High-temperature carbon dioxide capture in a porous material with terminal zinc hydride sites.

Carbon capture can mitigate point-source carbon dioxide (CO) emissions, but hurdles remain that impede the widespread adoption of amine-based technologies. Capturing CO at temperatures closer to those of many industrial exhaust streams (>200°C) is of interest, although metal oxide absorbents that operate at these temperatures typically exhibit sluggish CO absorption kinetics and instability to cycling. Here, we report a porous metal-organic framework featuring terminal zinc hydride sites that reversibly bind CO at temperatures above 200°C-conditions that are unprecedented for intrinsically porous materials.

Boosting the Quantum Efficiency of Ionic Carbon Nitrides in Photocatalytic HO Evolution via Controllable n → π* Electronic Transition Activation.

Hydrogen peroxide (HO) is a crucial chemical used in numerous industrial applications, yet its manufacturing relies on the energy-demanding anthraquinone process. Solar-driven synthesis of HO is gaining traction as a promising research area, providing a sustainable method for its production. Herein, a controllable activation of n → π* electronic transition is presented to boost the photocatalytic HO evolution in ionic carbon nitrides.

Elucidating the Supramolecular Interaction of Positively Supercharged Fluorescent Protein with Anionic Phthalocyanines.

Developing bioinspired materials to convert sunlight into electricity efficiently is paramount for sustainable energy production. Fluorescent proteins are promising candidates as photoactive materials due to their high fluorescence quantum yield and absorption extinction coefficients in aqueous media. However, developing artificial bioinspired photosynthetic systems requires a detailed understanding of molecular interactions and energy transfer mechanisms in the required operating conditions.

Smoother Semiclassical Dispersion for Density Functional Theory via D3S: Understanding and Addressing Unphysical Minima in the D3 Dispersion Correction Model.

One of the most widely used and computationally efficient models that accounts for London dispersion interactions within density functional theory (DFT) is the D3 dispersion correction model. In this work, we demonstrate that this model can induce the appearance of unphysical minima on the potential energy surface (PES) when the coordination number of atoms changes. Optimizing to these artifactual structures can lead to significant errors in determining the interaction energy between two molecules and in estimating the thermodynamic properties of the system.

Smooth Dispersion Is Physically Appropriate: Assessing and Amending the D4 Dispersion Model.

The addition of dispersion corrections to density functionals is essential for accurate energy and geometry predictions. Among them, the D4 scheme is popular due to its low computational cost and high accuracy. However, due to its design, the D4 correction can occasionally lead to anomalies, such as unphysical curvature and bumps in the potential energy surface.

Copper complexation of rosarin: formation of bis-copper rosarin and mono-copper linear tridipyrrin complexes.

A novel rosarin di-Cu complex 2Cu-1 and a linear six-pyrrolic mono-copper complex 1Cu-1 were synthesized using rosarin as the ligand. The molecular conformations of these complexes were confirmed by X-ray crystallography. The optical study of 1Cu-1 indicated NIR-II absorption due to the long six-pyrrolic ligand and the ICT effect.

Supramolecular scaffold-directed two-dimensional assembly of pentacene into a configuration to facilitate singlet fission.

Molecular assemblies featuring two-dimensionality have attracted increasing attention, whereas such structures are difficult to construct simply relying on spontaneous molecular assembly. Here, we present two-dimensional assemblies of acene chromophores achieved using a tripodal triptycene supramolecular scaffold, which have been shown to exhibit a strong ability to assemble molecular and polymer motifs two-dimensionally. We designed pentacene and anthracene derivatives sandwiched by two triptycene units.

Enhancing deep visible-light photoelectrocatalysis with a single solid-state synthesis: Carbon nitride/TiO heterointerface.

Visible-light responsive, stable, and abundant absorbers are required for the rapid integration of green, clean, and renewable technologies in a circular economy. Photoactive solid-solid heterojunctions enable multiple charge pathways, inhibiting recombination through efficient charge transfer across the interface. This study spotlights the physico-chemical synergy between titanium dioxide (TiO) anatase and carbon nitride (CN) to form a hybrid material.

Geometric Tuning of Coordinatively Unsaturated Copper(I) Sites in Metal-Organic Frameworks for Ambient-Temperature Hydrogen Storage.

Porous solids can accommodate and release molecular hydrogen readily, making them attractive for minimizing the energy requirements for hydrogen storage relative to physical storage systems. However, H adsorption enthalpies in such materials are generally weak (-3 to -7 kJ/mol), lowering capacities at ambient temperature. Metal-organic frameworks with well-defined structures and synthetic modularity could allow for tuning adsorbent-H interactions for ambient-temperature storage.

Conical Intersections at Interfaces Revealed by Phase-Cycling Interface-Specific Two-Dimensional Electronic Spectroscopy (i2D-ES).

Conical intersections (CIs) hold significant stake in manipulating and controlling photochemical reaction pathways of molecules at interfaces and surfaces by affecting molecular dynamics therein. Currently, there is no tool for characterizing CIs at interfaces and surfaces. To this end, we have developed phase-cycling interface-specific two-dimensional electronic spectroscopy (i2D-ES) and combined it with advanced computational modeling to explore nonadiabatic CI dynamics of molecules at the air/water interface.

The windmill, the dragon, and the frog: geometry control over the spectral, magnetic, and electrochemical properties of cobalt phthalocyanine regioisomers.

For the first time, we have prepared non-aggregating phthalocyanine cobalt complexes as a set of resolved positional isomers. These compounds comprise a unique test bed for the structure-properties studies, as their optical and electrochemical properties are influenced by the planarity of the phthalocyanine macrocycle, which can be controlled by the positional isomerism of the bulky aromatic substituents at the -phthalo sites. We support our conclusions with molecular modelling studies, which show a perfect match between the calculated and experimentally determined spectral/electrochemical values.

Conflicting Aromaticity in Trirhodium(I) Rosarin.

Aromaticity is one of the most important and widely used concepts in chemistry. Among the various experimentally discovered and theoretically predicted compounds that possess different types of aromaticity, conflicting aromaticity, where aromatic and antiaromatic electron delocalization is present in one molecule simultaneously, remains one of the most controversial and elusive concepts, although theoretically predicted 15 years ago. In this work, we synthesized a novel conflicting aromatic trirhodium complex that contains a σ-aromatic metal fragment surrounded by the π-antiaromatic organic ligand and characterized it by nuclear magnetic resonance spectroscopy, high-resolution mass spectrometry, and X-ray single crystal structure analysis.

Lytic Capsule-Specific Bacteriophages Encoding Polysaccharide-Degrading Enzymes.

The genus comprises both environmental and clinically relevant species associated with hospital-acquired infections. Among them, is a critical priority bacterial pathogen, for which the research and development of new strategies for antimicrobial treatment are urgently needed. spp.

Contactless analysis of surface passivation and charge transfer at the TiO-Si interface.

Transition metal oxides are pivotal in enhancing surface passivation and facilitating charge transfer (CT) in silicon based photonic devices, improving their efficacy and affordability through interfacial engineering. This study investigates TiO/Si heterojunctions prepared by atomic layer deposition (ALD) with different pre-ALD chemical and post-ALD thermal treatments, exploring their influence on the surface passivation and the correlation with the CT at the TiO-Si interface. Surface passivation quality is evaluated by the photoconductance decay method to study the effective carrier lifetime, while CT from Si to TiO is examined by transient reflectance spectroscopy.

Human Healthcare and Its Pharmacy Component from a Safety Point of View.

Healthcare plays a crucial role in public and national safety as a significant part of state activity and a component of national safety, whose mission is to organize and ensure affordable medical care for the population. The four stages of the genesis of healthcare safety development with the corresponding safety models of formation were defined: technical, human factor or security management, systemic security management, and cognitive complexity. It was established that at all stages, little attention is paid to the issues of the formation of the pharmaceutical sector's safety.

Transient Absorption Spectroscopy of Films: Impact of Refractive Index.

Transient absorption spectroscopy is a powerful technique to study the photoinduced phenomena in a wide range of states from solutions to solid film samples. It was designed and developed based on photoinduced absorption changes or that photoexcitation triggers a chain of reactions with intermediate states or reaction steps with presumably different absorption spectra. However, according to general electromagnetic theory, any change in the absorption properties of a medium is accompanied by a change in the refractive properties.

Analyzing global utilization and missed opportunities in debt-for-nature swaps with generative AI.

We deploy a prompt-augmented GPT-4 model to distill comprehensive datasets on the global application of debt-for-nature swaps (DNS), a pivotal financial tool for environmental conservation. Our analysis includes 195 nations and identifies 21 countries that have not yet used DNS before as prime candidates for DNS. A significant proportion demonstrates consistent commitments to conservation finance (0.

Effect of Single-Crystal TiO/Perovskite Band Alignment on the Kinetics of Electron Extraction.

The kinetics of electron extraction at the electron transfer layer/perovskite interface strongly affects the efficiency of a perovskite solar cell. By combining transient absorption and time-resolved photoluminescence spectroscopy, the electron extraction process between FACsPb(IBr) and TiO single crystals with different orientations of (100), (110), and (111) were probed from subpicosecond to several hundred nanoseconds. It was revealed that the band alignment between the constituents influenced the relative electron extraction process.

Opportunities for synthetic data in nature and climate finance.

This paper delves into the intricacies of synthetic data, emphasizing its growing significance in the realm of finance and more notably, sustainable finance. Synthetic data, artificially generated to simulate real-world data, is being recognized for its potential to address risk management, regulatory compliance, and the innovation of financial products. Especially in sustainable finance, synthetic data offers insights into modeling environmental uncertainties, assessing volatile social and governance scenarios, enhancing data availability, and protecting data confidentiality.

The Effect of Torsional Motion on Multiexciton Formation through Intramolecular Singlet Fission in Ferrocene-Bridged Pentacene Dimers.

A series of ferrocene(Fc)-bridged pentacene(Pc)-dimers [Fc-Ph(2,n)-(Pc) : n=number of phenylene spacers] were synthesized to examine the tortional motion effect of Fc-terminated phenylene linkers on strongly coupled quintet multiexciton ( TT) formation through intramolecular singlet fission (ISF). Fc-Ph(2,4)-(Pc) has a relatively small electronic coupling and large conformational flexibility according to spectroscopic and theoretical analyses. Fc-Ph(2,4)-(Pc) exhibits a high-yield TT together with quantitative singlet TT ( TT) generation through ISF.

The impact of intersectional racial and gender biases on minority female leadership over two centuries.

This study scrutinizes the enduring effects of racial and gender biases that contribute to the consistent underrepresentation of minority women in leadership roles within American private, public, and third sector organizations. We adopt a behavioural data science approach, merging psychological schema theory with sociological intersectionality theory, to evaluate the enduring implications of these biases on female leadership development using mixed methods including machine learning and econometric analysis. Our examination is concentrated on Black female leaders, employing an extensive analysis of leadership rhetoric data spanning 200 years across the aforementioned sectors.

Diagnostic accuracy and the first genotype-phenotype correlation in glycogen storage disease type V.

Background: Glycogen storage disease type V (GSDV) is an autosomal recessive metabolic condition caused by pathogenic PYGM variants. This is an underdiagnosed condition as it presents with exercise intolerance in children. We reviewed the GSDV cases of a tertiary hospital center to assess diagnostic timing/accuracy, as well as potential clinical/analytical predictors of such factors.