Tailored covalent organic frameworks with tunable fluorine groups for efficient adsorption of bisphenol analogues.

Oxygen vacancy-engineered BiOX catalysts: Synergistically boosting redox kinetics and suppressing hydrogen evolution in Iron chromium flow batteries.

Noncoordinating halogen groups in unsymmetric alkynes were found to have a novel function that can regulate regioselectivity and chemoselectivity in the Rh-catalyzed C-H active annulation of imines and alkynes. It provided up to single-regioisomeric level selectivity for ketimines. It is noteworthy that, for acyclic aldimines, it could not only give excellent control of regioselectivity but also control of chemoselectivity by affording addition products rather than imine products via dehydrogenation.

We report the synthesis of a series of structurally analogous tetrahedral imine cages with controlled variation in the number and position of fluorine atoms. Among these, only the cage (F2) with 12 inwardly directed fluorine atoms exhibits affinity for xenon in both chloroform and tetrachloroethane. Cages lacking fluorine (F0), having outwardly directed fluorine (F3), or featuring rotatable fluorine groups (F1) show negligible binding. These results, combined with cavity volume analysis and theoretical calculation, indicate that Xe-F London dispersion forces and size complementarity are the dominant factors for Xe recognition in solution.

OralAbsPredict: A data-driven framework to predict human intestinal absorption (HIA) and human oral bioavailability (HOB) from chemical structures.

3,6-Dihydro-2H-pyran heterocyclic framework is one of the currently developed heterocyclic building blocks in both pharmaceutical chemistry and organic synthesis, but with significant challenges. To overcome these challenges, herein, we report a robust synthetic methodology of palladium-catalyzed carboetherification of alkenes with alkynols for accessing polyfunctionalized 3,6-dihydro-2H-pyrans under aerobic oxidative conditions. In particular, this synthetic approach features excellent functional group compatibility, mild reaction conditions, and good step- and atom-economy. Additionally, an array of functional groups such as halogen group, ester, nitrile, aldehyde, phenoxy, and aromatic heterocycles were nicely tolerated, affording the synthetically challenging 2H-pyran derivatives in moderate-to-good yields. Notably, the practicability of this protocol is further verified by gram-scale synthesis and the late-stage diversification of pharmaceuticals and biologically active molecules.

Halogenocarbenes have attracted significant interest for almost a century because they combine classical singlet carbene reactivity with the presence of a readily substituted halogen group. Before this work, no halogenocarbenes had been isolated and taming their instability remained a synthetic challenge. This report describes the preparation of room temperature stable (amino)(chloro)carbenes and examples of their substitution chemistry at the carbene center, unlocking access to a wide range of acyclic carbenes.

Abstract The objective of this study is to assess the effectiveness and safety of once-weekly trelagliptin versus daily DPP-4 inhibitors in fasting people with Type 2 diabetes during Ramadan. This prospective, interventional, comparative study was conducted at the Baqai Institute of Diabetology and Endocrinology, Karachi, Pakistan, between January and April 2024. People with type 2 diabetes mellitus (T2DM) intending to fast were randomized to continue once/twice daily DPP-4i (Group A) or switch to once-weekly trelagliptin 100 mg (Group B). Pre- and post-Ramadan assessments included metabolic and anthropometric measures, medication adherence, dose adjustments, acute glycemic events, and treatment-emergent adverse events (TEAEs) that were recorded using patient logs along with fasting status. A total of 119 fasting people with T2DM were included, with 65 participants in Group A and 54 in Group B. The mean ages were 53.4 ± 9.9 and 52.5 ± 9.4 years, respectively. In Group A, hypoglycemia occurred in 12.3%, hyperglycemia in 18.5%, and TEAEs in 6.1%, with a mean HbA1c reduction of −0.20%. In Group B, hypoglycemia occurred in 13.0%, hyperglycemia in 9.3%, and TEAEs in 3.0%, with a greater reduction in HbA1c (−0.54%, p < 0.0001) post-Ramadan. On multivariate analysis, daily DPP-4 inhibitor use, higher diastolic blood pressure, poor glycemic control, noncompliance, and fewer fasting days were independently associated with adverse events. Trelagliptin showed comparable rates of hypoglycemia, hyperglycemia, and TEAEs, with improved glycemic control and adherence. Transitioning appears to be a safe and effective option for managing T2DM during Ramadan.

Cross-modal attention deep learning reveals how transformation products inherit life-cycle risks from parent antibiotics: Insights for environmental, ecological, health, and AMR risks.

In designing covalent organic frameworks (COFs) for ammonia adsorption, adding polar functional groups is a common strategy to improve uptake. However, the interplay between functionalization, stability, and crystallinity often limits performance, making it difficult to rationally design effective COF adsorbents. So far, clear guidelines for tailoring COFs for ammonia adsorption are still lacking. Herein, a series of COF-xOH (x = 0, 1, 2, 3) bearing halogen and hydrazide groups were systematically engineered with varying numbers of hydroxyl sites and evaluated for their ammonia adsorption performance. Remarkably, the ammonia uptakes of COF-xOH increase progressively to 5.18, 7.83, 9.24, and 12.50 mmol g-1, exhibiting a linear correlation with the number of hydroxyl sites, while crystallinity exerts only a minor influence. COF-3OH shows superior ammonia adsorption at 25.0°C and 1.0 bar, outperforming most reported COFs, and exhibits high selectivity in separating ammonia from low-concentration gas mixtures, demonstrating its potential as an efficient adsorbent for ammonia-containing tail gas in Haber-Bosch processes. The adsorption mechanism is primarily governed by synergistic interactions among multiple polar functional sites. This work not only presents a top-tier COF-based ammonia adsorbent but also establishes a general strategy for the functionalization-driven design of porous materials for gas capture and separation.

Altermagnets integrate key characteristics of both antiferromagnets and ferromagnets, exhibiting a vanishing net magnetic moment while breaking time-reversal symmetry and displaying momentum-dependent spin splitting in the absence of an external field. Recognized as one of the top ten Science breakthroughs of 2024, altermagnetism has drawn increasing attention, particularly in inorganic systems. In this work, using density functional theory calculations, we identify a g-wave altermagnetic state in thermally stable three-dimensional (3D) metal-organic frameworks (MOFs) based on Co(pymo)2 and its halogen-substituted derivatives, thereby extending the scope of altermagnetism to organic-containing 3D frameworks. A range of magnetic configurations was systematically evaluated for these systems, with the altermagnetic state being consistently found as the most energetically favorable. This feature is consistent with the antiferromagnetic coupling experimentally observed between Co ions connected via ligand bridges. The momentum-dependent spin splitting in the electronic structure emerges independently of spin-orbit coupling and is not significantly enhanced through the inclusion of heavy halogen elements. Additional canted spin configurations were also explored, which confirmed the robustness of the spin splitting against fluctuations. These results not only establish a momentous presence of g-wave altermagnetism in these 3D MOFs but also highlight the potential of molecular framework design for realizing symmetry-driven spin phenomena in a class of 3D materials beyond conventional inorganic systems.

A series of 6-azaindole pyridinium derivatives were synthesized, structurally characterized, and evaluated for their antimicrobial (against Staphylococcus aureus, Escherichia coli, and Candida albicans) and anticancer properties (against NCI 60 panel). Hemocompatibility was evaluated using the hemolytic index, while ADME properties were estimated using in silico methods. Structure-activity relationship analysis indicated that para-substitution of the phenyl ring, particularly with halogen or methoxy groups, influences antimicrobial activity, selectivity toward Gram-positive bacteria, and hemocompatibility. Compounds 2b and 2c showed the most notable antimicrobial effects, including inhibition of microbial adhesion at hemocompatible concentrations. Compound 2b exhibited growth inhibition against cancer cells, showing 57% percent growth inhibition (PGI) against the MDA-MB-468 breast cancer cell line at 10 mM. Overall, these results highlight 6-azaindole pyridinium salts as a promising class of compounds for further investigation.

Zr-based metal-organic framework UiO-66 is an attractive platform for hydrocarbon separations due to its exceptional chemical and thermal stability. We report a new UiO-66 derivative, UiO-66-F2(OH)2, integrating fluorine and hydroxyl groups into the framework. Compared to UiO-66-F4 and UiO-66-(OH)2, the coexistence of these two functionalities tunes the pore environment, resulting in enhanced differentiation for propylene and propane adsorption. The cyclic breakthrough experiments demonstrate the effective and stable dynamic separation of propylene and propane using UiO-66-F2(OH)2.

Lowering of surface free energy of Polythiophenes through entropy control in side chains without Perfluoroalkyl groups.

ABSTRACT A chemoselective method for the synthesis of acylals from aldehydes and carboxylic anhydrides has been developed using magnesium triflimide as the catalyst. The reaction proceeds smoothly at room temperature under neat conditions or in dichloromethane. The reaction conditions are mild, and a variety of functional groups, such as alkyl, ether, ester, nitrile, nitro, and halogen groups, remain intact under the reaction conditions.

ABSTRACT Strongly confined CsPbI 3 perovskite quantum dots (QDs) are urgently needed for stable pure‐red perovskite QDs light‐emitting diodes (PeLEDs). However, it's challenging for realization of high performance pure‐red PeLEDs with an intrinsic trade‐off between external quantum efficiency (EQE) and stability with single functional group ligands. In this report, we design an interfacial dynamic‐static matching strategy by designing a dual‐function ligand, Fluorobenzamine (PhFA), to construct dual‐mode interfacial domains that simultaneously suppress nonradiative pathways and stabilize the lattice structure. We find that the ammonium (‐NH 2 ) group contributes to promoting dynamic charge injection and defect passivation, while the fluorine (‐F) group anchors the surface to enhance structural stability. Hence, the PhFA‐treated QDs exhibited a high photoluminescence quantum yield (PLQY), boosted efficiency, and observably improved stability. PeLEDs based on these optimized QDs show the pure‐red electroluminescence (EL) emission with a maximum EQE of 29.2% and an operational half‐lifetime surpassing 950 min at an initial luminance of 140 cd m −2 , which are among the highest reported to date for pure‐red PeLEDs.

ABSTRACT Perylene diimides (PDIs) are used as cathode interlayers in organic solar cells (OSCs) due to their tunable energy levels and thickness‐insensitive properties. However, ammonium‐functionalized PDIs (PDIN, PDINN, etc) can cause photoinduced degradation of acceptor materials, impairing charge transport and stability of device. Herein, we introduce a multifunctional molecular bridging strategy by incorporating chloroacetic acid into PDIN. Theoretical calculations reveal that the hydroxyl group of chloroacetic acid anchors to the fluorine groups of the Y6 acceptor via hydrogen bonding, while the chlorine atoms form dipole‐dipole interaction with the ammonium cation of PDIN. This synergy establishes a molecular bridge between the acceptors and cathode interface, effectively preventing direct contact between PDIN and the acceptor, thereby suppressing acceptor photodegradation and accelerating charge transport. Optimizing monochloroacetic acid incorporation at 1% in PDIN yields power conversion efficiencies of 19.0% and 19.6% in binary PM6:Y6 and PM6:L8‐BO OSCs. Moreover, the generality of this strategy is demonstrated by evaluating three chloroacetic acid derivatives on three different acceptors. Therefore, this work demonstrates that the strategy not only suppresses the photo‐induced acceptors degradation but also enhances charge transport, offering new insights for achieving highly efficient and stable OSCs.

Reactive oxygen species (ROS) play a critical role in driving photocatalytic reactions. The predominant type of ROS generated determines the efficiency and feasibility of diverse photocatalytic transformations. However, limited research has focused on the targeted generation of ROS tailored for diverse catalytic transformations. Herein, four pillar-layered zinc-based organic frameworks (Zn-MOFs) were synthesized via linker engineering. By functionalizing the organic linkers, the prioritization of the generation of different ROS by these frameworks was modulated, thereby enhancing their efficiency in targeting photocatalytic transformations. Compared to the original Zn-MOF, the functionalized linker-constructed MOFs exhibit significantly enhanced charge carrier mobility. Notably, the Zn-MOF functionalized with electron-withdrawing fluorine groups (HIAM-3001F) demonstrated the highest catalytic efficiency in the superoxide anion-dominated photocatalytic cyclization synthesis of tetrahydroquinoline derivatives, achieving a near-unity conversion and a yield of 88.5% for gram-scale target compounds. In contrast, HIAM-3001Me, functionalized with electron-donating methyl groups, exhibited superior performance in the hydroxyl radical-driven photoelectrocatalytic (PEC) degradation of 4-fluorophenol, achieving almost complete degradation within 2 h. This work emphasizes the crucial role of rational linker design in regulating the photocatalytic performance of MOFs, and provides guidance for the construction of multifunctional and efficient MOF photocatalysts with targeted regulation of photocatalytic properties.

Chemical cognitive competence plays a fundamental role in applying acquired knowledge and skills and in exploring the natural world from a chemical perspective. Innovation in assessment methods for chemical cognitive competence contributes to enhancing the quality of teaching and learning, thereby promoting the development of learners’ competencies and attributes. This study aims to develop and propose innovative assessment tools for evaluating chemical cognitive competence in teaching the Halogen group. A descriptive survey was conducted with approximately 40 chemistry teachers in Hanoi using a structured questionnaire, and the data were analyzed through descriptive statistics. Based on research on competency-oriented assessment, and in accordance with the principles and procedures for developing assessment tools for chemical cognitive competence as well as the manifestations of this competence, the research team identified the criteria and levels for assessing chemical cognitive competence according to specific criteria. The system of criteria for assessing learners’ chemical cognitive competence is structured into three levels, reflecting a clear progression from basic recognition to higher-order thinking. The study proposes principles and a procedure for developing a set of assessment tools to evaluate chemical cognitive competence in teaching the Halogen unit. Overall, the proposed framework offers a practical and transferable model for strengthening competency-based assessment and advancing meaningful learning in chemistry education.

A series of Fischer-type carbenoids of groups 10 and11, bearingdiverse electron-donating and electron-withdrawing substituents, weresystematically analyzed using a descriptor-based framework groundedin Conceptual Density Functional Theory (CDFT), assessing whethershared electronic descriptors can rationalize the reaction profilesand reactivity in Ni­(II) and Cu­(I) complexes in a series of C–Hactivation reactions. The activation barriers for carbenoid insertionreactions were computed and correlated with reactivity indexes, includingthe Dual Descriptor and its Grand Canonical extensions based on softnessand hardness (SGCDD and PGCDD). Although Ni carbenoids display slightlyhigher activation barriers than their Cu analogues, both metals exhibitparallel qualitative trends. The PGCDD descriptor showed the strongestpredictive capability, yielding high correlations with computed barriers,particularly when refined through excited-state corrections usingthe Specific State Dual Descriptor (SSDD). Substituent effects especiallymesomeric contributions from halogen groups were critically evaluatedto establish a coherent electronic interpretation of reactivity. Thisunified descriptor-based framework provides a transferable methodologyfor rationalizing C–H activation mechanisms across transitionmetals, offering valuable insights for the predictive design of metal-carbenoidcatalysts.