Functionality Modulation Toward Thianthrene-based Metal-Free Electrocatalysts for Water Splitting.

The development of metal-free bifunctional electrocatalysts for hydrogen and oxygen evolution reactions (HER and OER) is significant but rarely demonstrated. Porous organic polymers (POPs) with well-defined electroactive functionalities show superior performance in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Precise control of the active sites' local environment requires careful modulation of linkers through the judicious selection of building units. Here, a systematic strategy is introduced for modulating functionality to design and synthesize a series of thianthrene-based bifunctional sp2 C═C bonded POPs with hollow spherical morphologies exhibiting superior electrocatalytic activity. This precise structural tuning allowed to gain insight into the effects of heteroatom incorporation, hydrophilicity, and variations in linker length on electrocatalytic activity. The most efficient bifunctional electrocatalyst THT-PyDAN achieves a current density of 10 mA cm─2 at an overpotential (η10) of ≈65 mV (in 0.5 m H2SO4) and ≈283 mV (in 1 m KOH) for HER and OER, respectively. THT-PyDAN exhibits superior activity to all previously reported metal-free bifunctional electrocatalysts in the literature. Furthermore, these investigations demonstrate that THT-PyDAN maintains its performance even after 36 h of chronoamperometry and 1000 CV cycling. Post-catalytic characterization using FT-IR, XPS, and microscopic imaging techniques underscores the long-term durability of THT-PyDAN.

Retinal Manifestations in High Altitude.

Dangi, Meenu, Arnab Sadhukhan, Poninder Kumar, S. Bandopadhayay, Vijay K. Sharma, V.K. Patra, Manu Chaudhary, and Vipin Rana. Retinal manifestations in high altitude. High Alt Med Biol. 24:296-301, 2023. Aim: To study the high altitude (HA)-related retinal manifestations among security personnel and thus to provide new insights into the characteristics and mechanisms of retinopathy. Materials and Methods: This was a multicentric, nonrandomized prospective observational and descriptive study. We studied 54 security personnel over 1 year, who were referred from HA areas of northern India and north-eastern India for ocular problems. Complete coagulation profile was performed among patients with vascular occlusion. Results: There were total of 54 patients with ages ranging from 22 to 55 years. HA retinopathy was noticed in 28 patients: central retinal vein occlusion (6 patients), branch retinal vein occlusion (4 patients), branch retinal artery occlusion (1 patient), central retinal artery occlusion (4 patients), ocular ischemic syndrome (1 patient), central serous chorioretinopathy (7 patients), acetazolamide-induced maculopathy (1 patient), and solar retinopathy (2 patients). Along with an increased hematocrit, serum homocysteine was raised in the majority of vascular occlusions. The mean age was 38.16 years, the mean altitude was 14,716 ft, and the mean duration of stay was 11.2 weeks. Conclusion: Hypobaric hypoxia due to HA is a potential risk for HA retinopathy and associated vascular occlusions. Aside from increased hematocrit, hyperhomocysteinemia is a potential cause of vascular occlusions.

Bottom-Up Synthesis of Crystalline Covalent Organic Framework Nanosheets, Nanotubes, and Kippah Vesicles: An Odd-Even Effect Induction.

Few-layer organic nanosheets are becoming increasingly attractive as two-dimensional (2D) materials due to their precise atomic connectivity and tailor-made pores. However, most strategies for synthesizing nanosheets rely on surface-assisted methods or top-down exfoliation of stacked materials. A bottom-up approach with well-designed building blocks would be the convenient pathway to achieve the bulk-scale synthesis of 2D nanosheets with uniform size and crystallinity. Herein, we have synthesized crystalline covalent organic framework nanosheets (CONs) by reacting tetratopic thianthrene tetraaldehyde (THT) and aliphatic diamines. The bent geometry of thianthrene in THT retards the out-of-plane stacking, while the flexible diamines introduce dynamic characteristics into the framework, facilitating nanosheet formation. Successful isoreticulation with five diamines with two to six carbon chain lengths generalizes the design strategy. Microscopic imaging reveals that the odd and even diamine-based CONs transmute to different nanostructures, such as nanotubes and hollow spheres. The single-crystal X-ray diffraction structure of repeating units indicates that the odd-even linker units of diamines introduce irregular-regular curvature in the backbone, aiding such dimensionality conversion. Theoretical calculations shed more light on nanosheet stacking and rolling behavior with respect to the odd-even effects.