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Alcohol-induced dose dumping (AIDD) remains a serious challenge in the controlled delivery of high potency drugs, such as opioids, which requires extensive investigation and innovative solutions. Current technologies rely on ethanol-insoluble excipients, such as guar gum and sodium alginate, to counteract the increased solubility of hydrophobic polymeric excipients in ethanol. However, these excipients pose several shortcomings, such as high viscosity of coating dispersion, high solution temperature, rapid gelation, and heterogeneity of resulted film. In this work, we explored the application of a cross-linked terpolymer nanoparticle (TPN) as an alcohol-resistant excipient in a water-insoluble controlled release film of ethylcellulose (EC) for the prevention of AIDD. Herein, we optimized the composition of TPN using a central composite design (CCD) to minimize swelling and weight loss of TPN-EC film in the presence of 20% ethanol. The optimized TPN showed a negligible effect on the viscosity of the coating dispersion, while guar gum increased the viscosity by 76-fold. Permeability studies in a pH 1.2 media containing 0% or 40% v/v ethanol revealed that cationic drugs (propranolol HCl, diltiazem HCl, and naloxone HCl (an opioid receptor-binding model drug)) exhibited significantly lower permeability ratios ( P 40% / P 0% ) than un-ionized drugs (theophylline and salicylic acid). FTIR analysis indicated an increase in ionic hydrogen bonding between TPN and the cationic drug in the presence of ethanol. These results suggest that drug-polymer-solvent interactions play an important role in alcohol-independent drug permeability through the TPN-EC film. By leveraging the drug permeability altering capability of the TPN-EC system, the release of cationic drugs in hydroethanolic media appeared to be suppressed, suggesting a promising new mechanism of alcohol resistance.

Developing antifouling biosensors capable of performing robustly in complex human body fluids is crucial for biomarker diagnosis and health monitoring. Herein, an antifouling and highly sensitive and stable biosensor was constructed through the self-assembly of the designed conjugates composed of a multifunctional peptide (MP) and PEGylated distearoylphosphatidylethanolamine (DSPE-PEG). The self-assembly capability of the DSPE-PEG-MP was demonstrated clearly through coarse-grained molecular dynamics simulation and transmission electron microscopy, and it can be effectively self-assembled onto the electrode surface modified with gold nanoparticles. The MP was designed to be antifouling and contained a peptide sequence that can specifically bind the target protein Annexin A1 (ANXA1), and the D-type amino acid composition of MP can enhance its resistance to enzymatic hydrolysis. The unique design of MP, in conjugation with the self-assembly capability of the PEGylated phospholipid DSPE-PEG, enabled the biosensor to exhibit excellent antifouling capability and stability in various complex human body fluids. The biosensor was capable of sensitively and selectively quantifying ANXA1 and achieved a limit of detection down to 0.12 pg mL -1 . More importantly, the biosensor demonstrated satisfactory accuracy for ANXA1 detection in clinical serum samples, as verified by the enzyme linked immunosorbent assay (ELISA) kits. It is expected that various antifouling biosensors suitable for application in complex biological environments can be constructed by utilizing the strategy of designing similar DSPE-PEG-MP conjugates.

Transition metal oxide semiconductors have great potential for use in H 2 sensors, but in recent years, the strange phenomena about gas-sensitive performance associated with their special properties have been more widely discussed in research. In some cases, the resistance of transition metal oxide gas sensors will emerge with some changes contrary to their intrinsic semiconductor characteristics, especially in gas sensor research of WO 3 . Based on the hydrothermal synthesis of WO 3 , our work focuses on the abnormal change of tungsten oxide resistance to different gases at low temperature (80-200 °C) and high temperature (above 200 °C). Through in situ FT-IR and in situ XPS, combined with density functional theory calculations, a new reasonable explanation of WO 3 is proposed for the abnormal resistance change caused by temperature and the strange response due to gas concentration. The occurrence of these findings can be attributed to the synergistic effect resulting from the presence of two contributing factors. One of them is attributed to the alteration in the surface valence state of WO 3 induced by gas, resulting in the reduction of W 6+ . The other one is due to the reaction between gas and adsorbed oxygen on the surface of WO 3 . This work presents a novel and rational concept for addressing the reaction mechanism between gas and transition metal oxide semiconductors, thereby paving the way for the development of highly efficient gas sensors based on transition metal oxide semiconductors.

Lysine lactylation has recently been discovered and demonstrated to be an essential player in immunity, cancer and neurodegenerative diseases. Genetic code expansion (GCE) technique is powerful in uncovering lactylation functions, since it allows site-specific incorporation of lactyllysine (Klac) into proteins of interest (POIs) in living cells. However, the inefficient uptake of Klac into cells, due to its high hydrophilicity, results in limited expression of lactylated POIs. To address this challenge, here we designed esterified Klac derivatives, exemplified by ethylated Klac (KlacOEt), to enhance Klac's lipophilicity and improve its cellular uptake. The expression level of site-specifically lactylated POIs was doubled using KlacOEt in both Escherichia coli and HEK293T cells. Immunoprecipitation mass spectrometry analysis verified the significantly increased yield of the precisely lactylated fructose-bisphosphate aldolase A using KlacOEt. Furthermore, in conjunction with the Target Responsive Accessibility Profiling approach, we found that lactylation at ALDOA-K147 altered the protein's conformation, which may explain the lactylation-induced reduction in enzyme activity. Together, we demonstrate that, through enhancing the yield of lactylated proteins with Klac esters via GCE, we are able to site-specifically reveal the effects of lactylation on POIs' interactions, conformations and activities using a suite of functional proteomics and biochemical tools.

The dormancy of cancer stem cells is a major factor leading to drug resistance and a high rate of late recurrence and mortality in estrogen receptor-positive (ER+) breast cancer. Previously, we demonstrated that a stiffer matrix induces tumor cell dormancy and drug resistance, whereas a softened matrix promotes tumor cells to exhibit a stem cell state with high proliferation and migration. In this study, we present a comprehensive analysis of the proteome and phosphoproteome in response to gradient changes in matrix stiffness, elucidating the mechanisms behind cell dormancy-induced drug resistance. Overall, we found that antiapoptotic and membrane transport processes may be involved in the mechanical force-induced dormancy resistance of ER+ breast cancer cells. Our research provides new insights from a holistic proteomic and phosphoproteomic perspective, underscoring the significant role of mechanical forces stemming from the stiffness of the surrounding extracellular matrix as a critical regulatory factor in the tumor microenvironment.

Preeclampsia, a significant cause of maternal and perinatal morbidity and mortality, remains poorly understood, in terms of its pathogenesis. This study aims to uncover novel and effective biomarkers for preeclampsia by conducting a comparative analysis of differential proteins in placentas from early onset preeclampsia (EOPE) and normal pregnancies. Utilizing tandem mass tag (TMT)-based quantitative proteomics, we identified differentially expressed proteins in placental tissues from 15 EOPE patients and 15 normal pregnant women. These proteins were subsequently validated by using parallel reaction monitoring (PRM). Our analysis revealed a total of 59 differentially expressed proteins, with 25 up-regulated and 34 down-regulated proteins in EOPE placental tissues compared to those from normal pregnancies. Validation through PRM confirmed the differential expression of 6 proteins. Our findings suggest these 6 proteins could play crucial roles in the pathogenesis of EOPE, highlighting the potential involvement of the estrogen signaling pathway and dilated cardiomyopathy (DCM) pathway in the development of preeclampsia. The data were deposited with the ProteomeXchange Consortium via the iProX partner repository with the identifier PXD055025.

Hepatocellular carcinoma (HCC) is a highly lethal cancer, and proteomic studies have shown increased protein diversity and abundance in HCC tissues, whereas the role of protein translation has not been extensively explored in HCC. Our research focused on key molecules in the translation process to identify a potential contributor in HCC. We discovered that EIF4G2, a crucial translation initiation factor, is significantly upregulated in HCC tissues and associated with poor prognosis. This study uniquely highlights the impact of EIF4G2 deletion, which suppresses tumor growth and metastasis both in vitro and in vivo . Furthermore, polysome analysis and nascent protein synthesis assays revealed EIF4G2's role in regulating protein translation, specifically identifying PLEKHA1 as a key translational product. This represents a novel mechanistic insight into HCC malignancy. RNA immunoprecipitation (RIP) and Dual-luciferase reporter assays further revealed that EIF4G2 facilitates PLEKHA1 translation via an IRES-dependent manner. Importantly, the synergistic effects of EIF4G2 depletion and PLEKHA1 reduction in inhibiting cell migration and invasion underscore the therapeutic potential of targeting this axis. This study not only advances our understanding of translational regulation in HCC but also identifies the EIF4G2-PLEKHA1 axis as a promising therapeutic target, offering new avenues for intervention in HCC treatment.

The limited expression of cellobiose 2-epimerase poses a significant constraint on the industrial enzymatic production of lactulose. Extensive modifications to the expression cassette offer a means to enhance the yield of recombinant proteins. In this study, an integrated strategy, combining individual and collaborative approaches, is proposed to fine-tune each stage of the Cs CE overexpression program. This strategy involves the multidimensional integration of standardized genetic elements at various levels, including transcription, translation, folding, and three-dimensional structure. The volumetric activity of the final recombinant strain was markedly increased by 12-fold compared to the wild-type strain, reaching 2260.62 U/L. The protein expression in the newly developed high-yield recombinant strain exhibited a significant enhancement, with a higher proportion of soluble protein compared to that of inclusion bodies. Our findings offer insights into the multifaceted synergistic regulation of protein expression processes, holding promising implications for the production of heterologous recombinant proteins.

The impact of ions on water has long been a subject of great interest, as it is closely tied to the hydration structure, dynamics, and properties of electrolyte solutions. Over centuries of investigation, the influence of ions on water's structure remains highly debated. Prevailing techniques, such as neutron and X-ray scattering, primarily focus on the microscopic structure of salt solutions at very high concentrations, mostly above 1 mol/L. In this study, we measured the structure of aqueous potassium iodide (KI) and potassium chloride (KCl) solutions using MeV liquid electron scattering (MeV-LES) across a concentration range of 0.10 to 0.75 mol/L. The obtained results provide detailed insights into the variations in ion-oxygen and oxygen-oxygen correlations as a function of concentration. The observed structural differences between KI and KCl solutions are in line with the structure maker/breaker theory, which suggests that iodide ions exert a more pronounced effect than chloride ions on disrupting the water shell. This work demonstrates the potency of MeV-LES for investigating the atomic structure in liquids, augmenting the modern analytical toolbox.

Oxygen vacancies (V O ) in metal oxide semiconductors play an important role in improving gas-sensing performance of chemiresistive gas sensors. Nonetheless, there is still a lack of clear understanding of the inherent mechanism of the influence of oxygen vacancies on gas sensing due to generally focusing on the concentration of V O . Herein, oxygen vacancies were rationally modulated in WO 3 nanoflower structures via an annealing process, resulting in a transformation of V O from neutral (V O 0 ) to a doubly ionized (V O 2+ ) state. Density functional theory (DFT) calculations indicate that V O 2+ is significantly more efficient than V O 0 for NO 2 detection in competition with atmospheric O 2 . Benefiting from a high concentration of V O 2+ , the WO 3 -450 (WO 3 annealed at 450 °C) sensor exhibits excellent sensing performance with an ultrahigh sensitivity (3674.1 to 5 ppm NO 2 ), superior selectivity, and long-term stability (one month). Furthermore, the sensor with the wide range of concentration detection not only can detect NO 2 gas with parts per million (ppm) but also can detect NO 2 with parts per billion (ppb) level concentration, with a high sensibility reaching 2.8 to 25 ppb NO 2 and over 100 to 100 ppb NO 2 . This study elucidates the oxygen vacancy mediated sensing mechanism toward NO 2 and provides an effective strategy for the rational design of gas sensors with high sensing performance.

The real world applications of conventional antifouling biosensors based on gold-thiol (Au-S) interfaces are hampered by the progressive competitive displacement of key functionality by ubiquitous biothiols. To overcome this limitation, we introduce here novel platinum-selenium (Pt-Se) interfaces. Thiol displacement tests, antifouling analyses, and density functional theory calculations confirm markedly improved interfacial stability. This was then leveraged through the application of a seleno-multifunctional peptide platform, tailored to the detection of murine double minute 2, in biological samples. A derived amperometric sensing platform exhibited a notably lower detection limit and more accurate target quantification than that supported by analogous Au-S and Pt-S interfaces. We believe that this work broadens the scope of electrochemical sensor construction and holds significant promise for the development of high-fidelity impactful bioassay platforms.

S -Adenosylmethionine (SAM) is a crucial metabolic intermediate playing irreplaceable roles in organismal activities. However, the synthesis of SAM by methionine adenosyltransferase (MAT) is hindered by low conversion due to severe product inhibition. Herein structure-guided semirational engineering was conducted on MAT from Escherichia coli ( Ec MAT) to mitigate the product inhibitory effect. Compared with the wild-type Ec MAT, the best variant E56Q/Q105R exhibited an 8.13-fold increase in half maximal inhibitory concentration and a 4.46-fold increase in conversion (150 mM ATP and l-methionine), leading to a SAM titer of 47.02 g/L. Another variant, E56N/Q105R, showed superior thermostability with an impressive 85.30-fold increase in half-life (50 °C) value. Furthermore, molecular dynamics (MD) simulation results demonstrate that the alleviation in product inhibitory effect could be attributed to facilitated product release. This study offers molecular insights into the mitigated product inhibition, and provides valuable guidance for engineering MAT toward enhanced catalytic performance.

Silicone rubber has broad applications in the field of industrial engineering due to its stable physical and chemical properties. However, the superhydrophobic properties, of silicone rubber, especially large deformation superhydrophobic properties, were not satisfactory for many harsh application environments and complex engineering structures. Here, we report the preparation of superhydrophobic tensile designable silicone rubber composites by a mixed deposition process that included powder deposition and smoke deposition. The infrared test showed that the deposited powder from silicone rubber combustion was mainly composed of SiO 2 and short chain siloxane. The mixed deposited surface with a rich micro-nanostructure, which was the key to the formation of superhydrophobic properties. The water contact angle (WCA) and sliding angle (SA) of coating surface could reach 157.6° and 5° ± 1°, respectively, and the tensile designability of superhydrophobic surface is closely related to the prestretched process. In addition, bounce tests, high temperature tests, and solvent resistance tests showed the application potential of modified silicone rubber composites in the field of engineering.

Rechargeable aqueous zinc-ion batteries (AZIBs) have developed into one of the most attractive materials for large-scale energy storage owing to their advantages such as high energy density, low cost, and environmental friendliness. Nevertheless, the sluggish diffusion kinetics and inherent impoverished conductivity affect their practical application. Herein, the β-MnO 2 composited with carbon nanotubes (CNT@M) is prepared through a simple hydrothermal approach as a high-performance cathode for AZIBs. The CNT@M electrode exhibits excellent cycling stability, in which the maximum specific discharge capacity is 259 mA h g -1 at 3 A g -1 , and there is still 220 mA h g -1 after 2000 cycles. The specific capacity is obviously better than that of β-MnO 2 (32 mA h g -1 after 2000 cycles). The outstanding electrochemical performance of the battery is inseparable from the structural framework of CNT and inherent high conductivity. Furthermore, CNT@M can form a complex conductive network based on CNTs to provide excellent ion diffusion and charge transfer. Therefore, the active material can maintain a long-term cycle and achieve stable capacity retention. This research provides a reasonable solution for the reliable conception of Mn-based electrodes and indicates its potential application in high-performance AZIB cathode materials.

Overcoming the influence of interfering substances in the environment and achieving superior sensing performance are significant challenges in biomarker detection within complex matrices. Herein, an integrated electrochemical sensing platform for sensitive detection of biomarkers in complex biofluids was developed based on a newly designed PEGylated multifunctional peptide (PEG-MPEP). The designed PEG-MPEP contains a poly(serine) sequence (-ssssss-) as the antifouling part and recognition peptide sequence (-avwgrwh) specific for the target human immunoglobulin G (IgG). To improve the peptide stability to protease hydrolysis, d-amino acids were adopted to synthesize the whole peptide. Additionally, the PEGylation can further enhance the stability of the peptide, and the PEG itself was also antifouling, ensuring superstrong antifouling capability of the PEG-MPEP. The designed PEG-MPEP-based biosensor possessed a high sensitivity for the detection of IgG in the range of 1.0 pg mL -1 to 1.0 μg mL -1 , with a low limit of detection (0.41 pg mL -1 ), and it was capable of assaying targets accurately in real serum samples. Compared with conventional peptide-modified biosensors, the PEG-MPEP-modified biosensor exhibited superior antifouling and antihydrolysis properties in complex biofluid, showcasing promising potential for practical assay applications.

Zeolites are important classes of crystalline materials and possess well-defined channels and cages with molecular dimensions. They have been extensively employed as heterogeneous catalysts and gas adsorbents due to their relatively large specific surface areas, high pore volumes, compositional flexibility, definite acidity, and hydrothermal stability. The zeolite synthesis normally undergoes high-temperature hydrothermal treatments with a relatively long crystallization time, which exhibits low synthesis efficiency and high energy consumption. Various strategies, e.g ., modulation of the synthesis gel compositions, employment of special silica/aluminum sources, addition of seeds, fluoride, hydroxyl (·OH) free radical initiators, and organic additives, regulation of the crystallization conditions, development of new approaches, etc., have been developed to overcome these obstacles. And, these achievements make prominent contributions to the topic of acceleration of the zeolite crystallization and promote the fundamental understanding of the zeolite formation mechanism. However, there is a lack of the comprehensive summary and analysis on them. Herein, we provide an overview of the recent achievements, highlight the significant progress in the past decades on the developments of novel and remarkable strategies to accelerate the crystallization of zeolites, and basically divide them into three main types, i.e., chemical methods, physical methods, and the derived new approaches. The principles/acceleration mechanisms, effectiveness, versatility, and degree of reality for the corresponding approaches are thoroughly discussed and summarized. Finally, the rational design of the prospective strategies for the fast synthesis of zeolites is commented on and envisioned. The information gathered here is expected to provide solid guidance for developing a more effective route to improve the zeolite crystallization and obtain the functional zeolite-based materials with more shortened durations and lowered cost and further promote their applications.

LIM domain binding 3 ( LDB3 ) serves as a striated muscle-specific Z-band alternatively spliced protein that plays an important role in mammalian skeletal muscle development, but its regulatory role and molecular mechanism in avian muscle development are still unclear. In this study, we reanalyzed RNA sequencing data sets of 1415 samples from 21 chicken tissues published in the NCBI GEO database. First, three variants ( LDB3 -X, LDB3 -XN1, and LDB3 -XN2) generated by alternative splicing of the LDB3 gene were identified in chicken skeletal muscle, among which LDB3 -XN1 and LDB3 -XN2 are novel variants. LDB3 -X and LDB3 -XN1 are derived from exon skipping in chicken skeletal muscle at the E18-D7 stage and share three LIM domains, but LDB3 -XN2 lacks a LIM domain. Our results preliminarily suggest that the formation of three variants of LDB3 is regulated by RBM20 . The three splice isomers have divergent functions in skeletal muscle according to in vitro and in vivo assays. Finally, we identified the mechanism by which different variants play different roles through interactions with IGF2BP1 and MYHC , which promote the proliferation and differentiation of chicken myoblasts, in turn regulating chicken myogenesis. In conclusion, this study revealed the divergent roles of three LDB3 variants in chicken myogenesis and muscle remodeling and demonstrated their regulatory mechanism through protein-protein interactions.

Efficient and economical separation of C 2 H 6 /C 2 H 4 is an imperative and extremely challenging process in the petrochemical industry. The C 2 H 6 -selective adsorbents with high working capacity and high selectivity are highly desirable from a practical application standpoint. In this study, we constructed a database of fluorinated ionic liquid@covalent organic frameworks (FIL@COFs) and screened out the high-performing FIL@COFs for C 2 H 6 -selective separation. Utilizing the optimal machine learning (ML) algorithm (XGBoost) and hyperparameters, we further revealed the key factors influencing the separation performance. The multiscale simulation not only validated the prediction accuracy of ML but also demonstrated that adjusting the largest cavity diameter of COFs with FILs could yield FIL@COFs with high performance for C 2 H 6 -selective separation. Our work provides essential guidance for designing new FIL@COF adsorbents for value-added gas purification.

The renewable energy industry demands rechargeable batteries that can be manufactured at low cost using abundant resources while offering high energy density, good safety, wide operating temperature windows, and long lifespans. Utilizing fluorine chemistry to redesign battery configurations/components is considered a critical strategy to fulfill these requirements due to the natural abundance, robust bond strength, and extraordinary electronegativity of fluorine and the high free energy of fluoride formation, which enables the fluorinated components with cost effectiveness, nonflammability, and intrinsic stability. In particular, fluorinated materials and electrode|electrolyte interphases have been demonstrated to significantly affect reaction reversibility/kinetics, safety, and temperature tolerance of rechargeable batteries. However, the underlining principles governing material design and the mechanistic insights of interphases at the atomic level have been largely overlooked. This review covers a wide range of topics from the exploration of fluorine-containing electrodes, fluorinated electrolyte constituents, and other fluorinated battery components for metal-ion shuttle batteries to constructing fluoride-ion batteries, dual-ion batteries, and other new chemistries. In doing so, this review aims to provide a comprehensive understanding of the structure-property interactions, the features of fluorinated interphases, and cutting-edge techniques for elucidating the role of fluorine chemistry in rechargeable batteries. Further, we present current challenges and promising strategies for employing fluorine chemistry, aiming to advance the electrochemical performance, wide temperature operation, and safety attributes of rechargeable batteries.

Using high-dielectric inorganic ceramics as fillers can effectively increase the dielectric constant of polymer-based composites. However, a high percentage of fillers will inevitably lead to a decrease in the mechanical toughness of the composite materials. By introducing high aspect ratio copper calcium titanate (CaCu 3 Ti 4 O 12 ) nanowires (CCTO NWs) and graphene as fillers, the ternary poly(vinylidene fluoride) (PVDF)-based composites (CCTO NWs-graphene)/PVDF with a significant one-dimensional orientation structure were prepared by hot stretching. CCTO NWs and graphene are arranged in a directional manner to form a large number of microcapacitor structures, which significantly improves the dielectric constant of the composites. When the ratio of CCTO NWs and graphene is 0.2 and 0.02, the oriented composites have the highest dielectric constant, which is 19.3% higher than the random composites, respectively. Numerical simulations reveal that the introduction of graphene and the construction of the one-dimensional oriented microstructure have a positive effect on improving the dielectric properties of the composites. This study provides a strategy to improve the dielectric properties of composite materials by structural design without changing the filler content, which has broad application prospects in the field of electronic devices., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Detoxification of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) with high efficiency and dynamic performance is challenging for a polymeric catalyst. Herein, a series of conjugated microporous polyanilines (CMPAs), capable of efficiently catalytically reducing 4-NP, were synthesized based on the Buchwald-Hartwig cross-coupling reaction mechanism. By adjusting the types of linkers and the molar ratios of linker to core, CMPAs with different Brunauer-Emmett-Teller (BET) specific surface areas and reduction degrees were obtained and used as the catalysts in reducing 4-NP. The ultrahigh catalytic reduction efficiency ( K = 141.32 s -1 g -1 , k app = 0.00353 s -1 ) was achieved when using CMPA-3-0.7 as the catalyst (prepared with 4,4'-diaminodiphenylamine as the linker and a 0.7:1 molar ratio of linker to core). The catalytic reduction performance exhibited a strong correlation with the reduction degree and BET specific surface area of CMPAs. Furthermore, they also exhibit excellent cycling stability and dynamic performance. The coexistence of a microporous structure and high BET specific surface area endowed CMPAs with an increased number of catalytic active centers. The reversible redox transformation of CMPAs in the presence of NaBH 4 and air enabled self-healing (the oxidation units in CMPAs were reduced to reduction units by NaBH 4 , and the newly generated reduction unit in CMPAs was subsequently oxidized to its original state by the O 2 in the air), leading to the reduction reaction of 4-NP proceeded continuously and stably. The aforementioned factors resulted in the high efficiency of CMPAs for reducing 4-NP to 4-AP, enhancing the practical application prospects of CMPAs in the detoxification of 4-NP wastewater., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The arylazopyrazole 3pzH as a novel photoswitch exhibits quantitative switching and high thermal stability. In this work, combined electronic structure calculations and ab initio multiple spawning (AIMS) dynamic simulations were performed to systemically investigate the cis ↔ trans photoisomerization mechanism and the chiral preference after photoexcitation of 3pzH to the first excited singlet state (S 1 ). Unlike most of the azoheteroarene photoswitches reported previously, many twisted and T-shaped cis isomers were found to be stable for 3pzH in the S 0 state, owing to the moderate interaction between the hydrogen atom and π electrons of the aromatic ring. Two twisted cis isomers with different chirality (( M )-Z 1 and ( P )-Z 1 ), the most stable T-shaped cis isomer (( T )-Z 2 ), and the most stable planar trans isomer (E 2 ) were selected as the initial structures to carry out the AIMS nonadiabatic dynamic simulations. Following excitation to the S 1 state, all of the cis isomers decayed to conical intersection (CI) regions via the same bicycle pedal mechanism, while the evolution of the trans isomers to their CI regions was achieved via rotation around the N═N bond. More importantly, chiral preferences were found for the twisted cis isomers in the S 1 state through the AIMS dynamic simulations due to the steric effect and static electronic repulsion. Notably, chirality was also observed in S 1 isomerization starting from the planar E 2 isomer because of the dynamic effect. After the nonadiabatic transition to the S 0 state, the bicycle pedal mechanism was found to play a crucial role in cis ↔ trans photoisomerization. The simulated photoisomerization productivities were generally consistent with past experimental observations. Our calculations not only uncover the underlying reason for the excellent photoswitching properties of 3pzH but also enrich the knowledge of photoisomerization for azoheteroarene photoswitches, which will surely benefit their rational design.

Fluorescence analysis is an increasingly important contributor to the early diagnosis of kidney diseases. To achieve precise visualization of the kidneys and early diagnosis of related diseases, an asymmetric pyrrolopyrrolidone (DPP) dye platform with C-aromatic substituents and N-lipophilic/hydrophilic modification was constructed. Based on these, we developed the renal-clearable, water-soluble, and kidney injury biomarker leucine aminopeptidase (LAP) activated ratiometric fluorescent probe DPP-S-L . In the mouse model of cisplatin-induced acute kidney injury and during the development of type 2 diabetes to diabetic kidney disease, we visualized for the first time the upregulation of LAP in the kidney and urine by dual-channel ratiometric fluorescence signal and diagnosed the kidney injury earlier and more sensitively than blood/urine enzyme detection and tissue analysis. This study showcases an excellent asymmetric DPP dye platform and renal-clearable ratiometric fluorescent probe design strategy that is extended to determination and visualization of other biomarkers for early disease diagnosis.

N 2 O is a common byproduct in the selective catalytic oxidation of ammonia, and its generation often needs to be inhibited due to its strong greenhouse effect. In this paper, using Ag/ZSO-Y as a model catalyst, the N 2 O selectivity was reduced by 30% through modulation of the electron metal-support interaction. The results demonstrate that the work function of the support can be regulated by the content of the doping element. As the Zr content increases in SnO 2 , the work function of the support decreases. Moreover, there is a positive correlation between the charge transfer amount and the work function of the support. A series of in situ DRIFTS and density functional theory calculations revealed that the -NO and -N reactions are the primary pathways for N 2 O formation. By adjustment of the work function of the support through varying the Zr doping level, the electronic structure of Ag NPs was further tuned, resulting in an increased reaction energy barrier for -NO and -N reactions, effectively suppressing N 2 O formation.

Electrochemical biosensing devices face challenges of severe nonspecific adsorption in complex biological matrices for the detection of biomarkers, and thus, there is a significant need for sensitive and antifouling biosensors. Herein, a sensitive electrochemical biosensor with antifouling and antiprotease hydrolysis ability was constructed for the detection of human epidermal growth factor receptor 2 (HER2) by integrating multifunctional branched peptides with distearoylphosphatidylethanolamine-poly(ethylene glycol) (DSPE-PEG) self-assembled bilayer. The peptide was designed to possess antifouling, antiprotease hydrolysis, and HER2 recognizing capabilities. Molecular dynamics simulations demonstrated that the DSPE was able to effectively self-assemble into a bilayer, and the water contact angle and electrochemical experiments verified that the combination of peptide with the DSPE-PEG bilayer was conducive to enhancing the hydrophilicity and antifouling performance of the modified surface. The constructed HER2 biosensor exhibited excellent antifouling and antiprotease hydrolysis capabilities, and it possessed a linear range of 1.0 pg mL -1 to 1.0 μg mL -1 , and a limit of detection of 0.24 pg mL -1 . In addition, the biosensor was able to detect HER2 in real human serum samples without significant biofouling, and the assaying results were highly consistent with those measured by the enzyme-linked immunosorbent assay (ELISA), indicating the promising potential of the antifouling biosensor for clinical diagnosis.

Developing a generalized strategy for the nonfouling detection of biomarkers in diverse biological fluids presents a significant challenge. Herein, a polyhydroxyproline helical peptide (PHHP) was designed and adopted to fabricate electrochemical microsensors capable of detecting targets in various biological media. The PHHP possessed unique properties such as strong hydrophilicity, rigid structure, and lack of ionizable side-chain groups. Compared with common zwitterionic peptides (ZIPs), the PHHP exhibited similar antifouling capability but exceptional stability, allowing its antifouling performance to be unaffected by environmental alteration. The PHHP can prevent biofouling even in fluctuating pH conditions, high ionic strength environments, and the presence of high-valence ions and resist the protease hydrolysis. The PHHP-modified carbon fiber microelectrode was further immobilized with an aptamer to construct an antifouling microsensor for cortisol detection across diverse biofluids, and the microsensor exhibited acceptable accuracy and higher sensitivity than the ELISA method. In addition, different biological samples of mice were collected in situ using a microsensing device, and cortisol levels were analyzed in each specifically tailored region. This nonfouling sensing strategy based on PHHP allows a comprehensive assessment of biomarkers in both spatial and temporal dimensions in diverse biological environments, holding promising potential for early disease diagnosis and real-time health monitoring.

Herein, a pH-responsive dual cross-linked hydrogel for controlled drug release is presented. The hydrogel was constructed with reversible borate ester bonds and crystalline poly(vinyl alcohol). By changing the environmental pH, its physicochemical characteristics, including rheological properties, mechanical properties, microstructural features, and the biocompatibility of the gels, were evaluated. The gels at tumor acidic conditions exhibited swelling and lower compressive strength and modulus than those in a physiological environment, which was attributed to the pH-responsive borate ester bonds and the protonation of amine groups on the PEI polyelectrolyte. Importantly, the drug-encapsulated biocompatible hydrogel showed sustained and increased release under an acidic environment, and it followed the Fickian diffusion mechanism. Therefore, it exemplifies that borate ester bond-based pH-responsive biomaterials have high promise in biomedical research, especially for drug delivery.

A complex regional air pollution problem dominated by particulate matter (PM) and ozone (O 3 ) needs drastic attention since the levels of O 3 and PM are not decreasing in many parts of the world. Limited evidence is currently available regarding the association between co-exposure to PM and O 3 and mortality. A multicounty time-series study was used to investigate the associations of short-term exposure to PM 1 , PM 2.5 , PM 10 , and O 3 with daily mortality from different causes, which was based on data obtained from the Mortality Surveillance System managed by the Jiangsu Province Center for Disease Control and Prevention of China and analyzed via overdispersed generalized additive models with random-effects meta-analysis. We investigated the interactions of PM and O 3 on daily mortality and calculated the mortality fractions attributable to PM and O 3 . Our results showed that PM 1 is more strongly associated with daily mortality than PM 2.5 , PM 10 , and O 3 , and percent increases in daily all-cause nonaccidental, cardiovascular, and respiratory mortality were 1.37% (95% confidence interval (CI), 1.22-1.52%), 1.44% (95% CI, 1.25-1.63%), and 1.63% (95% CI, 1.25-2.01%), respectively, for a 10 μg/m 3 increase in the 2 day average PM 1 concentration. We found multiplicative and additive interactions of short-term co-exposure to PM and O 3 on daily mortality. The risk of mortality was greatest among those with higher levels of exposure to both PM (especially PM 1 ) and O 3 . Moreover, excess total and cardiovascular mortality due to PM 1 exposure is highest in populations with higher O 3 exposure levels. Our results highlight the importance of the collaborative governance of PM and O 3 , providing a scientific foundation for pertinent standards and regulatory interventions.

The selective catalytic oxidation of NH 3 (NH 3 -SCO) to N 2 is an important reaction for the treatment of diesel engine exhaust. Co 3 O 4 has the highest activity among non-noble metals but suffers from N 2 O release. Such N 2 O emissions have recently been regulated due to having a 300× higher greenhouse gas effect than CO 2 . Here, we design CuO-supported Co 3 O 4 as a cascade catalyst for the selective oxidation of NH 3 to N 2 . The NH 3 -SCO reaction on CuO-Co 3 O 4 follows a de-N 2 O pathway. Co 3 O 4 activates gaseous oxygen to form N 2 O. The high redox property of the CuO-Co 3 O 4 interface promotes the breaking of the N-O bond in N 2 O to form N 2 . The addition of CuO-Co 3 O 4 to the Pt-Al 2 O 3 catalyst reduces the full NH 3 conversion temperature by 50 K and improves the N 2 selectivity by 20%. These findings provide a promising strategy for reducing N 2 O emissions and will contribute to the rational design and development of non-noble metal catalysts., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Microporous zeolites that can act as heterogeneous catalysts have continued to attract a great deal of academic and industrial interest, but current progress in their synthesis and application is restricted to single-phase zeolites, severely underestimating the potential of intergrowth frameworks. Compared with single-phase zeolites, intergrowth zeolites possess unique properties, such as different diffusion pathways and molecular confinement, or special crystalline pore environments for binding metal active sites. This review first focuses on the structural features and synthetic details of all the intergrowth zeolites, especially providing some insightful discussion of several potential frameworks. Subsequently, characterization methods for intergrowth zeolites are introduced, and highlighting fundamental features of these crystals. Then, the applications of intergrowth zeolites in several of the most active areas of catalysis are presented, including selective catalytic reduction of NOx by ammonia (NH 3 -SCR), methanol to olefins (MTO), petrochemicals and refining, fine chemicals production, and biomass conversion on Beta, and the relationship between structure and catalytic activity was profiled from the perspective of intergrowth grain boundary structure. Finally, the synthesis, characterization, and catalysis of intergrowth zeolites are summarized in a comprehensive discussion, and a brief outlook on the current challenges and future directions of intergrowth zeolites is indicated.

Ether-based electrolytes are competitive choices to meet the growing requirements for fast-charging and low-temperature lithium-ion batteries (LIBs) due to the low viscosity and low melting point of ether solvents. Unfortunately, the graphite (Gr) electrode is incompatible with commonly used ether solvents due to their irreversible co-intercalation into Gr interlayers. Here, we propose cyclopentyl methyl ether (CPME) as a co-intercalation-free ether solvent, which contains a cyclopentane group with large steric hindrance to obtain weakly solvating power with Li + and a wide liquid-phase temperature range (-140 to +106 °C). A weakly solvating electrolyte (WSE) based on CPME and fluoroethylene carbonate (FEC) cosolvents can simultaneously achieve fast desolvation ability and high ionic conductivity, which also induces a LiF-rich solid electrolyte interphase (SEI) on the Gr anode. Therefore, the Gr/Li half-cell with this WSE can deliver outstanding rate capability, stable cycling performance, and high specific capacity (319 mAh g -1 ) at an ultralow temperature of -60 °C. Furthermore, a practical LiFePO 4 (loading ≈25 mg cm -2 )/Gr (loading ≈12 mg cm -2 ) pouch cell with this WSE also reveals outstanding rate capability and stable long-term cycling performance above 1000 cycles with a high Coulombic efficiency (≈99.9%) and achieves an impressive low-temperature application potential at -60 °C.

The efficient recycling and utilization of plastic waste have become a hot topic of global concern, but conventional mechanical recycling not only deteriorates the performance of recycled plastic but also loses the intrinsic structure and properties of the original product. Herein, an upcycling strategy of a biaxially oriented polypropylene (BOPP) film was proposed by duplicating the lamellar configuration established in nature nacre. Especially the suspension of PP wax was deposited on the surface of the BOPP film by spray-coating, followed by layer-by-layer assembling and hot-pressing at 160 °C above the melting temperature of PP wax but below the initial melting temperature of the BOPP film. In this case, PP wax not only functioned as a binder to enable strong interfacial adhesion between the BOPP films via interfacial diffusion but also acted as a soft phase to insert between the rigid BOPP films, constructing a soft-hard alternatively aligned configuration similar to brick-and-mortar architecture in nature nacre. As a result, the mechanical properties of the lamellar sample markedly outperformed those of the conventional mechanically recycling sample, evidenced by 113 and 1141% increases in tensile strength and impact strength, respectively. This simple and effective method provides a new strategy for efficient upcycling of oriented packaging films, which is important to realize the sustainable recycling of plastic waste., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Typically, the basic method to enhance the dielectric response of polymer-based composites is to fill giant dielectric ceramic fillers, such as BaTiO 3 and CaCu 3 Ti 4 O 12 , into the polymer matrix. Here, by using low-k boron nitride (BN) with well-controlled microstructure and surface, we successfully prepared a high-k polymeric composite, where the improvement in the dielectric constant of the composite even exceeds that of composites containing BaTiO 3 and CaCu 3 Ti 4 O 12 particles at the same weight percent. First, a lamellar boron nitride nanosheet (BNNS) aerogel was prepared by bidirectional freezing and freeze drying, respectively, and then the aerogel was calcined at 1000 °C to obtain the lamellar BNNS skeleton with some hydroxyl groups. Finally, the epoxy resin (EP) was vacuum impregnated into the BNNS skeleton and cured inside to prepare the lamellar-structured BNNSs/EP (LBE) composites. Interestingly, the dielectric constants of LBE with a 10 wt % BNNS content reached 8.5 at 10 3 Hz, which was higher by 2.7 times than that of pure EP. The experimental data and the finite element simulations suggested that the increased dielectric constants of LBE resulted from the combination of two factors, namely, the lamellar microstructure and the hydroxyl groups. The stacking of the BNNS phase into a highly connected lamellar skeleton significantly increased the internal electric field and the polarization intensity, while the introduction of hydroxyl groups on the BNNS surface further improved the polarization of the composite, resulting in a significant increase in the dielectric constant of the LBE. This work provides a new strategy for improving the dielectric constant through the microstructure design of composites.

Volatile organic compounds (VOCs) harm the environment and human health and have been of wide concern and purified efficiently by catalytic oxidation. Spinel oxides, mainly composed of transition metal elements with low price and extensive sources, have been widely investigated as efficient and stable catalysts for VOCs oxidation due to their adjustable element composition, flexible structure, and high thermal/chemical stability. However, it is necessary to dissect the design of the spinel in a targeted way to satisfy the removal of different types of VOCs. This article systematically summarizes the recent advances regarding the application of spinel oxides for VOCs catalytic oxidation. Specifically, the design strategies of spinel oxides were first introduced to clarify their effect on the structure and properties of the catalyst. Then the reaction mechanism and degradation pathway of different kinds of VOCs on the spinel oxides were in detail summarized, and the characteristic requirements of the spinel oxides for various VOCs purification were analyzed. Furthermore, the practice applications were also discussed. Finally, the prospects were proposed to guide the rational design of spinel-based catalysts for VOCs purification and intensify the understanding of reaction mechanisms.

Brown adipose tissues (BATs) have been identified as a promising target of metabolism disorders. [ 18 F]FDG-PET (FDG = fluorodeoxyglucose; PET = positron emission tomography) has been predominantly employed for BAT imaging, but its limitations drive the urgent need for novel functional probes combined with multimodal imaging approaches. It has been reported that polymer dots (Pdots) display rapid BAT imaging without additional cold stimulation. However, the mechanism by which Pdots image BAT remains unclear. Here, we made an intensive study of the imaging mechanism and found that Pdots can bind to triglyceride-rich lipoproteins (TRLs). By virtue of their high affinity to TRLs, Pdots selectively accumulate in capillary endothelial cells (ECs) in interscapular brown adipose tissues (iBATs). Compared to poly(styrene- co -maleic anhydride)cumene terminated (PSMAC)-Pdots with a short half-life and polyethylene glycol (PEG)-Pdots with low lipophilicity, naked-Pdots have good lipophilicity, with a half-life of about 30 min and up to 94% uptake in capillary ECs within 5 min, increasing rapidly after acute cold stimulation. These results suggested that the accumulation changes of Pdots in iBAT can reflect iBAT activity sensitively. Based on this mechanism, we further developed a strategy to detect iBAT activity and quantify the TRL uptake in vivo using multimodal Pdots.

Specific peptide-protein interactions play an important role in biosensing systems based on functional peptides; however, the non-specific interactions with unrelated biomolecules and poor proteolytic stability restrict the clinical application of natural peptides. Here, we leveraged a self-designed multifunctional isopeptide (MISP) to construct an electrochemical biosensing platform for annexin A1 (ANXA1) detection in human blood. The MISP was designed to contain two parts: an antifouling cyclotide cyclo-C(EK) 4 and a d-amino acid-containing carbohydrate-mimetic recognizing peptide IF-7 (D-IF7) connected by the isopeptide bond. We have discussed the properties of the cyclotide and illustrated its unique advantage over the natural linear antifouling peptides by molecular dynamics simulations, and the results were further confirmed by dissipative quartz crystal microbalance (QCM-D). In addition, through electrochemical experiments and fluorescence imaging experiments, we demonstrated that the MISP-based biosensor possessed excellent antifouling ability and proteinase hydrolysis stability. Interestingly, the assaying results of the MISP-biosensor were consistent with those of the commercial ANXA1 kits in a variety of healthy and ANXA1-upregulated clinical blood samples, and, more importantly, for the analysis of blood samples with lower ANXA1 expressions, the sensing capability of the biosensor was greatly superior to that of the kits because of the lower detection limit of the MISP-biosensor. This biosensing platform based on the designed MISP offers enormous potential for achieving accurate biomarker detection with robust operation in complex biological samples.

Mesoporous silica nanoparticles (MSNs) are widely used in the biomedical field because of their unique and excellent properties. However, the potential toxicity of different shaped MSNs via injection has not been fully studied. This study aims to systematically explore the impact of shape and shear stress on the toxicity of MSNs after injection. An in vitro blood flow model was developed to investigate the cytotoxicity and the underlying mechanisms of spherical MSNs (S-MSN) and rodlike MSNs (R-MSN) in human umbilical vein endothelial cells (HUVECs). The results suggested that the interactions between MSNs and HUVECs under the physiological flow conditions were significantly different from that under static conditions. Whether under static or flow conditions, R-MSN showed better cellular uptake and less oxidative damage than S-MSN. The main mechanism of cytotoxicity induced by R-MSN was due to shear stress-dependent mechanical damage of the cell membrane, while the toxicity of S-MSN was attributed to mechanical damage and oxidative damage. The addition of fetal bovine serum (FBS) alleviated the toxicity of S-MSN by reducing cellular uptake and oxidative stress under static and flow conditions. Moreover, the in vivo results showed that both S-MSN and R-MSN caused cardiovascular toxicity in zebrafish and mouse models due to the high shear stress, especially in the heart. S-MSN led to severe oxidative damage at the accumulation site, such as liver, spleen, and lung in mice, while R-MSN did not cause significant oxidative stress. The results of in vitro blood flow and in vivo models indicated that particle shape and shear stress are crucial to the biosafety of MSNs, providing new evidence for the toxicity mechanisms of the injected MSNs.

Strong electron correlation effects are one of the major challenges in modern quantum chemistry. Polynuclear transition metal clusters are peculiar examples of systems featuring such forms of electron correlation. Multireference strategies, often based on but not limited to the concept of complete active space, are adopted to accurately account for strong electron correlation and to resolve their complex electronic structures. However, transition metal clusters already containing four magnetic centers with multiple unpaired electrons make conventional active space based strategies prohibitively expensive, due to their unfavorable scaling with the size of the active space. In this work, forefront techniques, such as density matrix renormalization group (DMRG), full configuration interaction quantum Monte Carlo (FCIQMC), and multiconfiguration pair-density functional theory (MCPDFT), are employed to overcome the computational limitation of conventional multireference approaches and to accurately investigate the magnetic interactions taking place in a [Co(II) 3 Er(III)(OR) 4 ] (chemical formula [Co(II) 3 Er(III)(hmp) 4 (μ 2 -OAc) 2 (OH) 3 (H 2 O)], hmp = 2-(hydroxymethyl)-pyridine) model cubane water oxidation catalyst. Complete active spaces with up to 56 electrons in 56 orbitals have been constructed for the seven energetically lowest different spin states. Relative energies, local spin, and spin-spin correlation values are reported and provide crucial insights on the spin interactions for this model system, pivotal in the rationalization of the catalytic activity of this system in the water-splitting reaction. A ferromagnetic ground state is found with a very small, ∼50 cm -1 , highest-to-lowest spin gap. Moreover, for the energetically lowest states, S = 3-6, the three Co(II) sites exhibit parallel aligned spins, and for the lower states, S = 0-2, two Co(II) sites retain strong parallel spin alignment.

Rapid urbanization drives increased emission of tire wear particles (TWPs) and the contamination of a transformation product derived from tire antioxidant, termed as N -(1,3-dimethylbutyl)- N '-phenyl- p -phenylenediamine-quinone (6PPD-Q), with adverse implications for terrestrial ecosystems and human health. However, whether and how 6PPD-Q could be formed during the aging of TWPs in soils remains poorly understood. Here, we examine the accumulation and formation mechanisms of 6PPD-Q during the aging of TWPs in soils. Our results showed that biodegradation predominated the fate of 6PPD-Q in soils, whereas anaerobic flooded conditions were conducive to the 6PPD-Q formation and thus resulted in a ∼3.8-fold higher accumulation of 6PPD-Q in flooded soils than wet soils after aging of 60 days. The 6PPD-Q formation in flooded soils was enhanced by Fe reduction-coupled 6PPD oxidation in the first 30 days, while the transformation of TWP-harbored environmentally persistent free radicals (EPFRs) to superoxide radicals (O 2 •- ) under anaerobic flooded conditions further dominated the formation of 6PPD-Q in the next 30 days. This study provides significant insight into understanding the aging behavior of TWPs and highlights an urgent need to assess the ecological risk of 6PPD-Q in soils.

Danshensu (DSS), a traditional Chinese medicine, is widely used for the treatment of cardiovascular and cancer diseases. Here, a one-pot multi-enzyme cascade pathway was designed for DSS synthesis from l-DOPA using tyrosine aminotransferase from Escherichia coli ( Ec TyrB) and d-isomer-specific 2-hydroxyacid dehydrogenase from Lactobacillus frumenti ( Lf D2-HDH). Glutamate dehydrogenase from Clostridium difficile ( Cd gluD) was also introduced for a self-sufficient system of α-ketoglutaric acid and NADH. Under optimal conditions (35 °C, pH 7.0, Ec TyrB: Lf D2-HDH: Cd gluD = 3:2:1, glutamate:NAD + = 1:1), 98.3% yield (at 20 mM l-DOPA) and space-time yield of 6.61 g L -1 h -1 (at 40 mM l-DOPA) were achieved. Decreased yields of DSS at elevated l-DOPA concentrations (100 mM) could be attributed to an inhibited Cd gluD activity caused by NH 4 + accumulation. This developed multi-enzyme cascade pathway (including Ec TyrB, Lf D2-HDH, and Cd gluD) provides an efficient and sustainable approach for the production of DSS from l-DOPA.

Droplets impacting superhydrophobic surfaces have been extensively studied due to their compelling scientific insights and important industrial applications. In these cases, the commonly reported impact regime was that of complete rebound. This impact regime strongly depends on the nature of the superhydrophobic surface. Here, we report the dynamics of droplets impacting three hydrophobic slippery surfaces, which have fundamental differences in normal liquid adhesion and lateral static and kinetic liquid friction. For an air cushion-like (super)hydrophobic solid surface (Aerogel) with low adhesion and low static and low kinetic friction, complete rebound can start at a very low Weber ( We ) number (∼1). For slippery liquid-infused porous (SLIP) surfaces with high adhesion and low static and low kinetic friction, complete rebound only occurs at a much higher We number (>5). For a slippery omniphobic covalently attached liquid-like (SOCAL) solid surface, with high adhesion and low static friction similar to SLIPS but higher kinetic friction, complete rebound was not observed, even for a We as high as 200. Furthermore, the droplet ejection volume after impacting the Aerogel surface is 100% across the whole range of We numbers tested compared to other surfaces. In contrast, droplet ejection for SLIPs was only observed consistently when the We was above 5-10. For SOCAL, 100% (or near 100%) ejection volume was not observed even at the highest We number tested here (∼200). This suggests that droplets impacting our (super)hydrophobic Aerogel and SLIPS lose less kinetic energy. These insights into the differences between normal adhesion and lateral friction properties can be used to inform the selection of surface properties to achieve the most desirable droplet impact characteristics to fulfill a wide range of applications, such as deicing, inkjet printing, and microelectronics.

Reverse-mode polymer-stabilized liquid crystal (PSLC) films have wide applications in smart windows for cars as well as buildings and dimming glasses due to their low haze, low energy consumption, and better safety in case of emergency power off. However, PSLC films usually have poor stability of electro-optical properties due to their low polymer content (ca. 5 wt %), and it still remains a challenging task to improve the stability and processability by increasing the polymer content in PSLC as the driving voltage might dramatically increase. In this work, a reverse-mode PSLC film with polymer walls was prepared, which showed excellent stability of electro-optical properties even after 150 000 cycles. The film was prepared through polymerization with a photomask, in which the monomers concentrated on specific areas to form patterned polymer walls. In this way, the polymer content could be increased dramatically and the anchoring effect would not be too strong, thus avoiding a sharp increase in the driving voltage. As a result, the desired reverse-mode film with high stability, relatively low driving voltage, and high contrast ratio was obtained. The effects of monomer compositions, curing temperature, UV light intensity, and the pattern of the photomask on the microstructures, as well as electro-optical performances of the films were carefully studied. This work provides a new idea for the preparation of reverse-mode electrically switchable light-transmittance controllable films with excellent stability and good electro-optical performance, which would broaden their application in smart cars, building windows, and dimming glasses for light management and potential energy saving.

Phytate as a root exudate is rare in plants as it mainly serves as a P storage in the seeds; however, As-hyperaccumulator Pteris vittata effectively secretes phytate and utilizes phytate-P, especially under As exposure. This study investigated the effects of As on its phytate and phytase exudation and the impacts of As and/or phytate on each other's uptake in P. vittata through two hydroponic experiments. Under 10-100 μM arsenate (AsV), the exudation of phytate and phytase by P. vittata was increased by 50-72% to 20.4-23.4 μmol h -1 g -1 and by 28-104% to 18.6-29.5 nmol h -1 plant -1 , but they were undetected in non-hyperaccumulator Pteris ensiformis at 10 μM AsV. Furthermore, compared to 500 μM phytate, the phytate concentration in the growth media was reduced by 69% to 155 μM, whereas the P and As contents in P. vittata fronds and roots were enhanced by 68-134% and 44-81% to 2423-2954 and 82-407 mg kg -1 under 500 μM phytate plus 50 μM AsV. The increased P/As uptake in P. vittata was probably attributed to 3.0-4.5-fold increase in expressions of P transporters PvPht1;3-1;4 . Besides, under As exposure, plant P may be converted to phytate in P. vittata roots, thereby increasing phytate's contents by 84% to 840 mg kg -1 . Overall, our results suggest that As-induced phytate/phytase exudation and phytate-P uptake stimulate its growth and As hyperaccumulation by P. vittata .

Surface oxidation chemistry involves the formation and breaking of metal-oxygen (M-O) bonds. Ideally, the M-O bonding strength determines the rate of oxygen absorption and dissociation. Here, we design reactive bridging O 2- species within the atomic Cu-O-Fe site to accelerate such oxidation chemistry. Using in situ X-ray absorption spectroscopy at the O K-edge and density functional theory calculations, it is found that such bridging O 2- has a lower antibonding orbital energy and thus weaker Cu-O/Fe-O strength. In selective NH 3 oxidation, the weak Cu-O/Fe-O bond enables fast Cu redox for NH 3 conversion and direct NO adsorption via Cu-O-NO to promote N-N coupling toward N 2 . As a result, 99% N 2 selectivity at 100% conversion is achieved at 573 K, exceeding most of the reported results. This result suggests the importance to design, determine, and utilize the unique features of bridging O 2- in catalysis., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Microbially mediated iron redox processes are of great significance in the biogeochemical cycles of elements, which are often coupled with soil organic matter (SOM) in the environment. Although the influences of SOM fractions on individual reduction or oxidation processes have been studied extensively, a comprehensive understanding is still lacking. Here, using ferrihydrite, Shewanella oneidensis MR-1, and operationally defined SOM components including fulvic acid (FA), humic acid (HA), and humin (HM) extracted from black soil and peat, we explored the SOM-mediated microbial iron reduction and hydroxyl radical ( • OH) production processes. The results showed that the addition of SOM inhibited the transformation of ferrihydrite to highly crystalline iron oxides. Although FA and HA increased Fe(II) production over four times on average due to complexation and their high electron exchange capacities, HA inhibited 30-43% of the • OH yield, while FA had no significant influence on it. Superoxide (O 2 •- ) was the predominant intermediate in • OH production in the FA-containing system, while one- and two-electron transfer processes were concurrent in HA- and HM-containing systems. These findings provide deep insights into the multiple mechanisms of SOM in regulating microbially mediated iron redox processes and • OH production.

The severe hazard of chlorinated volatile organic compounds (CVOCs) to human health and the natural environment makes their abatement technology a key topic of global environmental research. Due to the existence of Cl, the byproducts of CVOCs in the catalytic combustion process are complex and toxic, and the possible generation of dioxin becomes a potential risk to the environment. Well-qualified CVOC catalysts should process favorable low-temperature catalytic oxidation ability, excellent selectivity, and good resistance to poisoning, which are governed by the reasonable adjustment of acidity and redox properties. This review overviews the application of different types of multicomponent catalysts, that is, supported noble metal catalysts, transition metal oxide/zeolite catalysts, composite transition metal oxide catalysts, and acid-modified catalysts, for CVOC degradation from the perspective of balance between acidity and redox properties. This review also highlights the synergistic degradation of CVOCs and NO x from the perspective of acidity and redox properties. We expect this work to inspire and guide researchers from both the academic and industrial communities and help pave the way for breakthroughs in fundamental research and industrial applications in this field.

Surface lattice oxygen is crucial to the degradation of volatile organic compounds (VOCs) over transition metal oxides according to the Mars-van Krevelen mechanism. Herein, λ-MnO 2 in situ grown on the surface of CoMn spinel was prepared by acid etching of corresponding spinel catalysts (CoMn-H x -T y ) for VOC oxidation. Experimental and relevant theoretical exploration revealed that acid etching on the CoMn spinel surface could decrease the electron cloud density around the O atom and weaken the adjacent Mn-O bond due to the fracture of the surface Co-O bond, facilitating electron transfer and subsequently the activation of surface lattice oxygen. The obtained CoMn-H1-T1 exhibited an excellent catalytic performance with a 90% acetone conversion at 149 °C, which is 42 °C lower than that of CoMn spinel. Furthermore, the partially maintained spinel structure led to better stability than pure λ-MnO 2 . In situ diffuse reflectance infrared Fourier transform spectroscopy confirmed a possible degradation pathway where adsorptive acetone converted into formate and acetate species and into CO 2 , in which the consumption of acetate was identified as the rate-limiting step. This strategy can improve the catalytic performance of metal oxides by activating surface lattice oxygen, to broaden their application in VOC oxidation.