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Developing thermoelectric films without substrates-free-standing films-eliminates substrate-induced effects on performance and meets the flexibility requirements of emerging wearable thermoelectric applications. This study investigates Gallium-doped Zinc Oxide (GZO), composed of abundant and non-toxic elements, to fabricate a substrate-free GZO film via 3D printing and compares its structural, chemical, and thermoelectric properties with those of a substrate-constrained GZO film produced through chemical deposition. Both films exhibited uniform crystal structures and phase purity; however, the substrate-constrained film displayed additional diffraction peaks, suggesting potential substrate interactions. The 3D-printed free-standing film effectively eliminated the tensile stresses observed in the substrate-constrained film. FE-STEM analysis revealed nanostructures with homogeneous elemental distribution in both films, though the substrate-constrained film showed discontinuities, such as pores, likely caused by post-deposition annealing treatment. XPS analysis highlighted differences in chemical states and elemental compositions between the films, influenced by fabrication methods, substrate-induced stresses, and surface energy mismatches. The free-standing GZO film developed through 3D printing exhibited a more balanced incorporation of Zn and O, as it was not subject to substrate or post-deposition annealing constraints. Consequently, it demonstrated a 14 % increase in electrical conductivity and a 91 % improvement in the Seebeck coefficient compared to the substrate-constrained film, resulting in a higher room-temperature power factor of 261 nW/m·K 2 . These findings underscore the potential of 3D-printed free-standing GZO films to advance thermoelectric applications, offering a promising alternative to overcome the challenges of substrate-constrained films and further drive innovation in the field., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 Published by Elsevier Ltd.)

A 3D-printable polymer can provide an effective solution for developing piezoelectric structures. However, their nanocomposite formulation and 3D printing processability must be optimized for fabricating complex geometries with high printability. In the present study, we optimized the 3D-printable piezoelectric composite formulation for developing complex geometries by an additive manufacturing approach. The zinc oxide (ZnO) nanomaterial was synthesized by the hydrothermal method. The ZnO loading in the 3D-printed flexible resin was optimized to exhibit good interfacial adhesion and enable 3D printing. The lattice structure was fabricated to improve the piezoelectric response compared with the solid structure. The lattice structure block printed with 10 wt% ZnO showed a good piezoelectric response, with a linear increase in the generated output voltage for an increase in force. The maximum power density of 0.065 μW/cm 2 was obtained under 12 N force at 1 Hz. The fabricated structure generated a peak-peak voltage of ~3 V with a foot heel strike.

Cellular metabolism is a complex process involving the consumption and production of metabolites, as well as the regulation of enzyme synthesis and activity. Modeling of metabolic processes is important to understand the underlying mechanisms, with a wide range of applications in metabolic engineering and health sciences. Cybernetic modeling is a powerful technique that accounts for unknown intricate regulatory mechanisms in complex cellular processes. It models regulation as goal-oriented, where the levels and activities of enzymes are modulated by the cybernetic control variables to achieve the cybernetic objective. This study employed cybernetic model to study the enzyme competition between arachidonic acid (AA) and eicosapentaenoic acid (EPA) metabolism in murine macrophages. AA and EPA compete for the shared enzyme cyclooxygenase (COX). Upon external stimuli, AA produces pro-inflammatory 2-series prostaglandins (PGs) and EPA metabolizes to anti-inflammatory 3-series PGs, where pro- and anti- inflammatory responses are necessary for homeostasis. The cybernetic model adequately captured the experimental data for control and EPA-supplemented conditions. The model is validated by performing an F-test, conducting leave-one-out-metabolite cross-validation, and predicting an unseen experimental condition. The cybernetic variables provide insights into the competition between AA and EPA for the COX enzyme. Predictions from our model suggest that the system undergoes a switch from a predominantly pro-inflammatory state in the control to an anti-inflammatory state with EPA-supplementation. The model can also be used to analytically determine the AA and EPA concentrations required for the switch to occur. The quantitative outcomes enhance understanding of pro- and anti-inflammatory metabolism in RAW 264.7 macrophages., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Reaction of [V IV O(acac) 2 ] (Hacac = acetylacetone) with a Mannich base, N , N , N ', N '-tetrakis(2-hydroxy-3,5-di- tert- butyl benzyl)-1,2-diaminoethane (H 4 L, I ) in a 1:1 molar ratio in MeOH, leads to the formation of the nonoxidovanadium(IV) complex [V IV L] ( 1 ). Air stable complex 1 has been characterized using various spectroscopic techniques, DFT calculations, and single-crystal X-ray studies. 1 adopts distorted octahedral geometry where ligand coordinates through all coordination functionalities available. This complex has been used as a catalyst in the one-pot, three-component synthesis of 2-amino-3-cyano-4 H -pyrans using 1,3-dicarbonyls (1,3-cyclohexanedione, dimedone, barbituric acid, and 4-hydroxycoumarin), malononitrile, and various substituted aromatic aldehydes in equimolar amounts employing ethanol as a green solvent. The catalytic reaction revealed that the multicomponent synthesis of 4 H -pyrans and chromenes is greatly influenced by both types of 1,3-dicarbonyl compound employed and the nature of the substituent on the aromatic ring of the aldehyde. Synthesized catalyst has also been used in the synthesis of pharmacologically relevant oxygen-containing heterocycles, specifically, 1,8-dioxo-octahydro-1 H -xanthenes and biscoumarins. The possible mechanism for the synthesized one-pot, multicomponent product has been proposed by isolating intermediate(s) generated during synthesis.

In this report, four new Ni(II)-unsymmetrical salen complexes, [NiL 1-4 ], were prepared by refluxing Ni(Ac) 2 ·4H 2 O with unsymmetrical salen ligands, H 2 L 1-4 . All of the synthesized ligands and complexes were characterized by various physicochemical methods. Also, the solid-state structures of [NiL 1 ], [NiL 2 ], and [NiL 4 ] were defined through single-crystal X-ray diffraction methods. The catalytic potential of [NiL 1-4 ] was investigated by economic and environmentally friendly one-pot-three-component reactions (using reagent: 1,3-dicarbonyls, malononitrile, benzaldehyde, or its derivatives) for the synthesis of biologically active 2-amino-3-cyano-4 H -pyran derivatives (total 16 derivatives). After optimization of the reaction conditions, this new synthetic protocol by taking Ni(II)-unsymmetrical salen complexes as catalysts shows excellent conversion with a maximum yield of up to 98% of the effective catalytic products within 1 h of reaction time. In addition, it was observed that the aromatic aldehyde containing an electron-withdrawing group as a ring substituent shows better conversion (up to 98%), and the electron-donating group substituent shows similar or less conversion compared to benzaldehyde under the optimized reaction conditions. From the comparison of results between all these Ni complexes, it was found that the efficiency of the catalytic performance follows the order [NiL 1 ] > [NiL 3 ] > [NiL 2 ] > [NiL 4 ]. A possible reaction pathway was predicted and established through UV-vis spectroscopy. Intermediate II proposed in the reaction pathway was also trapped and characterized through 1 H and 13 C NMR., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Background: An understanding of mechanisms underlying colorectal cancer (CRC) development and progression is yet to be fully elucidated. This study aims to employ network theoretic approaches to analyse single cell transcriptomic data from CRC to better characterize its progression and sided-ness., Methods: We utilized a recently published single-cell RNA sequencing data (GEO-GSE178341) and parsed the cell X gene data by stage and side (right and left colon). Using Weighted Gene Co-expression Network Analysis (WGCNA), we identified gene modules with varying preservation levels (weak or strong) of network topology between early (pT1) and late stages (pT234), and between right and left colons. Spearman's rank correlation ( ρ ) was used to assess the similarity or dissimilarity in gene connectivity., Results: Equalizing cell counts across different stages, we detected 13 modules for the early stage, two of which were non-preserved in late stages. Both non-preserved modules displayed distinct gene connectivity patterns between the early and late stages, characterized by low ρ values. One module predominately dealt with myeloid cells, with genes mostly enriched for cytokine-cytokine receptor interaction potentiallystimulating myeloid cells to participate in angiogenesis. The second module, representing a subset of epithelial cells, was mainly enriched for carbohydrate digestion and absorption, influencing the gut microenvironment through the breakdown of carbohydrates. In the comparison of left vs. right colons, two of 12 modules identified in the right colon were non-preserved in the left colon. One captured a small fraction of epithelial cells and was enriched for transcriptional misregulation in cancer, potentially impacting communication between epithelial cells and the tumor microenvironment. The other predominantly contained B cells with a crucial role in maintaining human gastrointestinal health and was enriched for B-cell receptor signalling pathway., Conclusions: We identified modules with topological and functional differences specific to cell types between the early and late stages, and between the right and left colons. This study enhances the understanding of roles played by different cell types at different stages and sides, providing valuable insights for future studies focused on the diagnosis and treatment of CRC., Competing Interests: Competing interests The authors declare that they have no competing interests.

Reaction of 2-chloromethyl-1H-benzimidazole with known intermediates (i-iii), prepared from diaminoguanidine hydrochloride with salicylaldehyde, 5-bromosalicylaldehyde or 3,5-di-tert-butylsalicylaldehyde, in the presence of triethylamine (NEt 3 ) led to the formation of benzimidazole appended new ligands, H 4 L 1 -H 4 L 3 (I-III). The homogeneous nitrogen-bridged symmetrical binuclear complexes, [(Mo VI O 2 ) 2 (L 1 )(H 2 O) 2 ] (1), [(Mo VI O 2 ) 2 (L 2 )(H 2 O) 2 ] (2) and [(Mo VI O 2 ) 2 (L 3 )(MeOH) 2 ] (3) have been isolated by reacting these ligands with [Mo VI O 2 (acac) 2 ] in a 1 : 2 molar ratio in refluxing methanol. Using 1 : 1 (ligand to Mo precursor) molar ratio under above reaction conditions resulted in the corresponding mononuclear complexes, [Mo VI O 2 (H 2 L 1 )(MeOH)] (4), [Mo VI O 2 (H 2 L 2 )(H 2 O)] (5) and [Mo VI O 2 (H 2 L 3 )(MeOH)] (6). The binuclear heterogeneous compounds [(Mo VI O 2 ) 2 (L 1 )(DMF) 2 ]@PS (PS-1), [(Mo VI O 2 ) 2 (L 2 )(DMF) 2 ]@PS (PS-2) and [(Mo VI O 2 ) 2 (L 3 )(DMF) 2 ]@PS (PS-3) have been obtained by immobilization of 1-3 onto chloromethylated polystyrene (PS) beads. All synthesized ligands, homogeneous as well as supported compounds have been characterized by elemental analyses and various spectroscopic methods. Single crystal X-ray diffraction study of complexes 1 and 3 confirms their nitrogen-bridged symmetrical binuclear structures while 4 is mononuclear. Heterogeneous compounds (PS-1-PS-3) have further been studied by microwave plasma atomic emission spectroscopy, X-ray photoelectron spectroscopy, and field emission scanning electron microscopy along with energy dispersive spectroscopy. These compounds (homogeneous and heterogeneous) were explored for catalytic applications to one-pot multicomponent reactions (MCRs) for efficient synthesis of biologically active 2-amino-3-cyano-4H-chromenes/pyrans (21 examples). Optimising various reaction parameters helped in achieving as high as 97 % yields of products. Though, only half equivalent of the binuclear complexes (1-3) was required compared to mononuclear analogues (4-6) to achieve comparable yields, heterogeneous catalysts have an added advantage due to their stability and recyclability. Suitable reaction mechanism has also been proposed based on isolated intermediates., (© 2024 Wiley-VCH GmbH.)

Reaction of tris(2-hydroxybenzylidene)-triaminoguanidinium chloride ( I ·HCl) and tris(5-bromo-2-hydroxybenzylidene)-triaminoguanidinium chloride ( II ·HCl) with [V IV O(acac) 2 ] (1:1 molar ratio) in refluxing methanol resulted in mononuclear [V IV O] complexes, [V IV O(H 2 L 1' )(MeOH)] ( 1 ) and [V IV O(H 2 L 2' )(MeOH)] ( 2 ), respectively, where I and II undergo intramolecular triazole ring formation. Aerial oxidation of 1 and 2 in MeOH in the presence of Cs 2 CO 3 gave corresponding cis -[V V O 2 ] complexes Cs[(VO 2 )(H 2 L 1' )] ( 3 ) and Cs[(VO 2 )(H 2 L 2' )] ( 4 ). However, reaction of an aerially oxidized methanolic solution of [V IV O(acac) 2 ] with I ·HCl and II ·HCl in the presence of Cs 2 CO 3 (in 1:1:1 molar ratio) gave mononuclear complexes Cs[(VO 2 )(H 3 L 1 )] ( 5 ) and Cs[(VO 2 )(H 3 L 2 )] ( 6 ) without intramolecular triazole ring formation. Similar anionic trinuclear complexes Cs 2 [(VO 2 ) 3 ( L 1 )] ( 7 ) and Cs 2 [(VO 2 ) 3 ( L 2 )] ( 8 ) were isolable upon increasing the amounts of the vanadium precursor and Cs 2 CO 3 to 3 equiv to the reaction applied for 5 and 6 . Keeping the reaction mixture of 1 in MeOH under air gave [V V O(H 2 L 1' )(OMe)] ( 9 ). Structures of 3 , 7 , 8 , and 9 were confirmed by X-ray crystal structure study. A permanent porosity in the crystalline metal-organic framework of 7 confirmed by single-crystal X-ray investigation was further verified by the BET study. Along with a suitable reaction mechanism, these synthesized compounds were explored as effective catalysts for the synthesis of biomolecules 4 H -pyran/4 H -chromenes.

Quantitative understanding of cellular processes, such as cell cycle and differentiation, is impeded by various forms of complexity ranging from myriad molecular players and their multilevel regulatory interactions, cellular evolution with multiple intermediate stages, lack of elucidation of cause-effect relationships among the many system players, and the computational complexity associated with the profusion of variables and parameters. In this paper, we present a modeling framework based on the cybernetic concept that biological regulation is inspired by objectives embedding rational strategies for dimension reduction, process stage specification through the system dynamics, and innovative causal association of regulatory events with the ability to predict the evolution of the dynamical system. The elementary step of the modeling strategy involves stage-specific objective functions that are computationally determined from experiments, augmented with dynamical network computations involving endpoint objective functions, mutual information, change-point detection, and maximal clique centrality. We demonstrate the power of the method through application to the mammalian cell cycle, which involves thousands of biomolecules engaged in signaling, transcription, and regulation. Starting with a fine-grained transcriptional description obtained from RNA sequencing measurements, we develop an initial model, which is then dynamically modeled using the cybernetic-inspired method, based on the strategies described above. The cybernetic-inspired method is able to distill the most significant interactions from a multitude of possibilities. In addition to capturing the complexity of regulatory processes in a mechanistically causal and stage-specific manner, we identify the functional network modules, including novel cell cycle stages. Our model is able to predict future cell cycles consistent with experimental measurements. We posit that this innovative framework has the promise to extend to the dynamics of other biological processes, with a potential to provide novel mechanistic insights., Competing Interests: Declaration of interests The authors declare no competing interests., (Copyright © 2023 Biophysical Society. Published by Elsevier Inc. All rights reserved.)

Ligands derived from 2-(1-phenylhydrazinyl)pyridine and salicylaldehyde (HL 1 ), 3-methoxysalicylaldehyde (HL 2 ), 5-bromosalicylaldehyde (HL 3 ), and 3,5-di- tert -butylsalicylaldehyde (HL 4 ) react with [V IV O(acac) 2 ] in MeOH followed by aerial oxidation to give [V V O 2 (L 1 )] ( 1 ), [V V O 2 (L 2 )] ( 2 ), [V V O 2 (L 3 )] ( 3 ), and [V V O 2 (L 4 )] ( 4 ). Complex [V IV O(acac)(L 1 )] ( 5 ) is also isolable from [V IV O(acac) 2 ] and HL 1 in dry MeOH. Structures of all complexes were confirmed by single-crystal X-ray and spectroscopic studies. They efficiently catalyze benzyl alcohol and its derivatives' oxidation in the presence of H 2 O 2 to their corresponding aldehydes. Under optimized reaction conditions using 1 as a catalyst precursor, conversion of benzyl alcohol follows the order: 4 (93%) > 2 (90%) > 1 (86%) > 3 (84%) ≈ 5 (84%). These complexes were also evaluated for antifungal and antiproliferative activities. Complex 3 with MIC 50 = 16 μg/mL, 4 with MIC 50 = 12 μg/mL, and 5 with MIC 50 = 16 μg/mL are efficient toward planktonic cells of Candida albicans and Candida tropicalis . On Michigan cancer foundation-7 (MCF-7) cells, they show comparable cytotoxic effects and exhibit IC 50 in the 27.3-33.5 μg/mL range, and among these, 4 exhibits the highest cytotoxicity. A similar study on human embryonic kidney cells (HEK293) confirms their less toxicity at lower concentrations (4 to 16 μg/mL) compared to MCF-7.

Introduction: Kalmegh (Andrographis paniculata) is commonly used for treating uncomplicated Upper Respiratory Tract Infection (URTI) in complementary and alternative system of medicine. AP-Bio®(KalmCold®) is a standardized extract derived from the leaves of A. paniculata. This study was proposed to evaluate its efficacy using validated scales and objective measures., Methods: Participants were randomized in a ratio of 1:1:1 to receive either AP-Bio® 200 mg/day, AP-Bio® 400 mg/day or placebo for 7 days. The primary outcome measure was Wisconsin Upper Respiratory Symptom Survey (WURSS-21) score. The secondary outcome measures were nasal mucous weight, nasal muco-ciliary clearance function and Interleukin-8 in nasal wash, as well as safety and tolerability., Results: A total of n = 331 participants were screened and N = 300 participants were enrolled. The absolute WURSS-21 global score [mean (Standard Deviation - SD)] in the AP-Bio® 400 mg group [5.70 (5.31)] was less than the AP-Bio® 200 mg group [5.81 (4.83)] on Day-3. However, it was much higher in the placebo group [9.55 (14.27)]. AP-Bio® 400 mg group (Mean Difference - MD [Standard Error - SE] = -3.85 [1.52]; 95% CI = -6.85, - 0.85; adjusted p = 0.034) and 200 mg group (MD [SE] = -3.74 [1.51]; 95% CI = -6.73, - 0.76; adjusted p = 0.038) had significantly lower score than placebo. Similarly, on Day-3, the change in global score from baseline was significantly better in the AP-Bio® 400 mg group (MD [SE] = -3.91; [1.82] 95% CI = -7.50, - 0.32; adjusted p = 0.038) and AP-Bio® 200 mg group (MD [SE] = -3.84 [1.97]; 95% CI = -7.72, - 0.04; adjusted p = 0.044) in comparison to the placebo group. Nasal mucous weight, tissue paper counts used, and interleukin-8 showed a trend towards AP-Bio® groups having a favourable outcome when compared with placebo but did not reach statistical significance due to a small sample size. None of the study participants complained of any adverse physical symptoms. However, incident eosinophilia was noted in n = 20 participants on day 3. (n = 6 in AP-Bio® 200 mg group, n = 7 in Ap-Bio® 400 mg group and n = 13 in placebo group; p = 0.181)., Conclusions: Participants in both the AP-Bio® dose groups showed positive tendency towards resolution of URTI symptoms when compared with placebo on Day-3 but not on Day-5 and Day-7., Competing Interests: Conflicts of Interest The authors declare no conflict of interest. The sponsors had no role in the design, execution, interpretation, or writing of the study., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Two new meso -substituted oxido-molybdenum corroles were synthesized and characterized by various spectroscopic techniques. In the thermogram, MoO[TTC] ( 1 ) exhibited excellent thermal stability up to 491 °C while MoO[TNPC] ( 2 ) exhibited good stability up to 318 °C. The oxidation states of the molybdenum(V) were verified by electron paramagnetic resonance (EPR) spectroscopy and exhibited an axial compression with d xy 1 configuration. Oxido-molybdenum(V) complexes were utilized for the selective epoxidation of various olefins with high TOF values (2066-3287 h -1 ) in good yields in a CH 3 CN/H 2 O (3:2, v/v) mixture in the presence of hydrogen peroxide as a green oxidant and NaHCO 3 as a promoter. The oxidative bromination catalytic activity of oxido-molybdenum(V) complexes in an aqueous medium has been reported for the first time. Surprisingly, MoO[TNPC] ( 2 ) biomimics of the vanadium bromoperoxidase (VBPO) enzyme activity exhibited remarkably high TOF values (36 988-61 646 h -1 ) for the selective oxidative bromination of p -cresol and other phenol derivatives. Catalyst MoO[TNPC] ( 2 ) exhibited higher TOF values and better catalytic activity than catalyst MoO[TTC] ( 1 ) due to the presence of electron-withdrawing nitro groups evident from cyclic voltammetric studies.

Introduction: Since June 15, 2009, clinical trial registration in the Clinical Trial Registry-India (CTRI) has been made mandatory by the Drugs Controller General of India to improve transparency, accountability, conform to accepted ethical standards and reporting of all relevant results of registered trials. In this study, we planned to evaluate the compliance of Indian and global sponsors with clinical trials conducted in India in terms of reporting of clinical trial results at the CTRI., Methods: We included trials registered in the CTRI between January 2018 and January 2020. The CTRI and ClinicalTrials.gov registry was thoroughly searched for all completed interventional studies. A year-wise comparative analysis was performed to evaluate the number of clinical trials reporting results in both the registry., Results: The reporting of completed interventional clinical trial results was 25/112 (22.32%) in year 2018, y, 8/105 (7.6%) in year 2019 and 17/140 (12.14%) in year 2020. There was significantly less reporting of results of Pharmaceutical company sponsored Interventional Studies-Indian at CTRI when compared with ClinicalTrials.gov registry for the year 2019 (odds ratio [OR]-0.17 (95% confidence interval [CI]: 0.08-0.36) and P < 0.0001) and year 2020 (OR-0.45 [95% CI: 0.24-0.82] and P < 0.01). The difference in results reported at CTRI was significantly low for Pharmaceutical company sponsored Interventional Studies-Global only for year 2019 (OR-0.09 [95% CI: 0.005-1.45] and P = 0.04) compared with ClinicalTrials.gov., Conclusion: There is a need to develop the culture of reporting clinical trial results in CTRI to strengthen the transparency in the research for overall benefit of public, health care professionals, and research community., Competing Interests: There are no conflicts of interest., (Copyright: © 2022 Perspectives in Clinical Research.)

The field of strain sensing involves the ability to measure an electrical response that corresponds to a strain. The integration of synthetic and conducting polymers can create a flexible strain sensor with a wide range of applications, including soft robotics, sport performance monitoring, gaming and virtual reality, and healthcare and biomedical engineering. However, the use of insulating synthetic polymers can impede the semiconducting properties of sensors, which may reduce sensor sensitivity. Previous research has shown that the doping process can significantly enhance the electrical performance and ionic conduction of conducting polymers, thereby strengthening their potential for use in electronic devices. However the full effects of secondary doping on the crystallinity, stretchability, conductivity, and sensitivity of conducting polymer blends have not been studied. In this study, we investigated the effects of secondary doping on the properties of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)/poly(vinyl alcohol) (PEDOT:PSS/PVA) polymer blend thin films and their potential use as strain sensors. The thin films were prepared using a facile drop-casting method. Morphology analysis using profilometry and atomic force microscopy confirmed the occurrence of phase segregation and revealed surface roughness values. This evidence provided a comprehensive understanding of the chemical interactions and physical properties of the thin films, and the effects of doping on these properties. The best films were selected and applied as sensitive strain sensors. EG-PEDOT:PSS/PVA thin films showing a significant increase of conductivity values from the addition of 1 vol% to 12 vol% addition, with conductivity values of 8.51 × 10 -5 to 9.42 × 10 -3 S cm -1 . Our 12% EG-PEDOT:PSS/PVA sensors had the highest GF value of 2000 too. We compared our results with previous studies on polymeric sensors, and it was found that our sensors quantitatively had better GF values. Illustration that demonstrates the DMSO and EG dopant effects on PEDOT:PSS structure through bonding interaction, crystallinity, thermal stability, surface roughness, conductivity and stretchability was also provided. This study suggests a new aspect of doping interaction that can enhance the conductivity and sensitivity of PEDOT:PSS for device applications., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Complex 2,3,12,13-tetracyano-5,10,15,20-tetraphenylporphyrinatooxidovanadium(IV) {[V IV OTPP(CN) 4 ], 2 } has been prepared by nucleophilic substitution of β-bromo groups of the corresponding 2,3,12,13-tetrabromo-5,10,15,20-tetraphenylporphyrinatooxidovanadium(IV) {[V IV OTPP(Br) 4 ], 1 } using CuCN in quinoline. Both complexes show biomimetic catalytic activity similar to enzyme haloperoxidases and efficiently brominate various phenol derivatives in the presence of KBr, H 2 O 2 , and HClO 4 in the aqueous medium. Between these two complexes, 2 exhibits excellent catalytic activity with high turnover frequency (35.5-43.3 s -1 ) due to the strong electron-withdrawing nature of the cyano groups attached at β-positions and its moderate nonplanar structure as compared to 1 (TOF = 22.1-27.4 s -1 ). Notably, this is the highest turnover frequency value observed for any porphyrin system. The selective epoxidation of various terminal alkenes using complex 2 has also been carried out, and the results are good, specifying the importance of electron-withdrawing cyano groups. Catalysts 1 and 2 are recyclable, and the catalytic activity proceeds through the corresponding [V V O( OH )TPP(Br) 4 ] and [V V O( OH )TPP(CN) 4 ] intermediates, respectively., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Nanobiotechnology has been an encouraging approach to improving the efficacy of hydrophobic bioactive compounds. The biologically active constituents present in herbal extracts are poorly absorbed, resulting in loss of bioavailability and efficacy. Hence, herbal medicine and nanotechnology are combined to overcome these limitations. The surface-to-volume ratio of nanoparticles is high and as the size is small, the functional properties are enhanced. The present study reports the synthesis of cinnamon and cumin (Ci-Cu) dual drug-loaded poly (D, L-lactide-co-glycolide) (PLGA) nanoparticles (NPs) to overcome the limitations of oral bioavailability and extend the effect of these drugs for alleviating health problems. The solvent evaporation method was adopted for the synthesis, and the as-prepared nanoparticles were characterized by Scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, Transmission electron microscopy (TEM) and X-ray diffraction (XRD). The average size of the formed spherical Ci-Cu nanoparticles ranged between 90 and 120 nm. The encapsulation efficiency of the drug was found to be 79% ± 4.5%. XRD analysis demonstrated that cinnamon and cumin were amorphously scattered in the PLGA matrix. The FTIR bands showed no evident changes suggesting the no direct molecular interactions between the drug and the polymer. At pH 6.9, the release studies in vitro exhibited a burst initially followed by a tendency to obtain a slower steady release. The results indicated that the Cu-Ci dual drug-loaded polymeric NPs has drug release at a slower rate. The time taken for 25% release of drug in Ci-Cu-loaded PLGA NPs was twice as compared to cumin-loaded PLGA Nps, and three times compared to cinnamon-loaded PLGA NPs., Competing Interests: Conflict of interestThe authors declare no conflict of interest., (© The Author(s) 2023.)

Melanocortins are tiny protein molecules formed by the post-translational cleavage of proopiomelanocortin. These are bioactive peptides that are responsible for human and lower animal pigmentation patterns, energy homeostasis, and sexual function modulation. These peptides regulate numerous physiological functions by being generated in the central nervous system and peripheral tissues. Melanocortins elicit their varied biological effects by binding to a separate family of G protein, two primary proteolytic enzymes, proconvertases 1 and 2, according to recent research. These breakthroughs have opened up new avenues for research into the role of melanocortins, antagonists, and receptors in a number of physiological activities., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Background: Biomedical research often involves contextual integration of multimodal and multiomic data in search of mechanisms for improved diagnosis, treatment, and monitoring. Researchers need to access information from diverse sources, comprising data in various and sometimes incongruent formats. The downstream processing of the data to decipher mechanisms by reconstructing networks and developing quantitative models warrants considerable effort., Results: MetGENE is a knowledge-based, gene-centric data aggregator that hierarchically retrieves information about the gene(s), their related pathway(s), reaction(s), metabolite(s), and metabolomic studies from standard data repositories under one dashboard to enable ease of access through centralization of relevant information. We note that MetGENE focuses only on those genes that encode for proteins directly associated with metabolites. All other gene-metabolite associations are beyond the current scope of MetGENE. Further, the information can be contextualized by filtering by species, anatomy (tissue), and condition (disease or phenotype)., Conclusions: MetGENE is an open-source tool that aggregates metabolite information for a given gene(s) and presents them in different computable formats (e.g., JSON) for further integration with other omics studies. MetGENE is available at https://bdcw.org/MetGENE/index.php., (© The Author(s) 2023. Published by Oxford University Press GigaScience.)

Ligands H 4 sal-dag ( I ) and H 4 Brsal-dag ( II ) derived from 1,3-diaminoguanidine and salicylaldehyde or 5-bromosalicylaldehyde react with one or 2 mol equivalent of vanadium precursor to give two different series of vanadium complexes. Thus, complexes [V IV O(H 2 sal-dag) (H 2 O)] ( 1 ) and [V IV O(H 2 Brsal-dag) (H 2 O)] ( 2 ) were isolated by the reaction of an equimolar ratio of these ligands with [V IV O(acac) 2 ] in MeOH. In the presence of K + /Cs + ion and using aerially oxidized [V IV O(acac) 2 ], the above reaction gave complexes [K(H 2 O){V V O 2 (H 2 sal-dag)}] 2 ( 3 ), [Cs(H 2 O){V V O 2 (H 2 sal-dag)}] 2 ( 4 ), [K(H 2 O){VO 2 (H 2 Brsal-dag)}] 2 ( 5 ), and [Cs(H 2 O){V V O 2 (H 2 Brsal-dag)}] 2 ( 6 ), which could also be isolated by direct aerial oxidation of complexes 1 and 2 in MeOH in the presence of K + /Cs + ion. Complexes [(H 2 O)V IV O(Hsal-dag)V V O 2 ] ( 7 ) and [(H 2 O)V IV O(HBrsal-dag)V V O 2 ] ( 8 ) were isolated upon increasing the ligand-to-vanadium precursor molar ratio to 1:2 under an air atmosphere. When I and II were reacted with aerially oxidized [V IV O(acac) 2 ] in a 1:2 molar ratio in MeOH in the presence of K + /Cs + ion, they formed [K(H 2 O) 5 {(V V O 2 ) 2 (Hsal-dag)}] 2 ( 9 ), [Cs(H 2 O) 2 {(V V O 2 ) 2 (Hsal-dag)}] 2 ( 10 ), [K 2 (H 2 O) 4 {(V V O 2 ) 2 (Brsal-dag)}] 2 ( 11 ), and [Cs 2 (H 2 O) 4 {(V V O 2 ) 2 (Brsal-dag)}] 2 ( 12 ). The structures of complexes 3 , 4 , 5 , and 9 determined by single-crystal X-ray diffraction study confirm the mono-, bi-, tri-, and tetra-anionic behaviors of the ligands. All complexes were found to be an effective catalyst for the oxidation of benzoin to benzil via oxygen atom transfer (OAT) between DMSO and benzoin. Under aerobic condition, this oxidation also proceeds effectively in the absence of DMSO. Electron paramagnetic resonance and 51 V NMR studies demonstrated the active role of a stable V(IV) intermediate during OAT between DMSO and benzoin., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Exhaled breath (EB) contains several macromolecules that can be exploited as biomarkers to provide clinical information about various diseases. Hydrogen peroxide (H 2 O 2 ) is a biomarker because it indicates bronchiectasis in humans. This paper presents a non-invasive, low-cost, and portable quantitative analysis for monitoring and quantifying H 2 O 2 in EB. The sensing unit works on colorimetry by the synergetic effect of eosin blue, potassium permanganate, and starch-iodine (EPS) systems. Various sampling conditions like pH, response time, concentration, temperature and selectivity were examined. The UV-vis absorption study of the assay showed that the dye system could detect as low as ∼0.011 ppm levels of H 2 O 2 . A smart device-assisted detection unit that rapidly detects red, green and blue (RGB) values has been interfaced for practical and real-time application. The RGB value-based quantification of the H 2 O 2 level was calibrated against NMR spectroscopy and exhibited a close correlation. Further, we adopted a machine learning approach to predict H 2 O 2 concentration. For the evaluation, an artificial neural network (ANN) regression model returned 0.941 R 2 suggesting its great prospect for discrete level quantification of H 2 O 2 . The outcomes exemplified that the sensor could be used to detect bronchiectasis from exhaled breath., Competing Interests: The authors declare that they have no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Wearable sensors have drawn considerable interest in the recent research world. However, simultaneously realizing high sensitivity and wide detection limits under changing surrounding environment conditions remains challenging. In the present study, we report a wearable piezoresistive pressure sensor capsule that can detect pulse rate and human motion. The capsule includes a flexible silicon cover and is filled with different PVA/MXene (PVA-Mx) composites by varying the weight percentage of MXene in the polymer matrix. Different characterizations such as XRD, FTIR and TEM results confirm that the PVA-Mx silicon capsule was successfully fabricated. The PVA-Mx gel-based sensor capsule remarkably endows a low detection limit of 2 kPa, exhibited high sensitivity of 0.45 kPa -1 in the ranges of 2-10 kPa, and displayed a response time of ~ 500 ms, as well as good mechanical stability and non-attenuating durability over 500 cycles. The piezoresistive sensor capsule sensor apprehended great stability towards changes in humidity and temperature. These findings substantiate that the PVA/MXene sensor capsule is potentially suitable for wearable electronics and smart clothing., Competing Interests: Conflict of interestOn behalf of all authors, the corresponding author states that there is no conflict of interest., (© The Author(s) 2022.)

Background: While mechanisms contributing to the progression and metastasis of colorectal cancer (CRC) are well studied, cancer stage-specific mechanisms have been less comprehensively explored. This is the focus of this manuscript., Methods: Using previously published data for CRC (Gene Expression Omnibus ID GSE21510), we identified differentially expressed genes (DEGs) across four stages of the disease. We then generated unweighted and weighted correlation networks for each of the stages. Communities within these networks were detected using the Louvain algorithm and topologically and functionally compared across stages using the normalized mutual information (NMI) metric and pathway enrichment analysis, respectively. We also used Short Time-series Expression Miner (STEM) algorithm to detect potential biomarkers having a role in CRC., Results: Sixteen Thousand Sixty Two DEGs were identified between various stages (p-value ≤ 0.05). Comparing communities of different stages revealed that neighboring stages were more similar to each other than non-neighboring stages, at both topological and functional levels. A functional analysis of 24 cancer-related pathways indicated that several signaling pathways were enriched across all stages. However, the stage-unique networks were distinctly enriched only for a subset of these 24 pathways (e.g., MAPK signaling pathway in stages I-III and Notch signaling pathway in stages III and IV). We identified potential biomarkers, including HOXB8 and WNT2 with increasing, and MTUS1 and SFRP2 with decreasing trends from stages I to IV. Extracting subnetworks of 10 cancer-relevant genes and their interacting first neighbors (162 genes in total) revealed that the connectivity patterns for these genes were different across stages. For example, BRAF and CDK4, members of the Ser/Thr kinase, up-regulated in cancer, displayed changing connectivity patterns from stages I to IV., Conclusions: Here, we report molecular and modular networks for various stages of CRC, providing a pseudo-temporal view of the mechanistic changes associated with the disease. Our analysis highlighted similarities at both functional and topological levels, across stages. We further identified stage-specific mechanisms and biomarkers potentially contributing to the progression of CRC., (© 2022. The Author(s).)

Background: CYP3A5 enzymes belong to the phase I Group of drug-metabolizing enzymes, which are involved in the metabolism of 50% of the drugs. Participants with CYP3A5 genotype: CYP3A5 *1/*1 are fast metabolizers of drugs and hence will require higher dosing. Whereas those with CYP3A5 * 3/*3 are poor metabolizers of drugs and will require a lower dose to achieve target drug concentration in the blood and those with CYP3A5 * 1/*3 have intermediate drug metabolizing activity. Pharmacogenetic evaluation may improve disease outcomes by maximizing the efficacy and minimizing the toxicity of drugs in patients., Materials and Methods: This is a single-center cross-sectional study conducted in the year 2018-2019 to study the population prevalence of genetic polymorphisms of CYP3A5 in healthy participants from western India. Eligible participants willing to give written, informed consent were enrolled in the study. Subsequently, 2 ml venous blood was collected the deoxyribonucleic acid was extracted and then stored at ‒20°C. Genotyping was done by a polymerase chain reaction and restriction fragment length polymorphism., Results: A total of 400 participants with a median age of 22 years (range: 18-58 years) were included. Among them, the genotype prevalence for CYP3A5 * 1/*1 was 17% (n = 67/400); CYP3A5 * 1/*3 was 37% (n = 149/400) and that of CYP3A5 * 3/*3 was 46% (184/400). Out of the total 400 healthy participants analyzed, the allele frequency for CYP3A5 * 1 was 35% (142/400) and that of CYP3A5*3 was 65% (259/400)., Conclusion: The genotype prevalence for CYP3A5 * 3*3 (46%) and the allele frequency for CYP3A5 * 3 (65%) respectively were the highest among the western Indian population., Competing Interests: None

Human breath analysis of volatile organic compounds has gained significant attention recently because of its rapid and noninvasive potential to detect various metabolic diseases. The detection of ketones in the breath and blood is key to diagnosing and managing diabetic ketoacidosis (DKA) in patients with type 1 diabetes. It may also be of increasing importance to detect euglycemic ketoacidosis in patients with type 1 or type 2 diabetes or heart failure, treated with sodium-glucose transporter-2 inhibitors (SGLT2-i). The present research evaluates the efficiency of colorimetry for detecting acetone and ethanol in exhaled human breath with the response time, pH effect, temperature effect, concentration effect, and selectivity of dyes. Using the proposed multidye system, we obtained a detection limit of 0.0217 ppm for acetone and 0.029 ppm for ethanol in the detection range of 0.05-50 ppm. A smartphone-assisted unit consisting of a portable colorimetric device was used to detect relative red/green/blue values within 60 s of the interface for practical and real-time application. The developed method could be used for rapid, low-cost detection of ketones in patients with type 1 diabetes and DKA and patients with type 1 or type 2 diabetes or heart failure treated with SGLT2-I and euglycemic ketoacidosis., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Carbon dioxide (CO 2 ) is a greenhouse gas in the atmosphere and scientists are working on converting it to useful products, thereby reducing its quantity in the atmosphere. For converting CO 2 , different approaches are used, and among them, electrochemistry is found to be the most common and more efficient technique. Current methods for detecting the products of electrochemical CO 2 conversion are time-consuming and complex. To combat this, a simple, cost-effective colorimetric method has been developed to detect methanol, ethanol, and formic acid, which are formed electrochemically from CO 2 . In the present work, the highly efficient sensitive dyes were successfully established to detect these three compounds under optimized conditions. These dyes demonstrated excellent selectivity and showed no cross-reaction with other products generated in the CO 2 conversion system. In the analysis using these three compounds, this strategy shows good specificity and limit of detection (LOD, ~0.03-0.06 ppm). A cost-effective and sensitive Internet of Things (IoT) colorimetric sensor prototype was developed to implement these dyes systems for practical and real-time application. Employing the dyes as sensing elements, the prototype exhibits unique red, green, and blue (RGB) values upon exposure to test solutions with a short response time of 2 s. Detection of these compounds via this new approach has been proven effective by comparing them with nuclear magnetic resonance (NMR). This novel approach can replace heavy-duty instruments such as high-pressure liquid chromatography (HPLC), gas chromatography (G.C.), and NMR due to its extraordinary selectivity and rapidity.

Over the last decade, there has been a huge demand for health care technologies such as sensors-based prediction using digital health. With the continuous rise in the human population, these technologies showed to be potentially effective solutions to life-threatening diseases such as heart failure (HF). Besides being a potential for early death, HF has a significantly reduced quality of life (QoL). Heart failure has no cure. However, treatment can help you live a longer and more active life with fewer symptoms. Thus, it is essential to develop technological aid solutions allowing early diagnosis and consequently, effective treatment with possibly delayed mortality. Commonly, forecasts of HF are based on the generation of vast volumes of data usually collected from an individual patient by different components of the family history, physical examination, basic laboratory results, and other medical records. Though, these data are not effectively useful for predicting this failure, nevertheless, with the aid of advanced medical technology such as interconnected multi-sensory-based devices, and based on several medical history characteristics, the broad data provided machine learning algorithms to predict risk factors for heart disease of an individual is beneficial. There will be many challenges for the next decade of advancements in HF care: exploiting an increasingly growing repertoire of interconnected internal and external sensors for the benefit of patients and processing large, multimodal datasets with new Artificial Intelligence (AI) software. Various methods for predicting heart failure and, primarily the significance of invasive and non-invasive sensors along with different strategies for machine learning to predict heart failure are presented and summarized in the present study., (© 2021. International Federation for Medical and Biological Engineering.)

Monitoring exhaled breath is a safe, noninvasive method for determining the health status of the human body. Most of the components in our exhaled breath can act as health biomarkers, and they help in providing information about various diseases. Nitric oxide (NO) is one such important biomarker in exhaled breath that indicates oxidative stress in our body. This work presents a simple and noninvasive quantitative analysis approach for detecting NO from exhaled breath. The sensing is based on the colorimetric assisted detection of NO by m-Cresol Purple, Bromophenol Blue, and Alizaringelb dye. The sensing performance of the dye was analyzed by ultraviolet-visible (UV-Vis) spectroscopy. The study covers various sampling conditions like the pH effect, temperature effect, concentration effect, and selective nature of the dye. The m-Cresol Purple dye exhibited a high sensitivity towards NO with a detection limit of ~0.082 ppm in the linear range of 0.002-0.5 ppm. Moreover, the dye apprehended a high degree of selectivity towards other biocompounds present in the breath, and no possible interfering cross-reaction from these species was observed. The dye offered a high sensitivity, selectivity, fast response, and stability, which benchmark its potential for NO sensing. Further, m-Cresol Purple dye is suitable for NO sensing from the exhaled breath and can assist in quantifying oxidative stress levels in the body for the possible detection of COVID-19.

Background: The approval process of every drug regulatory agency differs, and hence, the time required for the approval of a new drug varies. This results in a drug lag and India is no exception to this phenomenon. A drug lag precludes Indian patients from accessing new medicines at the same time as they are approved elsewhere. Against this backdrop, we assessed the absolute and relative drug lags of the Indian regulator relative to three regulators in mature markets, namely United States (US), European Union (EU), and Japan., Methods: International nonproprietary names were used to identify new drugs. Their dates of approval (2004-2018) from the online database of four regulatory agencies were identified. Both absolute and relative drug lags were calculated for India as compared to US, EU, and Japan as well for all the agencies relative to the Indian regulator., Results: We identified a total of 453, 473, 424, and 472 new drugs approved over the study period in India, US, EU, and Japan, respectively. The absolute drug lag of Central Drugs Standard Control Organization (CDSCO) was 19 and 18 relative to the US Food and Drug Administration (FDA) and Japan Pharmaceuticals and Medical Devices Agency (PMDA), respectively. The relative drug lag for the CDSCO vis-a-vis the US FDA, European Medicines Agency, and PMDA was 43.2 (2.1-1287.8), 25.6 (0.03-1310.5), and 30.3 (1.2-1242) months, respectively., Conclusion: Our study shows a significant drug lag between India and other three developed nations (US, EU, and Japan). However, in some therapeutic areas, Indian regulator has proactively approved new drugs much before other agencies. The New Drugs and Clinical Trials Rule of 2019 has brought hope for reduction in drug lag in the near future., Competing Interests: The authors have no conflicts of interest to declare., (Copyright: © 2021 Perspectives in Clinical Research.)

The novel coronavirus infection (COVID-19) is not diminishing without vaccine, but it impinges on human safety and economy can be minimized by adopting smart technology to combat pandemic situation. The implementation of new innovations and novel tactics has proven to be effective in curbing the risk of COVID-19. The present study covers the role of smart technology in mitigating the spread of COVID-19 with specific focus on advancement in the field of drone, robotics, artificial intelligence (AI), mask, and sensor technology. The findings shed light on the robotics and drone technology-driven approaches that have been applied for assisting health system, surveillance, and disinfection process, etc. The AI technology strategies and framework is highlighted in terms of bulk data computing, predicting infection threats, providing medical assistance, and analyzing diagnosis results. Besides this, the technological shift in mask and sensor technology during the pandemic have been illustrated, which includes fabrication method like 3D printing and optical sensing, respectively. Furthermore, the strength, weakness, opportunities, and possible threats that have been shaped by the rigorous implementation of these technologies are also covered in detail., Competing Interests: Conflict of interestOn behalf of all authors, the corresponding author states that there is no conflict of interest., (© King Abdulaziz City for Science and Technology 2021.)

The two main blood flow patterns, namely, pulsatile shear (PS) prevalent in straight segments of arteries and oscillatory shear (OS) observed at branch points, are associated with atheroprotective (healthy) and atheroprone (unhealthy) vascular phenotypes, respectively. The effects of blood flow-induced shear stress on endothelial cells (ECs) and vascular health have generally been studied using human umbilical vein endothelial cells (HUVECs). While there are a few studies comparing the differential roles of PS and OS across different types of ECs at a single time point, there is a paucity of studies comparing the temporal responses between different EC types. In the current study, we measured OS and PS transcriptomic responses in human aortic endothelial cells (HAECs) over 24 h and compared these temporal responses of HAECs with our previous findings on HUVECs. The measurements were made at 1, 4, and 24 h in order to capture the responses at early, mid, and late time points after shearing. The results indicate that the responses of HAECs and HUVECs are qualitatively similar for endothelial function-relevant genes and several important pathways with a few exceptions, thus demonstrating that HUVECs can be used as a model to investigate the effects of shear on arterial ECs, with consideration of the differences. Our findings show that HAECs exhibit an earlier response or faster kinetics as compared to HUVECs. The comparative analysis of HAECs and HUVECs presented here offers insights into the mechanisms of common and disparate shear stress responses across these two major endothelial cell types., Competing Interests: The authors declare no competing interest.

Preeclampsia is a pregnancy-specific syndrome characterized by hypertension and proteinuria after 20 weeks of gestation. However, it is not well understood what lipids are involved in the development of this condition, and even less is known how these lipids mediate its formation. To reveal the relationship between lipids and preeclampsia, we conducted lipidomic profiling of maternal sera of 44 severe preeclamptic and 20 healthy pregnant women from a multiethnic cohort in Hawaii. Correlation network analysis showed that oxidized phospholipids have increased intercorrelations and connections in preeclampsia, whereas other lipids, including triacylglycerols, have reduced network correlations and connections. A total of 10 lipid species demonstrate significant changes uniquely associated with preeclampsia but not any other clinical confounders. These species are from the lipid classes of lysophosphatidylcholines, phosphatidylcholines (PCs), cholesteryl esters, phosphatidylethanolamines, lysophosphatidylethanolamines, and ceramides. A random forest classifier built on these lipids shows highly accurate and specific prediction (F1 statistic = 0.94; balanced accuracy = 0.88) of severe preeclampsia, demonstrating their potential as biomarkers for this condition. These lipid species are enriched in dysregulated biological pathways, including insulin signaling, immune response, and phospholipid metabolism. Moreover, causality inference shows that various PCs and lysophosphatidylcholines mediate severe preeclampsia through PC 35:1e. Our results suggest that the lipidome may play a role in the pathogenesis and serve as biomarkers of severe preeclampsia., Competing Interests: Conflict of interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

Novel dibasic Schiff bases with three tridentate sites were obtained from the condensation of the triketone 2,4,6-triacetylphloroglucinol (H3ptk) with four different hydrazides, benzoyl hydrazide (bhz), furoyl hydrazide (fah), isonicotinoyl hydrazide (inh) and nicotinoyl hydrazide (nah): H6ptk(bhz)3I, H6ptk(fah)3II, H6ptk(inh)3III and H6ptk(nah)3IV. These ligand precursors I-IV, each being an ONO donor, are tricompartmental building blocks able to form trinuclear complexes having C3 symmetry. The reaction of I-IV with [VIVO(acac)2] leads to the formation of [{VIVO(H2O)}3(ptk(bhz)3)] 1, [{VIVO(H2O)}3(ptk(fah)3)] 2, [{VIVO(H2O)}3(ptk(inh)3)] 3, and [{VIVO(H2O)}3(ptk(nah)3)] 4. In methanol/aqueous solutions of M2CO3 (M+ = Na+, K+ and Cs+), these complexes are slowly converted into dioxidovanadium(v) compounds, namely, M3[(VVO2)3{ptk(bhz)3}]·6H2O [M+ = K+5, Na+9, Cs+13], M3[(VVO2)3{ptk(fah)3}]·6H2O [M+ = K+6, Na+10, Cs+14], M3[(VVO2)3{ptk(inh)3}]·6H2O [M+ = K+7, Na+11, Cs+15] and M3[(VVO2)3{ptk(nah)3}]·6H2O [M+ = K+8, Na+12, Cs+16]. All ligand precursors and complexes are characterized by various techniques such as FT-IR, UV/Visible, EPR, NMR (1H, 13C and 51V), elemental analysis, thermal studies, cyclic voltammetry (CV) and single-crystal X-ray analysis. X-ray diffraction studies of complexes K2.7[{(VVO2)3ptk(fah)3}]·11.5H2O·MeOH 6a, Cs3[{(VVO2)3ptk(bhz)3}]·7H2O 13a and Cs3[{(VVO2)3ptk(nah)3}]·7.3H2O 16a reveal their distorted square pyramidal geometry by coordinating through phenolate oxygen (of ptk), azomethine nitrogen and enolate oxygen (of hydrazide) atoms. The reactivity of complexes 5-16 and their catalytic potential were screened towards their peroxidase mimetic activity in the oxidation of dopamine to aminochrome driven by H2O2 as an oxidant. The conversion of dopamine to aminochrome with different catalysts was monitored by HPLC showing high activity under mild conditions with good conversions within 1 h. Kinetic studies using compounds 13-16 as catalyst precursors reveal that the reaction follows a Michaelis-Menten-like kinetics.

Zinc oxide (ZnO) one-dimensional nanostructures are extensively used in ultra-violet (UV) detection. To improve the optical sensing capability of ZnO, various nickel oxide (NiO) based p-n junctions have been employed. ZnO/NiO heterojunction based sensing has been limited to UV detection and not been extended to the visible region. In the present work, p-NiO/n-ZnO composite nanowire (NW) heterojunction based UV-visible photodetector is fabricated. A porous anodic aluminum oxide template based electrochemical deposition method is adopted for well separated and vertically aligned growth of composite NWs. The photoresponse is studied in an out of plane contact configuration. The fabricated photodetector shows fast response under UV-visible light with a rise and decay time of tens of ms. The wide spectral photoresponse is analyzed in terms of conduction from defect states of ZnO and interfacial defects during p-n junction formation. Light interaction with heterojunction along the length of the composite NW results in enhanced visible photoresponse of the detector and is further supported by simulation.

Background: Biochemical networks are often described through static or time-averaged measurements of the component macromolecules. Temporal variation in these components plays an important role in both describing the dynamical nature of the network as well as providing insights into causal mechanisms. Few methods exist, specifically for systems with many variables, for analyzing time series data to identify distinct temporal regimes and the corresponding time-varying causal networks and mechanisms., Results: In this study, we use well-constructed temporal transcriptional measurements in a mammalian cell during a cell cycle, to identify dynamical networks and mechanisms describing the cell cycle. The methods we have used and developed in part deal with Granger causality, Vector Autoregression, Estimation Stability with Cross Validation and a nonparametric change point detection algorithm that enable estimating temporally evolving directed networks that provide a comprehensive picture of the crosstalk among different molecular components. We applied our approach to RNA-seq time-course data spanning nearly two cell cycles from Mouse Embryonic Fibroblast (MEF) primary cells. The change-point detection algorithm is able to extract precise information on the duration and timing of cell cycle phases. Using Least Absolute Shrinkage and Selection Operator (LASSO) and Estimation Stability with Cross Validation (ES-CV), we were able to, without any prior biological knowledge, extract information on the phase-specific causal interaction of cell cycle genes, as well as temporal interdependencies of biological mechanisms through a complete cell cycle., Conclusions: The temporal dependence of cellular components we provide in our model goes beyond what is known in the literature. Furthermore, our inference of dynamic interplay of multiple intracellular mechanisms and their temporal dependence on one another can be used to predict time-varying cellular responses, and provide insight on the design of precise experiments for modulating the regulation of the cell cycle.

Background: Community detection algorithms are fundamental tools to uncover important features in networks. There are several studies focused on social networks but only a few deal with biological networks. Directly or indirectly, most of the methods maximize modularity, a measure of the density of links within communities as compared to links between communities., Results: Here we analyze six different community detection algorithms, namely, Combo, Conclude, Fast Greedy, Leading Eigen, Louvain and Spinglass, on two important biological networks to find their communities and evaluate the results in terms of topological and functional features through Kyoto Encyclopedia of Genes and Genomes pathway and Gene Ontology term enrichment analysis. At a high level, the main assessment criteria are 1) appropriate community size (neither too small nor too large), 2) representation within the community of only one or two broad biological functions, 3) most genes from the network belonging to a pathway should also belong to only one or two communities, and 4) performance speed. The first network in this study is a network of Protein-Protein Interactions (PPI) in Saccharomyces cerevisiae (Yeast) with 6532 nodes and 229,696 edges and the second is a network of PPI in Homo sapiens (Human) with 20,644 nodes and 241,008 edges. All six methods perform well, i.e., find reasonably sized and biologically interpretable communities, for the Yeast PPI network but the Conclude method does not find reasonably sized communities for the Human PPI network. Louvain method maximizes modularity by using an agglomerative approach, and is the fastest method for community detection. For the Yeast PPI network, the results of Spinglass method are most similar to the results of Louvain method with regard to the size of communities and core pathways they identify, whereas for the Human PPI network, Combo and Spinglass methods yield the most similar results, with Louvain being the next closest., Conclusions: For Yeast and Human PPI networks, Louvain method is likely the best method to find communities in terms of detecting known core pathways in a reasonable time.

We hereby report the synthesis, characterization and catalytic applications in the epoxidation of alkenes by a vanadyl porphyrin having bulky bromo substituents at the β-positions viz. vanandyltetrabromotetraphenylporphyrin (1). The synthesized porphyrin was characterized by various spectroscopic techniques like UV-visible, FT-IR, EPR, MALDI-TOF mass spectrometry and single crystal X-ray analysis. Porphyrin 1 has a nonplanar structure as indicated by its X-ray structure, DFT and electrochemical studies. 1 was analyzed for its catalytic application in the epoxidation of various alkenes. The catalytic reactions were carried out in CH 3 CN/H 2 O mixture in 3 : 1 (v/v) ratio. 1 displayed good efficiency in terms of mild reaction conditions, lower reaction temperature and minimal catalyst amount consumption. 1 exhibited excellent selectivity, high conversion efficiency and huge TOF (7600-9800 h -1 ) in a significantly low reaction time of 0.5 h. Catalyst 1 was regenerated at the end of various catalytic cycles making it reusable and industrially important., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Zinc oxide (ZnO)-based ultraviolet (UV) detector has been fabricated and its photoresponse is studied in an out-of-plane contact configuration. Porous anodic aluminum oxide (AAO) template-based deposition method is adopted for the aligned and well-separated growth of ZnO nanorods (NRs). Through-hole in silicon (Si) by modified metal assisted chemical etching is used as a window for the electrochemical deposition of ZnO in the template and for out-of-plane electrical contacts during device analysis. The fabricated photodetector shows a fast response under UV (365 nm) light illumination, with rise and decay times of 31 ± 2 ms and 85 ± 3 ms, respectively. This fast response is analysed in terms of vertical growth and the waveguide nature of ZnO NRs embedded in anodic alumina. These results are further supported by a simulation comparing the electric field distribution of ZnO NR embedded in AAO with that of bare ZnO NR.

Understanding the mechanisms that control human cardiomyocyte proliferation might be applicable to regenerative medicine. We screened a whole genome collection of human miRNAs, identifying 96 to be capable of increasing proliferation (DNA synthesis and cytokinesis) of human iPSC-derived cardiomyocytes. Chemical screening and computational approaches indicated that most of these miRNAs (67) target different components of the Hippo pathway and that their activity depends on the nuclear translocation of the Hippo transcriptional effector YAP. 53 of the 67 miRNAs are present in human iPSC cardiomyocytes, yet anti-miRNA screening revealed that none are individually essential for basal proliferation of hiPSC cardiomyocytes despite the importance of YAP for proliferation. We propose a model in which multiple endogenous miRNAs redundantly suppress Hippo signaling to sustain the cell cycle of immature cardiomyocytes., (Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.)

The optimal expression of endothelial nitric oxide synthase (eNOS), the hallmark of endothelial homeostasis, is vital to vascular function. Dynamically regulated by various stimuli, eNOS expression is modulated at transcriptional, post-transcriptional, and post-translational levels. However, epigenetic modulations of eNOS, particularly through long non-coding RNAs (lncRNAs) and chromatin remodeling, remain to be explored. Here we identify an enhancer-associated lncRNA that enhances eNOS expression (LEENE). Combining RNA-sequencing and chromatin conformation capture methods, we demonstrate that LEENE is co-regulated with eNOS and that its enhancer resides in proximity to eNOS promoter in endothelial cells (ECs). Gain- and Loss-of-function of LEENE differentially regulate eNOS expression and EC function. Mechanistically, LEENE facilitates the recruitment of RNA Pol II to the eNOS promoter to enhance eNOS nascent RNA transcription. Our findings unravel a new layer in eNOS regulation and provide novel insights into cardiovascular regulation involving endothelial function.

The quality of the written informed consent process is one of the most important aspects of clinical research, as it is the single tool that serves as a metric of autonomy. Several challenges have been identified with the informed consent process in developing countries the most important of which is the ability to assimilate and understand the information presented in the consent form. In India, a unique aspect of the informed consent process is the need for audio-video [AV] recording of the process for vulnerable populations and new chemical entities. The present narrative summates authors' experiences as investigators with A-V recording of the informed consent process as also providing a brief narrative review of relevant literature. It also offers potential solutions for challenges faced during this process., Competing Interests: There are no conflicts of interest.

Blood flow and vascular shear stress patterns play a significant role in inducing and modulating physiological responses of endothelial cells (ECs). Pulsatile shear (PS) is associated with an atheroprotective endothelial phenotype, while oscillatory shear (OS) is associated with an atheroprone endothelial phenotype. Although mechanisms of endothelial shear response have been extensively studied, most studies focus on characterization of single molecular pathways, mainly at fixed time points after stress application. Here, we carried out a longitudinal time-series study to measure the transcriptome after the application of PS and OS. We performed systems analyses of transcriptional data of cultured human vascular ECs to elucidate the dynamics of endothelial responses in several functional pathways such as cell cycle, oxidative stress, and inflammation. By combining the temporal data on differentially expressed transcription factors and their targets with existing knowledge on relevant functional pathways, we infer the causal relationships between disparate endothelial functions through common transcriptional regulation mechanisms. Our study presents a comprehensive temporally longitudinal experimental study and mechanistic model of shear stress response. By comparing the relative endothelial expressions of genes between OS and PS, we provide insights and an integrated perspective into EC function in response to differential shear. This study has significant implications for the pathogenesis of vascular diseases., Competing Interests: The authors declare no conflict of interest.

Background: Atherosclerosis is a multifaceted inflammatory disease involving cells in the vascular wall (eg, endothelial cells [ECs]), as well as circulating and resident immunogenic cells (eg, monocytes/macrophages). Acting as a ligand for liver X receptor (LXR), but an inhibitor of SREBP2 (sterol regulatory element-binding protein 2), 25-hydroxycholesterol, and its catalyzing enzyme cholesterol-25-hydroxylase (Ch25h) are important in regulating cellular inflammatory status and cholesterol biosynthesis in both ECs and monocytes/macrophages., Methods: Bioinformatic analyses were used to investigate RNA-sequencing data to identify cholesterol oxidation and efflux genes regulated by Krüppel-like factor 4 (KLF4). In vitro experiments involving cultured ECs and macrophages and in vivo methods involving mice with Ch25h ablation were then used to explore the atheroprotective role of KLF4-Ch25h/LXR., Results: Vasoprotective stimuli increased the expression of Ch25h and LXR via KLF4. The KLF4-Ch25h/LXR homeostatic axis functions through suppressing inflammation, evidenced by the reduction of inflammasome activity in ECs and the promotion of M1 to M2 phenotypic transition in macrophages. The increased atherosclerosis in apolipoprotein E -/- /Ch25h -/- mice further demonstrates the beneficial role of the KLF4-Ch25h/LXR axis in vascular function and disease., Conclusions: KLF4 transactivates Ch25h and LXR, thereby promoting the synergistic effects between ECs and macrophages to protect against atherosclerosis susceptibility., (© 2017 American Heart Association, Inc.)

Zinc oxide (ZnO) based ultraviolet (UV) photodetectors have been fabricated and their photoresponse is studied in Schottky diode configuration. A cost-effective single-step electrochemical deposition method is adopted for the growth of ZnO film with nanorod (NR) and nanoflake morphology. A comparative study of the photodetection parameters based on surface trap states, crystallinity, and strain is done for two different morphology films. Significant photocurrent enhancement is observed for the nanorods under UV light, with appreciable photoresponse in the blue region. A template-assisted growth of ZnO NR film is proposed for better photoresponse and sensitivity of the device, useful for various optoelectronic applications., Competing Interests: The authors declare no competing financial interest.

The study of DNA/BSA interaction and the catalytic potential of four mononuclear oxidoalkoxido vanadium(v) [V V O(L 1-4 )OEt] (1-4) and one dinuclear oxidoalkoxido mixed-ligand vanadium(v) [{VO(L 2 )OEt} 2 (Q)]{Q = 4,4'-bipyridine}(5) complexes, with tridentate binegative aroylazine ligands are reported [where H 2 L 1 = anthranylhydrazone of 2-hydroxy-1-napthaldehyde, H 2 L 2 = salicylhydrazone of 2-hydroxy-1-napthaldehyde, H 2 L 3 = benzoylhydrazone of 2-hydroxy-1-acetonaphthone, H 2 L 4 = anthranylhydrazone of 2-hydroxy-1-acetonaphthone]. All the complexes are characterized by elemental analysis as well as various spectroscopic techniques. Single crystal X-ray diffraction crystallography of 2 reveals that the metal centre is in distorted square pyramidal geometry with O 4 N coordination spheres, whereas 5 exhibits a distorted octahedral geometry around the metal center. In addition, all the complexes (1-5) show moderate DNA binding propensity which is investigated using UV-vis absorption titration, circular dichroism, thermal denaturation and fluorescence spectral studies. The experimental results show that the complexes effectively interact with CT-DNA through both minor and major groove binding modes, with binding constants ranging from 10 4 -10 5 M -1 . Among 1-5, complexes 3 and 4 show higher binding affinity towards CT-DNA than others and at the same time also exhibit negative ΔT m values of about ∼1.5 and 1.0 °C which resembles the properties shown by cisplatin. All complexes show moderate photo-induced cleavage of pUC19 supercoiled plasmid DNA with complex 3 showing the highest photo induced DNA cleavage activity of ∼48%. In coherence with the DNA interaction studies, 3 and 4 also exhibit good binding affinity towards BSA in the range of 10 10 -10 11 M -1 , which is also supported by their ability to quench the tryptophan fluorescence emission spectra of BSA. All the complexes show remarkable photo-induced BSA cleavage activity (>90%) at a complex concentration of 50 μM. The catalytic potential of 1-5 is also tested for the oxidative bromination of styrene, salicylaldehyde and oxidation of methyl phenyl sulphide. All the reactions show a high percentage of conversion (>90%) with a high turnover frequency (TOF). Particularly, in the oxidative bromination of styrene the percentage of conversion and TOF vary from 96-98% and 8000-19 600 (h -1 ) respectively, which signifies the potential of these oxidovanadium(v) complexes to stimulate research for the synthesis of a better catalyst.

The ONO donor ligands obtained from the condensation of 4-benzoyl-3-methyl-1-phenyl-2-pyrazoline-5-one (Hbp) with benzoylhydrazide (H 2 bp-bhz I), furoylhydrazide (H 2 bp-fah II), nicotinoylhydrazide (H 2 bp-nah III) and isonicotinoylhydrazide (H 2 bp-inh IV), upon treatment with [V IV O(acac) 2 ], lead to the formation of [V IV O(bp-bhz)(H 2 O)] 1, [V IV O(bp-fah)(H 2 O)] 2, [V IV O(bp-nah)(H 2 O)] 3 and [V IV O(bp-inh)(H 2 O)] 4, respectively. At neutral pH the in situ generated aqueous K[H 2 V V O 4 ] reacts with ligands I and II, forming potassium salts, K(H 2 O) 2 [V V O 2 (bp-bhz)] 5 and K(H 2 O) 2 [V V O 2 (bp-fah)] 6, while ligands III and IV give neutral complexes, [V V O 2 (Hbp-nah)] 9 and [V V O 2 (Hbp-inh)] 10, respectively. Acidification of aqueous solutions of 5 and 6 with HCl also gives neutral complexes [V V O 2 (Hbp-bhz)] 7 and [V V O 2 (Hbp-fah)] 8, respectively. Complexes 1-4, upon slow aerial oxidation in methanol, convert into monooxidovanadium(v) complexes, [V V O(bp-bhz)(OMe)] 11, [V V O(bp-fah)(OMe)] 12, [V V O(bp-nah)(OMe)] 13 and [V V O(bp-inh)(OMe)] 14, respectively. All complexes were characterized by various spectroscopic techniques like FT-IR, UV-visible, EPR (for complexes 1-4) and NMR ( 1 H, 13 C and 51 V), elemental analysis, thermogravimetry and single crystal X-ray diffraction (for complexes 5-10 and 12). In the solid state, all complexes characterized by X-ray diffraction show the metal ion 5-coordinated in a distorted square pyramidal geometry. Complexes 11-14 were tested as catalysts for the one-pot three-component (ethylacetoacetate, benzaldehyde and ammonium acetate) dynamic covalent assembly, via Hantzsch reaction, using hydrogen peroxide as oxidant in solution and under solvent-free conditions. The complexes are also active catalysts for the oxidation of tetralin to tetralone with H 2 O 2 as oxidant. The influence of the amounts of catalyst and oxidant, and solvent, temperature and time on the catalyzed reactions was investigated.