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In disciplines like toxicology and pharmacology, oxygen (O 2 ) respiration is a universal metric for evaluating the effects of chemicals across various model systems, including mammalian and microalgal cells. However, for these cells the common practice is to segregate populations into control and exposure groups, which assumes direct equivalence in their responses and does not take into account heterogeneity among individual cells. This lack of resolution impedes our ability to precisely investigate differences among experimental groups with small or limited sample sizes. To overcome this barrier, we introduce SlipO 2 Chip, an innovative glass microfluidic platform for precisely quantifying single-cell O 2 respiration in the coordinated absence and presence of chemical solutes. SlipO 2 Chip comprises a wet-etched fused silica channel plate on the top and a dry-etched borosilicate microwell plate at the bottom. The microwells are coated with Pt(II) meso -tetra(pentafluorophenyl)porphine (PtTFPP), an O 2 sensing optode material and an O 2 -independent reference dye. A custom 3D-printed holder facilitates the controlled horizontal movement ('slipping') of the channel plate over the microwell plate, thereby establishing or disrupting the fluid path over microwells. Collectively, these design elements enable the immobilization of single-cells in microwells, their exposure to controlled fluid flows, the coordinated opening and closing of microwells and repeated measurements of single-cell O 2 respiration. Uniquely, by sequentially executing opening and closing it becomes possible to measure single-cell respiration prior to and after exposure to chemical solutes. In a proof-of-concept application, we utilized SlipO 2 Chip to measure the impact of increasing exposures of the marine bacterial signal 2-heptyl-4-quinolone (HHQ) on the dark respiration of the diatom Ditylum brightwellii at single-cell resolution. Results revealed a concentration-dependent decrease in per-cell O 2 dark respiration, with a maximum reduction of 40.2% observed at HHQ concentrations exceeding 35.5 μM, and a half-maximal effective concentration ( EC 50 ) of 5.8 μM, consistent with that obtained via conventional bulk respiration methods. The ability of SlipO 2 Chip to sequentially assess the effects of chemical substances on single-cell O 2 metabolism is advantageous for research where sample volumes are limited, such as clinical biopsies, studies involving rare microbial isolates, and toxicological studies aiming to address exposure effects while accounting for cell-to-cell variability.

Sulfonated biochar (SBC), as a functional carbon-based material, has attracted widespread attention due to its excellent adsorption properties. The composition of biochar-derived organic matter (B-DOM) is a key factor influencing the migration and transformation of soil elements and pollutants. However, molecular characteristics of sulfonated biochar-derived organic matter (SBC-DOM) are still unclear. In this study, the molecular composition of derived organic matter (DOM) from SBC prepared via one-step carbonization-sulfonation techniques was investigated by Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and then compared with those of DOMs from rice husk (RH), pyrochar (PYC), and hydrochar (HYC). The results show that the CHOS- and CHONS-containing formulae are predominant in SBC-DOM, accounting for 85% of the total molecular formula number, while DOMs from RH, PYC, and HYC are dominated by CHO-containing formulae. Compared to PYC-DOM and HYC-DOM, SBC-DOM has more unsaturated aliphatic compounds, which make it more labile and easily biodegraded. Additionally, SBC-DOM has higher O/C, (N + O)/C ratios and sulfur-containing compounds. These findings provide a theoretical basis for further research on the application of sulfonated biochar in soil improvement and remediation.

Background : Many studies have reported the effects of spicy food on human health, but no studies have been conducted on the impact of long-term spicy food consumption on bone mineral density (BMD). This study aimed to investigate the impact of daily consumption of spicy food on BMD in the population aged 50 years and older. Methods : This cross-sectional study was conducted from 2020 to 2022 in Jiangxi Province, China. This study investigated the differences in BMD between non-consumers and daily spicy food consumers in adults aged 50-85 years. A multiple linear regression model was used to investigate the association between spicy food consumption and BMD of the total lumbar spine (LS), femoral neck (FN), and total hip, as well as biochemical markers of bone metabolism (BMBM) levels. Results : The results showed that daily consumption of spicy food was negatively associated with total LS BMD ( β = -0.013, P = 0.015). Subgroup analyses showed this negative association was more pronounced among smokers and drinkers compared to non-smokers ( β : -0.006 vs. -0.042; P for interaction <0.05) and non-drinkers ( β : -0.004 vs. -0.037; P for interaction <0.05). In addition, according to the daily frequency of spicy food consumption, the daily spicy food consumers were categorized into one meal per day, two meals per day, and three meals per day groups. Further analysis revealed that the negative association between spicy food and total LS BMD was progressively stronger as the frequency of daily consumption of spicy food increased ( P for trend <0.05). For BMBM, daily consumption of spicy food was positively associated with serum PINP levels and negatively associated with serum Ca and serum Mg levels. Conclusions : Our study suggested that daily consumption of spicy food was associated with lower LS BMD in middle-aged and older Chinese adults, and this association was more pronounced in the smoking and drinking populations. The adverse effects of spicy food on LS BMD become progressively stronger with increasing frequency of daily consumption of spicy food. In addition, daily consumption of spicy food was associated with higher PINP levels and lower serum Ca and Mg levels.

C-H Functionalization of pyridines is an efficient strategy to access pyridine derivatives occurring in pharmaceuticals, agrochemicals, and materials. Nucleophilic additions to pyridiniums via both ionic and radical species have proven particularly useful. However, these reactions suffer from poor regioselectivity. By identifying an enzyme-mimic pocket-type urea activation reagent, we report a general platform for pyridine C-4 functionalization. Both ionic and radical nucleophiles can be incorporated to achieve the alkylation and arylation. Notably, the highly regioselective C-4 radical arylation is disclosed for the first time. The broad scope of nucleophiles and pyridines renders this platform applicable to the late-stage functionalization of drug-like molecules and the preparation of complex biologically important molecules., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Extracting knowledge from complex and diverse chemical texts is a pivotal task for both experimental and computational chemists. The task is still considered to be extremely challenging due to the complexity of the chemical language and scientific literature. This study explored the power of fine-tuned large language models (LLMs) on five intricate chemical text mining tasks: compound entity recognition, reaction role labelling, metal-organic framework (MOF) synthesis information extraction, nuclear magnetic resonance spectroscopy (NMR) data extraction, and the conversion of reaction paragraphs to action sequences. The fine-tuned LLMs demonstrated impressive performance, significantly reducing the need for repetitive and extensive prompt engineering experiments. For comparison, we guided ChatGPT (GPT-3.5-turbo) and GPT-4 with prompt engineering and fine-tuned GPT-3.5-turbo as well as other open-source LLMs such as Mistral, Llama3, Llama2, T5, and BART. The results showed that the fine-tuned ChatGPT models excelled in all tasks. They achieved exact accuracy levels ranging from 69% to 95% on these tasks with minimal annotated data. They even outperformed those task-adaptive pre-training and fine-tuning models that were based on a significantly larger amount of in-domain data. Notably, fine-tuned Mistral and Llama3 show competitive abilities. Given their versatility, robustness, and low-code capability, leveraging fine-tuned LLMs as flexible and effective toolkits for automated data acquisition could revolutionize chemical knowledge extraction., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Wound dressings can generally complete hemostasis and provide temporary protection after skin damage. Herein, a MXene-based hydrogel was prepared from MXene, gelatin, poly(ethylene glycol)diacrylate (PEGDA) and N , N '-methylenebis(acrylamide) (HEAA) to prepare wound-dressing hydrogels for skin repair. HEAA and PEGDA crosslink polymerization formed the first layer of the network. Hydrogen bonds between MXene, PHEAA, and gelatin formed the second layer of the network. To make the hydrogel more suitable for skin repair, the mechanical properties of the hybrid hydrogel were adjusted. The MXene-based hydrogel could recover its original shape in 16 s upon immersion in water or for a few minutes under light irradiation. The obtained hydrogel showed good photothermal properties upon light irradiation (808 nm, 1 W cm -2 ) for 20 s, and its temperature on the surface could reach 86.4 °C. Due to its good photothermal properties, this MXene-based hydrogel was suitable for skin repair.

Perfluorooctanoic acid (PFOA) is an emerging persistent organic pollutant. Exposure to PFOA was observed to have a correlation with the expression levels of phospholipids. However, there are currently no studies that directly visualize the effects of PFOA on phospholipids. To this end, matrix-assisted laser desorption/ionization time of flight imaging mass spectrometry (MALDI-TOF-IMS) was used to visualize changes in phospholipids in the different tissues of zebrafish following exposure to PFOA. This study found that the major perturbed phospholipids were phosphatidylcholine (PC), diacylglycerol (DG), phosphatidic acid (PA), phosphatidylglycerol (PG), sphingomyelin (SM), and triacylglycerol (TG). These perturbed phospholipids caused by PFOA were reversible in some tissues (liver, gill, and brain) and irreversible in others (such as the highly exposed intestine). Moreover, the spatial distribution of perturbed phospholipids was mainly located around the edge or center of the tissues, implying that these tissue regions need special attention. This study provides novel insight into the biological toxicity and toxicity mechanisms induced by emerging environmental pollutants.

Medium-sized lactones are important structural units, but their synthesis remains a great challenge. Herein, we report I 2 /CF 3 CO 2 Ag-mediated iodolactonization of allenoic acids to synthesize various 6- to 9-membered ring vinylic iodolactones in 16-89% yield. This protocol not only develops a new cyclization strategy of allenoic acids, but also provides highly functionalized medium-sized lactones containing alkene and halogen groups.

Probing the sequence alterations, structures, interactions, and other important aspects of nucleic acids serves as the cornerstone of understanding nucleic acid-mediated biology and etiology, as well as the development of nucleic acid-based therapeutics. New strategies capable of accommodating these imperatives without necessitating specialized instrument or skills and potentially complementing existing methods are highly desired. Herein, we describe a rationally designed molecular rotor CCVJ-H ((9-(2-carboxy-2-cyanovinyl)julolidine-hydrazide)) and its superior performances compared to the universal base excision reporter probe CCVJ-1 in applications such as nucleic acid detection and DNA glycosylase assays. Furthermore, we showcase that the CCVJ-H probe accurately profiles the interactions between nucleic acids and small molecules, providing binding affinity and binding site information in a single reaction. We subsequently demonstrate the feasibility of applying the CCVJ-H system in high-throughput screening to identify nucleic acid-binding small molecules such as DNA CTG repeat expansion binders, potentially providing therapeutic interventions for myotonic dystrophy type 1. Finally, we profile the recognition difference between DNA/DNA and DNA/RNA against a library of small molecules, uncovering two drug-like molecules that preferentially bind DNA/RNA. We anticipate the versatile CCVJ-H probe will be a useful tool for both fundamental and translational nucleic acid research and application., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Identifying the cellular targets of bioactive small molecules within tissues has been a major concern in drug discovery and chemical biology research. Compared to cell line models, tissues consist of multiple cell types and complicated microenvironments. Therefore, elucidating the distribution and heterogeneity of targets across various cells in tissues would enhance the mechanistic understanding of drug or toxin action in real-life scenarios. Here, we present a novel multi-omics integration pipeline called Single-cell TargEt Profiling (STEP) that enables the global profiling of protein targets in mammalian tissues with single-cell resolution. This pipeline integrates single-cell transcriptome datasets with tissue-level protein target profiling using chemoproteomics. Taking well-established classic drugs such as aspirin, aristolochic acid, and cisplatin as examples, we confirmed the specificity and precision of cellular drug-target profiles and their associated molecular pathways in tissues using the STEP analysis. Our findings provide more informative insights into the action modes of bioactive molecules compared to in vitro models. Collectively, STEP represents a novel strategy for profiling cellular-specific targets and functional processes with unprecedented resolution., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Using a hybrid simulation approach that combines a lattice-Boltzmann method for fluid flow and a molecular dynamics model for polymers, we investigate the inertial migration of star-like and crew-cut polymer micelles in a square microchannel. It is found that they exhibit two types of equilibrium positions, which shift further away from the center of the microchannel when the Reynolds number (Re) increases, as can be observed for soft particles. What differs from the behaviors of soft particles is that here, the blockage ratio is no longer the decisive factor. When the sizes are the same, the star-like micelles are always relatively closer to the microchannel wall as they gradually transition from spherical to disc-like with the increase of Re. In comparison, the crew-cut micelles are only transformed into an ellipsoid. Conversely, when the hydrophobic core sizes are the same, the equilibrium position of the star-like micelles becomes closer to that of the crew-cut micelles. Our results demonstrate that for polymer micelles with a core-shell structure, the equilibrium position is no longer solely determined by their overall dimensions but depends on the core and shell's specific dimensions, especially the hydrophobic core size. This finding opens up a new approach for achieving the separation of micelles in inertial migration.

Oxidative stress and blood-brain barrier (BBB) injury are two major stress disorders before and after ischemic stroke (IS) therapy. The intense inflammatory response also causes damage to nerve cells, affecting the repair of brain tissue. In this study, polyphenolic nanoparticles (PPNs) with strong free radical scavenging ability were designed to treat IS multimodally. To investigate the mechanism of polyphenolic polymerization, solid nanoparticles were synthesized using four kinds of polyphenol compounds as the basic unit under the control of temperature. The form of polymerization between monomers with different structures led to changes in the chemical properties of the corresponding nanoparticles as well as the antioxidant capacity at the cellular level. Particularly, PPNs can significantly improve cerebral infarction and penetrate and repair the BBB, and even downregulate levels of inflammatory cytokines. Molecular signaling pathway studies have shown that PPNs can provide comprehensive treatment of IS by promoting the expression of tight junction protein and enhancing the activity of antioxidant enzymes. Therefore, PPNs combined with the antioxidant, anti-inflammatory and BBB repair ability not only provide a perfect therapeutic pathway but also give ideas for the development of natural material carriers that have a wide application prospect.

Luminescent nanomaterials with outstanding optical properties have attracted growing interest due to their widespread applications. However, large-scale fabrication of luminescent nanomaterials with desired properties through a simple and economical process remains challenging. As a renewable natural resource, starch is non-toxic, easily accessible, and inexpensive, making it a popular choice for uses in various biomedical fields. In this work, we present a facile assembly strategy for the fabrication of starch-based luminescent nanoaggregates using starch as the host material and aggregation-induced emission luminogens (AIEgens) as guest molecules. By employing simple procedures under mild conditions, highly luminescent nanoparticles with small sizes, high water dispersibility, and low cytotoxicity are prepared on a large scale. The resulting nano-assemblies demonstrate significantly enhanced fluorescence intensities, reduced susceptibility to photobleaching and low cytotoxicity. These fluorescent supramolecular aggregates can be employed in various application fields, including the fabrication of fluorescent hydrogels, fingerprint detection, cell imaging and in vivo lymphatic system imaging. The methodology developed in this work has immense potential to greatly promote the production of high-quality nanoparticles on the industrial scale, offering a cost-effective solution that can meet the needs of various applications and pave the way for wider implementation of nanotechnology.

Ophioglossum vulgatum L. ( O. vulgatum ) is a species of fern used in traditional Chinese medicine, however, its application in cosmetics has not yet been studied. This study obtained O. vulgatum extract using 70% ethanol solution and evaporation. Fourier Transform Infrared Spectrometer (FTIR) analysis identified many active components in O. vulgatum extract, such as polyols, amino acids, and flavonoids. A Pickering emulsion of O. vulgatum extract was also prepared, stabilized by a type of carbon dot based on l-arginine (CDs-Arg). The prepared Pickering emulsion was characterized by metallographic microscope and contact angle measurement. The results demonstrated that it was a pH-responsive O/W emulsion. Facial cleanser was then created using the prepared Pickering emulsion as the main component. When squeezed onto hands, the cleanser produced many delicate foams and caused no skin irritation. The prepared Pickering emulsion facilitated the use of O. vulgatum in facial cleanser., Competing Interests: Authors declare no competing conflict of interests., (This journal is © The Royal Society of Chemistry.)

Inflammatory and thrombotic complications and a low loading of dual drugs with different hydrophilicities remain challenges to treat thrombosis with drug delivery systems (DDSs). Here, the reactive oxygen species (ROS)-responsive amphiphilic block polymer poly(ethylene glycol)- b -2-((((4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzyl)oxy)carbonyl)oxy)-ethyl methacrylate (PEG- b -PTBEM) was synthesized and nanovesicles (PPTV) were prepared successfully for the drug delivery platform by controlling the hydrophilic/hydrophobic ratio of molecular chains and molecular self-assembly. The anti-inflammatory drug indomethacin (IDM) was loaded in the wall of nanovesicles and the thrombolytic enzyme nattokinase (NK) was encapsulated in the aqueous cavity of nanovesicles. Both drugs could be rapidly released at the site of thrombosis and/or inflammation with an excessive ROS concentration. The dual drug-loaded nanovesicles not only eliminated ROS, but also alleviated inflammation and dissolved the generated thrombus, showing significant therapeutic efficacy in the in vivo mouse model of carrageenan tail thrombosis. Therefore, drug-delivery nanovesicles play multiple roles in the treatment of inflammation-induced thrombotic disorders, which offer a promising treatment for inflammatory and thrombotic complications.

The thermal transport properties of five-fold twinned (5FT) germanium-silicon (Ge-Si) heteronanowires (h-NWs) with varying cross-sectional areas, germanium (Ge) domain ratios and heterostructural patterns are investigated using homogeneous nonequilibrium molecular dynamics (HNEMD) simulations. The results demonstrate a distinctive behavior in the thermal conductivity ( κ ) of 5FT-NWs, characterized by a "flipped" trend at a critical cross-sectional area. This behavior is attributed to the hydrodynamic phonon flow, arising from the normal three-phonon scattering process in the low-frequency region. In addition, the composition ratio of 5FT-NWs has a significant impact on reducing the κ of 5FT-NWs and suppressing the hydrodynamic effect. Intriguingly, as the homogeneous element domains are separated, stronger phonon hydrodynamic flows are observed in comparison to the adjacent homogeneous element domains. By analyzing various phonon properties, including phonon dispersion, three-phonon scattering rate, and phonon mean free path, critical insights into the origin of the differential κ in different 5FT-NW structures are provided. The findings deepen the understanding of the thermal transport properties of nanomaterials and hold implications for the design and development of nanoelectronics and thermoelectric devices.

In this study, gold nanoparticles were dispersed on Co 3 O 4 nanoplates, forming a specific Au-Co 3 O 4 interface. Upon calcination at 300 °C in air, aberration-corrected STEM images evidenced that the gold nanoclusters (NCs) on Co 3 O 4 {111} were maintained at ca. 2.2 nm, which is similar to the size of the parent Au colloidal particles, demonstrating the stronger metal-support interaction (SMSI) on Co 3 O 4 {111}. Au/Co 3 O 4 {111} showed good catalytic activity (a full CO conversion achieved at 80 °C) and durability (over 10 hours) in CO oxidation, which was mainly due to the promotion by the surface oxygen vacancies and intrinsic defects of Co 3 O 4 {111} for activating O 2 and by Au 0 , Au δ + , and Au + species on the surface of gold NCs for CO activation, as evidenced by Raman and Fourier-transform infrared (FT-IR) spectroscopy analysis. Au/Co 3 O 4 catalyzed CO oxidation obeyed the Langmuir-Hinshelwood mechanism at low temperatures., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

An electrochemical glucose sensor based on flexible materials is significant for wearable devices used for real-time health monitoring and diagnosis. However, applying flexible electrodes involves complex fabrication processes and might reduce detection sensitivity. To overcome these obstacles, we herein report a novel strategy for preparing a highly flexible enzyme electrode based on an electrospun poly(vinyl alcohol) (PVA) mat decorated with in situ grown silver nanoparticles (nano-Ag) for electrochemical glucose sensing. Ferrocene (Fc) was selected as an electron acceptor for glucose oxidase (GOD) in order to minimize the influence of oxygen. Electron transfer between GOD and Fc was facilitated by confining them within a mixed self-assembled monolayer (SAM) formed on a thin layer of gold deposited on top of the PVA/nano-Ag film. Nano-Ag was found to significantly increase the surface area of the electrode and improve the stability of electrode conductivity during tensile deformation. Electrochemical glucose detection was performed by chronoamperometry in the electroactivity domain of ferrocene, and good linearity ( R 2 = 0.993) was obtained in the range of 0.2-7 mM with a detection limit of 0.038 mM and a relative standard deviation (RSD) of 1.45% ( n = 6). After being stuck to a bendable PDMS slice and bent, respectively, at 30° and 60° 50 times, the electrode showed slight changes in detection results (<4.78%), which remained within 8% when the bending angle increased to 90°. With its high flexibility, good detection performance, and convenient fabrication process, the proposed enzyme electrode showed good potential as a flexible platform for wearable glucose sensing systems.

Organic luminogens (OLs) that emit strong fluorescence in both solution and the aggregated state, referred to as dual-state emission luminogens (DSEgens), are highly desirable because of their capability to achieve multiple functions within onefold materials. The fluorescence of OLs, including DSEgens, with intramolecular charge transfer characteristics, often decreases in solution as the solvent polarity increases, namely the positive solvatokinetic effect, resulting in inferior environmental stability. In this work, fluorination to naphthalimide (NI)-cyanostilbene (CS) derivatives was adopted to construct novel DSEgens (NICSF-X, X = B, P, M, and T, respectively). Steady-state and transient spectroscopies were utilized to study their photophysical properties, evidencing their DSE properties with fluorescence quantum yields ( φ ) ∼0.2-0.4 in solution and ∼0.5-0.9 as solids. In particular, strong fluorescence emission in highly polar solvents i.e. , φ up to ∼0.4-0.5 in ethanol, was sustained for NICSF-Xs, possibly assisted by hydrogen bonding (H-bonding) formation. Theoretical calculations and single-crystal structure analysis rationalized the intense photoluminescence (PL) emission of NICSF-Xs in the solid state. In addition, NICSF-Xs showed two-photon absorption (2PA) behaviors in dual states and were successfully applied for HepG2 cell imaging with one-photon and 2PA excitation, with lipid droplet targeting. Our study suggests that functionalization of molecules by fluorination to introduce H-bonding is a promising strategy to enhance the environmental stability of fluorescence in solution and realize strong PL emission in highly polar solvents, which could be favorable for bioimaging.

Design of multifunctional nanoplatforms combined with ultrasound-targeted microbubble destruction (UTMD) technology for enhanced tumor accumulation is feasible to solve the bottleneck of theranostics. Herein, we present the development of zwitterion-modified gadolinium (Gd)-chelated core-shell tecto dendrimers (CSTDs) as a nanomedicine platform (PCSTD-Gd) for enhanced magnetic resonance (MR) imaging-guided chemo-gene therapy of orthotopic breast cancer with the assistance of UTMD. In our design, CSTDs synthesized via supramolecular recognition of β-cyclodextrin and adamantane were covalently linked with tetraazacyclododecane tetraacetic acid-Gd(III) chelators, modified with 1,3-propane sultone to achieve good protein-resistance property, and used for co-delivery of an microRNA 21 inhibitor (miR 21i) and an anticancer drug doxorubicin (DOX). The overall design is quite advantageous and cooperative. The CSTDs with a greater size than single-generation core dendrimers have amplified the enhanced permeability and retention effect for better passive tumor targeting, with a larger r 1 relaxivity for sensitive MR imaging and serum-enhanced gene delivery efficiency due to the better compaction ability as well as the protein resistance ability, and with larger interior space for improved drug loading. Through the unique design and the assistance of UTMD, the obtained PCSTD-Gd/DOX/miR 21i polyplexes enable enhanced MR imaging-guided combined chemo-gene therapy of an orthotopic breast cancer model in vivo .

DNA has been considered a promising alternative to the current solid-state devices for digital information storage. The past decade has witnessed tremendous progress in the field of DNA data storage contributed by researchers from various disciplines. However, the current development status of DNA storage is still far from practical use, mainly due to its high material cost and time consumption for data reading/writing, as well as the lack of a comprehensive, automated, and integrated system. Microfluidics, being capable of handling and processing micro-scale fluid samples in a massively paralleled and highly integrated manner, has gradually been recognized as a promising candidate for addressing the aforementioned issues. In this review, we provide a discussion on recent efforts of applying microfluidics to advance the development of DNA data storage. Moreover, to showcase the tremendous potential that microfluidics can contribute to this field, we will further highlight the recent advancements of applying microfluidics to the key functional modules within the DNA data storage workflow. Finally, we share our perspectives on future directions for how to continue the infusion of microfluidics with DNA data storage and how to advance toward a truly integrated system and reach real-life applications.

The CO 2 reduction reaction (CO 2 RR) into chemical products is a promising and efficient way to combat the global warming issue and greenhouse effect. The viability of the CO 2 RR critically rests with finding highly active and selective catalysts that can accomplish the desired chemical transformation. Single-atom catalysts (SACs) are ideal in fulfilling this goal due to the well-defined active sites and support-tunable electronic structure, and exhibit enhanced activity and high selectivity for the CO 2 RR. In this review, we present the recent progress of quantum-theoretical studies on electro- and photo-chemical conversion of CO 2 with SACs and frameworks. Various calculated products of CO 2 RR with SACs have been discussed, including CO, acids, alcohols, hydrocarbons and other organics. Meanwhile, the critical challenges and the pathway towards improving the efficiency of the CO 2 RR have also been discussed., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (This journal is © The Royal Society of Chemistry.)

The combination of DNA nanotechnology and nanopore sensing technology has greatly promoted research on target molecule or ion detection. The large solid-state nanopores/nanochannels show better mechanical stability and reproducibility, but metal ion detection in the large nanopores with diameters of hundreds of nanometers or several micrometers is rarely reported. Hence, it is meaningful and urgent to develop a large nanopore-based sensing platform for the detection of metal ions. Herein, we employed a salicylic aldehyde-modified DNA network in conjunction with a glass nanopipette (GN) with a diameter of hundreds of nanometers as a sensing platform for the detection of target metal ions. Upon the addition of different receptors with the amino group, the salicylic aldehyde could in situ specifically recognize and bind with Zn 2+ and Al 3 , forming Schiff base-metal ion complexes at the four vertices of one face per nanocube unit. The steric hindrance effect of multiple Schiff bases and metal ion complexes leads to the blockage of internal structure and decrease of ion current in the GN. Owing to this signal amplification strategy, the detection limit of the target metal ion reaches a level of fM in the GN with a diameter of about 300 nm. In the future, this functional nanopore sensing platform is expected to realize highly sensitive detection for more biological metal ions by choosing appropriate receptors.

Structural colors can be used in fabric coloring due to their bright color and non-fading properties. However, it is still a challenge to construct structural color on high crystallinity, smooth surfaced and yellow colored aramid fabrics. Herein, for the first time, photonic crystals (PCs) with structural color were constructed on aramid fabrics by introducing dopamine to modify aramid fabrics and synthesizing monodisperse high refractive index zinc sulfide nanoparticles (ZnS). The influence of the PC coatings on the structural color, mechanical properties, and thermal stability of the structurally colored aramid fabrics or fibers was further investigated. Moreover, due to the excellent catalytic properties of ZnS and the slow photon effects of PCs, the structurally colored fabrics showed good photocatalytic properties, which will be beneficial in reusing the catalysts, which is crucial to their application in the coloring of fabrics but also facilitates the recycling of waste PC coated aramid fabrics.

SrTiO 3 /LaAlO 3 heterostructures were constructed, which achieved a high ionic conductivity of 0.24 S cm -1 and fuel cell power output of 675 mW cm -2 at 520 °C. Theoretical calculations and experimental determinations found that the resultant built-in electric field plays an important role in fast ionic conduction through the interface with the electron accumulation layer in the interface region.

Photosensitizers with aggregation-induced emission (AIE PSs) were widely explored in photodynamic therapy. Numerous acceptors but few donors were reported to design AIE PSs. In this study, we developed a new kind of donor that can improve the comprehensive performance of AIE PSs by expanding the π extension of aromatic rings at the end of the triphenylamine group through acene enlargement. The absorption and fluorescence peaks of anthryl-substituted AIE PS are red-shifted by 29 nm and 42 nm; the photosensitization efficiency is enhanced by 1.16 times; the AIE factor is 86.1 and the fluorescence quantum yield is 9.3%. We also demonstrated that the anthryl-based AIE PS can image and ablate cancer cells well both in vitro and in vivo . The anthryl-triphenylamine donor provides an excellent option to design donor-acceptor AIE PSs with high comprehensive performance., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Self-healing materials have attracted widespread attention owing to their capacity to extend the lifetime of materials and improve resource utilization. However, achieving superior mechanical performance and high self-healable capability simultaneously under moderate conditions remains a long-standing challenge. Integrating multiple dynamic interactions in waterborne polyurethane (WPU) systems can overcome the above-mentioned issue. Herein, environmentally friendly WPU systems containing multiple hydrogen bonds and boronic ester bonds in their polymer backbones were synthesized, where 2,6-diaminopyridine (DAP) and boric acid (BA) served as a dynamic chain extender and reversible cross-linking agent, respectively. The chain structure of the polymer was adjusted by controlling the ratio (DAP/BA) of hard segments, which could effectively meet the requirement of mechanical robustness and desirable self-healable efficiency. Benefiting from multiple dynamic interactions, the prepared WPU elastomer exhibited good mechanical properties, such as tensile strength (from 18.89 MPa to 30.78 MPa), elongation (about 900%) and toughness (from 54.82 MJ m -3 to 92.74 MJ m -3 ). Driven by water and heat, the IP-DAP 40 -BA 10 -WPU film cut in the middle exhibited good self-healing ability, with healing efficiencies of tensile stress of 90.74% and elongation of 91.29% after self-healing at 80 °C for 36 h. Meanwhile, the synthesized WPU elastomer exhibited good water resistance and thermal stability. This work presents a novel way to design robust self-healable materials, which will have wide promising applications in flexible electronics, smart coatings and adhesives., Competing Interests: The authors report no declarations of interest., (This journal is © The Royal Society of Chemistry.)

With the increasing number of diabetic patients, chronic wound healing remains a great challenge in clinical medicine. As one of the main components secreted by stem cells, the exosome is considered to be a promising candidate for promoting chronic wound healing. Here, gingival mesenchymal stem cell (GMSC)-derived exosomes (GMSC-Exo) were isolated and demonstrated to promote the proliferation, migration, and tube formation of human umbilical vein endothelial cells (HUVECs) by regulating the Wnt/β-catenin signaling pathway in a diabetic-mimicking high glucose environment. In order to deliver GMSCs-Exo to the target site and prolong their local retention, porous microspheres consisting of poly-lactic-co-glycolic acid (PLGA), amphiphilic block copolymer (PLLA-PEG-PLLA), nano-hydroxyapatite (nHAP), and poly-ε-l-lysine (EPL) coating were fabricated through a double emulsion method and following surface treatment, hereafter referred to as PHE microspheres. PHE microspheres loaded with GMSCs-Exo were implanted into the full-thickness skin wound of a diabetic mouse model, resulting in significant vascularized wound healing when compared to a control group only injected with GMSCs-Exo suspension or filled with PHE microspheres. These findings indicated that the GMSCs-Exo-loaded porous microspheres could efficiently treat diabetic wounds and have promising potential for future clinical translations., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Single-cell RNA sequencing (scRNA-seq) has been developed for characterizing the transcriptome of cells that are rare but of biological significance. With cell barcoding and microchip technologies, a suite of high-throughput scRNA-seq protocols enable transcriptome profiling in thousands of individual cells at single-cell resolution for classifying cell types, discovering novel cell populations, investigating cellular heterogeneity and elucidating lineage trajectories. Microchip technologies including microfluidics- and microwell-based platforms play a major role in high-throughput scRNA-seq. As the emerging technology, spatial transcriptomics integrates cellular transcriptomics with their spatial coordinates within tissues for spatially deciphering cellular composition, heterogeneity and cell-cell communications. Spatial transcriptomics has been increasingly recognized as one of the most powerful tools for discovering new biology and advancing precision medicine. Microfluidics as an enabling technology plays an increasingly important role in spatial transcriptomics. We review the technological spectrum and advances in high-throughput scRNA-seq and spatial transcriptomics, discuss their advantages and limitations, and pitch into new biology learned from these new tools.

Most of the known senolytics are anti-cancer drugs or their derivative molecules. However, senolytics derived from the active ingredients of traditional Chinese medicine (TCM) are rarely reported. Here, we identified oridonin as a novel senolytic and further revealed that it might target a class of glutathione S -transferases to activate ROS-p38 signaling and induce apoptosis in senescent cells.

Platelets activation and hypercoagulation induced by tumor cell-specific thrombotic secretions such as tissue factor (TF) and cancer procoagulant (CP), microparticles (MPs), and cytokines not only increase cancer-associated thrombosis but also accelerate cancer progress. In addition, the tumor heterogeneity such avascular areas, vascular occlusion and interstitial fluid pressure still challenges efficient drug delivery into tumor tissue. To overcome these adversities, we herein present an antiplatelet strategy based on a proteinic nanoparticles co-assembly of l-arginine (LA) and photosensitizer IR783 for local NO release to inhibit the activation of tumor-associated platelets and normalize angiogenesis, suppressing thrombosis and increasing tumoral accumulation of the nanoagent. In addition, NIR-controlled release localizes the NO spatiotemporally to tumor-associated platelets and prevents undesirable systemic bleeding substantially. Moreover, NO can transform to more cytotoxic peroxynitrite to destroy cancer cells. Our study describes an antiplatelet-directed cancer treatment, which represents a promising area of targeted cancer therapy., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)

Water flooding increases the recovery factor of crude oil and has been proven to be an economical and viable technique for enhancing the oil recovery of oil fields. The process has been systematically studied previously, in which the oil was considered a substance of constant composition. However, the molecular selectivity during the water flooding process has rarely been addressed, especially for heavy oil. Herein, the properties and compositional changes of heavy oil have been investigated in a simulated water flooding process at 60 °C and 85 °C. The crude oil and produced oils from different water flooding stages were characterized by gas chromatography, gas chromatography-mass spectrometry, and Fourier transform ion cyclotron resonance mass spectrometry. The results show that with the increase in temperature, the content of resins in the produced oils from different water flooding stages decreases, and the content of asphaltenes increases slightly. The viscosity of the produced oils increases at low temperatures and decreases at high temperatures as the water cut increases. The composition of the produced oils from different water flooding stages is different. Compared with the no water cut and high water cut stages, the changes in the produced oils of the low water cut stages are significant at different temperatures. The molecular selectivity of heteroatoms is higher than that of hydrocarbons in the water flooding process. Water flooding preferentially extracts small-molecule low-carbon hydrocarbons and small-molecule heteroatoms with low condensation degrees. The compositional differences between the produced oils were characterized by the double bond equivalent versus carbon number distribution of the S, N, and O-containing compounds. This study can not only provide some explanations on the viscosity-forming mechanism of heavy oil but also explains the watered-out phenomena in the development of oilfields., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (This journal is © The Royal Society of Chemistry.)

Spontaneous collective oscillation may emerge from seemingly irregular active matter systems. Here, we experimentally demonstrate a spontaneous population oscillation of active granular particles confined in two chambers connected by a narrow channel, and verify the intriguing behavior predicted in simulation [M. Paoluzzi, R. Di Leonardo and L. Angelani, Self-sustained density oscillations of swimming bacteria confined in microchambers, Phys. Rev. Lett. , 2015, 115 (18), 188303]. During the oscillation, the two chambers are alternately (nearly) filled up and emptied by the self-propelled particles in a periodic manner. We show that the stable unidirectional flow induced due to the confined channel and its periodic reversal triggered by the particle concentration difference between two chambers jointly give rise to the oscillatory collective behavior. Furthermore, we propose a minimal theoretical model that properly reproduces the experimental results without free parameters. This self-sustained collective oscillation could serve as a robust active granular clock, capable of providing rhythmic signals.

Intrinsically polarized electrorheological fluids (ERFs) have better thermal stability than ERFs with polar molecules, so they have a broader application prospect. However, the electrorheological efficiency of the common intrinsically polarized ERF is still lower than 1500, which is related to the poor wettability between polarized materials and the continuous phase. Carbon dots (CDs) exhibit good stability, semiconductor properties and low toxicity. We prepared biomimetic chestnut-like cobalt hydroxide coupled with surface-functionalized CD particles (Co(OH) 2 @CDs) by a simple hydrothermal method. Then we prepared an ERF by mixing Co(OH) 2 @CDs with silicone oil and studied the effect of CDs on its rheology and electrorheology properties. The synergistic effect of the lipophilic groups on the surface of CDs and the biomimetic chestnut-like structure makes Co(OH) 2 @CDs exhibit good wettability with silicone oil, and the optimal zero-field viscosity of Co(OH) 2 @CDs-ERF is only 0.46 Pa s (particle mass fraction of 40%). Exceptional electrorheological efficiency (about 10 000, shear rate 0.1 s -1 , 5 kV mm -1 ) and dynamic shear stress stability of optimal Co(OH) 2 @CDs-ERF can be attributed to the dielectric enhancement of the biomimetic chestnut-like structure coupled with the semiconductor properties of CDs. In addition, Co(OH) 2 @CDs-ERF has excellent anti-settling performance, outstanding thermal stability and low current density.

A three-dimensional crosslinked CFs@CNT/CoS x nanocomposite was successfully synthesized by in situ growing carbon nanotubes on carbon nanofibers and a facile sulfurization process. The carbon nanotubes synthesized by sintering melamine under the catalysis of cobalt can increase the specific surface areas and provide abundant sodium ion diffusion channels for the composite. Meanwhile, the formed cobalt sulfide nanoparticles will increase the active sites on the surface of CFs@CNT/CoS x . Due to the rational design of the composite structure, such an anode can deliver a specific capacity of 423.7 mA h g -1 after 100 cycles at 100 mA g -1 and exhibit superior rate performance of retaining 324.1 mA h g -1 at 2 A g -1 for sodium storage.

Auricularia auricula fruiting body-derived polysaccharides (AAPs) were dried using different drying procedures, including hot air-, far infrared-, freeze-, and microwave-drying. The influences of different drying procedures on the chemical compositions and antioxidant activity in vitro and in vivo of AAPs were investigated. The results indicated that freeze-dried AAPs (AAPs-F) possessed the highest uronic acid content (33.53%) and the lowest molecular weight (406.77 kDa). Moreover, AAPs-F exhibited the most potent antioxidant abilities in vitro , including ABTS + and DPPH˙ scavenging abilities, ferric reducing power, and metal ion chelating capacity. Besides, AAPs-F could significantly prolong the lifespan of wild-type C. elegans under oxidative stress induced by H 2 O 2 and methyl viologen ( p < 0.05) and upregulate the mRNA expression levels of daf-16 (>2.7 fold), sod-3 (>9.2 fold), skn-1 (>4.5 fold) and sir-2.1 (>1.9 fold), and play a significant role in protecting C. elegans against apoptosis ( p < 0.05). Hence, freeze-drying was determined as the preferred procedure for obtaining high-quality AAPs.

Natural gas hydrates (NGHs) are rising as an unconventional energy resource. The fundamental thermal characteristics of NGHs are of importance for natural gas exploitation from permafrost and oceanic sediments that are geomechanically deformed. Here, utilizing classic molecular dynamics simulations with all-atom (AA) and coarse-grained (CG) models of the methane guest molecule, the effects of mechanical strain on the thermal conductivity of sI-type methane hydrate are for the first time examined. Upon triaxial tension and compression, methane hydrate exhibits strong asymmetry in the stress responses. As the triaxial loads go from compression to tension, a reduction trend in the thermal conductivity is revealed for methane hydrate with both AA and CG models of methane, within a maximum reduction of over 44%. This reduction is because triaxial strain from compression to tension softens the phonon modes. Interestingly, there is a sudden rise in thermal conductivity at critical triaxial strain of 0.06, originating from that, at which, the phonon modes are hardened and the peaks of radial distribution functions are shifted back. This study provides important information on the thermal conductivity of methane hydrate, which is helpful for the practical production of natural gas from geo-deformed NGH-bearing sediments via a heating technique as well as evaluating their stability.

Collagen provides a promising environment for 3D nerve cell culture; however, the function of perfusion culture and cell-growth guidance is difficult to integrate into such an environment to promote cell growth. In this paper, we develop a bio-inspired design method for constructing a perfusion culture platform for guided nerve cell growth and differentiation in collagen. Based on the anatomical structure of peripheral neural tissue, a biomimetic porous structure (BPS) is fabricated by two-photon polymerization of IP-Visio. The micro-capillary effect is then utilized to facilitate the self-assembly of cell encapsulated collagen into the BPS. 3D perfusion culture can be rapidly implemented by inserting the cell-filled BPS into a pipette tip connected with syringe pumps. Furthermore, we investigate the nerve cell behavior in the BPS. 7-channel aligned cellular structures surrounded with a Schwann cell layer can be stably formed after a long-time perfusion culture. Differentiation of PC12 cells and mouse neural stem cells shows 3D neurite outgrowth alignment and elongation in collagen. The calcium activities of differentiated PC12 cells are visualized for confirming the preliminary formation of cell function. These results demonstrate that the proposed bio-inspired 3D cell culture platform with the advantages of miniaturization, structure complexity and perfusion has great potential for future application in the study of nerve regeneration and drug screening.

By performing density functional theory (DFT) calculations, we investigated and identified the fundamental pathway for N-heterocyclic carbene (NHC)-catalyzed synthesis of axially chiral benzothiophene-fused biaryls using enal and 2-benzyl-benzothiophene-3-carbaldehyde, which includes (1) nucleophilic attack on enal by the organocatalyst NHC, (2) [1,2]-proton transfer, (3) oxidation, (4) stereoselective formation of the C-C σ bond, (5) intramolecular [2 + 2] cycloaddition, (6) dissociation of NHC, (7) release of CO 2 , and (8) transformation to axial chirality. Moreover, the calculated results can reasonably explain the observed chemo- and stereoselectivities for the formation of both benzothiophene/benzofuran-fused biaryls in these kinds of reactions. Further non-covalent interaction (NCI) and atoms-in-molecules (AIM) analyses demonstrate that the hydrogen bond interactions are responsible for the stability of key stereoselective transition states. This work would be useful for understanding the origin of stereoselectivity of NHC-catalyzed intermolecular cyclization reactions for the synthesis of axially benzothiophene/benzofuran-fused biaryl compounds.

Highly selective sensing of Fe 3+ is very important due to its great effect on biological systems. A novel ligand [1,1':4',1'':4'',1''':4''',1''''-quinquephenyl]-2,2'',2'''',5''-tetracarboxylic acid (H 4 qptca) was designed and successfully obtained for the first time via three steps in high total yields according to the absorption spectrum of Fe 3+ . The europium(III)-based metal-organic framework derived from H 4 qptca, {[Eu(qptca) 1/2 (H 2 qptca) 1/2 (H 2 O) 2 ]·DMF} n (referred to as SLX-1), was then synthesized and used as a water-stable and highly selective luminescent sensor for Fe 3+ in aqueous solution with a comparable detection limit using Ln-MOF probes (6.45 μM) through the antenna effect of SLX-1. Furthermore, the luminescence quenching mechanism was also proposed as a competitive absorption mechanism.

Similar to acetylcholinesterase, the activity of plant-derived esterase can also be inhibited by organophosphorus pesticides. Therefore, an electrochemical sensing platform using kidney bean esterase as a new detection enzyme was proposed for the highly sensitive determination of organophosphorus pesticides. Purified kidney bean esterase was obtained by an efficient and economical aqueous two-phase extraction method. Carboxylated graphene/carbon nanotube composites (cCNTs-cGR) and Au nanoparticles were used to provide a biocompatible environment to immobilize kidney bean esterase and also accelerate electron transport between the analyte and the electrode surface. Due to the good synergistic electrocatalytic effects of these nanomaterials, the biosensor exhibited an amplified electrocatalytic response to the oxidation of α-naphthalenol, which makes the sensor more sensitive. Based on the inhibitory effect of trichlorfon on kidney bean esterase activity, high sensitivity and low-cost detection of trichlorfon was achieved. Under optimum conditions, the inhibition of trichlorfon is proportional to its concentration in the range of 5 to 150 ng L -1 and 150 ng L -1 to 700 ng L -1 with an ultra-low detection limit of 3 ng L -1 . Moreover, the validity of the prepared biosensor was verified by analyzing several actual agricultural products (cabbage and rice) with satisfactory recoveries ranging from 94.05% to 106.76%, indicating that kidney bean esterase is a promising enzyme source for the analysis of organophosphorus pesticides in food samples., Competing Interests: The authors declare they have no conflicts of interest., (This journal is © The Royal Society of Chemistry.)

Bio-solubilization of lignite is a promising technology to transform coal into humic acids (HAs) which are broadly used in agriculture. In this work, HAs were extracted from lignite using the cell-free filtrate (CFF) of Penicillium ortum MJ51. The extraction method was optimized using response surface methodology (RSM) based on the interactive effects of nitric acid concentrations, coal loading ratio, extraction temperature and time as input factors, and the absorbance of HAs at 450 nm wavelength as the output response. Under optimized conditions (lignite pretreated with 4.7 N HNO 3 , coal loading ratio of 4.9%, temperature of 77.3 °C and time of 8.6 hours), the absorbance at 450 nm peaked at 70.28, and the concentration and extraction yield of HAs were 31.3 g L -1 and 63.9%, respectively, which were dramatically higher than those observed for traditional biological methods (0.7 g L -1 and 14.1%, respectively). The qualities of HAs produced under optimized conditions were evaluated and compared with those extracted by the conventional chemical method. The optimized process resulted in better HA quality indices, including lower molecular mass; higher nitrogen; less aromatic carbon; more aliphatic and carboxylic carbon; and higher bioactivity for promoting plant growth. Moreover, the anti-flocculation ability was improved, thereby supporting its applicability in agriculture. Extraction of HAs from lignite using the CFF of P. ortum MJ51 provides a novel technological approach for the efficient conversion of lignite to bio-active HAs., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (This journal is © The Royal Society of Chemistry.)

Sonodynamic therapy (SDT) is a highly attractive therapy due to its advantages of being non-invasive and having good penetration depth, but tumor hypoxia extremely restricts its therapeutic effect. Here, a novel oxygen-enhanced hybrid protein nanosonosensitizer system (MnPcS@HPO) is designed using human serum albumin (HSA) and hemoglobin (Hb) through disulfide reconfiguration, followed by encapsulating Mn-phthalocyanine (MnPcS), aiming to develop O 2 self-supplementing nanoparticles (NPs) for enhanced SDT. Benefitting from the O 2 -carrying ability of Hb and the tumor-targeting property of HSA, the MnPcS@HPO NPs are able to target tumor sites and alleviate hypoxia. Meanwhile, as a sonosensitizer, MnPcS is excited under US irradiation and activates dioxygen to generate abundant singlet oxygen ( 1 O 2 ), resulting in oxidative damage of tumor cells. Guided by photoacoustic and magnetic resonance dual-modal imaging, the MnPcS@HPO NPs alleviate tumor hypoxia and achieve good SDT efficiency for suppressing tumor growth. This work presents a novel insight into enhanced SDT antitumor activity through natural protein-mediated tumor microenvironment improvement.

G-quadruplex (G4) binding proteins regulate important biological processes, but their interaction networks are poorly understood. We report the first use of G4 as a warhead of a proteolysis-targeting chimera (G4-PROTAC) for targeted degradation of a G4-binding protein (RHAU/DHX36). G4-PROTAC provides a new way to explore G4-protein networks and to develop potential therapeutics.

Macrocyclic host molecules play the central role in host-guest chemistry and supramolecular chemistry. The highly structural symmetry of macrocyclic host molecules can meet people's pursuit of aesthetics in molecular design, and generally means a balance of design, synthesis, properties and applications. For macrocyclic host molecules with highly symmetrical structures, building blocks, which could be described as repeat units as well, are the most fundamental elements for molecular design. The structural features and recognition ability of macrocyclic host molecules are determined by the building blocks and their connection patterns. Using different building blocks, different macrocyclic host molecules could be designed and synthesized. With decades of developments of host-guest chemistry and supramolecular chemistry, diverse macrocyclic host molecules with different building blocks have been designed and synthesized. Aromatic building blocks are a big family among the various building blocks used in constructing macrocyclic host molecules. In this feature article, the recent developments of macrocyclic host molecules with aromatic building blocks were summarized and discussed.

Here is the first report on polyester-based nanocarriers fabricated via the ring-opening polymerization-induced self-assembly (ROPISA) of salicylic acid o -carboxyanhydride (SAOCA). This ROPISA process affords well-defined diblock copolymers that interestingly form an original cylindrical morphology.

Dissolved organic matter (DOM) in petroleum refinery wastewater is an extremely complex mixture. A better understanding of chemical compositions of DOM at the molecular level is necessary for the design and optimization of wastewater treatment processes. In this study, two largely different DOM samples, one from a petroleum refinery wastewater and the other from the Suwannee river water, were characterized by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) coupled with positive-/negative-ion electrospray ionization (ESI), and positive-ion atmospheric pressure photoionization (APPI). For wastewater DOM, a total of 6226 molecular formulae were assigned in the three ionization modes. However, only 1182 molecular formulae were common in all three mass spectra, indicating that the techniques were highly complementary in the types of molecules they ionize. Acid O x ( x = 1-9) and basic N 1 O x ( x = 0-2) classes were dominant in the wastewater DOM detected in negative-ion and positive-ion ESI mode, respectively. And the wastewater DOM contains considerable amounts of polycyclic aromatic hydrocarbons that did not respond to ESI but can be ionized selectively by APPI. Compared with riverine DOM, the refinery wastewater DOM has a higher molecular complexity and is more enriched in hydrocarbon, and nitrogen- and sulfur-containing compounds. The results show that the major components of refinery wastewater DOM were distinctive from those of the natural organic matter. Though not quantitative, the results obtained by various ionization techniques were found to be complementary, and are helpful to our understanding of the selectivity of different ionization techniques as well as the molecular compositions of DOM.

The interfacial perimeter is generally viewed as the catalytically active site for a number of chemical reactions over oxide-supported nanogold catalysts. Here, well-defined CeO 2 nanocubes, nanorods and nanopolyhedra are chosen to accommodate atomically precise clusters ( e.g. Au 25 (PET) 18 ) to give different Au cluster-CeO 2 interfaces. TEM images show that Au particles of ∼1.3 nm are uniformly anchored on the ceria surface after annealing in air at 120 °C, which can rule out the size hierarchy of nanogold in CO oxidation studies. The gold nanoclusters are only immobilized on the CeO 2 (200) facet in Au 25 /CeO 2 -C, while they are selectively loaded on CeO 2 (002) and (111) in the Au 25 /CeO 2 -R and Au 25 /CeO 2 -P catalysts. X-ray photoelectron spectroscopy (XPS) and in situ infrared CO adsorption experiments clearly demonstrate that the gold species in the Au 25 /CeO 2 samples are similar and partially charged (Au δ + , where 0 < δ < 1). It is observed that the catalytic activity decreases in the order of Au/CeO 2 -R ≈ Au/CeO 2 -P > Au/CeO 4 -C in the CO oxidation. And the apparent activation energy over Au 25 /CeO 2 -C (60.5 kJ mol -1 ) is calculated to be about two-fold of that over the Au 25 /CeO 2 -R (28.6 kJ mol -1 ) and Au 25 /CeO 2 -P (31.3 kJ mol -1 ) catalysts. It is mainly tailored by the adsorbed [O] species on the ceria surface, namely, Au 25 /CeO 2 (002) and Au 25 /CeO 2 (111) which were more active than the Au 25 /CeO 2 (200) system in the CO oxidation. These insights at the molecular level may provide guidelines for the design of new oxide-supported nanogold catalysts for aerobic oxidations., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The disruption of bone homeostasis with the decrease in osteoblastic bone formation and facilitated osteoclastic bone resorption is the leading cause of periprosthetic osteolysis. Accumulative studies have indicated that irisin has the function of maintaining and rebalancing bone homeostasis. In this study, we explored the protective effect of irisin on wear-particle-induced osteolysis in mice. The results showed that irisin effectively inhibited titanium (Ti) particle-induced calvarial osteolysis, supported by a lower bone loss and existence of more collagen, compared with the ones stressed by Ti particles. Further analysis demonstrated that irisin not only rescued Ti-particle-impaired osteogenesis derived from bone mesenchymal stem cells (BMSCs) but also alleviated the increase in wear-particle-induced nuclear factor-κB ligand (RANKL) secreted by BMSCs-derived osteoblasts, which consequently restrained the activation of osteoclasts. Meanwhile, irisin inhibited osteoclastogenesis by the direct inactivation of reactive oxygen species (ROS) signaling. These results revealed that irisin functions to fight against osteolysis caused by wear particles through rebalancing the periprosthetic bone homeostasis microenvironment, which may provide a potential therapeutic strategy for the management of osteolysis and induced prosthetic loosening.