Tunability of domain structure in partially inverse spinels NiAl2O4.

Re-arrangement of cationic distribution in partially inverse spinel NiAl2O4 by using chemical pressure perturbation is studied. Structural, impedance and magnetic analysis suggest presence of regions/domains inside the grain/bulk with same lattice arrangement but varying in cationic oxidation state. Perturbing the cationic distribution in the grain via low concentrations of ambivalence substituent rearranges the cationic distribution across these domains within the partially inverse spinel lattice without disturbing the crystal structure. A comprehensive explanation on the origin & tunability of cationic distribution within the partially-inverse lattice is proposed.

Air Quality, Pollution and Sustainability Trends in South Asia: A Population-Based Study.

INTRODUCTION: Worsening air quality and pollution lead to numerous environmental health and sustainability issues in the South Asia region. This study analyzes India, Nepal, Bangladesh, Pakistan, Sri Lanka, and Nepal for air quality data trends and sustainability indicators. METHODOLOGY: By using a population-based study design, six South Asian countries were analyzed using a step-wise approach. Data were obtained from government websites and publicly available repositories for region dynamics and key variables. RESULTS: Between 1990 and 2020, air quality data indicated the highest rise in CO2 emissions in India (578.5 to 2441.8 million tons) (MT), Bangladesh, Nepal, and Pakistan. Greenhouse gas emissions, from 1990 to 2018, nearly tripled in India (1990.4 to 3346.6 MT of CO2-equivalents), Nepal (20.6 to 54.6 MT of CO2-equivalents), and Pakistan, and doubled in Bangladesh. Methane emissions rose the highest in Pakistan (70.4 to 151 MT of CO2-equivalents), followed by Nepal (17 to 31 MT of CO2-equivalents) and India (524.8 to 669.3 MT of CO2-equivalents). Nitrous oxide nearly doubled in Bangladesh (16.5 to 29.3 MT of CO2-equivalents), India (141.6 to 256.9 MT of CO2-equivalents), Nepal (17 to 31 MT of CO2-equivalents), and more than doubled in Pakistan (27 to 61 MT of CO2-equivalents). On noting particulate matter 2,5 annual exposure, India saw the highest rise from 81.3 µg/m3 (in 1990) to 90.9 µg/m3 (2017), whereas trends were steady in Pakistan (60.34 to 58.3 µg/m3). The highest rise was noted in Nepal (87.6 to 99.7 µg/m3) until 2017. During the coronavirus disease 19 pandemic, the pre-and post-pandemic changes between 2018 and 2021 indicated the highest PM2.5 concentration in Bangladesh (76.9 µg/m3), followed by Pakistan (66.8 µg/m3), India (58.1 µg/m3), Nepal (46 µg/m3) and Sri Lanka (17.4 µg/m3). Overall, South Asian countries contribute to the worst air quality and sustainability trends regions worldwide. CONCLUSIONS: Air pollution is prevalent across a majority of South Asia countries. Owing to unsustainable industrial practices, pollution trends have risen to hazardous levels. Economic, environmental, and human health impacts have manifested and require urgent, concerted efforts by governing bodies in the region.

Synthesis, crystal structure, Hirshfeld surface investigation and comparative DFT studies of ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate.

The ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate (1), a thiazole ester, was synthesized by refluxing 1-(2-nitrobenzylidene)thiosemicarbazide and ethyl bromopyruvate. The compound is characterized by spectrometric, spectroscopic and single crystal (SC-XRD) techniques. Non-covalent interactions that are responsible for crystal packing are explored by Hirshfeld surface analysis. All theoretical calculations were performed by DFT quantum chemical methods using 6-311G(d,p) and cc-pVTZ basis sets and compared. Theoretical harmonic frequencies of ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate (1) were optimized. Confirmation of hydrogen bonding sites was analyzed by molecular electrostatic potential (MEP) and Mulliken population analysis. The vibrational frequencies of characteristic functional groups and chemical shifts were found in good agreement with experimental assignments. Frontier molecular orbital (FMO) revealed relatively small HOMO-LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital) gape, which speaks off the nearly planar geometry and extended conjugation, as compared to the substituents with no conjugation possible. It has also been observed that -NO2 substituent plays a vital role for this relatively small HOMO-LUMO gape and overall electronic properties when compared with similar thiazole carboxylates (2-6, Table 6). Ethyl 2-[2-(2-nitrobenzylidene)hydrazinyl]thiazole-4-carboxylate (1) was also evaluated for its anti-oxidant and anti-microbial activities.

The Evaluation of Inflammatory Biomarkers in Predicting Progression of Acute Pancreatitis to Pancreatic Necrosis: A Diagnostic Test Accuracy Review.

Acute pancreatitis is the acute inflammation of the pancreas; 30% of cases may progress to pancreatic necrosis. The aim of this study was to assess the diagnostic accuracy of inflammatory biomarkers (C-reactive protein (CRP), procalcitonin (PCT), and lactate dehydrogenase (LDH)) in detecting pancreatic necrosis in adults with confirmed acute pancreatitis within 14 days of symptom onset and without organ failure. A systematic search was conducted across the Cumulative Index of Nursing and Allied Health (CINAHL), Cochrane, Embase, PubMed, and Web of Science until May 30, 2022, with the following keywords: acute disease, biomarkers, C-reactive protein, calcitonin, differential, diagnosis, lactate dehydrogenase, pancreatitis, acute necrotizing, necrosis, sensitivity, specificity. Statistical analysis was conducted in RevMan 5.4.1 (Cochrane). Five studies pooling 645 participants were included of which 59.8% were males, with a mean age of 49 years. CRP was the best cutoff at 279 mg/L (χ2 = 47.43, p < 0.001), followed by 200 mg/L (χ2 = 36.54, p < 0.001). LDH was cut off at 290 units/L (χ2 = 51.6, p < 0.001), whereas PCT did not display the most reliable results at 0.05 ng/mL. Inflammatory biomarkers are scalable diagnostic tools that may confer clinical value by decreasing the mortality of acute pancreatitis sequelae.

Synthesis, acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE) activities, and molecular docking studies of a novel compound based on combination of flurbiprofen and isoniazide.

Synthesis of a compound with balanced bioactivities against a specific target is always a challenging task. In this study, a novel compound (1) has been synthesized by combination of flurbiprofen and isoniazide and shows ∼2.5 times enhanced acetylcholinesterase (AChE) inhibition activity and ∼1.7 times improved butyrylcholinesterase (BuChE) inhibition activity compared to flurbiprofen and a standard drug (i.e. physostigmine). A comparative AutoDock study has been performed, based on the optimized structure, by the DFT/B3LYP method, which confirmed that compound (1) is more active against AChE and BuChE, with calculated binding energies of -12.9 kcal mol-1 and -9.8 kcal mol-1 respectively as compared to flurbiprofen and an eserine (physostigmine) standard for which the binding energy was calculated to be -10.1 kcal mol-1 and -8.9 kcal mol-1, respectively. A mixed mode of inhibition of AChE and BuChE with compound 1 was confirmed by Lineweaver-Burk plots. AChE and BuChE inhibition activity alongside docking results suggests that compound (1) could be used for treatment of Alzheimer's disease. Moreover, compound (1) also exhibit better α-chymotrypsin activity compared to flurbiprofen. Furthermore, in vitro and in vivo analysis confirmed that compound (1) exhibit more activity and less toxicity than the parent compounds.

Synthesis, antimicrobial, antioxidant, cytotoxic, antiurease and molecular docking studies of N-(3-trifluoromethyl)benzoyl-N'-aryl thiourea derivatives.

An irrefutable advancement has been noted for the infectious diseases caused due to ureolytic bacteria through the development of various drugs. Keeping in mind the extremely valuable synthetic utility and medicinal significance of thiourea derivatives, synthesis of new 3-trifluoromethyl benzoic acid thiourea derivatives (3a-j) were carried out. The biological potential of all compounds in terms of antimicrobial, antioxidant, cytotoxic and antiurease activities were studied. The compounds 3a, 3c and 3i with dichloro and methoxy groups substitution on the aryl group showed significant activity against all strain of bacteria while moderate to no activity was observed in remaining compounds. Whereas the antifungal evaluation showed that all compounds were active againts C. Albican and no activity was observed against C. Prapsilosis. The cytotoxic findings revealed the non-toxic nature of these compounds as IC50 values of majority of the compounds are above 100 µm except for compounds 3f and 3g. In addition, these compounds exhibited better antioxidant potential as 100 µm concentration inhibited >50% reactive oxygen species (ROS) production except compounds 3e, 3f and 3j. The compound 3a proved to be the most potent urease inhibitor showing the highest enzyme % inhibition (93.1%) with IC50 value of 8.17 ±â€¯0.24 µM and found more active as compare to standard followed by compound 3e (92.6%), 3h (91.6%), 3d (90.8%), 3b (90.6%) and 3f (90.0%) with their respective IC50 values. All the synthesized compounds were docked into the binding cavity of Urease (PDB ID: 4ubp). The most active compound 3a was also ranked as top on the docking score as it was found to show valuable interactions with the target protein along with good docking scores. Hence our results revealed that the synthesized compounds have potential to be used as potent urease inhibitors after further detailed mechanistic studies.

Synthesis, spectroscopic characterization, molecular docking and theoretical studies (DFT) of N-(4-aminophenylsulfonyl)-2-(4-isobutylphenyl) propanamide having potential enzyme inhibition applications.

A mutual prodrug (1) of ibuprofen and sulphanilamide has been synthesized with dual activity and improved toxicity profile. The synthesized compound has been characterized by elemental analysis, FT-IR, 1HNMR, 13CNMR and ESI-MS. The molecular geometry of the compound (1) was optimized using density functional theory (DFT/B3LYP) method with the 6-311G(d,p) basis sets in ground state. Geometric parameters (bond lengths, bond angles, torsion angles), vibrational assignments, chemical shifts and thermodynamics of the compound (1) has been calculated theoretically and compared with the experimental data. Comparative AutoDock study of compound (1) with cyclooxygenase enzymes (COX-1 and COX-2) were performed involving docking for possible selectivity of our prodrug within the two Cox enzymes. The highest binding affinities of -8.7 Kcal/mol and -8.1 Kcal/mol has been obtained for COX-1 and COX-2 enzymes respectively. Compound (1) exhibited enhanced anti-inflammatory, anti-ulcer and free radical scavenging activities as compared with the parent drugs. Based on various in vitro and in vivo tests it is suggested that the Compound (1) is more active than the parent drugs. Moreover, LD50 of compound (1) is higher than parent drug i.e. ibuprofen and sulphanilamide suggesting that the synthesized compound is much safer than its parent analogous.

A "turn-on" fluorescent probe for the detection of permanganate in aqueous media.

A novel carbazole-based probe was synthesized and found to exhibit fluorescence upon introduction to potassium permanganate in aqueous media. Guided by a series of experimental studies and DFT calculations, the underlying mechanism is proposed to proceed through a series of tandem proton and electron transfer processes.

Halides with Fifteen Aliphatic C-H···Anion Interaction Sites.

Since the aliphatic C-H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C-H (Cali-H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic Cali-H groups. An X-ray structure of imidazolium-based scaffolds using Cali-H···A(-) interactions (A(-) = anion) shows that a halide anion is directly interacting with fifteen Cali-H groups (involving eleven hydrogen bonds, two bidentate hydrogen-bond-type binding interactions and two weakly hydrogen-bonding-like binding interactions). Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The Cali-H···A(-) interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms.

Violation of DNA neighbor exclusion principle in RNA recognition.

DNA intercalation has been very useful for engineering DNA-based functional materials. It is generally expected that the intercalation phenomenon in RNA would be similar to that in DNA. Here we note that the neighbor-exclusion principle is violated in RNA by naphthalene-based cationic probes, in contrast to the fact that it is usually valid in DNA. All the intercalation structures are responsible for the fluorescence, where small naphthalene moieties are intercalated in between bases via π-π interactions. The structure is aided by hydrogen bonds between the cationic moieties and the ribose-phosphate backbone, which results in specific selectivity for RNA over DNA. This experimentally observed mechanism is supported by computationally reproducing the fluorescence and CD data. MD simulations confirm the unfolding of RNA due to the intercalation of probes. Elucidation of the mechanism of selective sensing for RNA over DNA would be highly beneficial for dynamical observation of RNA which is essential for studying its biological roles.

Turn-On Ratiometric Fluorescent Probe for Selective Discrimination of Cr(3+) from Fe(3+) in Aqueous Media for Living Cell Imaging.

Pyrene-based turn-on ratiometric fluorescent probe 1 demonstrates high sensitivity and exceptional selectivity toward Cr(3+) in the presence of other metals, including Fe(3+) in aqueous media. Interaction of Cr(3+) with probe 1 brings pyrene moieties close enough to have better aligned π-π stacking, thus enhancing the excimer peak many fold. On the other hand, the interaction of Fe(3+) with probe 1 brings forth a negligible difference in stacking, resulting in an insignificant change in fluorescence intensity. Exceptional selectivity of probe 1 with Cr(3+) over Fe(3+) and other metals has been confirmed by theoretical studies in addition to experimental results. Imaging of HeLa cells observed by confocal fluorescence microscopy reveals that probe 1 can be used to monitor Cr(3+) in live cells to map its subcellular distribution.