Separating water isotopologues using diffusion-regulatory porous materials.

The discovery of a method to separate isotopologues, molecular entities that differ in only isotopic composition1, is fundamentally and technologically essential but remains challenging2,3. Water isotopologues, which are very important in biological processes, industry, medical care, etc. are among the most difficult isotopologue pairs to separate because of their very similar physicochemical properties and chemical exchange equilibrium. Herein, we report efficient separation of water isotopologues at room temperature by constructing two porous coordination polymers (PCPs, or metal-organic frameworks) in which flip-flop molecular motions within the frameworks provide diffusion-regulatory functionality. Guest traffic is regulated by the local motions of dynamic gates on contracted pore apertures, thereby amplifying the slight differences in the diffusion rates of water isotopologues. Significant temperature-responsive adsorption occurs on both PCPs: H2O vapour is preferentially adsorbed into the PCPs, with substantially increased uptake compared to that of D2O vapour, facilitating kinetics-based vapour separation of H2O/HDO/D2O ternary mixtures with high H2O separation factors of around 210 at room temperature.

ABSCISIC ACID-INSENSITIVE 5-KIP-RELATED PROTEIN 1-SHOOT MERISTEMLESS modulates reproductive development of Arabidopsis.

Soil (or plant) water deficit accelerates plant reproduction. However, the underpinning molecular mechanisms remain unknown. By modulating cell division/number, ABSCISIC ACID-INSENSITIVE 5 (ABI5), a key bZIP (basic (region) leucine zippers) transcription factor, regulates both seed development and abiotic stress responses. The KIP-RELATED PROTEIN (KRP) cyclin-dependent kinases (CDKs) play an essential role in controlling cell division, and SHOOT MERISTEMLESS (STM) plays a key role in the specification of flower meristem identity. Here, our findings show that abscisic acid (ABA) signaling and/or metabolism in adjust reproductive outputs (such as rosette leaf number and open flower number) under water-deficient conditions in Arabidopsis (Arabidopsis thaliana) plants. Reproductive outputs increased under water-sufficient conditions but decreased under water-deficient conditions in the ABA signaling/metabolism mutants abscisic acid2-1 (aba2-1), aba2-11, abscisic acid insensitive3-1 (abi3-1), abi4-1, abi5-7, and abi5-8. Further, under water-deficient conditions, ABA induced-ABI5 directly bound to the promoter of KRP1, which encodes a CDK that plays an essential role in controlling cell division, and this binding subsequently activated KRP1 expression. In turn, KRP1 physically interacted with STM, which functions in the specification of flower meristem identity, promoting STM degradation. We further demonstrate that reproductive outputs are adjusted by the ABI5-KRP1-STM molecular module under water-deficient conditions. Together, our findings reveal the molecular mechanism by which ABA signaling and/or metabolism regulate reproductive development under water-deficient conditions. These findings provide insights that may help guide crop yield improvement under water deficiency.

In vitro modeling of skeletal muscle ischemia-reperfusion injury based on sphere differentiation culture from human pluripotent stem cells.

Skeletal muscle ischemia-reperfusion (IR) injury poses significant challenges due to its local and systemic complications. Traditional studies relying on two-dimensional (2D) cell culture or animal models often fall short of faithfully replicating the human in vivo environment, thereby impeding the translational process from animal research to clinical applications. Three-dimensional (3D) constructs, such as skeletal muscle spheroids with enhanced cell-cell interactions from human pluripotent stem cells (hPSCs) offer a promising alternative by partially mimicking human physiological cellular environment in vivo processes. This study aims to establish an innovative in vitro model, human skeletal muscle spheroids based on sphere differentiation from hPSCs, to investigate human skeletal muscle developmental processes and IR mechanisms within a controlled laboratory setting. By eticulously recapitulating embryonic myogenesis through paraxial mesodermal differentiation of neuro-mesodermal progenitors, we successfully established 3D skeletal muscle spheroids that mirror the dynamic colonization observed during human skeletal muscle development. Co-culturing human skeletal muscle spheroids with spinal cord spheroids facilitated the formation of neuromuscular junctions, providing functional relevance to skeletal muscle spheroids. Furthermore, through oxygen-glucose deprivation/re-oxygenation treatment, 3D skeletal muscle spheroids provide insights into the molecular events and pathogenesis of IR injury. The findings presented in this study significantly contribute to our understanding of skeletal muscle development and offer a robust platform for in vitro studies on skeletal muscle IR injury, holding potential applications in drug testing, therapeutic development, and personalized medicine within the realm of skeletal muscle-related pathologies.

Formation and Transformation of CdS Clusters during the Prenucleation Stage and in a Dilute Dispersion at Room Temperature.

The formation and transformation of colloidal semiconductor clusters remain poorly understood. With CdS as a model system, we show that, in the reaction of cadmium myristate (Cd(MA)2) and S powder in 1-octadecene (ODE), clusters form in the prenucleation stage of quantum dots (QDs). Called precursor compounds (PCs), the clusters can transform to magic-size clusters (MSCs) in reaction at a relatively high temperature (MSC-322 displaying optical absorption peaking at 322 nm) or in a dispersion at room temperature (MSC-360). When the reaction temperature is increased, PC-360 forms at 140 °C, while PC-322 and MSC-322 form at 180 °C. In a dispersion of cyclohexane and octylamine, MSC-322 transforms to MSC-360 via MSC-345. The MSC-345 to MSC-360 transformation displays continuous and discontinuous shifts in the optical absorption. The PCs and MSCs are a group of isomers. The present findings bring insight into the cluster formation and isomerization in the prenucleation stage of QDs and in a dispersion.

Resistive Memristors Using Robust Electropolymerized Porous Organic Polymer Films as Switchable Materials.

Porous organic polymers (POPs) with inherent porosity, tunable pore environment, and semiconductive property are ideally suitable for application in various advanced semiconductor-related devices. However, owing to the lack of processability, POPs are usually prepared in powder forms, which limits their application in advanced devices. Herein, we demonstrate an example of information storage application of POPs with film form prepared by an electrochemical method. The growth process of the electropolymerized films in accordance with the Volmer-Weber model was proposed by observation of atomic force microscopy. Given the mechanism of the electron transfer system, we verified and mainly emphasized the importance of porosity and interfacial properties of porous polymer films for memristor. As expected, the as-fabricated memristors exhibit good performance on low turn-on voltage (0.65 ± 0.10 V), reliable data storage, and high on/off current ratio (104). This work offers inspiration for applying POPs in the form of electropolymerized films in various advanced semiconductor-related devices.

Quasi-Homogeneous Photocatalysis in Ultrastiff Microporous Polymer Aerogels.

The development of efficient and low-cost catalysts is essential for photocatalysis; however, the intrinsically low photocatalytic efficiency as well as the difficulty in using and recycling photocatalysts in powder morphology greatly limit their practical performance. Herein, we describe quasi-homogeneous photocatalysis to overcome these two limitations by constructing ultrastiff, hierarchically porous, and photoactive aerogels of conjugated microporous polymers (CMPs). The CMP aerogels exhibit low density but high stiffness beyond 105 m2 s-2, outperforming most low-density materials. Extraordinary stiffness ensures their use as robust scaffolds for scaled photocatalysis and recycling without damage at the macroscopic level. A challenging but desirable reaction for direct deaminative borylation is demonstrated using CMP aerogel-based quasi-homogeneous photocatalysis with gram-scale productivity and record-high efficiency under ambient conditions. Combined terahertz and transient absorption spectroscopic studies unveil the generation of high-mobility free carriers and long-lived excitonic species in the CMP aerogels, underlying the observed superior catalytic performance.

Glucose status within dark-grown etiolated cotyledons determines seedling de-etiolation upon light irradiation.

Exposure of dark-grown etiolated seedlings to light triggers the transition from skotomorphogenesis/etiolation to photomorphogenesis/de-etiolation. In the life cycle of plants, de-etiolation is essential for seedling development and plant survival. The mobilization of soluble sugars (glucose [Glc], sucrose, and fructose) derived from stored carbohydrates and lipids to target organs, including cotyledons, hypocotyls, and radicles, underpins de-etiolation. Therefore, dynamic carbohydrate biochemistry is a key feature of this phase transition. However, the molecular mechanisms coordinating carbohydrate status with the cellular machinery orchestrating de-etiolation remain largely opaque. Here, we show that the Glc sensor HEXOKINASE 1 (HXK1) interacts with GROWTH REGULATOR FACTOR5 (GRF5), a transcriptional activator and key plant growth regulator, in Arabidopsis (Arabidopsis thaliana). Subsequently, GRF5 directly binds to the promoter of phytochrome A (phyA), encoding a far-red light (FR) sensor/cotyledon greening inhibitor. We demonstrate that the status of Glc within dark-grown etiolated cotyledons determines the de-etiolation of seedlings when exposed to light irradiation by the HXK1-GRF5-phyA molecular module. Thus, following seed germination, accumulating Glc within dark-grown etiolated cotyledons stimulates a HXK1-dependent increase of GRF5 and an associated decrease of phyA, triggering the perception, amplification, and relay of HXK1-dependent Glc signaling, thereby facilitating the de-etiolation of seedlings following light irradiation. Our findings, therefore, establish how cotyledon carbohydrate signaling under subterranean darkness is sensed, amplified, and relayed, determining the phase transition from skotomorphogenesis to photomorphogenesis on exposure to light irradiation.

Efficient Decomposition of Perfluoroalkyl Substances by Low Concentration Indole: New Insights into the Molecular Mechanisms.

Perfluoroalkyl substances (PFAS) are a class of persistent organic pollutants known as "forever chemicals". Currently, the hydrated electron-based advanced reduction process (ARP) holds promise for the elimination of PFAS. However, the efficiency of ARP is often challenged by an oxygen-rich environment, resulting in the consumption of hydrated electron source materials in exchange for the high PFAS decomposition efficiency. Herein, we developed a ternary system constructed by indole and isopropyl alcohol (IPA), and the addition of IPA significantly enhanced the PFOA degradation and defluorination efficiency in the presence of low-concentration indole (<0.4 mM). Meanwhile, opposite results were obtained with a higher amount of indole (>0.4 mM). Further exploring the molecular mechanism of the reaction system, the addition of IPA played two roles. On one hand, IPA built an anaerobic reaction atmosphere and improved the yield and utilization efficiency of hydrated electrons with a low concentration of indole. On the other hand, IPA suppressed the attraction between indole and PFOA, thus reducing the hydrated electron transfer efficiency, especially with more indole. In general, the indole/PFAS/IPA system significantly improved the PFAS destruction efficiency with a small amount of hydrated electron donors, which provided new insights for development of simple and efficient techniques for the treatment of PFAS-contaminated wastewater.

Self-Assembled FeIII-TAML-Based Magnetic Nanostructures for Rapid and Sustainable Destruction of Bisphenol A.

This study focused on constructing iron(III)-tetraamidomacrocyclic ligand (FeIII-TAML)-based magnetic nanostructures via a surfactant-assisted self-assembly (SAS) method to enhance the reactivity and recoverability of FeIII-TAML activators, which have been widely employed to degrade various organic contaminants. We have fabricated FeIII-TAML-based magnetic nanomaterials (FeIII-TAML/CTAB@Fe3O4, CTAB refers to cetyltrimethylammonium bromide) by adding a mixed solution of FeIII-TAML and NH3·H2O into another mixture containing CTAB, FeCl2 and FeCl3 solutions. The as-prepared FeIII-TAML/CTAB@Fe3O4 nanocomposite showed relative reactivity compared with free FeIII-TAML as indicated by decomposition of bisphenol A (BPA). Moreover, our results demonstrated that the FeIII-TAML/CTAB@Fe3O4 composite can be separated directly from reaction solutions by magnet adsorption and reused for at least four times. Therefore, the efficiency and recyclability of self-assembled FeIII-TAML/CTAB@Fe3O4 nanostructures will enable the application of FeIII-TAML-based materials with a lowered expense for environmental implication.

Electrostatic Field in Contact-Electro-Catalysis Driven C-F Bond Cleavage of Perfluoroalkyl Substances.

Perfluoroalkyl substances (PFASs) are persistent and toxic to human health. It is demanding for high-efficient and green technologies to remove PFASs from water. In this study, a novel PFAS treatment technology was developed, utilizing polytetrafluoroethylene (PTFE) particles (1-5 µm) as the catalyst and a low frequency ultrasound (US, 40 kHz, 0.3 W/cm2) for activation. Remarkably, this system can induce near-complete defluorination for different structured PFASs. The underlying mechanism relies on contact electrification between PTFE and water, which induces cumulative electrons on PTFE surface, and creates a high surface voltage (tens of volts). Such high surface voltage can generate abundant reactive oxygen species (ROS, i.e., O2⋅-, HO⋅, etc.) and a strong interfacial electrostatic field (IEF of 109~1010 V/m). Consequently, the strong IEF significantly activates PFAS molecules and reduces the energy barrier of O2⋅- nucleophilic reaction. Simultaneously, the co-existence of surface electrons (PTFE*(e-)) and HO⋅ enables synergetic reduction and oxidation of PFAS and its intermediates, leading to enhanced and thorough defluorination. The US/PTFE method shows compelling advantages of low energy consumption, zero chemical input, and few harmful intermediates. It offers a new and promising solution for effectively treating the PFAS-contaminated drinking water.

Confining Water Nanotubes in a Cu10O13-Based Metal-Organic Framework for Propylene/Propane Separation with Record-High Selectivity.

Energy-efficient separation of propylene (C3H6)/propane (C3H8) is in high demand for the chemical industry. However, this process is challenging due to the imperceptible difference in molecular sizes of these gases. Here, we report a continuous water nanotube dedicatedly confined in a Cu10O13-based metal-organic framework (MOF) that can exclusively adsorb C3H6 over C3H8 with a record-high selectivity of 1570 (at 1 bar and 298 K) among all the porous materials. Such a high selectivity originates from a new mechanism of initial expansion and subsequent contraction of confined water nanotubes (∼4.5 Å) caused by C3H6 adsorption rather than C3H8. Such unique response was further confirmed by breakthrough measurements, in which one adsorption/desorption cycle yields each component of the binary mixture high purity (C3H6: 98.8%; C3H8: >99.5%) and good C3H6 productivity (1.6 mL mL-1). Additionally, benefiting from the high robustness of the framework, the water nanotubes can be facilely recovered by soaking the MOF in water, ensuring long-term use. The molecular insight here demonstrates that the confining strategy opens a new route for expanding the function of MOFs, particularly for the sole recognition from challenging mixtures.

Copper-Catalyzed Umpolung Reactivity of Propargylic Carbonates in the Presence of Diboronates: One Stone Four Birds.

Allylation and propargylation are two powerful synthetic strategies for making new substances that have been of significant importance in chemistry, medicine, and material fields. Conventional tactics employ various preformed allylation and propargylation reagents. In this study, a conceptually novel copper-catalyzed and B2pin2-mediated Umpolung reactivity of propargylic carbonates has been achieved for the first time, realizing both allylation and propargylation of aldehydes and ketones without additional reductants. Three types of allylation products and one type of propargylation product are generated efficiently, and all allylation products are formed with syn-configurations predominantly. The choice of ligands plays a vital role in modulating the Umpolung modes. The synthetic applications have been demonstrated in a myriad of further transformations including natural product synthesis, and systematic mechanistic studies have been conducted to reveal detailed insights into the Umpolung processes.

Bacterial community assembly and antibiotic resistance genes in soils exposed to antibiotics at environmentally relevant concentrations.

Understanding how bacterial community assembly and antibiotic resistance genes (ARGs) respond to antibiotic exposure is essential to deciphering the ecological risk of anthropogenic antibiotic pollution in soils. In this study, three loam soils with different land management (unmanured golf course, dairy-manured pasture, and swine-manured cornfield) were spiked with a mixture of 11 antibiotics at the initial concentration of 100 and 1000 µg kg-1 for each antibiotic and incubated over 132 days, mimicking a scenario of pulse disturbance and recovery in soils, with unspiked soil samples as the control treatment. The Infer Community Assembly Mechanisms by Phylogenetic-bin-based null model (iCAMP) analysis demonstrated that drift and dispersal limitation contributed to 57%-65% and 16%-25%, and homogeneous selection 12%-16% of soil bacterial community assembly. Interestingly, antibiotic exposure to 1000 µg kg-1 level significantly increased the contribution of drift to community assembly, largely due to the positive response from Acidobacteria-6 in the golf course and pasture soils and from Chthoniobacteraceae in the cornfield soil to the antibiotic exposure. However, ARG abundance and diversity in the three soils exhibited antibiotics-independent temporal fluctuations, but were associated with the changes in soil bacterial communities over time. This study provides the first insight into the relative contributions of different bacterial community assembly processes in soils upon antibiotic exposure at environmentally relevant concentrations.

SWATH-F: A Novel Nontarget Strategy Based on the SWATH-MS Deconvolution Method Assisting in Annotating PFAS Homologues in Multisample Studies.

In order to identify emerging per- and polyfluoroalkyl substances (PFASs) and their alternatives in the environment or population, we need to perform extensive profiling of PFASs to determine their distribution in samples. The sequential window acquisition of all theoretical fragment-ion spectra (SWATH mode) is capable of obtaining a wide range of MS2 spectra but is difficult for direct identification of PFASs due to its complex MS2 spectra, and the nontarget screening method is difficult to identify due to its lack of a priori information. In this study, we demonstrated the great potential of SWATH-F, a nontarget fragment-based homologue screening method in combination with the SWATH-MS deconvolution, for detecting PFASs. We evaluated the application of SWATH-F to gradient spiked samples and real population serum samples, compared it with nontarget homologue screening in the information-dependent acquisition mode (IDA mode), and obtained better results for SWATH-F with 276% improvement (IDA:17 PFASs, SWATH-F: 64 PFASs) in identification. In addition, we automated the screening and identification process of SWATH-F to facilitate its use by researchers. SWATH-F is freely available on GitHub (https://github.com/njuIrene/SWATH-F) under an MIT license.

Linear Conjugated Coordination Polymers for Electrocatalytic Oxygen Evolution Reaction.

Conjugated coordination polymers (CCPs) have attracted extensive attention for various applications related to energy storage and conversion in the past few years, despite that there are many CCPs with unclear chemical states and structures. Here, linear CCPs (LCCPs), with metal-O4 active sites grown on carbon paper (CP) for oxygen evolution reaction (OER), are presented. The LCCPs with high crystallinity and simple structures exhibit the order of electrocatalytic activity of Co-O4  > Ni-O4  > Fe-O4 in terms of the metal-O4 centers. The Co-based LCCP shows higher OER performance (263 mV at 10 mA cm-2 ) and better durability (90 h at 30 mA cm-2 ) than commercial IrO2 /CP. The structures and chemical states of LCCPs are carefully investigated, and density functional theory is used to reveal the mechanism of OER at the central metal site. This investigation into LCCPs provides new sights for a better understanding of CCPs and expands the applications of LCCPs with metal-O4 sites.

Cobalt(III)-catalyzed weakly coordinating arylurea-directed regioselective mono-olefination.

Here, we developed an air-stable, earth-abundant cobalt(III)-catalyzed regioselective mono-olefination of arenes directed by urea under mild conditions through a cross-dehydrogenative coupling (CDC) process. Under the optimized conditions, a high regioselectivity of mono-olefination was achieved with various electron-rich and electron-deficient arenes, which afforded E-alkenylated products (with yields of up to 90%). In contrast to the conditions used for noble-metal-catalyzed olefination directed by weakly coordinating groups, our reaction was operated under mild conditions, including mild temperature (40 °C) and non-metallic oxidant.

Roles of Natural Phenolic Compounds in Polycyclic Aromatic Hydrocarbons Abiotic Attenuation at Soil-Air Interfaces through Oxidative Coupling Reactions.

Little information is available on the roles of natural phenolic compounds in polycyclic aromatic hydrocarbons (PAHs) attenuation at dry soil-air interfaces. The purpose of this study was to determine the roles of model phenolic constituents of soil organic matter (SOM) on the abiotic attenuation of PAHs. The phenolic compounds can significantly change the attenuation rates of PAHs, among which hydroquinone was the most effective in promoting anthracene and benzo[a]anthracene attenuation. Product identification and sequential extraction experiments revealed hydroquinone enhanced the formation of oxidative coupling products and promoted the incorporation of PAHs into humic analogues, thereby reducing potential risks to humans and ecosystems. Electron paramagnetic resonance spectroscopy analyses showed both PAHs and phenolic compounds could donate electrons to Lewis acid sites of soil minerals, resulting in the generation of persistent free radicals (PFRs). PFRs could promote the generation of ·OH to enhance PAH oxidation and could cross-couple with PAHs, resulting in high-molecular-weight oxidative coupling products. This study revealed for the first time the reaction mechanism between PAHs and phenolic components of SOM under relatively dry conditions and provided new insights into promoting PAHs detoxification in soils but also a potential strategy to increase the organic carbon sequestration.

Photoaging of Typical Microplastics as Affected by Air Humidity: Mechanistic Insights into the Important Role of Water Molecules.

Recent studies showed that land is the most important sink for microplastics (MPs); however, limited information is available on the photoaging processes of land surface MPs that are exposed to the air. Herein, this study developed two in situ spectroscopic methods to systematically explore the effect of air humidity on MP photoaging using a microscope of Fourier transform infrared spectroscopy and a laser Raman microscope, which were equipped with a humidity control system. Polyethylene microplastics, polystyrene microplastics, and poly(vinyl chloride) microplastics (PVC-MPs) were used as model MPs. Our results showed that relative humidity (RH) could significantly influence the MP surface oxygen-containing moieties generated from photo-oxidation, especially for PVC-MPs. As the RH level varied from 10 to 90%, a decrease in the photogenerated carbonyl group and an increase in the hydroxyl group were observed. This could be attributed to the involvement of water molecules in the production of hydroxyl groups, which subsequently inhibited carbonyl generation. Moreover, the adsorption of coexisting contaminants (i.e., tetracycline) on photoaged MPs exhibited strong RH dependence, which could be assigned to the varied hydrogen bonding between tetracycline carbonyls and aged MP surface hydroxyls. This study reveals a ubiquitous but previously overlooked MP aging route, which may account for the changed MP surface physiochemical properties under solar irradiation.

Natural Solar Irradiation Produces Fluorescent and Biodegradable Nanoplastics.

Nanoplastics (NPs) have raised global concern owing to their potential health effects. Herein, after simulated and natural solar irradiation, polyethylene, polypropylene, polystyrene, and poly(vinyl chloride) nanoplastics (PVC NPs) were observed to exhibit enhanced fluorescence, particularly PVC NPs. Furthermore, the role of photoaged NPs as a potential fluorescence indicator was evaluated by exposing a model aquatic organism Daphnia magna to these NPs. Our results revealed that photoaged NPs exhibited strong fluorescence owing to the generation of conjugated π bonds, which can achieve π-π* electron transition with low energy consumption. Photogenerated fluorescence also enabled the photoaged NPs to act as efficient fluorescent tracers, which can help track NP migration in various organisms. The results of two-photon laser confocal scanning microscopy revealed that the photoaged NPs could translocate across biological barriers and accumulate in extraintestinal tissues in addition to being ingested and excreted. Moreover, compared with pristine NPs, the photoaged NPs underwent biodegradation more easily, probably because of increased hydrophilicity due to photogenerated oxygen-containing moieties. Therefore, in addition to producing fluorescent NPs without the attachment of external fluorescent dyes, the natural photoaging process can promote the migration and degradation of photoaged NPs in food chains.

Amine-Functionalized A-Center Sphalerite for Selective and Efficient Destruction of Perfluorooctanoic Acid.

Perfluorochemicals (PFCs), especially perfluorooctanoic acid (PFOA), have contaminated the ground and surface waters throughout the world. Efficient removal of PFCs from contaminated waters has been a major challenge. This study developed a novel UV-based reaction system to achieve fast PFOA adsorption and decomposition without addition of sacrificial chemicals by using synthetic photocatalyst sphalerite (ZnS-[N]) with sufficient surface amination and defects. The obtained ZnS-[N] has the capability of both reduction and oxidation due to the suitable band gap and photo-generated hole-trapping properties created by surface defects. The cooperated organic amine functional groups on the surface of ZnS-[N] play a crucial role in the selective adsorption of PFOA, which guarantee the efficient destruction of PFOA subsequently, and 1 µg L-1 PFOA could be degraded to <70 ng L-1 after 3 h in the presence of 0.75 g L-1 ZnS-[N] under 500 W UV irradiation. In this process, the photogenerated electrons (reduction) and holes (oxidation) on the ZnS-[N] surface work in a synergistic manner to achieve complete defluorination of PFOA. This study not only provides promising green technology for PFC-pollution remediation but also highlights the significance of developing a target system capable of both reduction and oxidation for PFC degradation.