Strategic Synthesis of Heptacoordinated FeIII Bifunctional Complexes for Efficient Water Electrolysis

In this research, highly efficient heterogeneous bifunctional (BF) electrocatalysts (ECs) have been strategically designed by Fe coordination (C_R) complexes, [Fe₂L₂(H₂O)₂Cl₂] (C1) and [Fe₂L₂(H₂O)₂(SO₄)].2(CH₄O) (C2) where the high seven C_R number synergistically modifies the electronic environment of the Fe centre for facilitation of H₂O electrolysis. The electronic status of Fe and its adjacent atomic sites have been further modified by the replacement of −Cl⁻ in C1 by −SO₄²⁻ in C2 . Interestingly, compared to C1 , the O−S−O bridged C2 reveals superior BF activity with extremely low overpotential (η) at 10 mA cm⁻² (140 mV_OER, 62 mV_HER) and small Tafel slope (120.9 mV dec⁻¹_OER, 45.8 mV dec⁻¹_HER). Additionally, C2 also facilitates a high-performance alkaline H₂O electrolyzer with cell voltage of 1.54 V at 10 mA cm⁻² and exhibits remarkable long-term stability. Thus, exploration of the intrinsic properties of metal–organic framework (MOF)-based ECs opens up a new approach to the rational design of a wide range of molecular catalysts.     

Tweaking Photo CO2 Reduction by Altering Lewis Acidic Sites in Metalated-Porous Organic Polymer for Adjustable H2/CO Ratio in Syngas Production

Herein, we have specifically designed two metalated porous organic polymers ( Zn-POP and Co-POP ) for syngas (CO+H₂) production from gaseous CO₂. The variable H₂/CO ratio of syngas with the highest efficiency was produced in water medium (without an organic hole scavenger and photosensitizer) by utilizing the basic principle of Lewis acid/base chemistry. Also, we observed the formation of entirely different major products during photocatalytic CO₂ reduction and water splitting with the help of the two catalysts, where CO (145.65 μmol g⁻¹ h⁻¹) and H₂ (434.7 μmol g⁻¹ h⁻¹) production were preferentially obtained over Co-POP & Zn-POP , respectively. The higher electron density/better Lewis basic nature of Co-POP was investigated further using XPS, XANES, and NH₃-TPD studies, which considerably improve CO₂ activation capacity. Moreover, the structure–activity relationship was confirmed via in situ DRIFTS and DFT studies, which demonstrated the formation of COOH* intermediate along with the thermodynamic feasibility of CO₂ reduction over Co-POP while water splitting occurred preferentially over Zn-POP .     

Late-Stage Halogenation of Peptides,Drugs and (Hetero)aromatic Compounds with a Nucleophilic Hydrazide Catalyst

Unlike its other halogen atom siblings, chlorination of a bioactive compound can change its physiological characteristics, improve its pharmacological profile, and function as a point of diversification through cross-coupling reactions. As a result, it has been a crucial strategy for drug discovery and development. However, functional groups such as amines, amides, hydroxy groups, or carboxylic acids trap the Cl⁺, severely limiting the reactivity and making direct chlorination far too difficult to be practical. Herein, we introduce a nucleophilic sulfonohydrazide catalyst for late-stage halogenation of peptides and drugs. This direct, mild and metal-free protocol shows high functional-group tolerance and is compatible with a range of structurally diverse peptides, drugs and aromatic compounds. Furthermore, DFT studies indicate that the reaction most likely proceeds via a cationic transition state. The gram-scale synthesis, high stability and efficiency of the catalyst provide a facile route for late-stage functionalization and intermediates for further derivatization.     

On Gravitational Form Factors and Transverse Spin Sum Rule

Using the light front wave functions of the scalar quark–diquark model for nucleon predicted by the soft-wall AdS/QCD, we calculate the flavor dependent gravitational form factors. We evaluate the matrix element of Pauli–Lubanski operator in this model and show that the intrinsic spin sum rule involves the higher twist form factor \({\bar{C}}\). The longitudinal momentum densities in the transverse impact parameter space are also discussed for both unpolarized and transversely polarized nucleons.     

A novel cation induced polymeric chain in Na8[{Cu(gly)2}2]{H2(H2W12O42)}]?·?24H2O: hydrothermal synthesis, spectroscopic characterization and X-ray structure analysis

A novel bis(glycinato)copper(II)paradodecatungstate Na₈[{Cu(gly)₂}₂]-{H₂(H₂W₁₂O₄₂)}] · 24H₂O (1) has been synthesized under hydrothermal conditions. The crystal structure of 1 reveals an infinite one-dimensional chain along the [100] direction and is built from paradodecatungstate (H₂W₁₂O₄₂)¹⁰⁻ clusters joined through [Cu(gly)₂] moieties. Parallel chains are interlinked by NaO₆ octahedra to generate a two-dimensional network.     

The RNA2-PNA2 hybrid i-motif-a novel RNA-based building block

We report the formation of a hybrid RNA2-PNA2 i-motif comprised of two RNA and two PNA strands based on the sequence specific self assembly of RNA, with potential as a building block for structural RNA nanotechnology.     

Complex dynamics at conical intersections: vibronic spectra and ultrafast decay of electronically excited trifluoroacetonitrile radical cation

An ab initio quantum dynamical study is performed here to examine the complex nuclear motion underlying the first two photoelectron bands of trifluoroacetonitrile. The highly overlapping structures of the latter are found to originate from transitions to the five lowest electronic states (viz., X(2)E, A(2)A1, B(2)A2, C(2)A1, and D(2)E) of the trifluoroacetonitrile radical cation. The Jahn-Teller (JT) instability of the doubly degenerate X and, D and their pseudo-Jahn-Teller (PJT) interactions with the nondegenerate A, B, and C electronic states along the degenerate vibrational modes lead to multiple multidimensional conical intersections and complex nuclear trajectories through them. It is found that the JT splitting is very weak in the X and relatively stronger in the D state. However, the PJT couplings play the pivotal role in the detailed shape of the vibronic bands of the radical cation. Ultrafast nonradiative decay of electronically excited radical cation has been examined. The findings of this paper are compared with the experimental data and are also discussed in relation to those observed for the methyl cyanide radical cation.     

Stability Property of Functional Equations in Modular Spaces: A Fixed-Point Approach

Mathematical Notes - We investigate the Hyers–Ulam–Rassias stability property of a quadratic functional equation. The analysis is done in the context of modular spaces. The type of...     

Ab initio study of dynamical E × e Jahn-Teller and spin-orbit coupling effects in the transition-metal trifluorides TiF3, CrF3, and NiF3

Multiconfiguration ab initio methods have been employed to study the effects of Jahn-Teller (JT) and spin-orbit (SO) coupling in the transition-metal trifluorides TiF(3), CrF(3), and NiF(3), which possess spatially doubly degenerate excited states ((M)E) of even spin multiplicities (M = 2 or 4). The ground states of TiF(3), CrF(3), and NiF(3) are nondegenerate and exhibit minima of D(3h) symmetry. Potential-energy surfaces of spatially degenerate excited states have been calculated using the state-averaged complete-active-space self-consistent-field method. SO coupling is described by the matrix elements of the Breit-Pauli operator. Linear and higher order JT coupling constants for the JT-active bending and stretching modes as well as SO-coupling constants have been determined. Vibronic spectra of JT-active excited electronic states have been calculated, using JT Hamiltonians for trigonal systems with inclusion of SO coupling. The effect of higher order (up to sixth order) JT couplings on the vibronic spectra has been investigated for selected electronic states and vibrational modes with particularly strong JT couplings. While the weak SO couplings in TiF(3) and CrF(3) are almost completely quenched by the strong JT couplings, the stronger SO coupling in NiF(3) is only partially quenched by JT coupling.     

Effect of secondary structure on the self-assembly of amphiphilic molecules: a multiscale simulation study

The self-assembly of amphiphilic molecules is of interest from a fundamental and practical standpoint. There has been recent interest in a class of molecules made from β-amino acids (which contain an additional backbone carbon atom when compared with natural amino acids). Block copolymers of β-peptides, where one block is hydrophobic and the other is hydrophilic, self-assemble into micelles. In this work, we use computer simulations to provide insight into the effect of secondary structure on the self-assembly of these molecules. Atomistic simulations for the free energy of association of a pair of molecules show that a homochiral hydrophobic block promotes self assembly compared to a heterochiral hydrophobic block, consistent with experiment. Simulations of a coarse-grained model show that these molecules spontaneously form spherical micelles.