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Very recently, a new single-element two-dimensional (2D) material borophene was successfully grown on a silver surface under pristine ultrahigh vacuum conditions which attracts tremendous interest. In this paper, the lattice thermal conductivity, phonon lifetimes, thermal expansion and temperature dependent elastic moduli of borophene are systematically studied by using first-principles. Our simulations show that borophene possesses unique thermal properties. Strong phonon–phonon scattering is found in borophene, which results in its unexpectedly low lattice thermal conductivity. Thermal expansion coefficients along both the armchair and zigzag directions of borophene show impressive negative values. More strikingly, the elastic moduli are sizably strengthened as temperature increases, and the negative in-plane Poisson's ratios are found along both the armchair and zigzag directions at around 120 K. The mechanisms of these unique thermal properties are also discussed in this paper. [ABSTRACT FROM AUTHOR]

Two dimensional materials have many outstanding intrinsic advantages that can be utilized to enhance the photocatalytic efficiency of water splitting. Herein, based on ab initio calculations, we reveal that for monolayer and multilayer rhenium disulphide (ReS2), the band gap and band edge positions are an excellent match with the water splitting energy levels. Moreover, the effective masses of the carriers are relatively light, and the optical absorption coefficients are high under visible illumination. Due to the feature of weak interlayer coupling, these properties are independent of the layer thickness. Our results suggest that ReS2 is a stable and efficient photocatalyst with potential applications in the use of solar energy for water splitting. [ABSTRACT FROM AUTHOR]

Epigallocatechin gallate (EGCG) has demonstrated potential effects on obesity-induced precocious puberty, but the underlying mechanisms remain unclear. Female mice were randomly assigned into control (CON), EGCG-treated (EGCG), high-fat diet (HFD), and HFD with EGCG treatment (HFDEGCG) groups. Key measurements included body weight, vaginal opening time, and serum sex hormone levels. The gut microbiota was analyzed through 16S rRNA sequencing, fecal metabolites were assessed via metabolomics, and the hypothalamic transcriptome was examined using RNA sequencing. EGCG mitigated weight gain and delayed vaginal opening in mice with obesity-induced precocious puberty. Additionally, it reduced serum estradiol levels and decreased the number of mature ovarian follicles in the HFDEGCG group compared to the HFD group. EGCG treatment partially reversed HFD-induced dysbiosis by increasing the abundance of beneficial bacteria such as Akkermansia . Metabolomic analysis revealed significant alterations in tryptophan metabolism, while transcriptome analysis identified genes involved in metabolic pathways. Correlation analyses underscored the importance of the gut-brain axis in mediating EGCG's effects. Overall, EGCG prevents obesity-induced precocious puberty by modulating the gut microbiota, altering metabolic pathways, and regulating hypothalamic gene expression.

Fatty acid (FA) metabolism plays an important role in the development of nonalcoholic fatty liver disease (NAFLD). However, data on the relationship between circulating FAs and NAFLD risk are limited. This study aims to assess the associations between specific circulating FAs and severe NAFLD risk among the general population. Overall 116 223 participants without NAFLD and other liver diseases from the UK Biobank were enrolled between 2006 and 2010 and were followed up until the end of 2021. Plasma concentrations of saturated fatty acids (SFAs), monounsaturated fatty acids (MUFAs), and polyunsaturated fatty acids (PUFAs) were analyzed using an NMR-based biomarker profiling platform. Hazard ratios (HRs) and 95% confidence intervals (CIs) of NAFLD risk were estimated using Cox proportional-hazard models adjusted for other potential confounders. During a mean follow-up of 12.3 years, we documented 1394 cases of severe NAFLD. After multivariate adjustment, plasma SFAs and MUFAs were associated with a higher risk of severe NAFLD, whereas plasma n-3 PUFAs, n-6 PUFAs, and linoleic acid (LA) were associated with a lower risk. As compared with the lowest quartile, HRs (95% CIs) of severe NAFLD risk in the highest quartiles were 1.85 (1.45-2.36) for SFAs, 1.74 (1.23-2.44) for MUFAs, 0.79 (0.65-0.97) for n-3 PUFAs, 0.68 (0.48-0.96) for n-6 PUFAs, and 0.73 (0.54-0.99) for LA. The significant relationships were mainly mediated by serum TG for SFAs, HDL-C for MUFAs and n-6 PUFAs, and C-reactive protein for n-3 PUFAs. Plasma SFAs were associated with a more pronounced increase in the risk of severe NAFLD among participants with fewer SFA-associated alleles ( P interaction = 0.032). Dietary recommendations for reducing plasma SFAs and MUFAs while increasing n-3 and n-6 PUFAs may be protective for severe NAFLD, which could be mediated by lipid metabolism and inflammation.

In recent decades, the escalating frequency of environmental risk events, arising from sources such as industrial accidents, chemical spills, or other anthropogenic activities, has intensified threats to the ecological environment. The targeted identification of high-risk areas, formulation of control lists for key risk sources within regions, and the implementation of differentiated management strategies remain significant challenges. This study employed an administrative region environmental risk assessment and gridded environmental risk analysis method to comprehensively evaluate the environmental risks in the city of Kunming, China. The results indicated a fourfold increase in the number of environmental risk sources from 2012 to 2022. The sources were found to be widely distributed across the entire region but exhibited localized clustering. The environmental risk receptors were primarily concentrated around a local lake, in densely populated counties, and near rivers and drinking water sources. Risk hotspot areas within the target region were identified using the gridded environmental risk analysis method. A list of 29 key control areas was proposed, including nine industrial parks and 20 streets. Measures were proposed for handling unexpected incidents. The findings provide data useful for policy formulation and environmental management in similar regions of mountainous cities.

Contrary to previous results, a unique anti-correlation effect of the alkyl chain size on the photovoltaic performance of acceptors was observed. For a centrally-extended acceptor, replacing linear alkyl chains ( n -undecyl for CH-BBQ) on the thienothiophene unit with branched ones (2-butyloctyl for CH-BO) leads to a plunge in the power conversion efficiency of organic solar cells (18.12% vs. 11.34% for binary devices), while the largely shortened ones ( n -heptyl for CH-HP) bring a surge in performance (18.74%/19.44% for binary/ternary devices). Compared with CH-BO, the more compact intermolecular packing of CH-HP facilitates carrier transport. The characterization of organic field effect transistors and carrier dynamics also echoes the above results. Molecular dynamics simulations indicate that the encounter of the branched alkyl chains and the extended central core hinders the effective interfacial interaction of polymer donors and acceptors, thus deteriorating the device performance. This work suggests that the conventional strategy for alkyl chain engineering of Y-series acceptors might need to be reconsidered in other molecular systems.

By employing an aptamer as the bridge and combining catalytic hairpin assembly with the Au aggregation amplification effect, a lateral flow assay (LFA) is designed for simultaneous detection of liver cancer-associated miRNA and exosomes. The LFA can differentiate between liver cancer patients and healthy individuals with simple operation and high accuracy.

Epigallocatechin gallate (EGCG), a prominent bioactive compound found in tea, offers numerous health benefits. Previous studies have highlighted its potential in mitigating hyperuricemia. In this study, hyperuricemic mice induced by potassium oxonate (PO) were treated with EGCG or the anti-hyperuricemia medication allopurinol (AP) to investigate the mechanisms underlying their anti-hyperuricemic effects. The results demonstrated that both EGCG and AP significantly reduced serum uric acid (UA) levels. Further analysis revealed that EGCG promoted the expression of UA secretion transporter genes ( Oat1 and Oct1 ) while inhibiting the expression of UA reabsorption transporter genes ( Urat1 and Glut9 ) in the kidney. By 16S rDNA sequencing, EGCG, but not AP, was found to alter the composition of the gut microbiota. Notably, EGCG induced significant changes in the relative abundance of specific bacteria such as Lactobacillus , Faecalibaculum , and Bifidobacterium , which displayed high correlations with serum UA levels and UA-related gene expression. Metabolomic analysis suggested that EGCG-induced modifications in bacterial metabolites might contribute to the alleviation of hyperuricemia. Transcriptomic analysis of the intestinal epithelium identifies 191 differentially expressed genes (DEGs) in EGCG-treated mice, including 8 purine-related genes. This study elucidates the anti-hyperuricemic mechanisms of EGCG, particularly its influence on the gut microbiota and gene expression in the intestinal epithelium.

Electrocatalytic hydrogen production in seawater to alleviate freshwater shortage pressures is promising, but is hindered by the sluggish oxygen evolution reaction and detrimental chloride electrochemistry. Herein, a dual strategy approach of Fe-doping and CeO 2 -decoration in nickel phosphide (Fe-Ni 2 P/CeO 2 ) is rationally designed to achieve superior bifunctional catalytic performance for the hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) in seawater. Notably, the two-electrode Fe-Ni 2 P/CeO 2 -based hybrid seawater electrolyzer realizes energy-efficient and chlorine-free hydrogen production with ultralow cell voltages of 0.051 and 0.597 V at 10 and 400 mA cm -2 , which are significantly lower than those needed in the hydrazine-free seawater electrolyzer. Density functional theory calculations manifest that the combination of Fe doping and heterointerface construction between Fe-Ni 2 P and CeO 2 can adjust the electronic structure of the Ni 2 P and optimize the water dissociation barrier and hydrogen adsorption free energy, leading to improvement of the intrinsic catalytic performance. This route affords a feasible solution for future large-scale hydrogen generation using abundant ocean water., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Cereals are the main source of energy in the human diet. Compared to refined grains, whole grains retain more beneficial components, including dietary fiber, polyphenols, proteins, vitamins, and minerals. Dietary fiber and bound polyphenols (biounavailable) in cereals are important active substances that can be metabolized by the gut microorganisms and affect the intestinal environment. There is a close relationship between the gut microbiota structures and various disease phenotypes, although the consistency of this link is affected by many factors, and the specific mechanisms are still unclear. Remodeling unfavorable microbiota is widely recognized as an important way to target the gut and improve diseases. This paper mainly reviews the interaction between the gut microbiota and cereal-derived dietary fiber and polyphenols, and also summarizes the changes to the gut microbiota and possible molecular mechanisms of related glycolipid metabolism. The exploration of single active ingredients in cereals and their synergistic health mechanisms will contribute to a better understanding of the health benefits of whole grains. It will further help promote healthier whole grain foods by cultivating new varieties with more potential and optimizing processing methods.

Electrochromic smart windows have attracted great attention due to their dynamic regulation of the solar spectrum. NiO and MnO 2 are typical anodic coloration materials and widely investigated as complementary electrodes with WO 3 . However, NiO and MnO 2 films often cannot be bleached to complete transparency, resulting in low transmittances and low optical modulations in the short-wavelength visible region. Herein, we report a porous nickel manganese layered double hydroxide (NiMn-LDH) nanosheet film directly grown on fluorine-doped tin oxide (FTO) glass using a one-step hydrothermal method, which demonstrates a high transmittance of 80.1% at 550 nm (without deduction of FTO glass). Induced by the double-redox couples of Ni 2+ /Ni 3+ and Mn 3+ /Mn 4+ associated synergistic electrochromic effect, the as-grown NiMn-LDH film electrode exhibits a large optical modulation of 68.5% at 550 nm, and a large solar irradiation modulation of 59.0% in the visible region of 400-800 nm. After annealing at 450 °C for 2 h, the NiMn-LDH film can be transformed into Ni 6 MnO 8 film with a reduced optical modulation of 30.0% at 550 nm. Furthermore, the NiMn-LDH film electrode delivers an areal capacitance of 30.8 mF cm -2 at a current density of 0.1 mA cm -2 . These results suggest that the as-prepared NiMn-LDH film electrode is a promising candidate for both electrochromic and energy storage applications., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Background and aims : Genetic and dietary factors contribute to adiposity risk, but little evidence supports genetic personalization of fried food intake recommendations for the management of obesity. This study aimed to assess the associations between fried food consumption and adiposity incidence and whether the associations were modified by an individual's genotype. Methods : We included 27 427 participants who had dietary data assessed by a validated 24 h dietary recall and available anthropometric information from the UK Biobank study. The genetic risk score (GRS) was calculated using 940 BMI associated variants. Results : With an average of 8.1 years of follow-up, 1472 and 2893 participants were defined as having overall obesity and abdominal obesity, respectively. Individuals in the highest categories of fried food consumption were positively associated with the risk of obesity (HR = 1.31; 95% CI 1.10-1.56) and abdominal obesity (HR = 1.27; 95% CI 1.12-1.45) compared with the lowest categories. Moreover, fried food consumption had a significant interatction with obesity GRS for abdominal obesity risk ( P interaction = 0.016). Fried food intake was associated with a higher abdominal obesity risk (HR = 1.59, 95% CI: 1.25-2.00) among participants with a lower genetic risk. Conclusions : Our findings indicated that fried food consumption had a higher abdominal obesity risk among individuals with a lower genetic risk, suggesting the restriction of fried food intake for this group of people.

Although peripheral hetero-di-halogenation of non-fullerene acceptors (NFAs) would allow more precise optimization of molecular properties by providing the complementary advantages of two different halogens, thus enabling further improvements of organic solar cells (OSCs), hetero-di-halogenated NFAs are seldom prepared due to the challenging construction of building blocks with two adjacent hetero-halogens. Herein, three CH-series acceptors with hetero-di-halogenated central units, named CH-FC, CH-FB and CH-CB, are constructed successfully. PM6:D18:CH-FB-based OSCs afforded an attractive PCE of 19.0% due to tighter intermolecular packing at both the single-crystal and blended-film levels, more efficient charge transfer/dissociation, and superior film morphology compared to those of PM6:D18:CH-FC (PCE 18.41%) and PM6:D18:CH-CB (PCE 18.21%). Our work highlights the effectiveness of such a CH-series molecular platform in conducting hetero-di-halogenation and achieving high-performance OSCs, and will stimulate further exploration of hetero-substitution-based acceptors.

Our recent study [M. Li et al.Phys. Chem. Chem. Phys ., 2023, 25 , 2595-2605] unveiled that the impact of an external electric field on molecular acidity and aromaticity for benzoic acid is directional, which can be understood using changes in frontier orbitals and partial charges. However, it is unclear if the effect will disappear when substituting groups are present and whether new patterns of changes will show up. In this work, as a continuation of our efforts to appreciate the impact of external electric fields on physiochemical properties, we find that the directionality effect is still in place for substituted benzoic acid derivatives and that there exists the additivity effect with respect to the number of substituent groups, regardless of the direction of the applied field and the type of substituting groups. We confirm the findings using electron-donating and electron-accepting groups with the electric field applied either parallelly or perpendicularly to the carboxyl group along the benzene ring. The directionality and additivity effects uncovered from this work should enrich the body of our knowledge about the impact of external electric fields on physiochemical properties and could be applicable to other systems and properties as well.

We developed an efficient MoS 2 nanosheet electrode coupled with CeO 2 via a hydrothermal process to facilitate water adsorption and dissociation, which displayed good HER activity and stability at a large current density of 500 mA cm -2 . In situ Raman spectroscopy confirmed the formation of hydroxide ions based on the strengthening of the Ce-O bond during the HER.

Purpose : Evidence is limited regarding the associations of different dietary patterns with cardiovascular disease (CVD) risk among the population with diabetes. Thus, we aimed to explore the associations between three dietary patterns and CVD incidence among the population with diabetes. Materials and methods : We prospectively followed 22 473 diabetic patients from the UK Biobank at the baseline. The healthy dietary pattern was derived from a food frequency questionnaire; meanwhile, the Alternate Mediterranean Diet (AMED) and the Dietary Approaches to Stop Hypertension (DASH) diet were assessed based on the Oxford WebQ online 24 h dietary questionnaire. Results : During an average of 10.8 years of follow-up, 5209 incident CVD cases, including 3552 coronary heart disease (CHD) events and 881 strokes, were documented. After multivariate adjustment, a higher healthy diet score was negatively associated with CVD, CHD, and stroke incidence. The hazard ratios and 95% confidence intervals across increasing quintiles of healthy diet score were 0.86 (0.79-0.95), 0.83 (0.75-0.93), and 0.71 (0.57-0.88) for CVD, CHD, and stroke, respectively. A similar protective association with CVD incidence was found for the AMED but not the DASH diet. Conclusions : Adherence to healthy dietary patterns is related to a lower risk of developing CVD among diabetic patients. Our findings further provide vigorous evidence for formulating dietary adherence guidelines for diabetic patients to reduce the burden of CVD complications.

Based on the newly synthesized seleno[3,2- b ]selenophene unit, two near-infrared non-fullerene acceptors (NFAs) of 4Se and 5Se are constructed by replacing four or all sulfurs with selenium in high-efficiency Y-series NFAs. Consequently, binary devices based on 4Se and 5Se afford PCEs of 15.17% and 15.23%, respectively, with a photoelectric response approaching 1000 nm. More excitingly, the energy loss of the 5Se-based device was as low as 0.477 eV along with almost the smallest non-radiative loss of ∼0.15 eV thus far.

Hierarchical Mn-Ni 2 P/NiFe LDH arrays were developed as a self-supported electrode. Because of the synergistic effect and self-supported structure, it presents brilliant bifunctional catalytic activities for the HER and UOR. Surprisingly, the voltage of a urea electrolytic cell coupling the HER with the UOR was as low as 1.494 V at 10 mA cm -2 .

Background : Acute lung injury (ALI) and acute respiratory distress syndrome (ARDS) are life-threatening disorders with a high risk of mortality. Astaxanthin (AST) is a supernatural antioxidant that has been extensively studied due to its role in immunomodulation, oxidative stress, and lipid peroxidation. However, the association between ferroptosis and AST is not well understood. The purpose of this study is to explore the regulatory role of AST on ferroptosis in lipopolysaccharide (LPS)-induced ALI. Methods : We established an MLE-12 cell injury model and a mouse ALI model by treating with LPS. The levels of IL-6, TNF-α, and IL-1β in the mouse serum were measured using an enzyme-linked immunosorbent assay. Moreover, immunohistochemical, immunofluorescence, western blot, and quantitative real-time polymerase chain reaction analyses were conducted to examine the effects of AST and ferrostatin-1. Results : We discovered that AST pretreatment greatly alleviated LPS-induced lung injury and inhibited ferroptosis, which was demonstrated by a decrease in the accumulation of malondialdehyde and Fe 2+ and an increase in the levels of glutathione and glutathione peroxidase 4 in the lung tissues of ALI mice and MLE-12 cells. Additionally, we found that AST also evidently suppressed ferritinophagy by upregulation of ferritin and downregulation of nuclear receptor co-activator 4 (NCOA4) in MLE-12 cells. Conclusions : AST pretreatment could lead to a relief of LPS-induced ALI, perhaps via suppressing ferroptosis, and could also reduce unstable iron accumulation by inhibiting NCOA4-mediated ferritin phagocytosis from mitigating lipid peroxidation and ferroptosis in lung epithelial cells.

Eutectogels are stretchable ionic conductors extensively developed in recent years, owing to their distinct advantages of low cost, non-volatility, non-toxicity, and outstanding biocompatibility. However, the susceptibility to humidity caused by the exchange of water molecules between the interiors of eutectogels and the external environment greatly restricts their practical applications. Here, a dip-coating strategy is proposed to fabricate a P(MEA- co -IBA) elastomer-coated P(AAC- co -AAM) eutectogel to achieve satisfactory humidity-resistant capability. The hydrophobic elastomer coating significantly suppresses water exchange without harming the stretchability (>500%) and conductivity of the eutectogel. Strong adhesion forms at the eutectogel-coating interface due to the formation of an interpenetrating layer. The superior electromechanical performances of encapsulated eutectogels enable stretchable ionotronic devices with stable electrical performance (>1 h) and remarkable water-droplet/moist resistances during static/dynamic loadings. A humidity-resistant encapsulated eutectogel-based wearable strain sensor is further demonstrated. The proposed humidity-resistant eutectogels are promising candidates for soft and wearable ionotronics for practical applications.

Herein, we report a novel visible light-induced photocatalytic system that enables intramolecular hydroarylation of unactivated alkenes. Thiosulfonate compounds were found to be the key radical precursor that mediates the Minisci-type intramolecular cyclization reaction. Under the optimal reaction conditions, a wide range of pyridyquinazolinone and pyrroloquinazolinone products were obtained in moderate to good yields.

Since procalcitonin (PCT) is a specific inflammation indicator of severe bacterial inflammation and fungal infection, it is of great significance to construct a sensitive and rapid microfluidic chip to detect PCT in clinical application. The design of micromixers using a lab-on-a-chip (LOC) device is the premise to realizing the adequate mixing of analytical samples and reagents and is an important measure to improve the accuracy and efficiency of determination. In this research study, we investigate the mixing characteristics of hyperbolic micromixers and explore the effects of different hyperbolic curvatures, different Reynolds numbers (Re) and different channel widths on the mixing performance of the micromixers. Then, an optimal micromixer was integrated into a microfluidic chip to fabricate a desirable hyperbolic microfluidic chip (DHMC) for the sensitive determination of inflammation marker PCT with a limit of detection (LOD) as low as 0.17 ng mL -1 via a chemiluminescence signal, which can be used as a promising real-time platform for early clinical diagnosis.

Covering: up to 2014-2022.Diterpenoid biosynthesis in plants builds on the necessary production of ( E , E , E )-geranylgeranyl diphosphate (GGPP) for photosynthetic pigment production, with diterpenoid biosynthesis arising very early in land plant evolution, enabling stockpiling of the extensive arsenal of (di)terpenoid natural products currently observed in this kingdom. This review will build upon that previously published in the Annual Review of Plant Biology, with a stronger focus on enzyme structure-function relationships, as well as additional insights into the evolution of (di)terpenoid metabolism since generated.

The impact of external fields on the molecular structure and reactivity properties has been of considerable interest in the recent literature. Benzoic acid as one of the most widely used compounds in medicinal and materials sciences is known for its dual propensity in aromaticity and acidity. In this work, we systematically investigate the impact of a uniform external electric field on these properties. We apply density functional theory, conceptual density functional theory, and an information-theoretic approach to appreciate the change pattern of aromaticity and acidity properties in external fields with different strengths. Our results show that they possess different change patterns under external fields, which can be satisfactorily rationalized by variations in reactivity descriptors and partial charges. The surprising yet novel results from this study should enrich the body of our knowledge about the impact of external fields for different kinds of electronic properties and provide guidance and foundation for future studies of this phenomenon in other molecular systems.

Photoaffinity labeling is a powerful technique to investigate the interactions between bioactive peptides and their targets. To construct a peptide-derived photoaffinity probe, at least two amino acids need to be modified or replaced, increasing experimental difficulties and negatively affecting activity. Herein, we report the synthesis of a clickable, photoreactive amino acid p -(4-(but-3-yn-1-yl)benzoyl)-l-phenylalanine (Abpa) and its Fmoc-protected version from 3-(4-bromophenyl)-1-propanol in 11 steps with an overall 12.5% yield. The amino acid contains both a photoreactive benzophenone and a clickable terminal alkyne which acts like a reporter tag by fast attachment to other functional groups via 'click' reaction, and a photoaffinity probe could be created by one single amino acid substitution during peptide synthesis. And its small size helps to retain bioactivity. The efficiency of Abpa was demonstrated by photoaffinity labeling experiments using photoactivatable probes of α-conotoxin MI., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

We reported a facile method for the preparation of POM-polymer hybrids in one-pot via polymerization-induced self-assembly. Polyoxometalate macroanions were complexed with cations to prepare cross-linking agents. RAFT dispersion polymerization was conducted in the presence of the cross-linking agent. The hybrid nanoparticles can be used as nanoreactors for the photocatalytic synthesis of Au nanoparticles.

Block copolymers with different topologies (linear, loop, 3-armed and 4-armed polymers) containing poly( N -vinylpyrrrolidone) (PVP) antifouling blocks and terminal poly(dopamine-acrylamide) (PDAA) anchoring blocks were synthesized. These polymers can form a robust antifouling nanolayer on various surfaces. The morphologies of the polymer-modified surfaces are strongly dependent on the topologies of the polymers: with the increase of arm numbers, the morphology evolves from the smooth surface to the nanoscale coarse surface. As a result, the hydrophilicity of the coatings increases with the increase of degree of nanoscale roughness, and the 4-armed block copolymer forms a superhydrophilic surface with a water contact angle (WCA) as low as 8.7°. Accordingly, the linear diblock copolymer exhibits the worst antifouling efficiency, while the 4-armed polymer exhibits the best antifouling efficiency. This is the first example systematically showing that the antifouling efficacy could be adjusted simply by the topology of the coatings. Cell viability studies revealed that all of the copolymers exhibit excellent cytocompatibility. These biocompatible polymers with narrowly distributed molecular weight might find niches for antifouling applications in various areas such as anti-protein absorption, anti-bacterial and anti-marine fouling.

Improving the utilization of noble metals is extremely urgent for fuel cell electrocatalysis, while three-dimensional hierarchical noble metal aerogels with abundant sites and channels are proposed to reinforce their electrocatalytic performances and decrease their amounts. Herein, novel Pd aerogels with tunable surface chemical states were prepared through a facile in situ electrochemical activation, starting with PdO x aerogels by the hydrolysis method. The hierarchical porous Pd aerogels showed unprecedented high activity towards the electrocatalytic oxidation of fuels including methanol (2.99 A mg Pd -1 ), ethanol (8.81 A mg Pd -1 ), and others in alkali, outperforming commercial catalysts (7.12- and 13.66-fold, corresponding to methanol and ethanol). Theoretical investigation unveiled the hybrid surface states with metallic and oxidized Pd species in Pd aerogels to regulate the adsorption of intermediates and facilitate the synergistic oxidation of adsorbed *CO, resulting in enhanced activity with the MOR as the model. Therefore, efficient Pd aerogels through the in situ electrochemical activation of PdO x aerogels were proposed and showed great potential for fuel cell anodic electrocatalysis., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A porphyrin containing covalent organic framework (COF) was developed as the glutathione responsive nitric oxide (NO) donor delivery nanoplatform for "1 + 1 > 2" synergistic cancer therapy of NO mediated therapy and photodynamic therapy.

Diffusion-based translocation along DNA or RNA molecules is essential for genome regulatory proteins to execute their biological functions. The reduced dimensionality of the searching process makes the proteins bind specific target sites at a "faster-than-diffusion-controlled rate". We herein report a photoresponsive slider-track diffusion system capable of self-assembly rate acceleration, which consists of (-)-camphorsulfonic acid, 4-(4'- n -octoxylphenylazo)benzenesulfonic acid, and isotactic poly(2-vinylpyridine). The protonated pyridine rings act as the footholds for anionic azo sliders to diffusively bind and slide along polycationic tracks via electrostatic interactions. Ultraviolet light triggers the trans to cis isomerization and aggregation of azo sliders, which can be monitored by multiple spectroscopic methods without labeling. The presence of vinyl polymer track increases the aggregation rate of cis azobenzene up to ∼20 times, depending on the stereoregularity of the polymer chain, the acid/base ratio and the addition of salt. This system has a feature of simplicity, monitorability, controllability, and could find applications in designing molecular machines with desired functionalities.

Since cancer has emerged as one of the most serious threats to human health, the highly sensitive determination of cancer cells is of significant importance to improve the accuracy of early clinical diagnosis. In our investigation, a novel cascade Fermat spiral microfluidic mixer chip (CFSMMC) combined with fluorescence sensors as a point-of-care (POC) testing system is successfully fabricated to detect and differentiate cancer cells (MCF-7) from normal cells with excellent sensitivity and selectivity. Here, copper ions (Cu 2+ ) with peroxidase properties can catalyze the oxidation of the non-fluorescent substrate Amplex Red (AR) to the highly fluorescent resorufin (ox-AR) in the presence of hydrogen peroxide (H 2 O 2 ). Subsequently, thanks to the quenching response of AS1411-AuNPs to ox-AR in the microchannel and the binding of AS1411 to nucleolin on the surface of cancer cells, a CFSMMC-based POC system is established for the highly sensitive detection and identification of human breast cancer cells in a "turn on" manner. The change in fluorescence intensity is linearly related to the concentration of MCF-7, ranging from 10 2 to 10 7 cells per mL with a limit of detection (LOD) as low as 17 cells per mL. Interestingly, the cascaded AND logic gate is integrated with CFSMMC for the first time to distinguish cancer cells from normal cells under the control of logic functions, which exhibits great potential in the development of one-step rapid and intelligent detection and logic discrimination.

Electrocatalytic hydrogen evolution reactions (HERs) are a key process for hydrogen production for clean energy applications. HERs have unique advantages in terms of energy efficiency and product separation compared to other methods. Molybdenum disulfide (MoS 2 ) has attracted extensive attention as a potential HER catalyst because of its high electrocatalytic activity. However, the HER performance of MoS 2 needs to be improved to make it competitive with conventional Pt-based catalysts. Herein, we summarize three typical strategies for promoting the HER performance, i.e. , defect engineering, heterostructure formation, and heteroatom doping. We also summarize the computational density functional theory (DFT) methods used to obtain insight that can guide the construction of MoS 2 -based materials. Additionally, the challenges and prospects of MoS 2 -based catalysts for the HER have also been discussed., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

A well-designed three-dimensional (3D) covalent organic framework (COF) was constructed as a nanocapsule for the encapsulation of horseradish peroxidase (HRP), which could realize sustained release of HRP to prolong the duration of the therapeutic agents and promote long-term enzyme prodrug therapy.

The application of supplementary cementitious materials (SCMs) in concrete can improve its durability in the marine environment. Calcium alumino silicate hydrate (CASH) is the main hydration product of SCMs; however, to date, the mechanism of the wetting discrepancy in CASH with different Al/Si ratios has not been revealed at the molecular scale. Herein, the molecular dynamics simulation method was used to study the wettability of water nanodroplets on the surface of CASH substrates with different Al/Si ratios, aiming to reveal the influence of CASH gel with different Al contents on the wettability of water molecules. The simulation results suggested that the CASH interface with a high Al/Si ratio has better wettability for nanodroplets. The microcosmic analysis showed that the interaction between particles and the CASH substrate is affected by the Al content. The electronegativity of the CASH substrate increases due to the substitution of Al-O tetrahedrons, which makes it stronger to solidify Ca ions on its surface and easier to form hydrogen bonds with water molecules in a nanodroplet. The orientation distribution of water molecules further revealed the source of the force of the CASH substrate on nanodroplets at the atomic level. The analysis of the dynamic properties showed that the H-bonds between CASH substrate with a high Al/Si ratio and water molecules are more stable, and thus the nanodroplets have better stability on the surface of CASH.

Suppressing intramolecular vibration of non-fullerene acceptors (NFAs) by molecular rigidification has been proven to be an effective way to reduce the non-radiative recombination loss and energetic disorder of organic solar cells (OSCs). Thus far, extensive attention has been drawn on rigidifying the fused-ring backbones of NFAs, whereas the highly flexible alkyl side chains are barely concerned. Herein, an effective strategy of side chain rigidification by introducing a spiro-ring is developed for the first time and applied to construct the NFA of Spiro-F. Compared to its counterpart F-2F, the rigid spirocyclic side chain can constrain the vibrational-rotational motion and control the orientation of two highly flexible n -octyl chains effectively. As a result, an optimal molecular packing with enhanced intermolecular actions and lower energetic disorder is achieved by Spiro-F, endowing the OSC based on the as cast blend of PM6:Spiro-F with a significantly improved PCE of 13.56% and much reduced recombination loss compared to that of PM6:F-2F. This work provides a feasible strategy to achieve efficient OSCs through the rigidification of the side chain and could boost the PCEs further if applied to some other efficient systems with smaller bandgaps., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Drug delivery systems (DDSs) show great application prospects in tumor therapy. So far, physical encapsulation and covalent grafting were the two most common strategies for the construction of DDSs. However, physical encapsulation-based DDSs usually suffered from low drug loading capacity and poor stability, and covalent grafting-based DDSs might reduce the activity of original drug, which greatly limited their clinical application. Therefore, it is of great research value to design a new DDS with high drug loading capacity, robust stability, and original drug activity. Herein, we report a super-amphiphile based drug delivery system (HBS-DDS) through self-assembly induced by hydrogen bonds between amino-substituted N-heterocycles of the 1,3,5-triazines and hydrophilic carmofur (HCFU). The resulting HBS-DDS had a high drug loading capacity (38.1%) and robust stability. In addition, the drug delivery system exhibited pH-triggered size change and release of drugs because of the pH responsiveness of hydrogen bonds. In particular, the anticancer ability test showed that the HBS-DDS could be efficiently ingested by tumor cells, and its half-maximal inhibitory concentration (IC 50 = 3.53 μg mL -1 ) for HeLa cells was close to that of free HCFU (IC 50 = 5.54 μg mL -1 ). The hydrogen bond-based DDS represents a potential drug delivery system in tumor therapy., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

In this work, the peel of hydrogels under a stiff backing constraint was studied using a finite element method. The finite element method was first validated by comparing the simulation results to theoretical predictions and experimental measurements. Then, the method was used to investigate the effects of adhesion thickness, adhesion length and backing thickness on the peel behaviors, as well as the stress distribution within the adhesion layer. The results indicated that the peel force-displacement curve has a constant profile when the adhesion thickness and backing thickness are prescribed so long as the adhesion length is sufficiently long. The peak peel force increases with the adhesion length and then plateaus. The larger the intrinsic peak stress or the thicker the backing, the higher the plateau. The steady-state peel force is independent of the backing thickness, while positively correlated with the strain energy storage of the hydrogel adhesion layer. The critical vertical displacement corresponding to the peak peel force increases with the hydrogel thickness and decreases with the backing thickness. However, the critical vertical displacement corresponding to the steady-state peel force increases with the backing thickness. The present work puts forward an effective numerical approach to probe the peel of hydrogels, which is beneficial for the design of relevant structures.

The production of reactive oxygen species (ROS) to elicit lethal cellular oxidative damage is an attractive pathway to kill cancer cells, but it is still hindered by the low ROS production efficiency of the current methods. Herein, we design a one-dimensional (1D) π-π conjugated ferriporphyrin covalent organic framework on carbon nanotubes (COF-CNT) for activating nanocatalytic and photodynamic cancer therapy. The COF-CNT can catalyze the generation of ROS and O 2 in the tumor microenvironment (TME), and realize a self-oxygen-supplying PDT under near-infrared (NIR) light irradiation, simultaneously. With the full electron delocalization at the atomically dispersed active center, the catalytic activity of COF-CNT with extended π-conjugation is 6.8 times higher than that without the π-conjugated structure. The formation of the COF structure with π-π conjugation also changes the density of states (DOS) profile of its functional building block for improving PDT. Through one single treatment, it successfully achieves complete tumor regression of 4T1 breast carcinoma in mice with immunoregulation.

Recently, much effort has been dedicated to ultra-thin two-dimensional metal-organic framework (2D MOF) nanosheets due to their outstanding properties, such as ultra-thin morphology, large specific surface area, abundant modifiable active sites, etc. However, the preparation of high-quality 2D MOF nanosheets in good yields still remains a huge challenge. Herein, we report 2D cadmium-based metal-organic framework (Cd-MOF) nanosheets prepared in a one-pot polyvinylpyrrolidone (PVP)-assisted synthesis method with high yield. The Cd-MOF nanosheets were characterized with good stability and dispersion in aqueous systems, and were highly selective and sensitive to the antibiotic metronidazole (MNZ) with low limit of detection (LOD: 0.10 μM), thus providing a new and promising fluorescent sensor for rapid detection of MNZ in aqueous solution., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Chlorogenic acid (CGA) possesses a wide variety of bioactive properties, such as antioxidation, anti-inflammation and anti-bacteria. This study was aimed at exploring the effects of CGA of anti-inflammation and anti-bacteria on mouse pneumonia prepared by immunosuppressed mice infected with Klebsiella pneumoniae ( K. pneumoniae ) in vivo and the cellular inflammasomes through lipopolysaccharide (LPS) and adenosine triphosphate (ATP)-induced RAW 264.7 murine macrophages in vitro . Mice received CGA treatment (30 and 90 mg kg -1 ) for 8 consecutive days and on the fourth day immunosuppression in mice was induced by cyclophosphamide (40 mg kg -1 ) for 5 days before inoculation of K. pneumoniae . Immunosuppressed mice infected with K. pneumoniae developed severe pneumonia, with marked interstitial vascular congestion, widened alveolar intervals, infiltration of monocytes, lymphocytes and macrophages as well as the damage of epithelial architecture, with growing mortality and count forming unit (CFU). CGA treatment significantly decreased the ratio of lung/body weight, reduced the severity of pneumonia induced by K. pneumoniae , decreased the lung injury, inflammatory cell infiltration scores and CD68 protein expression, inhibited the expression of interleukin (IL)-6, IL-8, tumor necrosis factor (TNF)-α, and elevated the expression of IL-10. Meanwhile, we investigated the mechanism of CGA to counter K. pneumoniae -induced pneumonia and found that CGA remarkably repressed the activation of nucleotide-binding domain like receptor protein 3 (NLRP3) inflammasome. Altogether, our results indicate that the dietary intake of CGA or its rich foods ameliorates K. pneumonia -induced pneumonia by inhibiting the activation of NLRP3 inflammasomes.

Droplet digital polymerase chain reaction (ddPCR) is an effective technique, with unparalleled sensitivity, for the absolute quantification of target nucleic acids. However, current commercial ddPCR devices for detecting the gene chip are time consuming due to complex image stitching. To address this issue, we propose a universal concentration determination system and realize one-time gene chip imaging with high resolution. All the functional units are controlled by self-developed software using the PyQt5 module in Python. Without stitching technology, images of the ddPCR chip (28 mm × 18 mm) containing 20 000 independent 0.81 nL micro chambers can be obtained in less than 15 seconds, which saves about 165 seconds. A white laser light source (2 mW cm -2 ) was employed as a substitute for the mercury lamp. Its wavelength matches well with typical fluorescent dyes ( e.g. , HEX, ROX and Cy5), and thus it can strengthen the fluorescence intensity for weak signals. The results also demonstrated that the correlation coefficient for the measured concentration and theoretical value was above 99%, by testing the ddPCR products with COVID-19 virus. Such a system can greatly reduce the time required for image acquisition and DNA concentration determination, and thus is able to speed up the lab-to-application process for ddPCR technology.

Hydrogel is a potential wound dressing material due to its ability to maintain a humid environment, the strong absorptive capacity of exuded tissue fluid, and gas exchange function. Herein, poly(N-isopropyl acrylamide)/keratin double network (PNIPAAm/keratin DN) gels were fabricated through covalent and ionic double cross-linking strategy. The effects of PNIPAAm/keratin ratios on the morphology and swelling rate of gels were characterized. The DN gels could swell up from 2600% to 4600% in proportion to the keratin content, demonstrating their great ability to absorb tissue fluid. The gels possessed thermo-sensitiveness, imparting self-stripping property. Moreover, the antibacterial chlorhexidine acetate (CHX) was loaded into gels with a post-fabrication drug-loading strategy. The release behavior showed that CHX-loaded DN gels exhibited multiple responsive characteristics (temperature, pH, and ROS). Furthermore, the drug-loaded gels showed greater antibacterial activity than free CHX due to the sustained drug release effect. Meanwhile, the antioxidant efficiency of PNIPAAm/keratin DN gels was ca. 33.1%, while the PNIPAAm gel was just ca. 18.2%, indicating the strong oxidation resistance of DN gels. In the Sprague Dawley (SD) rat skin defect model, the hydrogel had better tissue regeneration ability than the commercial film. Taken together, the multifunctional PNIPAAm/keratin DN gels are potential candidates for clinical wound treatment.

We synthesized Au@Cu2-xS core/shell nanorods (NRs) that have synergistic surface plasmon resonance (SPR) effects using a new cation exchange process in ethylene glycol (EG) phase. The dual effect - NIR photothermal and surface positive charge plasmon - of Au@Cu2-xS NRs, promote the capability to degrade Aβ1-42 fibrils into amorphous protein.

A porphyrin-containing covalent organic framework (COF) was synthesized as a substrate for decorating selenium nanoparticles (Se NPs) via in situ reduction. Se NP-mediated therapy (SeT) was carried out in conjunction with photodynamic therapy (PDT) to provide an increased anticancer effect and remedy the constrained efficacy of PDT.

N -Tosylhydrazones have proven to be versatile synthons over the past several decades. However, to our knowledge, the construction of isoxazolines based on N -tosylhydrazones has not been examined. Herein, we report the first demonstrations of [2 + 2 + 1] cycloaddition reactions that allow the facile synthesis of isoxazolines, employing N -tosylhydrazones, tert -butyl nitrite (TBN) and alkenes as reactants. This process represents a new type of cycloaddition reaction with a distinct mechanism that does not involve the participation of nitrile oxides. This approach is both general and practical and exhibits a wide substrate scope, nearly universal functional group compatibility, tolerance of moisture and air, the potential for functionalization of complex bioactive molecules and is readily scaled up. Both control experiments and theoretical calculations indicate that this transformation proceeds via the in situ generation of a nitronate from the coupling of N -tosylhydrazone and TBN, followed by cycloaddition with an alkene and subsequent elimination of a tert -butyloxy group to give the desired isoxazoline., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

An enzyme nanopocket constructed from a porphyrin-based covalent organic framework (COF) was developed to co-load glucose oxidase (GOx) and catalase (CAT) for long-term starvation therapy and enhanced photodynamic therapy (PDT).

Creating hierarchical polymer brushes possessing antifouling and bactericidal functionalities is a promising approach to combat biomaterial-associated infections. Hence, a well-constructed hierarchical structure is required to achieve optimized antibacterial performance. In this work, contact-killing cationic bactericidal poly(quaternary ammonium salts) (PQAs) bearing different alkyl chain lengths and zwitterionic antifouling poly(sulfobetaine methacrylate) (PSBMA) functional segments were grafted onto an activated substrate via surface-initiated atom transfer radical polymerization (SI-ATRP), and three kinds of polymer brushes with different architectures (Si-PQAs-b-PSBMA, Si-PSBMA-b-PQAs and Si-PQAs-r-PSBMA) were constructed. We demonstrate that the antibacterial effect simultaneously depends on the alkyl chain lengths of PQAs and the hierarchical structure of cationic/zwitterionic segments in polymer brushes. When the polymer brushes composed of a bactericidal bottom layer and an antifouling top layer, the ideal alkyl chain length of PQAs should be eight carbon atoms (Si-PQA8C-b-PSBMA), while in the opposite hierarchical structure, the optimized alkyl chain length of PQAs to synergize with PSBMA was four carbon atoms (Si-PSBMA-b-PQA4C). By appropriately adjusting the alkyl chain length or the hierarchical architecture, the interference between the antifouling and bactericidal functions could be avoided, thus achieving the outstanding long-term antibacterial performance against S. aureus, as well as good hemocompatibility and low cytotoxicity. This work provides fundamental guidance for the design and optimization of efficient and reliable antibacterial surfaces to inhibit biofilm formation.