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Unlike conventional natural gas reservoirs, shale gas development involves systematic changes in methane carbon isotopes that cannot be effectively described by existing isotope fractionation models and mechanisms. Therefore, based on fundamental theories such as Rayleigh fractionation, mass transfer flow, and mass conservation, this study established isotopic fractionation equations for methane in adsorbed and free gas. By considering adsorbed and free gases as two end-members and using an isotope mixing model, a fractionation model for methane carbon isotopes during shale gas desorption was constructed. This model quantifies the isotopic fractionation effects during shale gas desorption and elucidates the mechanism of methane carbon isotope fractionation. Using on-site desorbed gas content and isotope data, parameter fitting and model calculations were conducted to characterize methane carbon isotope variations throughout the process of shale core field desorption. The results show a pattern of "initially negative and then turning positive," consistent with those of physical simulation experiments. It was clarified that differences in mixing the two end-members and isotopic fractionation play key roles in the variation of methane carbon isotopic composition in shale gas. By applying the methane carbon isotope fractionation model, the contribution of adsorbed gas during shale gas production was explored. It was found that in the early stage of development, the adsorbed gas in Well JY 1 was negligible. After nearly seven years of development, the contribution of adsorbed gas in the later stage has only reached nearly 15%, indicating that the production contribution of adsorbed gas is still less than 0.3 million cubic feet per day. The open flow of Well JY 6-2 is more conducive to the production of adsorbed gas, but the production capacity is still mainly contributed by free gas, indicating that the shale gas production capacity in the later stage in the Jiaoshiba gas field is still primarily dominated by free gas., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Direct initiation of secondary explosives by a semiconductor laser is highly demanded, but it is challenging to exclude the use of sensitive primers. Most laser-sensitive energetic materials are usually mechanically sensitive. In order to reduce the mechanical sensitivity (MS) of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) while improving laser absorbance in the near-infrared band, spherical CL-20 composites (SCCs) embedded with nano aluminum (Al) powder and graphene-based catalyst (GO-CHZ-Co) were prepared by a spray drying method. These SCCs have been characterized comprehensively in terms of their morphologies, particle size distribution, laser absorbance, thermal decomposition behaviors, MS, and laser ignition properties. Results show that the maximum critical impact energy of SCCs was 3.8 J, which is 2.8 J higher than that of pristine ε-CL-20. The critical friction load was increased by at most 108 N compared to pristine CL-20. The absorbance has also been significantly increased up to almost 70% in the wavelength between 400 and 1400 nm, where the peak absorption is located in the region of 800-900 nm. In addition, the initial decomposition temperature ( T i ) of SCCs is lower than that of pure CL-20, especially in the presence of GO-CHZ-Co. The apparent activation energy ( E a ) for the decomposition of SCCs was largely dependent on the particle size of Al. Preliminary ignition tests indicate that the SCCs can be ignited successfully by a small-power laser.

Lactylation is a novel post-translational modification of proteins. Although the histone lactylation modification has been reported to be involved in glucose metabolism, its role and molecular pathways in gestational diabetes mellitus (GDM) are still unclear. This study aims to elucidate the histone lactylation modification landscapes of GDM patients and explore lactylation-modification-related genes involved in GDM. We employed a combination of RNA-seq analysis and chromatin immunoprecipitation sequencing (ChIP-seq) analysis to identify upregulated differentially expressed genes (DEGs) with hyperhistone lactylation modification in GDM. We demonstrated that the levels of lactate and histone lactylation were significantly elevated in GDM patients. DEGs were involved in diabetes-related pathways, such as the PI3K-Akt signaling pathway, Jak-STAT signaling pathway, and mTOR signaling pathway. ChIP-seq analysis indicated that histone lactylation modification in the promoter regions of the GDM group was significantly changed. By integrating the results of RNA-seq and ChIP-seq analysis, we found that CACNA2D1 is a key gene for histone lactylation modification and is involved in the progression of GDM by promoting cell vitality and proliferation. In conclusion, we identified the key gene CACNA2D1, which upregulated and exhibited hypermodification of histone lactylation in GDM. These findings establish a theoretical groundwork for the targeted therapy of GDM.

Incomplete combustion of Al in solid propellants can be effectively resolved by coating of an oxidizer at the microscale. In this paper, Al@CL-20 composites with polydopamine as the interfacial layer were prepared using this strategy. The structure, heat of reaction, thermal decomposition properties, and combustion performances of these composites under the effects of graphene oxide (GO) and graphene-based carbohydrazide complexes (GO-CHZ-M, M = Co 2+ , Ni 2+ ) have been comprehensively investigated. The experimental results show that the heat of reaction of Al@CL-20 is 6482 J g -1 , which is 561 J g -1 higher than that of the corresponding mechanical mixture. The presence of GO-CHZ-Co can further increase the heat of reaction of Al@CL-20 to 6729 J g -1 with a decreased activation energy by about 54.8%. Under the synergistic effect of interfacial control and GO-CHZ-M, the ignition delay time of Al@CL-20-Co decreases from 5.1 to 4.2 ms. Besides, the D 50 of the combustion condensed products (CCPs) decreased from 5.62 to 4.33 μm, indicating the combustion efficiency of Al is greatly improved.

Gut microbiota can influence cognitive ability via the gut-brain axis. Lactiplantibacillus plantarum MWFLp-182 ( L. plantarum MWFLp-182) was obtained from feces of long-living individuals and could exert marked antioxidant ability. Interestingly, this strain reduced the D-galactose-induced impaired cognitive ability in BALB/c mice. To comprehensively elucidate the underlying mechanism, we evaluated the colonization, antioxidant, and anti-inflammatory activities of L. plantarum MWFLp-182, along with the expression of potential genes associated with cognitive ability influenced and gut microbiota. L. plantarum MWFLp-182 enhanced the expression of anti-inflammatory cytokines, reduced the expression of proinflammatory cytokines, and increased tight junction protein expression in the colon. Moreover, L. plantarum MWFLp-182 could modify the gut microbiota. Notably, treatment with L. plantarum MWFLp-182 upregulated the expression of postsynaptic density protein-95, nuclear factor erythroid 2-related factor, nerve growth factor, superoxide dismutase, and brain-derived neurotrophic factor/neuronal nuclei, while downregulating the expression of bcl-2-associated X and malondialdehyde in the hippocampus and upregulating short-chain fatty acids against D-galactose-induced mouse brain deficits. Accordingly, L. plantarum MWFLp-182 could improve cognitive ability in a D-galactose-inducing mouse model.

Propane dehydrogenation (PDH), an atom-economic reaction to produce high-value-added propylene and hydrogen with high efficiency, has recently attracted extensive attention. The severe deactivation of Pt-based catalysts through sintering and coking remains a major challenge in this high-temperature reaction. The introduction of Sn as a promoter has been widely applied to improve the stability and selectivity of the catalysts. However, the selectivity and stability of PtSn catalysts have been found to vary considerably with synthesis methods, and the role of Sn is still far from fully understanding. To gain in-depth insights into this issue, we synthesized a series of PtSn/SiO 2 and SnPt/SiO 2 catalysts by varying the deposition sequence and Pt:Sn ratios using atomic layer deposition with precise control. We found that PtSn/SiO 2 catalysts fabricated by the deposition of SnO x first and then Pt, exhibited much better propylene selectivity and stability than the SnPt/SiO 2 catalysts synthesized the other way around. We demonstrate that the presence of Sn species at the Pt-SiO 2 interface is of essential importance for not only the stabilization of PtSn clusters against sintering under reaction conditions but also the promotion of charge transfers to Pt for high selectivity. Besides the above, the precise regulation of the Sn content is also pivotal for high performance, and the excess amount of Sn might generate additional acidic sites, which could decrease the propylene selectivity and lead to heavy coke formation. These findings provide deep insight into the design of highly selective and stable PDH catalysts., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Co-published by University of Science and Technology of China and American Chemical Society.)

Transition metal-catalyzed asymmetric hydrogenation possesses unparalleled advantages to prepare chiral amines. Here we reported a novel ligand that combined Josiphos and a spirobiindane scaffold and simultaneously investigated its application in Ir-catalyzed asymmetric hydrogenation for the synthesis of chiral amines. Excellent catalytic activity (5000 TON), high enantioselectivity (up to 99% ee ), and broad substrate scope (different C═N substrates) make it highly promising for both academic research and industrial applications.

A highly enantioselective catalytic reduction of pyrazolo[1,5- a ]pyrimidine to zanubrutinib has been realized by the Ir/( R )- t -Bu-FcPhox complex. This chiral product could be obtained in up to >99% ee in the asymmetric transformation without any other additives, providing a new route for the asymmetric synthesis of zanubrutinib.

Dielectric ceramics with ultrahigh polarization and energy density are the core components used in next-generation pulse power generators based on explosive energy conversion. However, the low polarization of ferroelectric materials and high depolarized pressure hinder their development toward miniaturization, light weight, and integration, while antiferroelectric materials possessing larger nonlinear saturated polarization and rich phase structure are neglected in pulse power energy conversion. Here, an effective strategy of constructing antiferroelectric-to-ferroelectric overlap zone is achieved in binary system (1 - x )(Pb,La)(Zr,Ti)O 3 - x Ba(Al 1/2 Nb 1/2 )O 3 antiferroelectric ceramics to realize an excellent polarization of 41 μC/cm 2 and a large depolarization efficiency of >99% under 150 MPa as well as a record high energy harvesting density of 2.5 J/cm 3 under 400 MPa. The excellent comprehensive energy conversion and energy harvesting performance is mainly attributed to the strategy of antiferroelectric-to-ferroelectric overlap zone and improved microdomain density, at which orthorhombic-to-rhombohedral structure evolution is confirmed by transmission electron microscopy, piezo-response force microscopy, and Raman spectrum, resulting in substantially enhanced remanent polarization compared to ferroelectric ceramics. Besides, excellent temperature stability (∼180 °C) and optimized depolarization pressure also support that this binary system is a candidate for energy conversion and energy harvesting application. This work demonstrates that antiferroelectric-to-ferroelectric overlap based on antiferroelectric materials is an excellent strategy to develop dielectric materials with excellent depolarized polarization and energy harvesting density for energy conversion and harvesting.

Alkoxy side chain engineering on the β-position of the thienothiophene units of Y6 derivatives plays a vital role in improving photovoltaic performances with simultaneously increasing open-circuit voltage ( V oc ) and fill factor (FF). In this work, we prepared a series of asymmetric non-fullerene acceptors (NFAs) by introducing alkoxy side chains and phenoxy groups on the state-of-the-art Y6-derivative BTP-BO-4F. For the comparison, 2O-BO-4F with a symmetric alkoxy side chain on the outer thiophene units and BTP-PBO-4F with an asymmetric N -attached phenoxy alkyl chain on the pyrrole ring are synthesized from BTP-BO-4F. Thereafter, we construct four asymmetric NFAs by introducing different lengths of linear/branched alkoxy chains on the β-position of the thienothiophene units of BTP-PBO-4F. The resulting NFAs, named L10-PBO, L12-PBO, B12-PBO, and B16-PBO (L = linear and B = branched alkoxy side chains), are collectively called OR-PBO-series. Unexpectedly, all OR-PBO NFAs exhibit strong edge-on molecular packing and weaker π-π interactions in the film state, which diminish the charge transfer in organic solar cell (OSC) devices. As a consequence, the optimal devices of OR-PBO-based binary blends show poor photovoltaic performances [power conversion efficiency (PCE) = 6.52-9.62%] in comparison with 2O-BO-4F (PCE = 12.42%) and BTP-PBO-4F (PCE = 15.30%) reference blends. Nevertheless, the OR-PBO-based binary devices show a higher V oc and smaller V loss . Especially, B12-PBO- and B16-PBO-based devices achieve V oc over 1.00 V, which is the highest value of Y-series OSC devices to the best of our knowledge. Therefore, by utilizing higher V oc of OR-PBO binary blends, B12-PBO and B16-PBO are incorporated into the PM6:BTP-PBO-4F-based binary blend and fabricated ternary devices. As a result, the PM6:BTP-PBO-4F:B12-PBO ternary device delivers the best PCE of 15.60% with an increasing V oc and FF concurrently.

ABBV-167, a phosphate prodrug of BCL-2 inhibitor venetoclax, was recently progressed into the clinic as an alternative means of reducing pill burden for patients in high-dose indications. The dramatically enhanced aqueous solubility of ABBV-167 allowed for high drug loading within a crystalline tablet and, when administered in phase I clinical study, conferred venetoclax exposure commensurate with the equivalent dose administered as an amorphous solid dispersion. In enabling the progression into the clinic, we performed a comprehensive evaluation of the CMC development aspects of this beyond the rule of five (bRo5) prodrug. Adding a phosphate moiety resulted in excessively complex chemical speciation and solid form landscapes with significant physical-chemical stability liabilities. A combination of experimental and computational methods including microelectron diffraction (MicroED), total scattering, tablet colorimetry, finite element, and molecular dynamics modeling were used to understand CMC developability across drug substance and product manufacture and storage. The prodrug's chemical structural characteristics and loose crystal packing were found to be responsible for the loss of crystallinity during its manufacturing, which in turn led to high solid-state chemical reactivity and poor shelf life stability. The ABBV-167 case exemplifies key CMC development challenges for complex chemical matter such as bRo5 phosphate prodrugs with significant ramifications during drug substance and drug product manufacturing and storage.

The structural investigation of amorphous pharmaceuticals is of paramount importance in comprehending their physicochemical stability. However, it has remained a relatively underexplored realm primarily due to the limited availability of high-resolution analytical tools. In this study, we utilized the combined power of X-ray pair distribution functions (PDFs) and solid-state nuclear magnetic resonance (ssNMR) techniques to probe the molecular packing of amorphous posaconazole and its amorphous solid dispersion at the molecular level. Leveraging synchrotron X-ray PDF data and employing the empirical potential structure refinement (EPSR) methodology, we unraveled the existence of a rigid conformation and discerned short-range intermolecular C-F contacts within amorphous posaconazole. Encouragingly, our ssNMR 19 F- 13 C distance measurements offered corroborative evidence supporting these findings. Furthermore, employing principal component analysis on the X-ray PDF and ssNMR data sets enabled us to gain invaluable insights into the chemical nature of the intermolecular interactions governing the drug-polymer interplay. These outcomes not only furnish crucial structural insights facilitating the comprehension of the underlying mechanisms governing the physicochemical stability but also underscore the efficacy of synergistically harnessing X-ray PDF and ssNMR techniques, complemented by robust modeling strategies, to achieve a high-resolution exploration of amorphous structures.

Insulating thermally conductive polymer composites are in great demand in integrated-circuit packages, for efficient heat dissipation and to alleviative short-circuit risk. Herein, the continuous oriented hexagonal boron nitride (h-BN) frameworks (o-BN@SiC) were prepared via self-assembly and in situ chemical vapor infiltration (CVI) interface welding. The insulating o-BN@SiC/epoxy (o-BN@SiC/EP) composites exhibited enhanced thermal conductivity benefited from the CVI-SiC-welded BN-BN interface. Further, multiscale simulation, combining first-principles calculation, Monte Carlo simulation, and finite-element simulation, was performed to quantitatively reveal the effect of the welded BN-BN interface on the heat transfer of o-BN@SiC/EP composites. Phonon transmission in solders and phonon-phonon coupling of filler-solder interfaces enhanced the interfacial heat transfer between adjacent h-BN microplatelets, and the interfacial thermal resistance of the dominant BN-BN interface was decreased to only 3.83 nK·m 2 /W from 400 nK·m 2 /W, plunging by over 99%. This highly weakened interfacial thermal resistance greatly improved the heat transfer along thermal pathways and resulted in a 26% thermal conductivity enhancement of o-BN@SiC/EP composites, compared with physically contacted oriented h-BN/EP composites, at 15 vol % h-BN. This systematic multiscale simulation broke through the barrier of revealing the heat transfer mechanism of polymer composites from the nanoscale to the macroscale, which provided rational cognition about the effect of the interfacial thermal resistance between fillers on the thermal conductivity of polymer composites.

In this paper, several binary and ternary metastable intermixed nanocomposites Al/CuO, Al/PVDF, CuO/PVDF, and Al/CuO/PVDF have been prepared by simple mechanical mixing and ball milling followed by spray drying methods. In this way, the interfacial structure could be well tuned and compared in terms of reactivity. The nonisothermal DSC curves results showed that the exothermic reaction of Al/CuO/PVDF could be divided into three steps. In addition, it has been shown that for the same formulation, the reaction efficiency, pressurization capacity, and thermal reactivity are greatly dependent on the interfacial structure. As a typical example, composite Al@PVDF/CuO, where Al is fully covered with PVDF, exhibited a higher energy release of 10.7 kJ·cm -3 and pressurization rates of 22.79 MPa·s -1 ·g -1 . The reaction between Al and PVDF has been facilitated in both extent of reaction and efficiency due to their intimate contact. Based on the thermal analysis, condensed combustion product analysis, and gaseous phase identification, the mutual reaction mechanisms of Al/CuO/PVDF have been proposed. The most likely reactions that occurred at each stage of the reaction are summarized, providing insight into the complicated underlying mechanisms. It shows that the regulation of energy release rates and improved efficiency could be easily realized by predesigned interfacial structures.

This work describes an effective C3-H halogenation of quinoline-4(1 H )-ones under electrochemical conditions, in which potassium halides serve as both halogenating agents and electrolytes. The protocol provides expedient access to different halogenated quinoline-4(1 H )-ones with unique regioselectivity, broad substrate scope, and gram-scale synthesis employing convenient, environmentally friendly electrolysis, in an undivided cell. Mechanism studies have shown that halogen radicals can promote the activation of N-H bonds in quinolones.

In this study, a 2D structured triaminoguanidine-glyoxal polymer with a high nitrogen content has been coordinated with metal ions to produce energetic metal complexes (TAGP-Ms) employed as energetic burn rate inhibitors. The metal ions (Ba 2+ , K + , and Ca 2+ ) are elaborately selected based on their ability of suppressing the burn rate of composite propellants. The CL-20 crystals were intercalated with prepared TAGP-Ms materials via a solvent-antisolvent method for realization of the precise control on burning behaviors of studied propellants. The influence of TAGP-Ms inhibitors on thermal decomposition and combustion characteristics of high-energy composite propellants was evaluated using thermal analysis and a combustion diagnostic method. Results of TGA/DSC-FTIR measurements suggest that the thermal decomposition of CL-20-containing composite propellants was found to be constrained by varied degrees as a result of TAGP-Ms additions, in which the TAGP-K displays a stronger effect on suppressing the thermal decomposition of CL-20 compared with that of other TAGP-Ms. The FTIR spectra indicate that the primary gaseous phase products are composed of N 2 O, H 2 O, and CO 2 in CL-20 decomposition, as well as by HCl, H 2 O, NO 2 , and N 2 O in the decomposition of AP for all studied composite propellants. The combustion characterizations show that the TAGP-K-containing composite propellant exhibits a significantly reduced rate of heat release but is associated with a higher flame radiation intensity increased by 4.2% compared with that of the reference propellant, which clearly implies that the TAGP-K is capable of suppressing the energy release rate while ensuring the high energetic features of propellants to be well maintained. Moreover, the burn rate pressure exponents are considerably decreased by ∼10% for the TAGP-K-containing propellants in comparison with those of propellants with the typical formulation, which strongly suggests that TGAP-Ms are promising candidates for tuning the combustion behaviors of composite propellants by influencing the decomposition processes of CL-20 and AP collectively.

There is an interactive effect between ammonium perchlorate (AP) and aluminum (Al) powder during the combustion process of composite solid propellants, but the mechanism of this effect is still lacking. Using quantum chemical methods, we investigated this mechanism from a molecular perspective. The interaction process between Al and AP was analyzed by comparing the chemical bond changes between the atoms during the reaction process of the Al/AP system and the AP unimolecular thermal decomposition system. The results show that Al atoms alter the reaction mechanism of AP thermal decomposition, significantly decreasing the activation energy of AP decomposition at high temperature but increasing that at low temperature. Meanwhile, the temperature-dependent rate constant of each basic reaction was calculated by transition state theory. The rate constants increase with temperature. Under high temperature and pressure, Al can increase the high-temperature decomposition rate of AP by up to 1-3 orders of magnitude.

At present, polyethylene pipeline is widely used in urban gas projects, but a relatively mature and reliable nondestructive testing technology has not been formed. Therefore, it is urgent to develop a new nondestructive testing technology to meet the increasing demand for inspection of non-metallic pipes. The terahertz testing technology and related equipment have played an increasingly important role in the nondestructive testing of many nonmetallic structures, but they have not been applied to polyethylene (PE) pipes. In this work, terahertz time-domain spectroscopy was used to detect prefabricated defects inside the PE pipe specimens. The results show that the terahertz nondestructive testing technology can be used to detect common defects in nonblack PE pipes with a detection error of less than 10%. Higher-power terahertz devices can detect defects in black PE pipe, while lower-power terahertz devices cannot. Because the black PE pipe contains carbon and has a strong absorption of terahertz waves. The penetration of lower-power terahertz devices to the black PE pipe is not enough, resulting in a low resolution of the imaging. The results of this work may promote the progress of the nondestructive testing technology of nonmetallic pipelines., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Selenium (Se) and tellurium (Te) nanomaterials with novel chain-like structures have attracted widespread interest owing to their intriguing properties. Unfortunately, the still-unclear catalytic mechanisms have severely limited the development of biocatalytic performance. In this work, we developed chitosan-coated Se nanozymes with a 23-fold higher antioxidative activity than Trolox and bovine serum albumin coated Te nanozymes with stronger prooxidative biocatalytic effects. Based on density functional theory calculations, we first propose that the Se nanozyme with Se/Se 2- active centers favored reactive oxygen species (ROS) clearance via a LUMO-mediated mechanism, while the Te nanozyme with Te/Te 4+ active centers promoted ROS production through a HOMO-mediated mechanism. Furthermore, biological experiments confirmed that the survival rate of γ-irritated mice treated with the Se nanozyme was maintained at 100% for 30 days by inhibiting oxidation. However, the Te nanozyme had the opposite biological effect via promoting radiation oxidation. The present work provides a new strategy for improving the catalytic activities of Se and Te nanozymes.

Although previous studies have yielded valuable insights into shale gas reservoirs, a comprehensive understanding of the organic geochemical characteristics and organic matter enrichment of marine-continental transitional shale has yet to be achieved. The Longtan Formation transitional shales were extensively deposited in Southern Anhui Province, South China, during the Late Permian. Our analysis of twenty-two rock samples from one core (Gangdi-1 well) and two outcrops (Daoshanchong outcrop and Changqiao outcrop) revealed that the Longtan Formation shale extracts exhibit a wide range of C 11 -C 35 n -alkanes and acyclic isoprenoids, with unimodal, bimodal, and multimodal distributions. The carbon peak ranges from n C 15 to n C 24 , with high quantities of medium-chain n -alkanes ( n C 22 - n C 25 ), indicating that the organic matter in Longtan Formation shale originates from a mixed source of higher plant debris and lower aquatic organisms. Our conclusion is supported by the ternary diagram of C 27 -C 28 -C 29 regular steranes and the variations of the δ 13 C values of C 15 -C 32 n -alkanes, which is higher than the corresponding value (<1.6‰) of n -alkanes from a single source. Furthermore, thermal maturity proxies based on organic petrography ( R o and T max ) and biomarkers, such as the ratios of C 31 22S/(22S + 22R), C 29 20S/(20S + 20R), and C 29 ββ/(αα + ββ), suggest that organic matter is in a mature stage of hydrocarbon generation. By analyzing the Pr/Ph ratio and pyrite morphology combined with a plot of total organic carbon (TOC) versus total sulfur (TS) and the Pr/ n C 17 -Ph/ n C 18 diagram, we speculate that the Longtan Formation shales were chiefly developed in a dysoxic-to-oxic water environment. Finally, we establish depositional models of organic matter enrichment in deltaic and tidal flat-lagoon environments, emphasizing that the abundant mixed-sourced organic matter can significantly enhance primary productivity, and a higher sedimentation rate can distinctly shorten organic matter exposure time in the oxidized water environment, thereby promoting organic matter accumulation in such a setting., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

In alkaline solutions, the electrocatalytic conversion of nitrates to ammonia (NH 3 ) (NO 3 RR) is hindered by the sluggish hydrogenation step due to the lack of protons on the electrode surface, making it a grand challenge to synthesize NH 3 at a high rate and selectivity. Herein, single-stranded deoxyribonucleic acid (ssDNA)-templated copper nanoclusters (CuNCs) were synthesized for the electrocatalytic production of NH 3 . Because ssDNA was involved in the optimization of the interfacial water distribution and H-bond network connectivity, the water-electrolysis-induced proton generation was enhanced on the electrode surface, which facilitated the NO 3 RR kinetics. The activation energy ( E a ) and in situ spectroscopy studies adequately demonstrated that the NO 3 RR was exothermic until NH 3 desorption, indicating that, in alkaline media, the NO 3 RR catalyzed by ssDNA-templated CuNCs followed the same reaction path as the NO 3 yield rate of 2.62 mg h 3 yield rate of 2.62 mg h -1 cm -2 and a Faraday efficiency of 96.8% at -0.6 V vs reversible hydrogen electrode. The results of this study lay the foundation for engineering catalyst surface ligands for the electrocatalytic NO 3 RR.

The free transport of anions through commercial polyolefin separators used in lithium metal batteries (LMBs) gives rise to concentration polarization and rapid growth of lithium dendrites, leading to poor performance and short circuits. Here, a new poly(ethylene- co -acrylic acid) (EAA) separator with functional active sites (i.e., carboxyl groups) distributing along the pore surface was fabricated, forming bioinspired ion-conducting nanochannels within the separator. As the carboxyl groups effectively desolvated Li + and immobilized anion, the as-prepared EAA separator selectively accelerated the transport of Li + with transference number of Li + ( t ) up to 0.67, which was further confirmed by molecular dynamics simulations. The battery with the EAA separator can be stably cycled over 500 h at 5 mA cm Li + ) up to 0.67, which was further confirmed by molecular dynamics simulations. The battery with the EAA separator can be stably cycled over 500 h at 5 mA cm -2 . The LMBs with the EAA separator have exceptional electrochemical performance of 107 mAh g -1 at 5 C and a capacity retention of 69% after 200 cycles. This work provides new commercializable separators toward dendrite-free LMBs.

An inexpensive electrochemical induction system was used for the efficient reductive defunctionalization of sulfoximines through a radical pathway. This practical and robust strategy could be used for the removal of the S═N bond-directing group from various sulfoximines. The practicability of this method was demonstrated by its mild conditions, simple operation, one-pot procedure, gram-scale synthesis, and the undivided cell. Furthermore, preliminary mechanistic studies suggested that the reaction might proceed via a homocoupling reaction and a denitrification procedure.

Conventional enzyme-based glucose biosensors have limited extensive applications in daily life because glucose oxidase is easily inactivated and is expensive. In this paper, we propose a strategy to prepare a new type of cost-effective, efficient, and robust nonenzymatic Ni-CNT-O for electrochemical glucose sensing. It is first followed by the pyrolysis of Ni-ABDC nanostrips using melamine to grow carbon nanotubes (CNTs) to give an intermediate product of Ni-CNT , which is further accompanied by partial oxidation to enable the facile formation of hierarchical carbon nanomaterials with improved hydrophilicity. A series of physicochemical characterizations have fully proved that Ni-CNT-O is a carbon-coated heterostructure of Ni and NiO nanoparticles embedded into coordination polymer-derived porous carbons. The obtained Ni-CNT-O exhibits a better electrocatalytic activity for glucose oxidation stemming from the synergistic effect of a metal element and a metal oxide than unoxidized Ni-CNT , which also shows high performance with a wide linear range from 1 to 3000 μM. It also offers a high sensitivity of 79.4 μA mM -1 cm -2 , a low detection limit of 500 nM (S/N = 3), and a satisfactory long-term durability. Finally, this glucose sensor exhibits good reproducibility, high selectivity, as well as satisfactory results by comparing the current response of simulated serum within egg albumen.

An efficient and practical SO 2 insertion protocol of NH-sulfoximines with aryldiazonium tetrafluoroborates and DABSO toward N -sulfonyl sulfoximines has been developed under mildly basic conditions. This transformation features easy operation, readily available substrates, and mild conditions. A tentative mechanism is proposed, which indicates that the aryldiazonium tetrafluoroborates would be radical donors under standard reaction conditions. The aryl radical produced in situ from diazonium salts would be trapped by SO 2 to generate an arylsulfonyl radical and then undergo further transformation to generate the final N -sulfonyl sulfoximines.

Ferroptosis is an inflammatory programmed cell death process that is dependent on iron deposition and lipid peroxidation. The P2X7 receptor not only is involved in the pain process but also is closely related to the onset of depression. Gallic acid (3,4,5-trihydroxybenzoic acid), which is naturally found in a variety of plants, exhibits anti-inflammatory, antioxidant, and analgesic effects. This study established a rat model with the comorbidity of chronic constrictive injury (CCI) plus chronic unpredictable mild stress (CUMS) to explore the role and mechanism of gallic acid in the treatment of pain and depression comorbidity. Our experimental results showed that pain and depression-like behaviors were more obvious in the chronic constriction injury (CCI) plus chronic unpredictable mild stimulation (CUMS) group than they were in the sham operation group, and the P2X7-reactive oxygen species (ROS) signaling pathway was activated. The tissue iron concentration was increased, and mitochondrial damage was observed in the CCI plus CUMS group. These results were alleviated with gallic acid treatment. Therefore, we speculate that gallic acid inhibits the ferroptosis of the spinal microglia by regulating the P2X7-ROS signaling pathway and relieves the behavioral changes in rats with comorbid pain and depression.

Compressor outlets are subject to high temperatures and vibrations; when pipelines are subject to such conditions, degradation of the anticorrosive layer on the pipeline is likely. Fusion-bonded epoxy (FBE) powder coating is the most common type of anticorrosion coatings on compressor outlet pipelines. It is necessary to study the reliability of anticorrosive layers in compressor outlet pipelines. In this paper, a service reliability test method for the corrosion-resistant coatings of compressor outlet pipelines of natural gas stations is proposed. Testing involving the simultaneous exposure of the pipeline to high temperatures and vibrations is conducted to evaluate, on a compressed timescale, the applicability and service reliability of FBE coatings. The failure mechanism of FBE coatings exposed to high temperatures and vibrations is analyzed. It is found that, due to the influence of initial imperfections in the coatings, FBE anticorrosion coatings typically do not meet the standard requirements for use in compressor outlet pipelines. After simultaneous exposure to high temperatures and vibrations, the impact resistance, abrasion resistance, and bending resistance of the coatings are found not to meet the requirements for their intended applications. It is therefore suggested that FBE anticorrosion coatings be used with extreme caution in compressor outlet pipelines., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Developing new electron transport layers has been an effective way to fabricate high-performance bulk-heterojunction organic solar cells (OSCs). Resolving the longstanding problems associated with commonly used zinc oxide (ZnO), such as electron traps and light-induced device deterioration, however, is still a great challenge. In this study, glycerol diglycidyl ether (GDE) and 1,4-butanesultone (BS) are blended with polyethyleneimine (PEI) to produce cross-linkable PEI-based materials, PEI-GDE and PEI-GDE-BS, which can function as alternative electron transport layers to replace conventional ZnO cathode-modifying layers in inverted OSCs. PEI-GDE and PEI-GDE-BS are amendable to low-temperature annealing processes to produce cross-linked films. The inverted device structure of ITO/ETL/PM6:BTP-BO-4F:PC 71 BM/MoO 3 /Ag was used to evaluate the effects of incorporating PEI-GDE and PEI-GDE-BS as electron transport materials. Compared with ZnO-based devices, the PEI-GDE- and PEI-GDE-BS-based devices exhibit significant improvements in photovoltaic performances due to smoother surface roughness, higher charge collection and exciton dissociation efficiencies, higher electron mobilities, and stronger π-π interactions. In particular, a PEI-GDE-BS-based device shows an outstanding power conversion efficiency (PCE) of 17.55% with a V OC of 0.83 V, a J SC of 27.88 mA/cm 2 , and an FF of 75.96%, which offers great possibilities in the applications of flexible solar cells.

Catalyzing polysulfide conversion is a promising way toward accelerating complex and sluggish sulfur redox reactions (SRRs) in lithium-sulfur batteries. Reasonable alteration of an enzyme provides a new means to expand the natural enzyme universe to catalytic reactions in abiotic systems. Herein, we design and fabricate a denatured hemocyanin (DHc) to efficiently catalyze the SRR. After denaturation, the unfolded β-sheet architectures with exposed rich atomically dispersed Cu, O, and N sites and intermolecular H-bonds are formed in DHc, which not only provides the polysulfides for a strong spatial confinement effect in microenvironment via S-O and Li···N interactions but also activates chemical channels for electron/Li + transport into the Cu active center via H/Li-bonds to catalyze polysulfide conversion. As expected, the charge/discharge kinetics of DHc-containing cathodes is fundamentally improved in cyclability with nearly 100% Coulombic efficiency and capacity even under high sulfur loading (4.3 mg cm -2 ) and lean-electrolyte (8 μL mg -1 ) conditions.

Polymer composites have great potential applications in the hip joint replacement, where the combinations of high mechanical strength and excellent biotribological properties are required. In this work, a well-dispersed three-dimensional (3D) silicon nitride nanowire membrane (SNm) designed as a reinforcement and brushite (Bs) served as bioactive filler are constructed into the polymer matrix, forming SNm-reinforced Bs/polymer composites (SNm-Bs/Pm). Especially, SNm could form a 3D interlocked structure, where the ultralong silicon nitride nanowires are entangled with each other. SNm could effectively facilitate the penetration of the polymer matrix and improve the cohesion strength of the polymer, thereby promoting mechanical and biotribological properties for SNm-Bs/Pm. The performances for polymer composites are optimized by increasing the layer number of preform. By comparing SNm-Bs/Pm with one-layer preform, the tensile strength of SNm-Bs/Pm with six-layer preforms reaches 83.3 MPa with an increase of 767.7%. In addition, the friction coefficient and wear rate of SNm-Bs/Pm with six-layer preforms in fetal bovine serum medium achieve 0.06 and 0.21 × 10 -14 m 3 (N·m) -1 and decrease by 82.4 and 72.4%, respectively. The present work provides a promising methodology of preparing interlocked SNm-reinforced polymer composites with enhanced mechanical and biotribological properties that are potential for hip joint replacement applications.

Superoxide dismutase (SOD) is one of the major antioxidants in vivo and is expected to play critical roles on the defense against reactive oxygen species (ROS)-mediated damages, such as ionizing radiation damages. Herein, inspired by the function and structure of natural SODs and cerium oxide nanozymes, two monovalent cerium-based metal organic frameworks (Ce-MOFs), Ce III BTC and Ce IV BTC, were designed for superoxide radical (O 2 •- ) elimination and ionizing radiation protection. These two Ce-MOFs selectively scavenge O 2 •- and are excellent SOD mimics. Like natural SODs and cerium oxide nanozymes, the SOD-like catalytic mechanism of Ce-MOFs involves a cycle between Ce(IV) and Ce(III). Furthermore, by constructing monovalent Ce-MOFs, we found that high-valent Ce IV BTC are more effective SOD-like nanozymes compared to Ce III BTC. With smaller size, better monodispersity, and more effective SOD-like activity, Ce IV BTC nanozymes were further applied for ionizing radiation protection. Both in vitro and in vivo results demonstrated that Ce IV BTC nanozymes could efficiently scavenge ROS, prevent cells from γ-ray radiation-induced cell viability decrease and DNA damages, and improve the survival rate of irradiated mice by recovering the bone marrow DNA damage and alleviating oxidative stress of tissues. The protective effect and good biocompatibility of Ce IV BTC nanozymes will enable the development of Ce-MOFs-based radioprotectants and facilitate treatment of other ROS-related diseases.

Thermal conductivity k dominates in a heat transfer medium, and a field modulated k would facilitate delicate control in thermal management technology, yet it is hardly realized in a single solid material unless with changing temperature. Herein, in BaTiO 3 ceramic, a modulated k was discovered by adjusting ferroelectric polarization P , which was a conventional strategy in ferroelectric functional materials. Four different states (P1, P2, P3, P4) were obtained by controlling poling time and field strength, showing that k leaped from 2.704 ± 0.054 to 3.201 ± 0.070 W (m K) -1 with increased P . Moreover, the strong correlation between P and k was also verified by the thermal depolarization measurement from room temperature to Curie temperature. The underlying origin of P modulated k was attributed to the internal bias field, which is born in the oriented ferroelectric domains, tightening special phonon modes in BaTiO 3 ceramics. Raman spectrum, P - E loops, first-order reversible curve, XRD analysis, and PFM measurement were then employed to clarify how ferroelectric polarization structurally influences phonon transport and subsequent thermal conductivity. This work will pave a brand-new research route for conventional ferroelectric ceramic, also potentiating the idea of the electric field-controlled k component and active solid heat-transport device in the future.

Metal nanoparticles stabilized by crystalline metal-organic frameworks (MOFs) are highly promising for green heterogeneous catalysis. In this work, in situ formed ultrafine Pd nanocatalysts with an average size of 3.14 nm have been successfully immobilized into the mesopores or defects of a water-stable indium-based MOF by the double-solvent method and subsequent reduction. Significantly, the obtained Pd@InOF-1 displays an obvious and satisfactory size-selective effect in the Suzuki-Miyaura coupling reaction between arylboronic acids and aryl bromides. On the basis of the synergistic effect, microporous InOF-1 nanorods afford a confined space for improving the selectivity of target products while Pd nanoparticles endow abundant active sites for catalysis. Herein, choosing the smallest size reactant with only one benzene ring gives the highest isolated yield of 90%, and if the size is larger, the yield is obviously reduced or even the target product could not be collected. Looking forward, this demonstrated study not only assembles a well-designed Pd@MOF composite with unique micro-nanostructures but also delivers an impressive option for cross-coupling reaction, which has implications for the further development of MOF hybrids for sustainable applications.

Wigs provide a common service as hair accessories in people's daily life. However, the traditional wigs, regardless of the matrices derived from human hair or synthetic fibers, are faced with limitations such as short service life, dry and brittle texture, and static electricity. In this work, we described a new strategy for surface coating of wigs via the Langmuir-Blodgett (LB) technique using a nanocomposite composed of hair-derived keratin and graphene oxide (Ker/GO). In contrast to the conventionally used immersion method, this strategy achieved a significantly higher surface coverage with a close-packed structure and controlled deposition layers of the coating, thus delivering high performances, including greatly enhanced ultraviolet (UV) resistance, antistatic electricity, heat dissipation, hydroscopicity, and moisturizing ability, and durability against washing, for both the human hair and synthetic-fiber-based wigs.

The molecular design of wide-bandgap conjugated polymer donors (WB-CPDs) is a promising strategy for tuning the bulk heterojunction blend film morphologies to achieve high-performance organic photovoltaic (OPV) devices. Herein, we synthesize two WB-CPDs, namely, PBQ-H and PBQ-M, with and without methyl groups on the fused-dithieno[3,2- f :2',3'- h ]quinoxaline (DTQx) moiety. We systematically investigate their structure-property relationship and OPV performances. The AFM and 2D grazing-incidence wide-angle X-ray scattering (GIWAXS) studies reveal that the PBQ-H:BO-4Cl BHJ blend shows strengthened aggregation behavior and stronger π-π stacking on face-on orientation compared with the PBQ-M:BO-4Cl BHJ blend, enhancing the phase separation, charge transport, and fill factor (FF). Blend film absorption spectra, however, show that the PBQ-H:BO-4Cl BHJ blend exhibits a lower absorption coefficient than that of the PBQ-M:BO-4Cl BHJ blend, which decreases the short-circuit current density ( J ). As a consequence, the optimized PBQ-H:BO-4Cl BHJ blend delivers a higher power conversion efficiency (PCE) of 12.88% with a SC ). As a consequence, the optimized PBQ-H:BO-4Cl BHJ blend delivers a higher power conversion efficiency (PCE) of 12.88% with a J SC of 23.97 mA/cm 2 , an open-circuit voltage ( V OC ) of 0.86 V, and an FF of 62.46%, compared with the PBQ-M:BO-4Cl BHJ blend (PCE of 11.81% with a J SC of 24.78 mA/cm 2 , a V OC of 0.85 V, and an FF of 56.11%). Overall, this work demonstrates that alkyl group substitution on the DTQx moiety on the basis of WB-CPDs is critical for controlling the film morphology and thus obtaining high OPV performances.

Cucurbit[ n ]urils (Q[ n ]s or CB[ n ]s), as a classical of artificial organic macrocyclic hosts, were found to have excellent advantages in the fabricating of tunable and smart organic luminescent materials in aqueous media and the solid state with high emitting efficiency under the rigid pumpkin-shaped structure-derived macrocyclic-confinement effect in recent years. This review aims to give a systematically up-to-date overview of the Q[ n ]-based supramolecular organic luminescent emissions from the confined spaces triggered host-guest complexes, including the assembly fashions and the mechanisms of the macrocycle-based luminescent complexes, as well as their applications. Finally, challenges and outlook are provided. Since this class of Q[ n ]-based supramolecular organic luminescent emissions, which have essentially derived from the cavity-dependent confinement effect and the resulting assembly fashions, emerged only a few years ago, we hope this review will provide valuable information for the further development of macrocycle-based light-emitting materials and other related research fields.

The electrocatalytic nitrogen reduction reaction (eNRR) is regarded as promising sustainable ammonia (NH 3 ) production alternative to the industrial Haber-Bosch process. However, the current electrocatalytic systems still exhibit a grand challenge to simultaneously boost their eNRR activity and selectivity under ambient conditions. Herein, we construct Pd/PdO electrocatalysts with a controlled oxygen level by a facile electrochemical deposition approach at different gas atmospheres. Theoretical calculation results indicate that the introduction of an oxygen atom into a pure Pd catalyst would modulate the electron density of the Pd/PdO heterojunction and thus influence the adsorption energy for nitrogen and hydrogen. The calculation results and experiments show that the Pd/PdO heterojunction with a moderate oxygen level (O-M) exhibits optimal eNRR performance with a high NH 3 yield of 11.0 μg h -1 mg cat -1 and a large Faraday efficiency (FE) of 22.2% at 0.03 V (vs RHE) in a 0.1 M KOH electrolyte. The moderate affinity of Pd to N in the Pd/PdO heterojunction and the inhibition of the hydrogen evolution reaction (HER) can facilitate the breaking of the triple bond of N 2 and promote the protonation of N, which is confirmed by ex situ X-ray photoelectron spectroscopy (XPS) and in situ Raman spectroscopy. In situ Fourier transform infrared spectroscopy (FTIR) and density functional theory (DFT) calculations further disclose that the O-M catalysts prefer the distal association pathway during the eNRR process. This work opens a new way to construct heterostructures by controlling the oxygen level in other electrochemical fields.

The key challenges facing the commercialization of lithium-sulfur (Li-S) batteries are shortening the lithium polysulfide (LiPS) intermediate existence time while accelerating solid-phase conversion reactions. Herein, inspired by highly efficient natural enzymes with Fe/N active sites for oxygen reduction reactions, we report a periodic expansion catalysis concept, i.e., Ru and P synergic stereoselectivity, for designing sulfur reduction reaction (SRR) catalysts. As a proof of concept, a RuP 2 -configuration molecular catalyst was exploited to assemble an interlayer in Li-S batteries that adsorbs LiPSs, optimizes Li + migration paths, and catalyzes SRRs. Comprehensive investigation identified the elimination of steric hindrance and strong electron orbital couplings between metallic d band and nonmetallic p band as the main contributing factors of PEC for the SRRs. As a result, the Li-S battery with ∼0.5 wt % catalyst additive showed enhanced cycling stability even under a high sulfur loading (6.5 mg cm -2 ) and low electrolyte/sulfur ratio (9 μL mg -1 ).

With control by N1-substituents, the switchable divergent C-H functionalization reaction of quinoxalin-2(1 H )-ones is achieved for the synthesis of ( Z )-enaminones and furo[2,3- b ]quinoxalines using the combination of a copper catalyst and an oxidant. This new protocol features mild reaction conditions, readily available materials, and a broad substrate scope. Gram-scale and mechanistic studies were also investigated. Furthermore, the desired products exhibited excellent antitumor activity against A549, HepG-2, MCF-7, and HeLa cells, which were tested by MTT assay.

Exploiting zeolitic imidazolate framework (ZIF)-based nanoparticles to synergistically enhance starvation-combined chemotherapy strategies remains an urgent demand. Herein, glucose oxidase (GOX) and doxorubicin (DOX) were facilely incorporated into ZIFs for starvation-combined chemotherapy. The as-prepared DOX/GOX-loaded ZIF (DGZ) exhibited uniform size with good dispersity, effective protection of the GOX activity, and stable delivery of the drugs into tumor. Correspondingly, it could achieve the glucose- and pH-responsive degradation and thus the controllable drug release. As a result, the acidification of glucose accompanied with reactive oxygen species (ROS) production was observed for the starvation-enhanced chemotherapy and the improved degradation. Most importantly, adjustable Zn 2+ release was achieved with the biodegradation of DGZ, which thus contributed to an augmented therapeutic outcome via the Zn 2+ -induced mitochondrial dysfunction and antioxidation dyshomeostasis. These findings, synergized with the enhancement of starvation-combined chemotherapy by inhibiting the mitochondrial energy metabolism and boosting the ROS accumulation using pristine ZIF-based nanoparticles, provide a new insight into the metal-organic framework-based nanomedicine for further cancer treatments.

Tunable crystalline defects endow WO 3- x catalysts with extended functionalities for a broad range of photo- and electric-related applications. However, direct visualization of the defect structures and their evolution mechanism is lacking. Herein, aberration-corrected and in situ transmission electron microscopy was complemented by theoretical calculations to investigate the effect of temperature on the defect evolution behavior during hydrogenation treatment. Low processing temperature (100-300 °C) leads to the occurrence of randomly distributed oxygen vacancies within WO 3- x nanosheets. At higher temperatures, oxygen vacancies become highly mobile and aggregate into stacking faults. Planar defects are prone to nucleate at the surface and develop in a zigzag form at 400 °C, while treating at 500 °C promotes the growth of {200}-type stacking faults. Our work clearly establishes that the atomic configuration of the defects in WO 3- x samples could be manipulated by regulating the hydrogenation temperature. This study not only expands our understanding of the structure-function relationships of sub-stoichiometric tungsten oxides but also unlocks their full potential as advanced catalysts by tuning stoichiometry in a controlled manner.

In this work, we report the strategy of one-pot synthesis of protoberberine alkaloid derivatives via palladium-catalyzed cascade α-arylation and cyclization, which can afford the target molecules in moderate to excellent isolated yields using commercially available raw materials under solvent-free conditions. This protocol provides an efficient and convenient path to multisubstituted protoberberine derivatives. In addition, it can directly afford natural alkaloids.

In this work, two asymmetric non-fullerene acceptors (NFAs), BTP-EHBO-4F and BTP-PHD-4F, are designed to be applied in green-solvent-processable organic photovoltaics (OPVs). BTP-EHBO-4F and BTP-PHD-4F show good solubilities in green solvent o -xylene. As a result, PM6:BTP-EHBO-4F-based devices exhibit outstanding photovoltaic performances using o -xylene as a solvent. By comparison, due to the poor solubility of Y6 in o -xylene, PM6:Y6-based devices show poor performances. Owing to the favorable phase separation, molecule packing, and orientation observed from atomic force microscopy (AFM) and grazing-incidence wide-angle X-ray scattering (GIWAXS) measurements, PM6:BTP-PHD-4F-based devices demonstrate a PCE of 15.91% with a V OC of 0.87 V, a J SC of 25.64 mA/cm 2 , and an FF of 71.34%. Moreover, PM6:BTP-EHBO-4F-based devices exhibit an impressive PCE of 16.82% with a V OC of 0.85 V, a J SC of 26.12 mA/cm 2 , and an FF of 75.78%, which is outstanding for OPVs using o -xylene as a solvent.

A unique supramolecular approach of preparing and using a cucurbit[8]uril (Q[8])-based dynamic host-guest assembly for cyanide sensing in and removal from water has been successfully developed. The dicyanovinyl-attached cationic guest ( 1 ) was designed as the fluorescent response moiety for the detection of the cyanide anion via a nucleophilic addition reaction in the assist of the Q[8]-based 2:2 quaternary complexes. Furthermore, the reaction of cyanide with 1 further switched the Q[8]-based host-guest assemblies from the 2:2 complexes to the 1:1 supramolecular polymers that precipitate in water. Thus, the macrocyclic-based dynamic host-guest assembly has potential use in applications for solving the problem of toxic anion pollutants present in aqueous environments.

The NRF2-mediated cytoprotective response is central to cellular homoeostasis, and there is increasing interest in developing small-molecule activators of this pathway as therapeutics for diseases involving chronic oxidative stress. The protein KEAP1, which regulates NRF2, is a key point for pharmacological intervention, and we recently described the use of fragment-based drug discovery to develop a tool compound that directly disrupts the protein-protein interaction between NRF2 and KEAP1. We now present the identification of a second, chemically distinct series of KEAP1 inhibitors, which provided an alternative chemotype for lead optimization. Pharmacophoric information from our original fragment screen was used to identify new hit matter through database searching and to evolve this into a new lead with high target affinity and cell-based activity. We highlight how knowledge obtained from fragment-based approaches can be used to focus additional screening campaigns in order to de-risk projects through the rapid identification of novel chemical series.

Searching for high-quality air electrode catalysts is the long-term goal for the practical application of Zn-air batteries. Here, a series of coexistent composite materials (CoNi/NHCS-TUC- x ) of cobalt-nickel supported on nitrogen-doped hollow spherical carbon and tubular carbon are obtained using a simple pyrolysis strategy. Co and Ni in the composites are mainly present in the form of alloy nanoparticles, M-N x and M-C x (M = Co or Ni) species, with high oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) electroactivity. The materials containing different proportions of spherical carbon and tubular carbon obtained by simply adjusting the raw materials for generating tubular carbon exhibit interesting bifunctional performance: samples with an abundant tubular content have the highest ORR onset potential (0.91 V vs reversible hydrogen electrode), while those with a rich spherical content have the highest ORR current density (5.13 mA·cm -2 ). Furthermore, CoNi/NHCS-TUC-3 provides the lowest potential difference (Δ E = E j =10 - E , and a specific capacity of 756.5 mA h·g 1/2 . The rechargeable battery could be cycled stably for more than 55 h at 10 mA·cm -2 , and a specific capacity of 756.5 mA h·g Zn -1 . The rechargeable battery could be cycled stably for more than 55 h at 10 mA·cm -2 . These characteristics make CoNi/NHCS-TUC-3 a superior electrocatalyst for both the ORR and OER, as well as a suitable bifunctional electrode applied to a rechargeable Zn-air battery.

Diabetic cardiac autonomic neuropathy (DCAN) is a complication that affects more than 60% of diabetic patients. There is evidence for the involvement of P2X4 receptor in DCAN. This study showed that the expression of the long noncoding RNA (lncRNA) UC.360+ was increased in the stellate ganglion (SG) of type 2 diabetes mellitus (DM) rats, and in situ hybridization revealed a clear presence of UC.360+ in SG neurons. The potential roles of UC.360+ in DCAN and its relationship with P2X4 receptor in SG were further explored via application of the short hairpin RNA (shRNA) against lncRNA UC.360+ in DM rats. The abnormal cardiac sympathetic changes in diabetic rats were improved after treatment with lncRNA UC.360+ shRNA. In the SG of these shRNA-treated DM rats, the upregulation of P2X4, tumor necrosis factor-α (TNF-α), interleukin 1β (IL-1β), and phosphorylated ERK1/2 was inhibited. Thus, lncRNA UC.360+ shRNA treatment may improve DCAN mediated by the P2X4 receptor in SG.

Microplastics (MPs) are universally present in the ecosystem and pose great threats to the environment and living organisms. Research studies have shown that small MPs (<50 μm in diameter) are especially toxic and account for more than half of all MPs collected in the Atlantic Ocean. Nevertheless, current methods for the detection and analysis of MPs are incapable of achieving rapid and in situ analysis of small MPs in the biota to ultimately enable the study of their biological effects. In this work, we report a method that allows rapid in situ identification and spatial mapping of small MPs directly from paramecia with high accuracy by acquiring chemical composition information using secondary-ion mass spectrometry (SIMS) imaging. Specifically, six types of common MPs (polymethyl methacrylate, polyvinyl chloride, polypropylene, polyethylene terephthalate, polyglycidyl methacrylate, and polyamide 6) with a diameter of 1-50 μm were simultaneously imaged with high chemical specificity at a spatial resolution of 700 nm. In situ spatial mapping of a group of MPs ingested by paramecia was performed using SIMS fragments specific to the plastic composition with no sample pretreatment, revealing the aggregation of MPs in paramecia after ingestion. Compared with existing methods, one additional advantage of the developed method is that the MPs and the organism can be analyzed in the same experimental workflow to record their fingerprint spectra, acquiring biochemical information to evaluate MP fate, toxicity, and the MP-biota interaction.

Self-healing polymer electrolytes are reported with light-switchable conductivity based on dynamic N -donor ligand-containing diarylethene (DAE) and multivalent Ni 2+ metal-ion coordination. Specifically, a polystyrene polymer grafted with poly(ethylene glycol- r -DAE)acrylate copolymer side chains was effectively cross-linked with nickel(II) bis(trifluoromethanesulfonimide) (Ni(TFSI) 2 ) salts to form a dynamic network capable of self-healing with fast exchange kinetics under mild conditions. Furthermore, as a photoswitching compound, the DAE undergoes a reversible structural and electronic rearrangement that changes the binding strength of the DAE-Ni 2+ complex under irradiation. This can be observed in the DAE-containing polymer electrolyte where irradiation with UV light triggers an increase in the resistance of solid films, which can be recovered with subsequent visible light irradiation. The increase in resistance under UV light irradiation indicates a decrease in ion mobility after photoswitching, which is consistent with the stronger binding strength of ring-closed DAE isomers with Ni 2+ . 1 H- 15 N heteronuclear multiple-bond correlation nuclear magnetic resonance (HMBC NMR) spectroscopy, continuous wave electron paramagnetic resonance (cw EPR) spectroscopy, and density functional theory (DFT) calculations confirm the increase in binding strength between ring-closed DAE with metals. Rheological and in situ ion conductivity measurements show that these polymer electrolytes efficiently heal to recover their mechanical properties and ion conductivity after damage, illustrating potential applications in smart electronics.