Stacking Interactions Research Articles

Minimizing Voltage Deficit in Perovskite Indoor Photovoltaics by Interfacial Engineering.

Metal halide perovskites with bandgap of ≈1.8eV are competitive candidates for indoor photovoltaic (IPV) devices, owing to their superior photovoltaic properties and ideal absorption spectra matched to most indoor light sources. However, these perovskite IPVs suffer from severe trap induced non-radiative recombination, resulting in large open-circuit voltage (VOC) losses, particularly under low light intensity. Herein, an effective approach is developed to minimizing trap density by modifying the buried interface of perovskite layer with bifunctional molecular 2-(4-Fluorophenyl)ethylamine Hydrobromide (F-PEABr). The benzene ring of F-PEABr molecules can firmly anchor at the hole transporting layer by π-π stacking interaction, and the other ends can passivate the defects on the buried interface of perovskite layer. Based on that, the F-PEABr modified perovskite IPVs achieved power conversion efficiency (PCE) of 42.3% with a remarkable VOC of 1.13V under 1000 lux illumination from a 4000K LED lamp. Finally, perovskite IPV mini-modules with area of 10.40cm2 are demonstrated with a PCE of 35.2%. This interface modification strategy paves the way for crafting high-performance perovskite IPVs, holding great potential for self-powered internet of things applications.

Oligopeptide template-guided nanoconfined in situ mineralization of nanotherapeutics boosts self-sufficient immunogenic phototherapy.

As a promising cancer treatment modality that has emerged, photodynamic / photothermal therapy can harness antitumor immunity by triggering immunogenic cell death in addition to direct cell ablation. However, the efficacy of this phototherapy is always limited due to the hypoxic tumor microenvironment, and the induccd immune stimulation is insufficient to achieve satisfactory cancer eradication. We herein address the above issues by nanoconfined in situ mineralization of manganese oxide (MnO2) guided with an oligopeptide as template. The synthetic nanocomposites can be co-assembled efficiently with the photosensitiser through π-π stacking interactions. Crucially, the mineralised MnO2 composition catalytically decomposes tumor-derived hydrogen peroxide to alleviate the hypoxic microenvironment, thereby improving the efficacy of the photosensitiser in ROS generation. In the murine model of 4 T1 xenograft tumors, the fabricated nanotherapeutics elicited robust antitumor immune responses and boost immunogenic phototherapy toward malignant tumors.

The charge transport properties of dicyanomethylene-functionalised violanthrone derivatives

The study of organic small molecule semiconductor materials as active components of organic electronic devices continues to attract considerable attention due to the range of advantages these molecules can offer. Here, we report the synthesis of three dicyanomethylene-functionalised violanthrone derivatives (3a, 3b and 3c) featuring different alkyl substituents. It is found that the introduction of the electron-deficient dicyanomethylene groups significantly improves the optical absorption compared to their previously reported precursors 2a–c. All compounds are p-type semiconductors with low HOMO–LUMO gaps (≈1.25 eV). The hole mobilities, measured from fabricated organic field-effect transistors, range from 3.6 × 10−6 to 1.0 × 10−2 cm2 V−1 s−1. We found that the compounds featuring linear alkyl chains (3b and 3c) displayed a higher mobility compared to the one with branched alkyl chains, 3a. This could be the result of the more highly disordered packing arrangement of this molecule in the solid state, induced by the branched side chains that hinder the formation of π–π stacking interactions. The influence of dicyanomethylene groups on the charge transport properties was most clearly observed in compound 3b which has a 60-fold improvement in mobility compared to 2b. This study demonstrates that the choice of the solubilising group has a profound effect on the hole mobility on these organic semiconductors.

All-Polymer Composite Film with Outstanding Mechanical, Thermal Conductive, and EMI Shielding Performances.

Robust polymer-based composites with high thermal conductivity (TC) and electromagnetic interference shielding effectiveness (EMI SE) hold great promise for applications in rapidly developing electronics. Traditional composites containing inorganic fillers often suffer from increases in processing difficulty, density, and significant deterioration in mechanical properties. Herein, we report for the first time a flexible multilayered all-polymer composite of poly(p-phenyl-2,6-phenylene bisoxazole) (PBO) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), featuring excellent mechanical strength of 203.9 MPa, in-plane TC of 21.9 W/mK, EMI shielding effectiveness (SE) of 44.2 dB, high-temperature stability, and flame retardancy. The excellent TC, mechanical strength, and flame retardancy of PBO, the remarkable EMI shielding performance of PEDOT:PSS, and the π-π stacking interactions between adjacent layers contribute to the comprehensive properties, which outperform most of the traditional composites of polymers and inorganic fillers reported so far. This full-polymer design may pioneer a new strategy for the preparation of robust and lightweight multifunctional composites.

Structure-based design and synthesis of novel FXIa inhibitors targeting the S2' subsite for enhanced antithrombotic efficacy.

Factor XIa (FXIa), a key component of the intrinsic coagulation pathway, has recently been recognized as a safe and effective target for antithrombotic therapy. Research indicates that FXIa inhibitors can lower bleeding risk compared to novel oral anticoagulants. In this study, we designed and synthesized a series of novel FXIa inhibitors based on the structure of Asundexian, with a particular focus on optimizing the P2' region to enhance binding to the S2' subsite of FXIa. This strategy led to the discovery of compound F47, which demonstrated significantly greater FXIa inhibition (IC50 = 2.0nM) compared to Asundexian (IC50 = 5.0nM). F47 also showed excellent anticoagulant activity in the aPTT assay (EC2x = 0.4μM), with strong efficacy and minimal impact on the extrinsic coagulation pathway. Additionally, F47 exhibited inhibitory activity against plasma kallikrein (PKal), with selectivity comparable to that of Asundexian. The compound also displayed acceptable stability in human liver microsomal stability assays. Molecular modeling revealed that F47 binds tightly to the S1, S1', and S2' pockets of FXIa while maintaining key interactions; notably, its P2' moiety forms two additional π-π stacking interactions with the crucial amino acid TYR143. Further studies demonstrated that F47 exhibits dose-dependent antithrombotic efficacy in a rat FeCl3-induced thrombosis model. Ongoing research aims to further elucidate the potential of compound F47 as a promising lead in antithrombotic therapy.

Building Asymmetric Zn−N3 Bridge between 2D Photocatalyst and Co‐catalyst for Directed Charge Transfer toward Efficient H2O2 Synthesis

AbstractTwo‐dimensional (2D) polymeric semiconductors are a class of promising photocatalysts; however, it remains challenging to facilitate their interlayer charge transfer for suppressed in‐plane charge recombination and thus improved quantum efficiency. Although some strategies, such as π–π stacking and van der Waals interaction, have been developed so far, directed interlayer charge transfer still cannot be achieved. Herein, we report a strategy of forming asymmetric Zn−N3 units that can bridge nitrogen (N)‐doped carbon layers with polymeric carbon nitride nanosheets (C3N4−Zn−N(C)) to address this challenge. The symmetry‐breaking Zn−N3 moiety, which has an asymmetric local charge distribution, enables directed interfacial charge transfer between the C3N4 photocatalyst and the N‐doped carbon co‐catalyst. As evidenced by femtosecond transient absorption spectroscopy, charge separation can be significantly enhanced by the interfacial asymmetric Zn−N3 bonding bridges. As a result, the designed C3N4−Zn−N(C) catalyst exhibits dramatically enhanced H2O2 photosynthesis activity, outperforming most of the reported C3N4‐based catalysts. This work highlights the importance of tailoring interfacial chemical bonding channels in polymeric photocatalysts at the molecular level to achieve effective spatial charge separation.

Reproduction of experimental data for stacked caffeine dimers using various computational methods

Reliable description of stacking interaction of aromatic molecules is important for the understanding structure, stability, and functions of biopolymers. The caffeine molecule is an ideal object for this study as the stacking interactions are the preferential ones for self-associations of this hydrophobic molecule without H-bond donor groups. The analysis of anhydrous caffeine crystal structures revealed five types of caffeine stacking dimers. Geometry optimization of these dimers was performed using two molecular mechanics force fields, ab-initio method Møller Plesset of the second order (MP2), and density functional theory (DFT) with different functionals. The comparison of geometric parameters of the caffeine dimers obtained using different theoretical methods with those in crystals enables us to suggest the methods providing the most reliable stacking characteristics. These methods are: the MP2 with Basis Set Superposition Error correction (MP2/CP), Poltev force field, along with PBE0-DH, SCAN and PBE-D3 functionals of DFT. For the methods, which give the dimer interaction energy close to that obtained by MP2/CP method, the evaluated sublimation enthalpy values are shown to be close to the experimental data. Additionally, MP2/CP, Poltev FF and PBE0-DH functional showed to be the methods that describe well both the energy and geometry of the caffeine stacking dimer.

An advanced sensitive detection method for internal and external exposures assessment of para-phenylenediamines and their quinone derivatives based on hierarchical pore-structured nitro-microporous organic networks

para-Phenylenediamines (PPDs) and their quinone derivatives (PPD-Qs) are emerging pollutants that are associated with neurotoxicity, reproductive toxicity, and genetic toxicity, raising significant public health concerns globally. In this study, a novel hierarchical pore-structured nitro-microporous organic networks (NO2-MONs) characterized by multiple adsorption interactions and rapid mass transfer rates was synthesized. Model fitting and adsorption experiments confirmed diverse interaction mechanisms, including pore effects, hydrogen bonding, π-π stacking, and hydrophobic interactions. Utilizing these advantages, NO2-MONs-coated solid-phase microextraction fibers facilitated the effective extraction of trace PPDs and PPD-Qs. Subsequently, a highly sensitive analytical approach was developed for detecting trace amounts of PPDs and PPD-Qs using GC-MS/MS analysis. This method significantly improved upon existing techniques, addressing the low accuracy associated with current semi-quantitative methods and enhancing sensitivity by two orders of magnitude. Notably, the achieved detection limits ranged from 0.38 to 2.6 pg mL−1, with recovery rates between 75.7 % and 117.5 % (RSD ≤ 9.8 %). This proposed approach provides technical support for investigating concentration-dose-effect relationships related to the environmental presence of PPDs and PDD-Qs, facilitating the development of relevant regulatory standards.

Versatile silicate-modified hydrochar based on Scutellaria baicalensis-residue for efficiently removing heavy metal-antibiotic co-contamination and relevant bio-contaminants from wastewater

In this study, we utilized typical Chinese medicine herbal residues (CMHRs)－Scutellaria baicalensis (Scutellaria baicalensis Georgi) residue (SR), as the raw material and employed Na2SiO3 and Fe2(SO4)3 as modifying agents to fabricate a novel and multifunctional hydrochar (FeSi-SRHC), which was designed for comprehensive removal of typical contaminants such as Cu2+, Zn2+, tetracycline (TC), and ciprofloxacin (CIP), along with relevant bio-contaminants (resistant bacteria (RBs) and resistance genes (RGs)) present in wastewater. Based on the analysis of adsorption kinetics and Freundlich isotherm, it was found that FeSi-SRHC exhibited physical monolayer adsorption for Cu2+/Zn2+ while mainly chemical multilayer adsorption for TC/CIP in single-contamination system. Furthermore, Langmuir isotherm demonstrated excellent adsorption capacity of FeSi-SRHC towards Cu2+/Zn2+/TC/CIP with maximum capacities of 255.75, 265.26, 425.53, and 404.86 mg/g, respectively. In the co-contamination system, the presence of Cu2+, Zn2+, TC, and CIP exhibited varying degrees of inhibitory or promotive effects on the mutual adsorption by FeSi-SRHC. This divergence stemmed from differences in complexation intensities and concentration ratios among diverse co-existing contaminants. Based on XPS and Density Functional Theory (DFT) analyses, the adsorption process for Cu2+, Zn2+, TC, and CIP by FeSi-SRHC primarily involves pore fill, complexation reactions, ion exchange, hydrogen bonding, π-π stacking interactions, and electrostatic interactions. Bio-contaminant removal experiments revealed that the release of baicalin and wogonoside from FeSi-SRHC disrupts the structure of RBs cells and compromises the integrity of resistance plasmids. The practical application experiment showed that FeSi-SRHC displayed favorable performance for removing heavy metals, antibiotics, and bio-contaminants in actual wastewater. This study presented a “Treating waste with waste” strategy, which provided a method with low carbon, eco-friendly, and inexpensive for CMHRs resources and turning waste into treasure while proposing a idea to address the challenges associated with treating heavy metal, antibiotic, and bio-contaminant contamination in wastewater.

Disulfide-Rich Self-Assembling Peptides Based on Aromatic Amino Acid.

Aromatic residues in assembling peptides play a crucial role in driving peptide self-assembly through π-π stacking and hydrophobic interactions. Although various aromatic capping groups have been extensively studied, systematic investigations into the effects of single aromatic amino acids in assembling peptides remain limited. In this study, the influence of aromatic-aromatic interactions on disulfide-rich assembling peptides is systematically investigated by incorporating three different aromatic amino acids. Their folding propensity, self-assembling properties, and rheological behaviors are evaluated. These results indicate that different aromatic-aromatic interactions have a significant effect on self-assembly abilities, as determined by critical aggregation concentration (CAC) measurements. Furthermore, the biocompatibility of these hydrogels is assessed, and their potential for 3D cell culture is explored. The injectable F1-ox hydrogel demonstrate excellent biocompatibility for SHED and NIH3T3 cells and exhibit a porous structure that facilitates nutrient and cellular metabolic waste exchange. This work provides new insights into the molecular design of peptide-based biomaterials, with a focus on the impact of aromatic residues on disulfide-rich assembling peptides.

Theoretical Insights into Ultrafast Separation of Photogenerated Charges in a Push-Pull Polarized Molecular Triad.

Herein, we propose a purely-organic donor-acceptor (D-A) molecular triad, with a light-absorbing polarized molecular wire (PMW) used as a central linkage, as a proof of concept for the possible future applications of the D-PMW-A arrangement in molecular photovoltaics. This work builds upon our earlier study on the PMW unit itself, which proved to be highly promising for the ultrafast photogeneration of free charge carriers. Quantum-chemical calculations performed for the D-PMW-A triad at a semi-empirical level of theory reveal a large electric dipole moment of the system, and show strong charge-transfer (CT) character of its lowest-energy excited electronic states, including the S1, which favours efficient dissociation of an exciton initially formed upon the absorption of light. The confirmation for this effect was found with nonadiabatic molecular dynamics simulations, revealing an ultrafast relaxation from higher, bright excited states to S1, completed on a subpicosecond timescale. The architecture of the proposed molecular triad enables its electronic coupling to the surrounding environment through chemical bonds, or noncovalent stacking interactions, which might open way for synthesis of a new class of D-PMW-A efficient molecular organic photovoltaic materials.

Photocatalytic nanocomposite based on pyrene functionalized reduced graphene oxide in situ decorated with TiO2 nanorods

Hybrid nanocomposites based on 1-pyrene carboxylic acid (PCA) functionalized High Porous Reduced Graphene Oxide (HPRGO) sheets, decorated with oleic acid (OLEA)-coated TiO2 nanocrystals (NCs), have been obtained by means of an in situ colloidal route, starting from titanium isopropoxide (TTIP) precursor, in presence of OLEA surfactant and trimethylamino-N-oxide dihydrate (TMAO) base catalyst. The effect of the synthesis parameters, namely the PCA-HPRGO:TTIP w/w and the OLEA:TTIP molar ratio, on the morphological, spectroscopic and structural properties of the nanocomposites, has been explored, to achieve highly crystalline TiO2 nanostructures, with a reproducible control on morphology and crystalline phase (anatase). The TiO2 NCs have been found to effectively heteronucleate and grow onto the –COOH groups of the PCA molecules anchoring onto the HPRGO basal plane by aromatic π-π stacking interactions. The OLEA ligand coordinating their surface endows the nanocomposites with dispersibility in organic solvents, with a morphology dictated by the PCA coordinating sites, OLEA, and the mode of the TMAO supply to the reaction mixture. A significantly higher coating density has been found for the TiO2 in nanorod (NR) morphology, which organize in a uniform and high packed layout onto the PCA-HPRGO basal plane. The TiO2 NRs decorated PCA-HPRGO nanocomposites (TiO2 NRs/PCA-HPRGO) have been tested as photocatalysts for the degradation of methyl red (MR) and nalidixic acid (NA) under UV- and solar-light irradiation. Their photocatalytic activity has been evaluated against TiO2 reference and commercial nanostructures and discussed in terms of electronic level alignment between the hybrid nanostructure components, considering the role of the PCA anchoring molecule at the interphase.

Synthesis of curcumin polyprodrug via click chemistry and construction of dual-drug-loaded nano platform for highly efficient tumor treatment

Micellar nanostructures formed by amphiphilic polymers are prone to dissociation when the in vivo environment changes. Polyprodrug micelles can cross-link with other hydrophobic drugs through non-covalent bonds, which has the advantage of fixed structure and avoids the use of chemical cross-linking agents. In this study, we prepared a polyprodrug with hydrophobic curcumin (CUR) and hydrophilic poly(ethylene glycol) (PEG) in the main chain through a click reaction between CUR derivatives containing azide groups and di-alkynly-capped PEG. Due to the presence of benzene rings in the structure of CUR, the polyprodrug can form non-covalent cross-linked nanoparticles (NCCL-CUR NPs) through hydrophobic and π-π stacking interaction. The structure, molecular weight, and self-assembly properties of the polyprodrug were characterized. The anti-cancer drug camptothecin (CPT) was encapsulated in the polyprodrug nanoparticles, producing dual-drug-loaded nanoparticles (abbreviated as CPT@NCCL-CUR NPs). The test results indicate that the NPs have reductive responsiveness and can release the original drugs CUR and CPT in phosphate buffer (PB) solution containing glutathione (GSH), while remaining stability in physiological environment. Cell and in vivo experiments further demonstrate that the dual-drug-loaded CPT@NCCL-CUR NPs can inhibit the growth of tumor through synergistic effects. This work provides a valuable approach for the preparation of amphiphilic polyprodrug with anti-tumor CUR as the backbone, and the stable dual-drug-loaded NPs containing both CUR and CPT through non-covalent crosslinking for synergistic therapy.

Structural analysis and theoretical studies of 2-(2-chlorobenzylidene) malononitrile (CS) “a riot controlling agent”

In solvent methanol, malononitrile and 2-chlorobenzaldehyde were stirred in the presence of base piperidine to synthesise the target chemical 2-(2-chlorobenzylidene) malononitrile (CS). The crystal structure of the target compound C10H5ClN2 has been elucidated through X-ray crystallographic analysis. It crystallises in the monoclinic crystal system within the P21 space group, containing four molecules per asymmetric unit. The unit cell dimensions are a = 3.8825(3) Å, b = 21.0202(18) Å, c = 21.3481(18) Å, and β = 95.096(4)°. The phenyl and malononitrile groups, which make up the molecular components, are each planar but slanted towards one another at a dihedral angle of 12.7° (4). Besides this, target molecule is also stabilized by hydrogen bonding, halogen bonding and π stacking interactions. Solid-state structure has been analysed through Hirshfeld surface analysis, including the evaluation of the different energy frameworks, indicating that the molecular sheets are primarily formed by hydrogen bonds and halogen bonds and the stabilization is dominated via the electrostatic energy contribution. Fingerprint plots were carried out to study the relative contribution of noncovalent interactions in the target compound CS. Further, the density functional theory calculations were employed using B3LYP hybrid functional with 6-311++G level basic set to optimize the structural coordinates in gas phase and in different solvents (chloroform, water, and methanol). The chemically active regions of the target compound were identified by the analysis of molecular electrostatic potential surface. Further, from PASS analysis and literature reports, molecular docking of title compounds was carried out with human transient receptor potential ankyrin 1 ion channel (hTRPA1) (PDB-ID 6PQO). ΔGb (docking energy) and inhibition constant was calculated to be −7.53 kcal/mol and 3.33 μM respectively, with the target ion channel.

BCP Buffer Layer Enables Efficient and Stable Dopant-Free P3HT Perovskite Solar Cells.

Poly(3-hexylthiophene) (P3HT) has garnered significant attention as a novel hole transport material (HTM). Principally, its cost-effective synthesis, excellent hole conductivity, and stable film morphology make it one of the most promising HTMs for perovskite solar cells (PSCs). However, the efficiency of PSCs employing P3HT remains less than ideal, primarily due to the mismatch of energy levels and insufficient interface contact between P3HT and the perovskite film. In this work, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was inserted into the P3HT/perovskite interface for effectively alleviating the recombination loss. BCP could effectively anchor uncoordinated Pb2+ and establish π-π stacking interactions with P3HT. These interactions not only neutralize flaws to reduce energy depletion but also enhance the configuration of P3HT, aiding in carrier transfer. Consequently, the BCP-modified device achieved an efficiency of 19.27%, which is significantly superior to the control device (12%).

Azole Derivatives: Cutting‐Edge Agents in Cancer Therapy

AbstractMonocyclic 5‐membered heterocycles including imidazoles, thiazoles, oxazoles, and their related compounds have gained significant attention in medicinal chemistry because of their potent anticancerous activity. These small heterocyclic molecules possess versatile properties, including biological activity, absorption, distribution, metabolism, excretion, and chemical diversity that give them immense potential as anticancer agents. It is also a fact that inherent characteristic of azoles to combine with many biological molecules through hydrogen bond, stacking, and hydrophobic interaction makes them effective against almost all cancer types. In the present paper the author discusses the way which is connected with chemical structure of monocyclic azoles and their anticancer activity namely the ability of these compounds to intercalate with DNA, to inhibit some enzymes and to interfere cellular signaling pathways. Interestingly, several azole derivatives have been seen to be effective in preclinical efficacy studies as well as in clinical trials and are considered to be potent in overcoming the problem of resistance and side effects of the common anticancer agents. As the synthetic chemistry progresses, the structural system of the azoles has diversified and development in the pharmacology has become more specific. This has helped in enhancing the formation of new molecules in the azole class with improved selectivity and efficacy. Furthermore, the comprehensive review explains how computational chemistry and structure‐activity relationship (SAR) approaches are applied to the design of future‐generation azole compounds. In light of these facts, this article is designed to give a broad overview of the current state of monocyclic azole‐based anticancer agents in an attempt to further assert its therapeutic promise and spur further attempts at infusing the said agents into the cancer therapeutics fray. The discoveries made in this study may allow the development the radical different therapeutic approaches, which could lead to improved and targeted treatment of cancer.

Organophosphorus Flame Retardants and Metabolic Disruption: An in Silico, in Vitro, and in Vivo Study Focusing on Adiponectin Receptors.

Environmental chemical exposures have been associated with metabolic outcomes, and typically, their binding to nuclear hormone receptors is considered the molecular initiating event (MIE) for a number of outcomes. However, more studies are needed to understand the influence of such exposures on cell membrane-bound adiponectin receptors (AdipoRs), which are critical metabolic regulators. We aimed to clarify the potential interactions between AdipoRs and environmental chemicals, specifically organophosphorus flame retardants (OPFRs), and the resultant effects. Employing in silico simulation, cell thermal shift, and noncompetitive binding assays, we screened eight OPFRs for interactions with AdipoR1 and AdipoR2. We tested two key events underlying AdipoR modulation upon OPFR exposure in a liver cell model. The Toxicological Prioritization Index (ToxPi)scoring scheme was used to rank OPFRs according to their potential to disrupt AdipoR-associated metabolism. We further examined the inhibitory effect of OPFRs on AdipoR signaling activation in mouse models. Analyses identified pi-pi stacking and pi-sulfur interactions between the aryl-OPFRs 2-ethylhexyl diphenyl phosphate (EHDPP), triphenyl phosphate (TPhP), and tricresyl phosphate (TCP) and the transmembrane cavities of AdipoR1 and AdipoR2. Cell thermal shift assays showed a rightward shift in the AdipoR proteins' melting curves upon exposure to these three compounds. Although the binding sites differed from adiponectin, results suggest that aryl-OPFRs noncompetitively inhibited the binding of the endogenous peptide ligand ADP355 to the receptors. Analyses of key events underlying AdipoR modulation revealed that glucose uptake was notably lower, whereas lipid content was higher in cells exposed to aryl-OPFRs. EHDPP, TCP, and TPhP were ranked as the top three disruptors according to the ToxPi scores. A noncompetitive binding between these aryl-OPFRs and AdipoRs was also observed in wild-type (WT) mice. In db/db mice, the finding of lower blood glucose levels after ADP355 injection was diminished in the presence of a typical aryl-OPFR (TCP). WT mice exposed to TCP demonstrated lower AdipoR1 signaling, which was marked by lower phosphorylated AMP-activated protein kinase (pAMPK) and a higher expression of gluconeogenesis-related genes. Moreover, WT mice exposed to ADP355 demonstrated higher levels of pAMPK protein and peroxisome proliferator-activated receptor- messenger RNA. This was accompanied by higher glucose disposal and by lower levels of long-chain fatty acids and hepatic triglycerides; these metabolic improvements were negated upon TCP co-treatment. In silico, in vitro, and invivo assays suggest that aryl-OPFRs act as noncompetitive inhibitors of AdipoRs, preventing their activation by adiponectin, and thus function as antagonists to these receptors. Our study describes a novel MIE for chemical-induced metabolic disturbances and highlights a new pathway for environmental impact on metabolic health. https://doi.org/10.1289/EHP14634.

Fabrication and application of aminated metal–organic cages doped monolithic column for pipette tip micro solid-phase extraction of eight phenolic compounds in milk

A Zr-based metal–organic tetrahedron (ZrT-1-NH2) doped monolithic column was sythesized and applied for pipette tip micro solid-phase extraction (PT-μSPE) of 8 phenolic compounds. Scanning electron microscopy, energy dispersive spectrometry, Fourier transform infrared spectroscopy, thermogravimetric analysis and N2 adsorption and desorption experiment were employed to characterize the morphology, composition, structure and thermal stability of the monolithic column. The experimental results showed that the monolithic column had good stability and excellent adsorption selectivity for phenolic compounds. The adsorption mechanism was speculated to be π-π stacking and H-bond interaction based on ESP maps. After the extraction conditions were optimized, a PT-μSPE-high performance liquid chromatography-ultraviolet detector (HPLC-UV) method was established for the detection of 8 phenolic compounds in milk. The PT-μSPE-HPLC-UV method has wide linearities (0.3–1000 μg L−1) (R2 > 0.997), low limits of detection (0.1–0.3 μg L−1), satisfactory recoveries (80.5–113.6 %) and high precision (RSDs < 6.7 %). Thus, the ZrT-1-NH2 doped monolithic column is an ideal medium for the separation and determinaton of phenolic compounds in milk.

Quinoline-Piperazine Derivatives as Potential α-Glucosidase Inhibitors: Synthesis, Biological Evaluation, and In Silico Studies

α-Glucosidase inhibitors are crucial therapeutic agents for managing postprandial hyperglycemia in type 2 diabetes mellitus (T2DM). This study focuses on designing, synthesizing, and evaluating a new series of quinoline-piperazine-acetamide derivatives as potential α-glucosidase inhibitors. These derivatives introduce a unique combination of a quinoline core with a flexible piperazine linker, as new scaffold for α-glucosidase inhibition. This structural modification is hypothesized to enhance enzyme interaction. The synthesized derivatives were tested in vitro for their inhibitory activity, with compounds 6m (benzyl) and 6f (2-nitrophenyl) showing significant inhibition, having IC50 values of 280.0 µM and 546.2 µM, respectively, compared to the standard drug acarbose (IC50 = 750.7 µM). Molecular docking studies revealed crucial pi-pi stacking and pi-cation interactions with key residues such as His239 and Phe231, along with hydrogen bonding with Lys155, Pro309, and Thr215, which enhanced the inhibitory potency of the active compounds. Furthermore, molecular dynamics simulations confirmed that 6m consistently maintained stability within the active site of α-glucosidase throughout the simulation. These findings suggest that the synthesized compounds hold promise as α-glucosidase inhibitors for adjusting blood sugar control and metabolic health.

A Supramolecular‐Nanocage‐Based Framework Stabilized by π‐π Stacking Interactions with Enhanced Photocatalysis

Abstractπ frameworks, defined as a type of porous supramolecular materials weaved from conjugated molecular units by π‐π stacking interactions, provide a new direction in photocatalysis. However, such examples are rarely reported. Herein, we report a supramolecular‐nanocage‐based π framework constructed from a photoactive Cu(I) complex unit. Structurally, 24 Cu(I) complex units stack together through π‐π stacking interactions, forming a truncated octahedral nanocage with sodalite topology. The inner diameter of the nanocage is 2.8 nm. By sharing four open faces, each nanocage connects with four equivalent ones, forming a 3D porous π framework (π‐2). π‐2 shows good thermal and chemical stability, which can adsorb CO2, iodine, and methyl orange molecules. More importantly, π‐2 can serve as a photocatalyst for hydrogen evolution reaction. With ultrafine Pt subnanometer particles (0.9±0.1 nm) incorporated into the nanocages as a co‐catalyst, the hydrogen evolution rate reaches a record‐high value of 524012 μmol/gPt/h in the absence of any additional photosensitizers. The high photocatalytic activity can be ascribed to the ultrafine size of the Pt particles, as well as the fast electron transfer from π‐2 to the highly active Pt upon illumination. π‐2 represents the unique stable supramolecular‐cage‐based π framework with excellent photocatalytic activity.