Curious Behavior of Fe3+-As3+ Chemical Interactions and Nucleation of Clusters in Aqueous Medium.

The simultaneous presence of Fe3+ and As3+ ions in groundwater (higher ppb or lower ppm level concentrations at circumneutral pH) as well as in acid mine drainages (AMDs)/industrial wastewater (up to few thousand ppm concentration at strongly acidic pH) are quite common. Therefore, understanding the chemical interactions prevalent between Fe3+ and As3+ ions in aqueous medium leading to nucleation of ionic clusters/solids, followed by aggregation and growth, is of great environmental significance. In the present work, we attempt to probe the nucleation process of Fe3+-As3+ clusters in solutions of various concentrations and pHs (from AMD to groundwater-like) using a combination of experimental and theoretical techniques. Interestingly, our study reveals nucleation of primary FeAs clusters in nearly all of them independent of concentration or pH. Theoretical studies employed density functional theory (DFT) to predict the primary clusters as stable Fe4As4 units. The surprising resemblance of these clusters with known Fe3+-As3+ minerals at the local level was observed experimentally, which provides an important clue about solid-phase growth from a range of Fe3+-As3+ solutions. Our experimental findings are further supported by a stepwise reaction mechanism established from detailed DFT studies.

Netarsudil monotherapy as the initial treatment for open-angle glaucoma and ocular hypertension in Indian patients: A real-world evaluation of efficacy and safety.

Purpose: Glaucoma is the second leading cause of blindness worldwide, affecting more than 64 million people aged 40-80. The best way to manage primary open-angle glaucoma (POAG) is by lowering the intraocular pressure (IOP). Netarsudil is a Rho kinase inhibitor, the only class of antiglaucoma medications that reorganizes the extracellular matrix to improve the aqueous outflow through the trabecular pathway. Methods: An open-label, real-world, multicentric, observation-based 3-month study was performed for assessing the safety and ocular hypotensive efficacy of netarsudil ophthalmic solution (0.02% w/v) in patients with elevated IOP. Patients were given netarsudil ophthalmic solution (0.02% w/v) as a first-line therapy. Diurnal IOP measurements, best-corrected visual acuity, and adverse event assessments were recorded at each of the five visits (Day-1: screening day and first dosing day; subsequent observations were taken at 2 weeks, 4 weeks, 6 weeks, and 3 months). Results: Four hundred and sixty-nine patients from 39 centers throughout India completed the study. The mean IOP at baseline of the affected eyes was 24.84 ± 6.39 mmHg (mean ± standard deviation). After the first dose, the IOP was measured after 2, 4, and 6 weeks, with the final measurement taken at 3 months. The percentage reduction in IOP in glaucoma patients after 3 months of once-daily netarsudil 0.02% w/v solution use was 33.34%. The adverse effects experienced by patients were not severe in the majority of cases. Some adverse effects observed were redness, irritation, itching, and others, but only a small number of patients experienced severe reactions, as reported in a decreasing order: redness > irritation > watering > itching > stinging > blurring. Conclusion: We found that netarsudil 0.02% w/v solution monotherapy when used as the first-line treatment in primary open-angle glaucoma and ocular hypertension was both safe and effective.

Metal-Thiolate Framework for Electrochemical and Photoelectrochemical Hydrogen Generation.

Hydrogen has evolved as the cleanest and most sustainable fuel, produced directly from naturally abundant water resources. Generation of hydrogen by electrochemical or photoelectrochemical splitting of water has been conceived as the most effective method for hydrogen production. Herein, a robust solid metal-thiolate framework (MTF-1) was obtained by hydrothermal crystallization of the reaction mixture consisting of 1,3,5-triazine-2,4,6-trithioltrisodium salt and CuII under mild synthesis conditions. The material was thoroughly characterized and explored as efficient catalyst for electrochemical and photoelectrochemical hydrogen evolution reaction (HER) via water splitting reactions. MTF-1 showed onset potential 0.045 VRHE and overpotential η(@10 mA cm-2 ) at 0.096 VRHE . The electrochemical surface area of MTF-1 was found to be 509 m2 g-1 . The photo current density at pH 5.0 was found to be 0.487 mA cm-2 at 0.6 VRHE . The feasibility of the reaction pathway was correlated from the density function theory study, which suggested the complete downhill energetics indicating spontaneous electrochemical hydrogen generation in the acidic medium.

Isomerization-Induced Excimer Formation of Pyrene-Based Acylhydrazone Controlled by Light- and Solvent-Sensing Aromatic Analytes.

Pyrene is a fluorescent polycyclic aromatic hydrocarbon, and it would be interesting to determine whether its C═N-based conjugate can be used for sensing of aromatic analytes at its supramolecular aggregated state. For this purpose, we have synthesized (E)-3,4,5-tris(dodecyloxy)-N'-(pyren-1-ylmethylene)benzohydrazide (Py@B) by alkylation, substitution, and the Schiff base reaction methodology. The E-isomer of Py@B (E-Py@B) exhibits a bright fluorescence due to excimer formation in nonaromatic solvents. Upon photoirradiation with λ = 254 nm, it exhibits E-Z isomerization across the C═N bond at a low concentration (10-4 M), resulting in a quenched fluorescence intensity, and interestingly, upon photoirradiation with λ = 365 nm, the Z-isomer of Py@B returns to the E-isomer again, indicating that E-Z isomerization of Py@B is reversible in nature. The thick supramolecular aggregated morphology of E-Py@B changes to a flowery needlelike morphology after photoirradiation with λ = 254 nm. The UV-vis absorption band at 370 nm for 10-4 M Py@B in methyl cyclohexane (MCH) is due to excimer formation for closer proximity of pyrene moieties present in E-Py@B and changes to the absorption peak at 344 nm for its Z-isomer formation. The fluorescence spectroscopy results also support the fact that the optimum concentration of the E-isomer of Py@B is 2 × 10-4 M in MCH for excimer formation. From spectral results, it may be concluded that nonaromatic solvents assist in constructing the excimer, but aromatic solvents resist forming an excimer complex of E-Py@B. The fluorescent emission of E-Py@B in MCH is quickly quenched on addition of different aromatic analytes through both static and dynamic pathways. In the solid state, E-Py@B also senses aromatic vapors efficiently via fluorescence quenching. Absorbance spectra of a model molecule obtained using time-dependent density functional theory (TDDFT) calculations on a DFT-optimized structure indicate complex adduct formation between E-Py@B and aromatic analytes from the well-matched theoretical and experimental UV-vis spectra on addition of different analytes with E-Py@B.

A robust stimuli responsive Eu3+ - Metalo organic hydrogel and xerogel emitting white light.

Recently, there is incredible growth on optoelectronic properties of new supramolecular gels and white-light-emitting (WLE) metalo-organic gel comprised with single lanthanide metal ion having stimuli-responsive property is not yet reported. Here, we report a mandelic acid (MA)-triethylene tetraamine (TETA)-Eu-acetate conjugate (4.5:1:0.4 mol ratio), producing stimuli-sensitive WLE hydrogel exhibiting thermoreversible, thixotropic, pH-switchable, self-standing and self-healing properties. Energy minimized structure suggests complexation between MA-TETA conjugate and Eu3+ ion. Fluorescence intensity of MA-TETA conjugate decreases with increasing Eu3+ concentration indicating energy transfer from MA-TETA to Eu3+. Decay of donor fluorescence intensity follows Stern-Volmer equation and energy transfer efficiency is 42%. WLE gel has Quantum yield 11.4% and Förster distance 1.7 Å. Hydrogel and xerogel show WLE on excitation at 330 and 350 nm having CIE coordinates (0.34, 0.33) and (0.28, 0.32), respectively. WLE gel has Correlated colour temperature 5148 K, appropriate for cool day light emission and on coating over UV-LED bulb it emits bright white light.

Understanding the Role of Aromaticity and Conformational Changes in Bond Dissociation Processes of Photo-Protecting Groups.

Photoremovable protecting groups (PPGs) provide spatial and temporal control over the release of various chemicals. Using surface hopping studies with multireference electronic structure methods we have unravelled the nuclear and the electronic events at play. Furthermore, the electronic changes along the reaction path were probed using excited state aromaticity quantifiers and orbital analysis. We find that upon irradiation with light of appropriate wavelength on the substituted coumarin system a π-π* electronic excitation occurs which is followed by an electron loss from the aromatic ring on gaining proper alignment between the π* and the C-LG (LG = leaving group) σ*. This alignment is brought about by a critical dihedral angle change in the molecule, which subsequently triggers C-LG bond cleavage. The sequence of events is indicative of an intramolecular electron catalyzed process which is established through investigations of changes in aromaticity of the phenyl ring which acts as an electron reservoir.

Deciphering the cryptic role of a catalytic electron in a photochemical bond dissociation using excited state aromaticity markers.

The breaking of bonds by catalytic electrons has gained prominence very recently but has been limited to cases where electrons from external sources have been used. Here, we show that upon photoexcitation, an electron of intramolecular origin is transferred from one part of a molecule to another followed by bond cleavage and then returns to its original moiety on completion of its catalytic function. By a proper assessment of the dramatic changes in aromaticity in excited-state intermediates along the photoreaction coordinate captured by the magnetically induced current density (MICD) technique, we show that in 5-phenyltetrazole, an excited electron, which migrates from the phenyl ring to the tetrazole ring, induces bond cleavage catalytically. Using the MICD technique, we establish for the first time a link between the phenomenon of excited-state electron/charge transfer among aromatic rings and the intricate interplay of aromatic, antiaromatic and non-aromatic states.

Effect of seasonal variation on hospital admission due to cardiovascular disease - findings from an observational study in a divisional hospital in Bangladesh.

BACKGROUND: Seasonal variation in the hospital admission due to cardiovascular disease (CVDs) has been widely reported. However, very limited data on Bangladesh is available regarding this matter. The aim of the current study was to investigate the effect of seasonal variation on hospital admission due to CVDs in a leading hospital of Bangladesh. METHODS: Over a period of two years (from May 2010 to April 2012), the number of patients hospitalized due to various CVDs and number of death among these hospitalized patients were recorded on a day-to-day basis. The data were recorded according to the chief reason of hospital admission such as myocardial infarction or MI (acute, old and non-ST elevation), unstable angina (UA), exaggeration of stable angina, acute left ventricular failure (LVF), cardiomyopathy (ischemic and dilated) or heart failure, syncope and arrhythmia. The data were cumulated and analyzed on month-wise and season-wise manner. RESULTS: A total of 8371 patients were admitted over the study period (5909 male and 2462 female; M/F ratio - 2.4:1). The highest number of patients were admitted during winter (n = 2839, 33.9%) and lowest during summer (n = 1648, 19.7%). The hospital admission was also significantly higher in winter compared to other seasons (p-value versus summer, autumn and spring was 0.018, 0.020 and 0.023 respectively). Acute MI (n = 2374), Acute LVF (n = 1582) and UA (n = 1277) were the top three reasons for hospitalization. Number of death also significantly higher in winter compared to other seasons (p-value versus summer, winter and spring was 0.044, 0.050 and 0.014 respectively). CONCLUSION: A seasonal variation in the hospital admission due to CVDs with a peak in winter was clearly demonstrated in the study. These data could be useful to improve causative prevention measures, therapeutic management, and educational strategies.