficial effects on the plants in terms of growth, quality, yield and plant defense system thus, enhancing plant tolerance to mineral deficiency. METHODS AND RESULTS: The present research was accomplished to find out the effect of Se priming on common bean plant (SFB-1 variety) under phosphorus (P) stress. The seeds were grown invitro on four different MGRL media which are normal MGRL media as control with non-Se primed seeds (Se- P+), non -Se primed seeds grown on P deficient MGRL media (Se- P-), Se primed seeds grown on normal MGRL media (Se+P+) and Se primed seeds grown on P deficient MGRL media (Se+P -). The various morphological and biochemical parameters such as proline content, total sugar content, polyphenols and expression of proteins were analyzed under P stress. The results showed that Se priming has significantly (p ≤ 0.05) affected the morphological as well as biochemical parameters under normal and P stress conditions. The morphological parameters-length, weight, number of nodes and leaves of Se+P+, Se+P- root and shoot tissue showed significant increase as compared to Se-P+, Se-P-. Similarly various biochemical parameters such as total chlorophyll content, proline, total sugar content and polyphenols of Se+P+, Se+P- increased significantly as compared to Se-P+, Se-P-. The differential protein expression in both Se+P+, Se+P- and Se-P+, Se-P- plants were determined using MALDI-MS/MS. The differentially expressed proteins in Se+P+, Se+P- plants were identified as caffeic acid-3-O-methyltransferase (COMT) and SecA protein (a subunit of Protein Translocan transporter), and are found responsible for lignin synthesis in root cell walls and ATP dependent movement of thylakoid proteins across the membranes in shoot respectively. The differential expression of proteins in plant tissues, validated morphological and biochemical responses such as maintaining membrane integrity, enhanced modifications in cellular metabolism, improved polyphenol activities and expression of defensive proteins against mineral deficiency. CONCLUSIONS: The study provided an understanding of Se application as a potential approach increasing tolerance and yield in crop plants against mineral deficiency.

The microbiome-derived metabolite TMAO drives immune activation and boosts responses to immune checkpoint blockade in pancreatic cancer.

The composition of the gut microbiome can control innate and adaptive immunity and has emerged as a key regulator of tumor growth, especially in the context of immune checkpoint blockade (ICB) therapy. However, the underlying mechanisms for how the microbiome affects tumor growth remain unclear. Pancreatic ductal adenocarcinoma (PDAC) tends to be refractory to therapy, including ICB. Using a nontargeted, liquid chromatography-tandem mass spectrometry-based metabolomic screen, we identified the gut microbe-derived metabolite trimethylamine N-oxide (TMAO), which enhanced antitumor immunity to PDAC. Delivery of TMAO intraperitoneally or via a dietary choline supplement to orthotopic PDAC-bearing mice reduced tumor growth, associated with an immunostimulatory tumor-associated macrophage (TAM) phenotype, and activated effector T cell response in the tumor microenvironment. Mechanistically, TMAO potentiated the type I interferon (IFN) pathway and conferred antitumor effects in a type I IFN-dependent manner. Delivering TMAO-primed macrophages intravenously produced similar antitumor effects. Combining TMAO with ICB (anti-PD1 and/or anti-Tim3) in a mouse model of PDAC significantly reduced tumor burden and improved survival beyond TMAO or ICB alone. Last, the levels of bacteria containing CutC (an enzyme that generates trimethylamine, the TMAO precursor) correlated with long-term survival in patients with PDAC and improved response to anti-PD1 in patients with melanoma. Together, our study identifies the gut microbial metabolite TMAO as a driver of antitumor immunity and lays the groundwork for potential therapeutic strategies targeting TMAO.

HBV cccDNA-A Culprit and Stumbling Block for the Hepatitis B Virus Infection: Its Presence in Hepatocytes Perplexed the Possible Mission for a Functional Cure.

Hepatitis B virus infection (HBV) is still a big health problem across the globe. It has been linked to the development of liver cirrhosis and hepatocellular carcinoma and can trigger different types of liver damage. Existing medicines are unable to disable covalently closed circular DNA (cccDNA), which may result in HBV persistence and recurrence. The current therapeutic goal is to achieve a functional cure, which means HBV-DNA no longer exists when treatment stops and the absence of HBsAg seroclearance. However, due to the presence of integrated HBV DNA and cccDNA functional treatment is now regarded to be difficult. In order to uncover pathways for potential therapeutic targets and identify medicines that could result in large rates of functional cure, a thorough understanding of the virus' biology is required. The proteins of the virus and episomal cccDNA are thought to be critical for the management and support of the HBV replication cycle as they interact directly with the host proteome to establish the best atmosphere for the virus while evading immune detection. The breakthroughs of host dependence factors, cccDNA transcription, epigenetic regulation, and immune-mediated breakdown have all produced significant progress in our understanding of cccDNA biology during the past decade. There are some strategies where cccDNA can be targeted either in a direct or indirect way and are presently at the point of discovery or preclinical or early clinical advancement. Editing of genomes, techniques targeting host dependence factors or epigenetic gene maintenance, nucleocapsid modulators, miRNA, siRNA, virion secretory inhibitors, and immune-mediated degradation are only a few examples. Though cccDNA approaches for direct targeting are still in the early stages of development, the assembly of capsid modulators and immune-reliant treatments have made it to the clinic. Clinical trials are currently being conducted to determine their efficiency and safety in patients, as well as their effect on viral cccDNA. The influence of recent breakthroughs in the development of new treatment techniques on cccDNA biology is also summarized in this review.

Unravelling rutin content of tartary buckwheat of north western Himalayas and insights into nucleotide polymorphisms in PAL gene to infer the associations with rutin biosynthesis.

Buckwheat (Fagopyrum spp.) has immense nutritional and nutraceutical potential. All the plant parts of buckwheat possess various metabolites, such as rutin, quercetin, vitexin etc. The high content of rutin in this pseudo cereal crop strongly adapts it to grow under adverse environments. In the present study 50 germplasm lines of Fagopyrum tataricum were used for estimation of seed endosperm rutin content through HPLC. Furthermore, molecular analysis of PAL gene (Phenylalanine Ammonia Lyase), an upstream gene in rutin biosynthesis pathway was targeted for detection of SNPs to understand the variations in the concentrations of seed endosperm rutin content, among tartary buckwheat genotypes with highest and lowest seed endosperm rutin content. Three primer pairs were employed for amplification of PAL gene for F. tartaricum (covering whole gene) followed by sequencing. Rutin concentration in seed endosperm of F. tartaricum ranged from 194.86 to 1403.22 ppm with an average of 617.06 ppm. Highest rutin concentration was found in genotype BWZ90 and lowest in BWZ16. Significant variations were observed in the seed endosperm rutin content among the genotypes of tartary buckwheat. Furthermore, alignment of PAL gene sequences of genotypes with high seed endosperm rutin content and low seed endosperm rutin content revealed variations at 21 polymorphic sites. The amino acid sequences obtained from the nucleotide sequences were also aligned and the variations were detected at 19 positions. The putative protein structure showed conformational changes among predicted proteins from two contrasting genotypes for endosperm rutin content. We here established an inventory of seed endosperm rutin content of tartary buckwheat. This study also provided insights about role of these SNPs in rutin biosynthesis. Furthermore, this information can be used for breeding buckwheat for high metabolite contents. Supplementary Information: The online version contains supplementary material available at 10.1007/s13205-022-03218-y.

Polyphenolics, antioxidant characterization and DNA barcoding of Kala zeera [Bunium persicum (Boiss.) Fedtsch] through multiple barcode analysis to unravel best barcode combination.

BACKGROUND: Kala zeera [Bunium persicum (Boiss.) Fedtsch] is one of the important spice crops of North Western Himalayas with lot of medicinal and culinary values. In spite of having great importance, this crop is under the threat of extinction due to loss of habitat and lack of awareness. The limited availability of the seeds has ultimately increased the economic value of this spice. The upmarket of Kala zeera leads to its adulteration with other black seeds and cumin seeds. The present investigation was undertaken to evaluate polyphenolics and antioxidant properties of Kala zeera genotypes collected from North Western Himalayas and to develop DNA barcodes that can ensure their purity and can also guide in conservation of selected Kala zeera germplasm lines. METHODS AND RESULTS: Various locations of North Western Himalayas were explored for collecting 31 diverse germplasm lines of Kala zeera. The collected germplasm was maintained at our experimental stations during 2019-2020 and 2020-2021. These genotypes were evaluated for different seed traits and the methanolic extract from Kala zeera seeds was examined for total phenolic content, total flavonoid content, antioxidant activities by DPPH and FRAP. The results revealed significant variation in seed traits, polyphenolic content and antioxidant properties. 100 seed weight ranged from 0.05 to 0.35 g, TPC ranged from 7.5 to 22.56 mg/g, TFC ranged from 0.58 to 4.15 mg/g, antioxidant properties DPPH ranged from 168 to 624.4 µg/ml and FRAP ranged from 0.72 to 6.91 mg/g. Further, three different barcodes (ITS, rbcL and psbA-trnH) were used to reveal the authenticity of selected Kala zeera. MEGA 5 software was used for clustering and the barcodes did clustering based on geographical distribution of Kala zeera germplasm. CONCLUSION: Based on molecular barcoding, best barcode combination was identified that may discriminate the Kala zeera germplasm vis-a-vis can authenticate their purity. Moreover, the identified DNA barcodes will have significant role in studying the evolutionary biology of Bunium species and will be important for designing a strategy to conserve the selected Kala zeera germplasm lines. The identified genotypes with high phenolic content and antioxidant activity can further be utilized in Kala zeera breeding programmes.

Dynamics, phylogeny and phyto-stimulating potential of chitinase synthesizing bacterial root endosymbiosiome of North Western Himalayan Brassica rapa L.

The less phytopathogen susceptibility in Himalayan Brassica rapa L. has made it an exceptional crop eluding synthetic pesticide inputs, thereby guarantying economically well-founded and ecologically sustainable agriculture. The relevance of niche microflora of this crop has not been deliberated in this context, as endosymbiosiome is more stable than their rhizosphere counterparts on account of their restricted acquaintance with altering environment; therefore, the present investigation was carried out to study the endophytic microfloral dynamics across the B. rapa germplasm in context to their ability to produce chitinase and to characterize the screened microflora for functional and biochemical comportments in relevance to plant growth stimulation. A total of 200 colonies of bacterial endophytes were isolated from the roots of B. rapa across the J&K UT, comprising 66 locations. After morphological, ARDRA, and sequence analysis, eighty-one isolates were selected for the study, among the isolated microflora Pseudomonas sp. Bacillus sp. dominated. Likewise, class γ-proteobacteria dominated, followed by Firmicutes. The diversity studies have exposed changing fallouts on all the critical diversity indices, and while screening the isolated microflora for chitinase production, twenty-two strains pertaining to different genera produced chitinase. After carbon source supplementation to the chitinase production media, the average chitinase activity was significantly highest in glycerol supplementation. These 22 strains were further studied, and upon screening them for their fungistatic behavior against six fungal species, wide diversity was observed in this context. The antibiotic sensitivity pattern of the isolated strains against chloramphenicol, rifampicin, amikacin, erythromycin, and polymyxin-B showed that the strains were primarily sensitive to chloramphenicol and erythromycin. Among all the strains, only eleven produced indole acetic acid, ten were able to solubilize tricalcium phosphate and eight produced siderophores. The hydrocyanic acid and ammonia production was observed in seven strains each. Thus, the present investigation revealed that these strains could be used as potential plant growth promoters in sustainable agriculture systems besides putative biocontrol agents.

Transcriptome Signature of Vγ9Vδ2 T Cells Treated With Phosphoantigens and Notch Inhibitor Reveals Interplay Between TCR and Notch Signaling Pathways.

Gamma delta (γδ) T cells, especially the Vγ9Vδ2 subtype, have been implicated in cancer therapy and thus have earned the spotlight in the past decade. Although one of the most important properties of γδ T cells is their activation by phosphoantigens, which are intermediates of the Mevalonate and Rohmer pathway of isoprenoid biosynthesis, such as IPP and HDMAPP, respectively, the global effects of such treatments on Vγ9Vδ2 T cells remain elusive. Here, we used the high-throughput transcriptomics approach to elucidate the transcriptional changes in human Vγ9Vδ2 T cells upon HDMAPP, IPP, and anti-CD3 treatments in combination with interleukin 2 (IL2) cytokine stimulation. These activation treatments exhibited a dramatic surge in transcription with distinctly enriched pathways. We further assessed the transcriptional dynamics upon inhibition of Notch signaling coupled with activation treatments. We observed that the metabolic processes are most affected upon Notch inhibition via GSI-X. The key effector genes involved in gamma-delta cytotoxic function were downregulated upon Notch blockade even in combination with activation treatment, suggesting a transcriptional crosstalk between T-cell receptor (TCR) signaling and Notch signaling in Vγ9Vδ2 T cells. Collectively, we demonstrate the effect of the activation of TCR signaling by phosphoantigens or anti-CD3 on the transcriptional status of Vγ9Vδ2 T cells along with IL2 stimulation. We further show that the blockade of Notch signaling antagonistically affects this activation.

Morphological, Biochemical, and Proteomic Studies Revealed Impact of Fe and P Crosstalk on Root Development in Phaseolus vulgaris L.

Mineral stress is one of the major abiotic stresses faced by crop plants. The present study was undertaken to investigate the impact of mineral stress (iron (Fe) and phosphorus (P)) on various morphological and biochemical responses of the shoot and root tissues and root architecture of common bean (Phaseolus vulgaris L.). This study also leads us to the identification of P stress responsive proteins. The study was conducted under in vitro conditions, in which seeds of Shalimar French Bean-1 (SFB-1) variety were cultured on four different MGRL medium (control (P1Fe1), iron deficient (P1Fe0), phosphorus deficient (P0Fe1), and phosphorus and iron deficient (P0Fe0)). Chlorophyll content of leaves, Fe/P content of root tissues, total sugars, proline, length, and weight of shoot and root tissues were assessed and compared within and between the treatments. The analyzed data revealed significant difference between control and other three treatments. Chlorophyll content of shoots was found significantly decreased under mineral stress treatments P0Fe1, P1Fe0, and P0Fe0 than control. Length and weight of shoot and root were also observed significantly decreased under P0Fe1, P1Fe0, and P0Fe0 as compared to control. Total sugar was significantly higher in P0Fe1 of roots in comparison to control. Proline content was significantly higher in both tissues of shoots and roots of plants grown under P1Fe0, P0Fe1, and P0Fe0 than control condition. Furthermore, we unexpectedly observed the recovery of roots (mainly primary roots) under P0Fe0 as compared to P1Fe0 and P0Fe1. Interestingly higher concentration of Fe was also observed in P0Fe1 compared to other treatments and also higher concentration of P was observed in P1Fe1. These findings suggested that there is a crosstalk between Fe and P and also revealed that there is a disruption in the ability of PR (primary root) to sense local P deficiency in the absence of Fe. Furthermore, proteomics analysis (SDS-PAGE followed by MALDI MS) helped in identification of defensive proteins in P stress condition compared to control.

Eureka Moment: An Archimedean Alternative for the Determination of cmc of Surfactants via Weight Measurements.

Critical micelle concentration (cmc) is a key parameter of generally used surfactants, and many experimental techniques like tensiometry, conductivity, spectrophotometry, fluorometry, etc. for its determination have been reported. However, these contemporary methods for cmc determination are tedious, are time-consuming, are sensitive, and require sophisticated instrumentation. Herein, we demonstrate that the cmc of the surfactants can be estimated via monitoring the variation in the apparent weight of a density bottle floating in a surfactant solution as a function of surfactant concentration. The proposed method requires the use of a simple weighing balance; a cost-affordable instrument always available in scientific laboratories. The proposed method is simple to execute and does not require any complicated data analysis procedures. As an experimental proof attached to the claim, we demonstrate the estimation of the cmcs of all types of surfactants, viz., anionic, cationic, and nonionic, through the formulated method. The results obtained in terms of cmc values of the chosen surfactants closely match those reported through the use of different standardized protocols. The formulated experimental protocol is desirable in terms of the simplicity of the protocol, accuracy, and reproducibility of the results, and cost and accessibility of the required instrument. All these attributes of the presented protocol qualify it as an appropriate substitute to the modern techniques commonly used for the cmc determination.

Mechanistic insight into the electrocatalytic performance of reduced graphene oxide supported palladium, silver and palladium-silver nanodeposits toward electro-dehalogenation of halocarbons in room temperature ionic liquids.

Herein, we report the results from our extensive voltammetric investigations designed to explore, assess and explain the electrocatalytic performance of reduced graphene oxide supported metal nano-deposits toward the electro-dehalogenation of halocarbons in room temperature ionic liquids (RTILs). Specifically, we investigated the electro-reductive dechlorination of the model halocarbon, carbon tetrachloride over glassy carbon electrode (GCE) and palladium-graphene (Pd-Gr), silver-graphene (Ag-Gr) and palladium-silver-graphene (PdAg-Gr) nanocomposites in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][NTf2]). Analysis of the voltammetric data in light of Marcus-Hush formulation reveals that the electro-reductive cleavage of the C-Cl bond of CCl4 over GCE in [BMIM][NTf2] follows a sticky dissociative electron transfer (SDET) pathway. The significantly stronger interaction energy between electrogenerated Cl- and CCl3˙ (radical) fragments in RTILs makes electroreduction of CCl4 in [BMIM][NTf2] much easier than in organic solvents. The activation-driving force relationship for electro-catalytic dechlorination of CCl4 over Pd-Gr was observed to follow a modified sticky dissociative electron transfer model wherein apart from the ion-radical interaction, the adsorptive interaction of chlorinated species with the electrocatalytic surface needs to be taken into consideration to account for the apparent activation energy-driving force dependence. Interestingly the activation energy-driving force relationships for the electroreduction of CCl4 over Ag-Gr and PdAg-Gr were observed to fit a modified stepwise ET (MSET) pathway. In the MSET pathway, the adsorption and the implied free energy change of the electroreducible halocarbon significantly alter the solvent re-organization energy and the inherent barrier for the heterogeneous ET process. The adsorptive interaction and hence the electrocatalytic performance of PdAg-Gr were observed to be more than that observed for Ag-Gr. This is attributed to the Ag to Pd charge transfer in the PdAg-Gr nanodeposits. Our results besides underlining the positive influence of RTILs in facilitating the electroreductive detoxification of halocarbons, very well establish the mechanistic basis for the electrocatalytic performance of graphene based nanodeposits toward electrodehalogenation of halocarbons.

Transforming micelles into mixed micelles: a promising approach to tune the catalytic performance of imidazolium-based surface active ionic liquids toward degradation of rhodamine B.

Herein, we demonstrate that the catalytic performance of imidazolium-based surface-active ionic liquid (SAIL) micelles can be significantly enhanced through the addition of an appropriate type and amount of intelligently conceived amphiphile to form mixed micelles. Specifically, we show that the catalytic performance of 1-dodecyl-3-methyl imidazolium chloride (DDMIMCl) micelles toward the reductive degradation of rhodamine B (RhB), a carcinogenic dye extensively used in multiple industrial applications, can be appreciably boosted through addition of Brij56, a nonionic surfactant. Detailed kinetic investigations on the catalytic performance of pre- and post-micellar concentrations of DDMIMCl and its mixed micelles with Brij56 over various mole fractions, toward the reductive degradation of RhB, are presented. The data analyzed in light of Berezin's kinetic model suggest that the addition of Brij56 to DDMIMCl micelles significantly enhances their catalytic performance. The catalytic activity exhibited by the DDMIMCl-Brij56 (XBrij56 = 0.2) mixed micellar system is better than that reported for many state-of-the-art nanoparticle/homogenous catalysts. The results explained in light of Berezin's kinetic model are well supported by physico-chemical studies like conductometry, fluorimetry and dynamic light scattering. The presented results anticipate stimulation of extensive research activity for exploiting the mixed micellization approach as a novel avenue for modulating the catalytic performance of SAILs.

Trends in colorectal cancer incidence in western Kazakhstan through the first decade of the screening implementation, 2009-2018 / Tendências na incidência do câncer colorretal no Cazaquistão ocidental durante a primeira década da implementação do rastreamento, 2009-2018

Abstract Introduction The study is aimed to outline the vector of colorectal cancer incidence in the industrial Aktobe province of western Kazakhstan through the first decade of the screening implementation, 2009-2018. Methods Rough incidence rates and annual percent changes were estimated for each age group at diagnosis, ethnicities, gender, residences, the disease stages and anatomic subsites (total N 1128) via regression analysis. Results Within 2009-2018 colorectal cancer rates increased from 14.74 to 23.19, with annual percent changes of 4.69%. The most significant growth was traced in men compared to women, up to 28.39 by 2018, with annual percent changes 6.64% vs. 2.64% (p = 0.0009). Annual percent changes in Kazakhs reached 8.7%, whereas Slavic groups showed decline in the incidence, annual percent changes −4.3% (p = 0.002). Declining in rates was also observed in urban population compared to rural one, annual percent changes −3.3% vs. 17.6%, respectively. Patients aged 60-69 made 31% of all cases and showed the largest annual percent changes 9.37% (p = 0.002). Patients at Stage II made 61% of all observations, but general trend evidenced sharp growth in the group of Stage I (annual percent changes 28.91%, p < 0.0001). Conclusion Overall, during the last decade colorectal cancer incidence increased 1.5 fold with expected further rise. However, the increment of Stage I portion by 2018 vs. advanced stages at diagnosis and the trend to decrease in rates among urban population inspire a definite assurance in potential efficiency of the screening program in long run. The next researches on colorectal cancer should include scenarios to reveal the role of disadvantaged environment in the region and consuming unhealthy ultra-processed food.

Resumo Introdução O objetivo do estudo é delinear o vetor da incidência do câncer colorretal na província industrial de Aktobe, no oeste do Cazaquistão, durante a primeira década da implementação do rastreamento, 2009‒2018. Métodos Taxas de incidência brutas e alterações percentuais anuais foram estimadas para cada faixa etária ao diagnóstico, etnias, sexo, residências, estágios da doença e localizações anatômicas (N total de 1.128) através da análise de regressão. Resultados Entre 2009‒2018, as taxas de câncer colorretal aumentaram de 14,74 para 23,19, com alteração percentual anual de 4,69%. O crescimento mais significativo foi evidenciado em homens em comparação com as mulheres, até 28,39 em 2018, com alterações percentuais anuais de 6,64% contra 2,64% (p = 0,0009). Alterações percentuais anuais nos cazaques atingiu 8,7%, enquanto os grupos eslavos mostraram declínio na incidência, alterações percentuais anuais -4,3% (p = 0.002). O declínio nas taxas também foi observado na população urbana em comparação com a rural, alterações percentuais anuais -3,3% vs. 17,6%, respectivamente. Pacientes com idade entre 60‒69 anos eram 31% de todos os casos e apresentaram as maiores alterações percentuais anuais 9,37% (p = 0,002). Os pacientes no Estágio II eram 61% de todas as observações, mas a tendência geral evidenciou crescimento acentuado no grupo do Estágio I (alterações percentuais anuais 28.91%; p < 0,0001). Conclusão No geral, durante a última década, a incidência de câncer colorretal aumentou 1,5 vezes com expectativa de maior aumento. No entanto, o incremento da porção do Estágio I em 2018 em comparação com os estágios avançados no momento do diagnóstico e a tendência de diminuição nas taxas entre a população urbana inspira uma garantia definitiva de eficiência potencial do programa de rastreamento em longo prazo. As próximas pesquisas sobre o câncer colorretal devem incluir cenários para revelar o papel do ambiente desfavorecido na região e o consumo de alimentos ultraprocessados não saudáveis.

Quality control, HPTLC analysis, antioxidant and antimicrobial activity of hydroalcoholic extract of roots of qust (Saussurea lappa, C.B Clarke).

OBJECTIVES: Saussurea lappa, CB Clarke (S.lappa) is a perennial herb of the Compositae family. The root of S.lappa has been used for the treatment of various diseases such as hepatitis, jaundice, intestinal worms, bronchial asthma, and a variety of skin diseases. The aim of the study was to ensure quality control of S.lappa and its preparation HAESL (hydroalcoholic extract of S.lappa) along with assessment of HAESL antimicrobial and antioxidant activities in vitro. METHODS: HAESL was prepared with 50% ethanol, (v/v). Physiochemical analysis of the root of S.lappa, and phytochemical screening, thin-layer chromatography (TLC), high-performance thin-layer chromatography (HPTLC), and in vitro antimicrobial and antioxidant activity of HAESL were performed using the standard protocol. RESULTS: Physiochemical and phytochemical assessments of S.lappa and HAESL showed the greater quality of the drug. HAESL showed the presence of many phytochemical constituents corresponding to colorful spots, peaks, area under the curve, and corresponding Rf values as evident in the TLC and HPTLC analysis. HAESL showed a concentration-dependent effect on radical scavenging activity against DPHH (2,2-diphenyl-1-picrylhydrazyl) and hydroxyl radical with IC50 value of 19.10 µg/mL and 82.23 µg/mL, respectively. HAESL exhibited antimicrobial activity against the growth of micro-organisms such as Escherichia coli, Staphylococcus aureus, Klebsiella pneumoniae, Pseudomonas aeruginosa, Salmonella typhi, Aspergillus flavus, and Candida albicans. HASEL showed no antimicrobial activity against Aspergillus niger. CONCLUSIONS: The procured and an identified sample of Saussurea lappa was good in quality and the prepared HAESL contained many phytochemical compounds. HAESL substantiated significant antioxidant and antimicrobial activity in vitro.

PdAg Bimetallic Nanoalloy-Decorated Graphene: A Nanohybrid with Unprecedented Electrocatalytic, Catalytic, and Sensing Activities.

Recent reports about the promising and tunable electrocatalytic activity and stability of nanoalloys have stimulated an intense research activity toward the design and synthesis of homogeneously alloyed novel bimetallic nanoelectrocatalysts. We herein present a simple one-pot facile wet-chemical approach for the deposition of high-quality bimetallic palladium-silver (PdAg) homogeneous nanoalloy crystals on reduced graphene (Gr) oxide sheets. Morphological, structural, and chemical characterizations of the so-crafted nanohybrids establish a homogeneous distribution of 1:1 PdAg nanoalloy crystals supported over reduced graphene oxide (PdAg-Gr). The PdAg-Gr nanohybrids exhibit outstanding electrocatalytic, catalytic, and electroanalytical performances. The PdAg-Gr samples were found to exhibit exceptional durability when subjected to repeated potential cycles or long-term electrolysis. In the CVs recorded for fuel cell reactions, viz. methanol oxidation reaction and oxygen reduction reaction, and for detoxification of environmental pollutants, viz. electroreduction of methyl iodide and chloroacetonitrile over PdAg-Gr with potential sweep rate of 25 mVs-1, the peak potentials were observed to be just -0.221, -0.297, (vs Ag/AgCl, 3 M KCl) -1.508, and -1.189 V (vs Fc+/Fc), respectively. The potential of PdAg-Gr nanohybrid for simultaneous and sensitive electrochemical sensing and estimation of hydroxybenzene isomers with very low detection limits (0.05 µM for hydroquinone, 0.06 µM for catechol, 6.7 nM for 4-aminophenol, and 13.7 nM for 2-aminophenol) is demonstrated. Additionally, PdAg-Gr was observed to offer excellent solution-phase catalytic performance in bringing about the reduction of notorious environmental pollutant 4-nitrophenol to pharmaceutically important 4-aminophenol with an apparent rate constant ( kapp) of 3.106 × 10-2 s-1 and a normalized rate constant ( knor) of 6.21 × 102 s-1 g-1. The presented synthetic scheme besides being high yielding, low cost, and easy to carry out results in the production of PdAg-Gr nanohybrids with stability and activity significantly better than most of the nanomaterials purposefully designed and testified so far by various groups.

Oxides in silver-graphene nanocomposites: electrochemical signatures and electrocatalytic implications.

Herein we report an electrochemical approach to establish the presence of silver oxides in silver-reduced graphene oxide (Ag-rGO) nanocomposites synthesised under alkaline conditions. The recorded electrochemical signatures, further supported and validated by UV-Vis spectroscopy, XRD and TEM analysis, clearly establish the presence of an oxide phase of silver in the nanodimensional silver present in Ag-rGO. The Ag-rGO was tested for its electrocatalytic and electrosensing activity for hydroquinone (H2Q) and ascorbic acid (AA). The presented results establish that the electrocatalytic and electrosensing potential of the Ag-rGO for H2Q and AA can be enhanced through electroreduction of the oxide phase of silver in these nanocomposites. Our results prove that the electrocatalytic and electroanalytic activities of electroreduced Ag-rGO for AA are better than most of the electrode materials reported so far in the literature.

Determination of cmc of imidazolium based surface active ionic liquids through probe-less UV-vis spectrophotometry.

In the first of its kind we herein report the results of our studies undertaken on the micellization behaviour of imidazolium based surface active ionic liquids (SAILs) to prove that their critical micelle concentration (cmc) can be estimated through ultraviolet-visible (UV-vis) spectroscopy without using any external probe. Tensiometric and spectrophotometric investigations of a series of freshly prepared SAILs viz. 1-octyl-3-methylimidazolium chloride ([OMIM][Cl]), 1-octyl-3-methylimidazolium dodecylsulphate ([OMIM][DS]), 1-octyl-3-methylimidazolium benzoate ([OMIM][Bz]), 1-octyl-3-methylimidazolium salicylate ([OMIM][Sc]), 1-octyl-3-methylimidazolium acetate ([OMIM][Ac]) are presented as a case study in support of the said claim. The cmcs estimated through spectrophotometric method were found to be close to the values estimated through tensiometry for the said SAILs. The cmcs for the investigated SAILS were found to vary in order of [OMIM][Cl]>[OMIM][Ac]>[OMIM][Bz]>[OMIM][Sc]>[OMIM][DS]. To the best of our knowledge the present communication will be the first report about the synthesis, characterization and micellization behaviour of [OMIM][Bz] and [OMIM][Sc].