Mono and Dinuclear Palladium Pincer Complexes of NNSe Ligand as a Catalyst for Decarboxylative Direct C-H Heteroarylation of (Hetero)arenes.

This report describes the synthesis of a new NNSe pincer ligand and its mono- and dinuclear palladium(II) pincer complexes. In the absence of a base, a dinuclear palladium pincer complex (C1) was isolated, while in the presence of Et3 N base a mononuclear palladium pincer complex (C2) was obtained. The new ligand and complexes were characterized using techniques like 1 H, 13 C{1 H} nuclear magnetic resonance (NMR), fourier transform infrared (FTIR), high-resolution mass spectrometry (HRMS), ultraviolet-visible (UV-Visible), and cyclic voltammetry. Both the complexes showed pincer coordination mode with a distorted square planar geometry. The complex C1 has two pincer ligands attached through a Pd-Pd bond in a dinuclear pincer fashion. The air and moisture-insensitive, thermally robust palladium pincer complexes were used as the catalyst for decarboxylative direct C-H heteroarylation of (hetero)arenes. Among the complexes, dinuclear pincer complex C1 showed better catalytic activity. A variety of (hetero)arenes were successfully activated (43-87 % yield) using only 2.5 mol % of catalyst loading under mild reaction conditions. The PPh3 and Hg poisoning experiments suggested a homogeneous nature of catalysis. A plausible reaction pathway was proposed for the dinuclear palladium pincer complex catalyzed decarboxylative C-H bond activation reaction of (hetero)arenes.

A palladium complex of a macrocyclic selenium ligand: catalyst for the dehydroxymethylation of dihydroxy compounds.

This report describes the synthesis of a seventeen-membered macrocyclic ring containing ligand (L1) by the reaction of 1,8-bis(2-(chloromethyl)phenoxy)octane with selenium powder. The trans-palladium dichloride complex (C1) of the macrocyclic selenium ligand was synthesized from its reaction with the Pd(CH3CN)2Cl2 precursor. The formation of the ligand and complex was authenticated with the help of various analytical techniques like 1H and 13C{1H} NMR, HRMS, FTIR, UV-visible spectroscopy, and elemental analysis. The structure of the ligand and its coordination mode with the palladium precursor were authenticated with the help of single crystal X-ray diffraction. The complex possesses a distorted square planar geometry around the palladium center. The new ligand and complex are air and moisture insensitive and stable at room temperature for over three months. The variable temperature NMR data and computational studies suggest selenium inversion in the palladium complex (C1) with an inversion barrier of ∼22.6 kcal mol-1. The palladium complex C1 was used as a catalyst for the dehydroxymethylation of long alkyl chain containing dihydroxy compounds. Generally, two separate catalysts are used for dehydroxymethylation (one for the oxidation of the alcohol and the other for the decarbonylation of the aldehyde). Here a single catalyst shows the dual action of dehydroxymethylation with up to 91% yield under only 5.0 mol% catalyst loading. A broad substrate scope can be achieved with good functional group tolerance. The PPh3 and Hg poisoning tests suggest the homogeneous nature of the reaction. Interestingly, the same long alkyl chain containing dihydroxy compounds were reported to undergo macrolactonization when reacted with a ruthenium catalyst.

Titania Nanorod-Supported Mercaptoundecanoic Acid-Grafted Palladium Nanoparticles as a Highly Reusable Heterogeneous Catalyst for Substrate-Dependent Ullmann Coupling and Debromination of Aryl Bromides.

Herein, by implanting palladium nanoparticles (Pd NPs) onto titanium dioxide (TiO2) nanorods (NRs) through 11-mercaptoundecanoic acid (MUA), we devised a robust heterogeneous catalyst. The formation of Pd-MUA-TiO2 nanocomposites (NCs) was authenticated using Fourier transform infrared spectroscopy, powder X-ray diffraction, transmission electron microscopy, energy-dispersive X-ray analysis, Brunauer-Emmett-Teller analysis, atomic absorption spectroscopy, and X-ray photoelectron spectroscopy techniques. Pd NPs were synthesized directly onto TiO2 nanorods without the MUA support for comparative studies. As a means of evaluating the endurance and competency of Pd-MUA-TiO2 NCs compared to their counterpart (Pd-TiO2 NCs), both were used as the heterogeneous catalyst for Ullmann coupling of a wide variety of aryl bromides. When Pd-MUA-TiO2 NCs were used, the reaction produced high yields of homocoupled products (54-88%), whereas the yield was only 76% when Pd-TiO2 NCs were used. Moreover, Pd-MUA-TiO2 NCs impressed with their outstanding reusability property, allowing over 14 reaction cycles without losing efficiency. On the flip side, just after seven reaction cycles, the productivity of Pd-TiO2 NCs dropped around 50%. Presumably, the strong affinity of Pd for the thiol groups of MUA allowed for the substantial control of leaching out of Pd NPs during the reaction. Nonetheless, another crucial feature of the catalyst is that the di-debromination reaction took place with an excellent yield of 68-84% from di-aryl bromides with long alkyl chains instead of macrocyclic or dimerized products. It is worth mentioning that AAS data confirmed that only 0.30 mol % catalyst loading was sufficient to activate a broad substrate scope with large functional group tolerance.

Effect of heat stress mitigations on physiological, behavioural, and hormonal responses of Buffalo calves.

This study assessed the effect of heat stress mitigations on the physiological, behavioural, and hormonal responses of buffalo during the hot summer season. Twenty Murrah buffalo male calves were distributed randomly into controlled (C, n = 10) and treatment groups (T, n = 10). The buffalo calves in the C group were housed in the existing shed (10-12-ft height and 10-ft width). Buffalo calves of the T group were allocated in the modified shed: 15-ft height and 20-ft width along with time-controlled pressure mist with fans and rubber mats on the floor. Fans were running all days. The cool water was misted on calves at the rate of 1 min in 5 min, from 11:00 to 18:00 h. The water misting system was installed below the roof, but at 3.5 m above the floor. The calves' body weight, rectal temperature, infrared temperature of the eye, blood samples, respiration rate, and pulse rate were recorded fortnightly for two consecutive months. In one-way ANOVA, rectal temperature, eye temperature, cortisol level, and afternoon's respiration and pulse rate were higher in the calves of C group than that of T group (P < 0.05). Conversely, eating and resting time (min/day) and triiodothyronine were lower in the calves of C group than that of T group (P < 0.05). Therefore, an increase in shed's height and width, using rubber mats on the floor, and cool water misting to buffaloes during the hot summer seasons positively influence their physiological, hormonal, and behavioural responses.

Sparse-FCM and Deep Convolutional Neural Network for the segmentation and classification of acute lymphoblastic leukaemia.

Leukaemia detection and diagnosis in advance is the trending topic in the medical applications for reducing the death toll of patients with acute lymphoblastic leukaemia (ALL). For the detection of ALL, it is essential to analyse the white blood cells (WBCs) for which the blood smear images are employed. This paper proposes a new technique for the segmentation and classification of the acute lymphoblastic leukaemia. The proposed method of automatic leukaemia detection is based on the Deep Convolutional Neural Network (Deep CNN) that is trained using an optimization algorithm, named Grey wolf-based Jaya Optimization Algorithm (GreyJOA), which is developed using the Grey Wolf Optimizer (GWO) and Jaya Optimization Algorithm (JOA) that improves the global convergence. Initially, the input image is applied to pre-processing and the segmentation is performed using the Sparse Fuzzy C-Means (Sparse FCM) clustering algorithm. Then, the features, such as Local Directional Patterns (LDP) and colour histogram-based features, are extracted from the segments of the pre-processed input image. Finally, the extracted features are applied to the Deep CNN for the classification. The experimentation evaluation of the method using the images of the ALL IDB2 database reveals that the proposed method acquired a maximal accuracy, sensitivity, and specificity of 0.9350, 0.9528, and 0.9389, respectively.

Role of alpha-melanocyte stimulating hormone (α-MSH) in modulating the molecular mechanism adopted by melanocytes of Bos indicus under UVR stress.

Ultraviolet radiations (UVR) are responsible for a wide variety of acute and chronic effects on the animal skin. However, the effect of UVR-induced oxidative stress and protection through paracrine factors on animal skin has received little attention. We previously demonstrated how heat stress-induced adaptation in Bos indicus melanocytes was dependent on the level of melanin and reduction of apoptosis. Therefore, in the present investigation, the survival mechanisms adopted by melanocytes under UV stress and the role of α-MSH in cell survival under in vitro conditions were studied. After the treatment of melanocyte cells with UVR (using Osram ultravitalux 300 W lamp), analysis of Gene expression using Real-Time PCR was done to study the adopted molecular pathways under stressful conditions. In addition, α-MSH was used to assess its modulating role in cell survival under stress. This study revealed the increase in the expression of genes related to melanogenesis, cell cycle, heat shock proteins, and apoptosis of the cells after UVR stress and demonstrated the role of paracrine factor (α-MSH) in elevating the protection response to stressful conditions like UVR stress by increasing the melanogenesis and decreasing the mitochondrial-mediated apoptosis. Based on the results of the present study, it can be stated that α-MSH can play a pivotal role in the protection of animal skin cells under stressful conditions in climate-changing scenario.

Novel extraction of high quality genomic DNA from frozen bovine blood samples by using detergent method.

DNA is the prerequisite for life's inception that transfers hereditary information, past several years; various types of commercial kits are made available which vary depending on the type of the biological sample being used. The present study is focused on developing an improvised methodology for the isolation of genomic DNA from stored bovine blood samples. DNA was isolated by using the conventional Phenol: Chloroform: Isoamyl alcohol (PCI) method and Detergent method. The aim of the study was to make a comparative analysis and evaluation of these two methods to identify the one that gives a superior quality and quantity of genomic DNA. Total (n=48) each duplicate blood samples from three different buffalo(Bubalus bubalis) breeds Banni, Surti, Murrah, three zebu cattle (Bos indicus) breeds Kankerj, Gir, Sahiwal were collected from the jugular vein. The quantity, purity of the genomic DNA was assessed based on the total DNA yield, purity ratios, spectral profile, agarose gel electrophoresis analysis and polymerase chain reaction amplification of MC1R gene product without any inhibitors. The results of our study suggest that detergent method is also suitable for extraction of genomic DNA from the bovine blood and results were significant (*P>0.05). The total mean yield was found to be 329.05±11 µg/5ml for all six breeds while the PCI method was employed. The total mean yield of the gDNA for all six breeds was 406.6±43 µg/5ml of blood when the detergent method was used. One way ANOVA test showed that the total DNA yield varied depending on the isolation method used. The DNA yield obtained from the DG method was (***P< 0.001) significant as compared to the PCI method (**P<0.01).

Unrelated and related donor transplantation for beta-thalassemia major: A single-center experience from India.

Hematopoietic stem cell transplantation (HSCT) remains the only curative treatment in patients with ß-thalassemia major. A matched sibling or a related donor is usually found in only 25%-30% of the patients. There are limited data on matched unrelated donor (MUD) transplants from India. We reviewed HSCT outcome in 56 children with TM who underwent 57 transplants at our center. Related donor (RD) (n=43) and MUD (n=14) transplants were performed with TreoFluT-based conditioning regimen in majority (95%) of patients. Peripheral blood stem cells (PBSC) were the preferred (85%) source of stem cells. The overall survival (OS) at 1 year in RD and MUD groups was 87.6±5.2% and 85.7±9.4% at a median follow-up of 25 (1-92) months and 22.5 (1-50) months, respectively (P=.757). The thalassemia-free survival (TFS) at 1 year was 87.6±5.2% and 77.1±11.7% with a median follow-up of 24 (1-92) and 16.5 (1-50) months, respectively (P=.487). Although acute (14% vs 64%) and chronic graft-versus-host disease (GVHD) (13.9% vs 42.9%), infectious (39.5% vs 71.4%), and non-infectious (37.2% vs 78.5%) complications are higher in MUD transplant group, the present data show a comparable OS and TFS among RD and MUD group with treosulfan-based regimen using PBSC grafts.

Validation of putative reference genes for gene expression studies in heat stressed and α-MSH treated melanocyte cells of Bos indicus using real-time quantitative PCR.

Normalization of cellular mRNA data using internal reference gene (IRG) is an essential step in expression analysis studies. MIQE guidelines ensure that the choice and appropriateness of IRG should be validated for particular tissues or cell types and specific experimental designs. The objective of the present study was to assess 15 IRGs from different functional classes that could serve as best IRGs for Bos indicus (Tharparkar cattle) melanocyte cells under heat stress and hormonal treatment. We implemented the use of geNorm, NormFinder and BestKeeper algorithm to measure the stability of the gene transcript. A total of 15 IRGs (ACTB, BZM, EEF1, GAPDH, GTP, HMBS, HPRT, RPL22, RPL4, RPS15, RPS18, RPS23, RPS9, UBC and UXT) from different functional classes were evaluated. Pair wise comparisons using geNorm revealed that HPRT and RPS23 were the most stable combination of IRGs with M-value of 0.29 followed by UXT (0.30) and RPL4 (0.31). The NormFinder analysis also identified the same set of stably expressed genes (UXT, RPL4, RPS23 and HPRT); however, the rank order was little different. The UXT gene showed lowest crossing point SD and CV values of 0.30 and 1.17, respectively indicating its maximum expression stability through BestKeeper analysis. The present study indicated that, ACTB and HMB were not reliable IRGs for melanocytes cells on account of their lower expression stability. Current study further revealed that UXT, HPRT and RPS23 are the best IRGs for normalization of qPCR data in Bos indicus melanocyte cells under heat stress and hormonal treatment.

Novel SNP identification in exon 3 of HSP90AA1 gene and their association with heat tolerance traits in Karan Fries (Bos taurus × Bos indicus) cows under tropical climatic condition.

Heat shock proteins (HSPs) act as molecular chaperones those are preferentially transcribed in respose to heat stress and the polymorphism in HSP genes associated with heat tolerance traits in cows. HSP90AA1 gene has been mapped on Bos taurus autosome 21 (BTA-21) and spans nearly 5368 bp comprising of 11 exons out of which the first exon does not translate. The present study was done on Karan Fries (5/8 HF × 3/8 Tharparkar) cows reared in tropical climate with the objectives of identifying single-nucleotide polymorphisms (SNPs) in targeted regions (exon 3) of HSP90AA1 gene and analyzing their association with heat tolerance traits in Karan Fries cows. Respiration rate (RR) and rectal temperature (RT) were recorded once daily for four consecutive days during probable extreme hours in different seasons or temperature humidity index (THI), viz., winter, spring, and summer. For detecting single-nucleotide polymorphisms, sequence data were analyzed using BioEdit software (version 7.2). Comparative sequence analysis of HSP90AA1 gene showed point mutation, viz., g.1209A>G (exon 3) as compared to Bos taurus (NCBI Ref Seq: AC_000178.1). Association analysis indicated that THI was influenced (P < 0.01) by RR, RT, and HTC. Similarly, SNPs at locus g.1209A>G were categorized into three genotypes, i.e., AA, AG, and GG, and the least squares means (LSMEANS) of RR, RT, and HTC for GG (homozygous) genotype were significantly lower (P < 0.01) than AA (homozygous) and AG (heterozygous) genotypes. These findings may partly suggest that cows with GG genotypes were favored for heat tolerance trait, which can be used as an aid to selection for thermo-tolerance Karan Fries cows for better adaptation in subtropical and tropical hot climate.

Is Early Onset Androgenic Alopecia a Marker of Metabolic Syndrome and Carotid Artery Atherosclerosis in Young Indian Male Patients?

BACKGROUND: Androgenic alopecia (AGA) is a common cosmetically and psychosocially distressing condition. High androgen level contributes to the development of atherosclerosis, thrombosis leading to hypertension and hypercholesterolemia. OBJECTIVES: To study the clinico-epidemiological profile of AGA and the presence of metabolic syndrome (MetS) and carotid artery atherosclerosis in male patients with early onset AGA as compared to controls. MATERIALS AND METHODS: In this case-control study, 100 male patients of age 18-35 years with AGA and an equal number of age-matched healthy controls attending skin and STD OPD were included. Assessment of the degree of hair loss, evaluation of MetS and carotid artery color Doppler for the atherosclerotic plaque was done in all patients. RESULTS: Statistically significant number of patients with early onset AGA 22/100 (22%) (P < 0.05) fulfilled the criteria for MetS compared to 8/100 (8%) in the control group. There were statistically significant differences in mean values of waist circumference, serum triglycerides, serum cholesterol, systolic blood pressure, diastolic blood pressure, fasting glucose concentration, and very low-density lipoprotein (LDL). However, no significant differences were observed in the mean values of high-density lipoprotein cholesterol and LDL cholesterol. The atherosclerotic plaque was found in two patients of the study group, and no plaque was found in control patients. CONCLUSION: We suggest that all men with AGA should be thoroughly investigated, and lifestyle changes should be started in the early period of life so as to reduce the risk of various problems associated with MetS. AGA can be considered as an early marker for MetS.

Expression of skin color genes in lymphocytes of Karan Fries cattle and seasonal relationship with tyrosinase and cortisol.

To evaluate difference in the expression of skin color genes (melanocortin 1 receptor (MC1R) and premelanosome (PMEL)) in lymphocytes during winter and summer season and their correlation with tyrosinase enzyme and cortisol, ten Karan-Fries heifers were selected from National Dairy Research Institute (NDRI) cattle farm. Blood samples were collected from the animals during winter (THI = 60) and summer (THI = 83) season at weekly intervals. Relative MC1R and PMEL messenger RNA (mRNA) expression of Karan Fries cattle was found to be significantly (P < 0.01) higher during winter than summer. Similarly, tyrosinase activity during winter was found to be significantly (P < 0.01) higher than summer season. However, plasma cortisol level was significantly (P < 0.01) higher during summer than winter. Thus, expression of the skin color genes showed positive correlation with tyrosinase enzyme, but negative correlation with cortisol level. Expression of MC1R and PMEL in lymphocytes and tyrosinase activity of Karan Fries cattle was highly reduced during summer. The present study showed that the ability of Karan Fries cattle to protect themselves from the harmful radiation of sunlight by melanization decreased with increased heat stress on them.

Uterine Artery Notching on Color Doppler Ultrasound and Roll over Test in Prediction of Pregnancy Induced Hypertension.

OBJECTIVE: To study the role of uterine artery notch on color Doppler ultrasound and roll over test in prediction of PIH. METHODS: 100 women with high risk pregnancies were studied for presence or absence of uterine artery diastolic notch by Doppler ultrasound at 16-28 weeks. Same women were then subjected to roll over test at 28-32 weeks. RESULTS: The primary outcome was that uterine diastolic notching alone and combined together with roll over test shows a high specificity (98.53%) for predicting PIH than roll over test (76.47%) alone. PPV of uterine artery diastolic notching (83.33%) was higher than roll over test alone (54.29%) and both tests combined together (80%). CONCLUSION: After analyzing all the results, it has been concluded that uterine artery Doppler notching is better predictor for PIH than roll over test or even combined Doppler + Roll over test together.