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The unique 4f orbitals and abundant electronic energy levels of rare earth elements enable effective doping and modification to enhance hydrogen storage performance, making it an increasingly prominent focus of research. The structures of neutral and cationic CeHn0/+ (n = 2–20) clusters have been determined using the Crystal Structure AnaLYsis by Particle Swarm Optimization (CALYPSO) method in conjunction with density functional theory (DFT). Interestingly, the CeH13 and CeH14+ exhibit remarkable stability in the doublet state with Cs and C2v symmetry, respectively. The adsorption energy of CeHn0/+ (n = 2–20) suggests a preference for H atoms to chemically adsorb on Ce atoms. The analysis of molecular orbital composition reveals that the stability of both CeH13 and CeH14+ is attributed to the significant hybridization between the H 1s and Ce 4f orbitals. Both CeH13 and CeH14+ demonstrate significant hydrogen storage capacities, with values reaching 8.5 wt% and 9.1 wt%, respectively. [ABSTRACT FROM AUTHOR]

Nonlinear optical (NLO) effects originating from materials doped with rare-earth ions possess colossal potential for application in all-optical switches. However, among previous studies, Er3+ ion-doped glass ceramics (GCs) with remarkable NLO features have been investigated with respect to optical modulation applications by tailoring their nonlinear transmittance upon excitation at various near-infrared (NIR) wavelengths, which might prove to be a simple way of achieving “on–off” optical modulation in future all-optical switches. Here, we present the first observation of tailorable nonlinear transmittance in germanate oxyfluoride GCs containing Er3+:LaF3 nanocrystals, manipulated by excitation at 808, 980, and 1550 nm, which is consistent with the results from theoretical calculations and simulations. Furthermore, we conduct experimental investigation and analysis related to energy level transitions and dynamical evolution, indicating that these intriguing NLO features can be attributed to the differentiation between excited state absorption accompanied by up-conversion luminescence and stimulated emission processes during excitation at discrepant NIR wavelengths. Importantly, bidirectional optical switching for the “on–off” toggle effect has been successfully demonstrated by selectively tailoring the nonlinear transmittance of the single Er3+-doped GCs. This tailorable NLO behavior of Er3+-doped GCs, which is dependent on excitation at different NIR wavelengths, might provide a versatile strategy for the development of next-generation bidirectional all-optical switches. [ABSTRACT FROM AUTHOR]

Improvements in the electrical conductivity and lithium (Li) mobility for Li ion batteries are of particular importance for their high-power applications. Mapping of electron energy loss spectroscopy shows that the electrochemical reaction front region is under electron-rich conditions during lithiation. In this paper, the electron-rich effect on the diffusion behaviors of Li in pristine and phosphorus-doped group IVA elements, e.g., silicon, germanium and tin, were investigated using the first principles density functional theory (DFT) calculations in combination with a climbing-image nudged elastic band and ab initio DFT molecular dynamics. Phosphorus doping was found to be a non-critical factor for enhanced Li diffusion into Si. Instead, the results showed that the diffusion barriers and diffusivity of Li are mainly affected by the electron-rich effect, i.e. the energy barriers decrease and diffusivity increases in an electron-rich environment. The decrease in diffusion barriers was attributed to the relaxation of Si-Si bonds with extra electrons, which can also apply to the case of Ge but not for metallic Sn. These new findings provide a theoretical and experimental basis for the design and fabrication of next generation batteries with a high power density. [ABSTRACT FROM AUTHOR]

There is an increased trend towards the use of drug and enteric coated sugar spheres for controlled oral delivery of active pharmaceutical ingredients (API). This trend is driven by increased efficacy and ease of formulation of different dosage levels. However, difficulties exist in determining the thickness of drug and enteric coatings in a time efficient manner during manufacture, quality assurance and stability testing. The thickness of the coating determines the dosage of the API and the thickness of the enteric coating determines the release rate of the drug in the gastro-intestinal tract. Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS) offers a rapid new approach to characterising the enteric coating thickness and the raw materials used in their manufacture. BARDS applications are based on reproducible changes in the compressibility of a solvent during dissolution which is monitored acoustically due to associated changes in the speed of sound in solution. It is demonstrated how core delivery sugar spheres have unique acoustic spectra attributable to the mean size distribution of the spheres. A steady state acoustic lag time is associated with the disintegration of the enteric coating, in basic solution. This lag time can be manipulated by varying the concentration of the base which affects the rate at which the coating dissolves. It is anticipated that the thickness/loading of the spheres can be estimated from the lag time. [ABSTRACT FROM AUTHOR]

A hemodynamic Lab-on-a-chip system was developed in this study. This system has two unique features: (1) it consists of a microfluidic network with an array of endothelial cell seeding sites for testing them under multiple conditions, and (2) the flow rate and the frequency of the culture medium in the microchannel are controlled by a pulsation free pump to mimic the flow profile of the blood in the blood vessel under different physiological conditions. The investigated physiological conditions were: (1) the resting condition in a normal shear stress of 15 dyne cm−2with a normal heart rate of 70 bpm, (2) an exhaustive exercise condition with a high shear stress of 30 dyne cm−2and a fast heart rate of 140 bpm, and (3) a constant high shear stress of 30 dyne cm−2. Two chemical conditions were investigated (10 mM and 20 mM glucose) to mimic hyperglycemic conditions in diabetes patients. The effects of various shear stresses either alone or in combination with different glucose concentrations on endothelial cells were examined using the developed hemodynamic Lab-on-a-chip system by assessing two parameters. One is the intracellular level of reactive oxygen species (ROS) determined by a fluorescent probe, H2DCFDA. Another is the mitochondrial morphology revealed with a fluorescent dye, MitoTracker Green FM. The results showed that ROS level was elevated nearly 4-fold after 60 min of exhaustive exercise. We found that the pulsatile nature of the fluid was the determination factor for causing ROS generation in the cells as almost no increase of ROS was detected in the constant shear stress condition. Similarly, much higher level of ROS was detected when 10 mM glucose was applied to the cells under normal or high pulsatile shear stresses compared with under a static condition. These results suggest that it is necessary to use pulsatile shear stress to represent the physiological conditions of the blood flow, and demonstrate the advantage of utilizing this newly developed hemodynamic Lab-on-a-chip system over the conventional non-pulsatile system in the future shear stress related studies. [ABSTRACT FROM AUTHOR]

A successful attempt to fabricate nanoparticle arrays with subnanometre spacing by thermal annealing of the prepared nanoparticle self-assembly was made. The molecular dynamics simulation indicated that the spacing decrease could be attributed to the temperature-enhanced mobility of the ligand, which promoted the relaxation of the nanoparticles to a more compact arrangement. [ABSTRACT FROM AUTHOR]

The forces required for the detachment of ferrocene (Fc) from β-cyclodextrin (βCD) in a single host (βCD)--guest (Fc) complex were investigated using force spectroscopy under electrochemical conditions. The red ox state of the guest Fc moiety as well as the structure of the supporting matrix was found to decisively affect the nanomechanical properties of the complex. [ABSTRACT FROM AUTHOR]

Gastrointestinal (GI) mucus is a biologically complex hydrogel that acts as a partially permeable barrier between the contents of the GI tract and the mucosal epithelial lining. Its structural integrity is essential for the lubrication of the tract thereby aiding smooth transit of contents, and the protection of the epithelium from pathogens that seek to colonise and invade. Understanding its physical response to drugs and the microbiome is essential for treating many gastrointestinal infectious diseases. Given this, a static in vitro model of a GI mucus-on-a-chip has been developed with integrated electronics to monitor the barrier properties of mucus hydrogels. Its application for investigating the effect of drugs and biofilm formation on the mucus structure is validated using rheological techniques, confocal microscopy and electrochemical impedance spectroscopy (EIS).

As an important gaseous pollutant, SO 2 derivatives generally exist and significantly threaten the environment and organism health. Meanwhile, polarity is a disease-related indicator in the organism's microenvironment, where an unregulated variation may disturb the physiological metabolisms. Hence, a superior FRET-based fluorescent sensor (TLA) is presented to track polarity and sulfur dioxide derivatives by dual emission channel, i.e. an elevated red emission at 633 nm with decreasing polarity as well as a reduced red emission at 633 nm and improved blue emission at 449 nm with increasing concentration of SO 2 derivatives. The probe TLA could sensitively detect SO 2 derivatives with ultra-large Stokes shift (273 nm), excellent stability, high selectivity, and low detection limit. Importantly, TLA can accurately detect sulfur dioxide derivatives in real food as well as water samples. Besides, TLA was also fabricated as testing strips and applied to detect SO 2 derivatives in the solution., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Electrochemiluminescence (ECL) has emerged as a valuable tool for understanding multiphasic and compartmentalized systems, which have crucial wide-ranging applications across diverse fields. However, ECL reactions are limited to the vicinity of the electrode surface due to spatial constraints of electron transfer and the short lifetime of radical species, making ECL emission in bulk multiphasic solution challenging. To address this limitation, we propose a novel bipolar electrochemistry (BPE) approach for wireless dual-color ECL emission at the water/organic (w/o) interface. Firstly, amphiphilic glassy carbon (GC) microbeads with distinct hydrophilic and hydrophobic regions are prepared by bipolar electrografting of hydrophobic trifluoromethyl diazonium salt, then the resulting Janus beads are positioned at the w/o interface. Subsequently, two model ECL systems containing luminol and H 2 O 2 in the aqueous phase, and [Ru(bpy) 3 ] 2+ and benzoyl peroxide (BPO) in the organic phase, are selected based on their solubility to confine light-emitting reactions to their respective phases. Upon application of an electric field perpendicular to the interface, the Janus microbeads get polarized, triggering simultaneous oxidative blue ECL (425 nm) and reductive red ECL (620 nm) in the aqueous and organic phases, respectively. Taking advantage of ECL imaging, the potential gradient distribution on the GC microbead at the w/o interface is revealed, indicating a "pseudo-closed" bipolar system due to limited ion transfer between phases. We also investigate the effect of changing the electric field direction parallel to the interface, which alters the ECL emission area from a hemisphere to a quarter of the microbead's surface. This bipolar ECL approach at the w/o interface not only offers opportunities for imaging the aqueous phase and organic phase simultaneously, but also enables ECL imaging and light generation in the bulk solution, thus overcoming the usual spatial limitation requiring proximity to the electrode surface., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Bioactive protein-derived hydrogels are highly attractive three-dimensional (3D) platforms for in vitro cell culture. However, most protein and polypeptide hydrogels are extracted from animal tissues or chemically synthesized, with many drawbacks. Herein, we fabricated an optically transparent ZmT-PEG hydrogel via a facile one-pot strategy. The modified Z1Z2 (Zm) was obtained by introducing cysteine at the C-terminus of Z1Z2 (ZC) and inserting the RGD sequence into the low conserved (CD) loop (ZR). A Michael addition reaction occurred between Zm and 4-arm PEG-MAL, and Zm-PEG self-assembled with truncated Telethonin (Tm) to form the hydrogel. We expressed the Zm and Tm proteins in Escherichia coli . CD spectroscopy showed that genetic modification and the reaction with 4-arm PEG-MAL had no effect on the secondary structure of the Zm protein. When Zm was at 10 wt% and the ratio of Zm : 4-arm PEG-MAL : Tm was 2 : 1 : 1, the gelation time was 6-8 hours. SEM results revealed that the hydrogels had an interconnected porous structure with pore diameters of 20-150 μm. Cell experiments showed that MCF-7 cells could grow and proliferate significantly on the hydrogel after 7 days of culture. Immunofluorescence results suggested that MCF-7 cells on the ZmT hydrogel had a spherical structure similar to that on Matrigel. These results indicate that the ZmT-PEG hydrogel can be used for cell culture in vitro and is promising for large-scale production.

An effective approach for the highly selective synthesis of selenium-containing ( E )- N -propenolquinazolinones via an FeCl 3 ·6H 2 O mediated cascade reaction of propargyl quinazoline-4-yl ethers and diselenides has been developed. Mechanistic investigations revealed that the reaction of FeCl 3 and (PhSe) 2 generates, in situ , the electrophilic species PhSe[FeCl 4 ]·6H 2 O, which triggers the cascade reaction.

Upconversion nanoparticles (UCNPs) have been used as a potential nanocarrier for photosensitizers (PSs), which have demonstrated a great deal of promise in achieving an effective photodynamic therapy (PDT) for deep-seated tumors. However, overcoming biological barriers to achieve mitochondria-targeted PDT remains a major challenge. Herein, CD44- and mitochondria-targeted photodynamic nanosystems were fabricated through the self-assembly of hyaluronic acid-conjugated-methoxy poly(ethylene glycol)-diethylenetriamine-grafted-(chlorin e6-dihydrolipoic acid-(3-carboxypropyl)triphenylphosphine bromide) polymeric ligands (HA-c-mPEG-Deta- g -(Ce6-DHLA-TPP)) and NaErF 4 :Tm@NaYF 4 core-shell UCNPs (termed CMPNs). The CMPNs presented ideal physiological stability, a good drug loading capacity and an improved capacity for the generation of singlet oxygen ( 1 O 2 ) based on the FRET mechanism. Significantly, confocal images revealed that CMPNs not only facilitated cellular uptake through CD44-receptor-targeted endocytosis, subsequently enabling rapid evasion from endo-lysosomal sequestration, but also specifically targeted mitochondria, ultimately inducing a profound disruption of mitochondrial membrane potential, which triggered apoptosis upon laser irradiation, thereby significantly enhancing the therapeutic effect. Furthermore, in vitro antitumor experiments further confirmed the substantial enhancement in cancer cell killing efficiency achieved by treating with CMPNs upon near-infrared (NIR) laser irradiation. This innovative approach holds promise for the development of NIR-laser-activated photodynamic nanoagents specifically designed for mitochondria-targeted PDT, thus addressing the limitations of the current PDT treatments.

Monolayer MoTe 2 and WTe 2 within the two-dimensional transition metal dichalcogenides (TMDCs) material family exhibit broad potential for application in optoelectronic devices owing to their direct band gap characteristics. In this work, upon alloying these materials into a monolayer system denoted as Mo 1- x W x Te 2 , intriguing alterations are observed in the electronic and optoelectronic properties. The photoelectric attributes of these alloys can be tailored by manipulating the respective ratios of molybdenum to tungsten (Mo/W). This investigation employs first-principles calculations based on density functional theory (DFT) to assess physical traits of two-dimensional monolayered structures composed from varying compositions of Mo 1- x W x Te 2 . Our findings reveal that while maintaining a direct band gap characteristic across all compositions studied, there is also a reduction observed in electron effective mass near the Fermi level. Moreover, changing in the Mo/W ratio allows gradual adjustments in electronic properties such as density of states (DOS), work function, dielectric function, absorptivity, and reflectivity. Phonon dispersion curves further demonstrate the stability of Mo 1- x W x Te 2 systems. Notably, Mo 0.5 W 0.5 Te 2 exhibits lower polarizability and reduced band gap when compared against MoTe 2 and WTe 2 counterparts. This research underscores how alloying processes enable customizable modifications in the electronic and optoelectronic properties of Mo 1- x W x Te 2 monolayer materials which is essential for enhancing nanoscale electronic and optoelectronic device design., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We herein developed an effective approach for the construction of 2- or 4-(1,4-dioxan-2-yl) substituted quinazolines under mild conditions. A silver-K 2 S 2 O 8 catalyzed direct CDC reaction between quinazolines and 1,4-dioxane for the synthesis of a series of 2- or 4-(1,4-dioxan-2-yl) substituted quinazoline hybrids is reported. The reaction proceeded well in water under mild conditions and showed a broad substrate scope and good functional group compatibility.

Obesity has emerged as a significant global health burden, exacerbated by serious side effects associated with existing anti-obesity medications. Celastrol (CLT) holds promise for weight loss but encounters challenges related to poor solubility and systemic toxicity. Here, we present chondroitin sulfate (CS)-derived micelles engineered for adipocyte-specific targeting, aiming to enhance the therapeutic potential of CLT while minimizing its systemic toxicity. To further enhance adipocyte affinity, we introduced a biguanide moiety into a micellar vehicle. CS is sequentially modified with hydrophilic metformin and hydrophobic 4-aminophenylboronic acid pinacol ester (PBE), resulting in the self-assembly of CLT-encapsulated micelles (MET-CS-PBE@CLT). This innovative design imparts amphiphilicity via the PBE moieties while ensuring the outward exposure of hydrophilic metformin moieties, facilitating active interactions with adipocytes. In vitro studies confirmed the enhanced uptake of MET-CS-PBE@CLT micelles by adipocytes, while in vivo studies demonstrated increased distribution within adipose tissues. In a diet-induced obese mouse model, MET-CS-PBE@CLT exhibited remarkable efficacy in weight loss without affecting food intake. This pioneering strategy offers a promising, low-risk, and highly effective solution to address the global obesity epidemic.

In contemporary society, the conversion and efficient utilization of waste biomass and its derivatives are of great significance. Carbonized wood (CW) is an easily accessible and cost-effective green resource, but it has limitations as an electrode material due to its low specific surface area, limited active sites and poor conductivity. Therefore, it is crucial to improve the performance of biomass-based materials by using activation, heteroatom doping and modification methods to enhance the specific surface area and active sites. In this study, we developed acid-modified urea-doped activated carbonized wood (AUACW) with a three-dimensional (3D) porous structure and porosity, achieving a high specific surface area of 1321.3 m 2 g -1 . In addition, the degree of graphitization ( I D / I G = 1.0) provides good conductivity and a large number of active sites, which are conducive to charge transfer and ion diffusion. The increase of nitrogen and oxygen elements enhances the surface wettability of the material and provides additional pseudocapacitance. The specific capacitance of AUACW reaches 435.84 F g -1 at 0.8 A g -1 with a 93.6% capacitance retention after 10 000 cycles in a 1 M KOH electrolyte. More attractively, a symmetrical supercapacitor (SSC) based on AUACW delivers an energy density of 22.61 W h kg -1 at a power density of 533.26 W kg -1 . This work demonstrates the promising potential of utilizing waste biomass to develop green and valuable carbon materials for supercapacitors.

The light-induced photocycloaddition of 9,10-phenanthrenequinone (PQ) with electron-rich alkenes (ERA), known as the PQ-ERA reaction, is a highly attractive photoclick reaction characterized by its operational simplicity and high biocompatibility. One essential aspect of photoclick reactions is their high rate, however the limited solubility of PQs often requires the use of a co-solvent. Evaluating the effect of different co-solvents on the PQ-ERA reaction and their influence on the reaction rate, we discovered that sulfur-containing compounds, in particular the frequently used solubilizing co-solvent DMSO, quench the triplet state of the PQ. These experimental results, supported by nanosecond-microsecond and ultrafast transient absorption data, show that even minimal amounts of DMSO result in a decreased lifetime of the reactive triplet state, essential for the photoclick reaction. Without DMSO as co-solvent, exceptionally high photoreaction quantum yields ( Φ P up to 93% with only 1 equivalent ERA) and complete conversion in seconds can be achieved. With these outstanding efficiencies, the PQ-ERA reaction can be used without excess ERA and at low light intensities, facilitating photoclick transformations in various future applications., Competing Interests: There are no competing conflicts of interests to declare., (This journal is © The Royal Society of Chemistry.)

Background : The escalating prevalence of hyperuricemia is emerging as a significant public health concern. The association between dietary lignans and hyperuricemia is yet to be fully elucidated. Our study aims to evaluate the relationships between dietary lignan intake and hyperuricemia among middle-aged and elderly Chinese individuals, with an additional focus on investigating the underlying mechanisms. Methods : Dietary lignan intake was measured using a validated Food Frequency Questionnaire in 3801 participants at the baseline. Among them, 2552 participants were included in the longitudinal study with a median follow-up of 10.5 years. The gut microbiota was analyzed by shotgun metagenome sequencing in 1789 participants, and the targeted fecal metabolome was determined in 987 participants using UPLC-MS/MS at the midpoint of follow-up. Results : The multivariable-adjusted HRs (95% CIs) for hyperuricemia incidence in the highest quartile ( vs. the lowest quartile) of dietary intake of total lignans, matairesinol, pinoresinol, and secoisolariciresinol were 0.93 (0.78-1.10), 0.77 (0.66-0.90), 0.83 (0.70-0.97), and 0.85 (0.73-1.00), respectively. The gut microbial and fecal metabolic compositions were significantly different across the dietary lignan groups and the hyperuricemia groups. The beneficial associations between dietary lignans and hyperuricemia might be mediated by several gut microbes ( e.g. , Fusobacterium mortiferum and Blautia sp. CAG-257) and the downstream bile acid products ( e.g. , NorCA, glycochenodeoxycholic acid, and glycoursodeoxycholic acid). Conclusion : We found that dietary lignans were inversely associated with hyperuricemia incidence, and the gut microbiota-bile acid axis might mediate this association. Our findings provide new perspectives on precise therapeutic targets and underlying mechanisms for conditions associated with elevated uric acid.

An effective approach for the construction of 4-short-chain ether attached carbonyl group-substituted quinazolines was developed. Visible-light-induced three-component reactions of α-diazoesters, quinazolinones, and cyclic ethers, with a broad substrate scope and excellent functional group tolerance, under extremely mild conditions without the need for any additional additives and catalysts, selectively led to quinazoline-based hybrids in good to excellent yields. The synthesized hybrids, which are a conglomeration of a quinazoline, a short-chain ether, and a carbonyl group in one molecular skeleton, have potential for application in the development of new drugs or drug candidates.

The unique 4f orbitals and abundant electronic energy levels of rare earth elements enable effective doping and modification to enhance hydrogen storage performance, making it an increasingly prominent focus of research. The structures of neutral and cationic CeH n 0/+ ( n = 2-20) clusters have been determined using the Crystal Structure AnaLYsis by Particle Swarm Optimization (CALYPSO) method in conjunction with density functional theory (DFT). Interestingly, the CeH 13 and CeH 14 + exhibit remarkable stability in the doublet state with C s and C 2v symmetry, respectively. The adsorption energy of CeH n 0/+ ( n = 2-20) suggests a preference for H atoms to chemically adsorb on Ce atoms. The analysis of molecular orbital composition reveals that the stability of both CeH 13 and CeH 14 + is attributed to the significant hybridization between the H 1s and Ce 4f orbitals. Both CeH 13 and CeH 14 + demonstrate significant hydrogen storage capacities, with values reaching 8.5 wt% and 9.1 wt%, respectively.

Cancer is one of the primary health concerns among humans due to its high incidence rate and lack of effective treatment. Currently, medical techniques to achieve the precise elimination of local cancer lesions with negligible damage to normal tissues are still intensely desired. Herein, we synthesized BaTiO 3 -TiO 2 hollow spheres (BTHSs) for use in microwave dynamic therapy (MWDT) for cancer. Under UV irradiation, BTHSs can mediate the production of multiple reactive oxygen species (ROS), mainly 1 O 2 , which results in a rapid photocatalytic degradation rate (97%), 1.6-fold that of commercial P25. Importantly, the ROS production process can be triggered by microwaves to effectively execute MWDT for cancer. Under microwave irradiation, BTHSs exhibit a remarkable therapeutic effect and slight cytotoxicity. In terms of mechanism, the enhanced ROS production efficiency of BTHSs can be attributed to their unique hollow structure and the formation of a type-II heterojunction by the incorporation of BaTiO 3 . The hollow structure increases the availability of active sites and enhances light scattering, while the BaTiO 3 -TiO 2 heterojunction enhances the photocatalytic activity of TiO 2 through charge transfer and electron-hole separation. Overall, this study provides important insights into the design and optimization of sensitizers for MWDT applications.

The therapeutic efficacy of Fenton or Fenton-like nanocatalysts is usually restricted by the inappropriate pH value and limited concentration of hydrogen peroxide (H 2 O 2 ) at the tumor site. Herein, calcium carbonate (CaCO 3 )-mineralized cobalt silicate hydroxide hollow nanocatalysts (CSO@CaCO 3 , CC) were synthesized and loaded with curcumin (CCC). This hybrid system can simultaneously realize nanocatalytic therapy, chemotherapy and calcium overload. With the stabilization of liposomes, CCC is able to reach the tumor site smoothly. The CaCO 3 shell first degrades in an acidic tumor environment, releasing Cur and Ca 2+ , and the pH value of the tumor is increased simultaneously. Then the exposed CSO catalyzes the Fenton-like reaction to convert H 2 O 2 into ˙OH and enhances the cytotoxicity of curcumin (Cur) by catalytically oxidizing it to a ˙Cur radical. Curcumin not only induces the chemotherapy effect but also serves as a nucleophilic ligand and an electron donor in the catalytic system, enhancing the Fenton-like activity of CCC by electron transfer. In addition, calcium overload also amplifies the efficacy of ROS-based therapy. In vitro and in vivo results show that CCC exhibited an excellent synergistic tumor inhibition effect without any clear side effect. This work proposes a novel concept of nanocatalytic therapy/chemotherapy synergistic mechanism by the ligand-induced enhancement of Fenton-like catalytic activity, and inspires the construction of combined therapeutic nanoplatforms and multifunctional nanocarriers for drug and ion delivery in the future.

Genetically modified (GM) food is still highly controversial nowadays. Due to the disparate policies and attitudes worldwide, demands for a rapid, cost-effective and user-friendly GM crop identification method are increasingly significant for import administration, market supervision, etc. However, as the most-recognized methods, nucleic acid-based identification approaches require bulky instruments, long turn-around times and trained personnel, which are only suitable in laboratories. To fulfil the urgent needs of on-site testing, we develop a point-of-care testing platform that is able to identify 12 types of GM crops in less than 40 minutes without using laboratory settings. Our system integrates sample pre-treatment modules in a microfluidic chip, performs DNA amplification via a battery-powered portable kit, and presents results via eye-recognized colorimetric change. A paraffin-based reflow method and a slip plate-based fluid switch are developed to encapsulate and release amplification primers in individual microwells on demand, thus enabling identification of varied targets simultaneously. Our system offers an efficient, affordable and convenient tool for GM crop identification, thus it will not only benefit customs and market administration bureaus, but also satisfy demands of numerous consumers.

A practical carbon dioxide (CO 2 ) conversion and utilization system shows great potential for ameliorating the greenhouse effect. Herein, an integrated carbon aerogel-based photothermal catalysis microreactor with photothermal conversion, enhanced mass transfer adsorption and a thermal catalytic reactor is designed. As a solar-powered CO 2 utilization module, this microreactor can conveniently convert CO 2 into economically valuable products without elaborate equipment and operation processes.

The anti-obesity effect of conjugated linoleic acid (CLA) has been well elucidated, but whether CLA affects fat deposition by regulating intestinal dietary fat absorption remains largely unknown. Thus, this study aimed to investigate the effects of CLA on intestinal fatty acid uptake and chylomicron formation and explore the possible underlying mechanisms. We found that CLA supplementation reduced the intestinal fat absorption in HFD (high fat diet)-fed mice accompanied by the decreased serum TG level, increased fecal lipids and decreased intestinal expression of ApoB48 and MTTP. Correspondingly, c9, t11-CLA, but not t10, c12-CLA induced the reduction of fatty acid uptake and TG content in PA (palmitic acid)-treated MODE-K cells. In the mechanism of fatty acid uptake, c9, t11-CLA inhibited the binding of CD36 with palmitoyltransferase DHHC7, thus leading to the decreases of CD36 palmitoylation level and localization on the cell membrane of the PA-treated MODE-K cells. In the mechanism of chylomicron formation, c9, t11-CLA inhibited the formation of the CD36/FYN/LYN complex and the activation of the ERK pathway in the PA-treated MODE-K cells. In in vivo verification, CLA supplementation reduced the DHHC7-mediated total and cell membrane CD36 palmitoylation and suppressed the formation of the CD36/FYN/LYN complex and the activation of the ERK pathway in the jejunum of HFD-fed mice. Altogether, these data showed that CLA reduced intestinal fatty acid uptake and chylomicron formation in HFD-fed mice associated with the inhibition of DHHC7-mediated CD36 palmitoylation and the downstream ERK pathway.

Anxiety- and depression-like behaviors are commonly observed clinical features of depression and many other mental disorders. Recent evidence has revealed the crucial role of the microbiota-gut-brain axis in the bidirectional communication between the gastrointestinal tract and the central nervous system. Supplementation with psychobiotics may provide a novel approach for the adjunctive treatment of mental disorders by regulating the intestinal microecology. We isolated and identified a novel probiotic, Lactiplantibacillus plantarum D-9 (D-9), from traditional Chinese fermented foods in our previous work, which exhibited a high yield of gamma-aminobutyric acid (GABA). Herein, it was proved that the oral administration of D-9 could alleviate the depression- and anxiety-like behaviors of Chronic Unpredicted Mild Stress (CUMS) mice, and show non-toxicity or side-effects in the mice. Physiological and biochemical analyses demonstrated that D-9 regulated tryptophan metabolism, the HPA-axis and inflammation in CUMS mice. Moreover, D-9 modulated the structure and composition of the gut microbiota, leading to an increase in the relative abundance of Ligilactobacillus murinus and Lactobacillus johnsonii , and a decrease in the levels of Kineothrix alysoides and Helicobacter bilis compared to those in CUMS mice. Our work demonstrates that D-9 alleviated anxiety- and depression-like disorders in CUMS mice by modulating tryptophan metabolism and the gut microbiota. These findings provide an innovative strategy for the intervention and treatment of depressive disorders.

In the era of the Internet of Things and wearable electronics, 3D-printed micro-batteries with miniaturization, aesthetic diversity and high aspect ratio, have emerged as a recent innovation that solves the problems of limited design diversity, poor flexibility and low mass loading of materials associated with traditional power sources restricted by the slurry-casting method. Thus, a comprehensive understanding of the rational design of 3D-printed materials, inks, methods, configurations and systems is critical to optimize the electrochemical performance of customizable 3D-printed micro-batteries. In this review, we offer a key overview and systematic discussion on 3D-printed micro-batteries, emphasizing the close relationship between printable materials and printing technology, as well as the reasonable design of inks. Initially, we compare the distinct characteristics of various printing technologies, and subsequently emphatically expound the printable components of micro-batteries and general approaches to prepare printable inks. After that, we focus on the outstanding role played by 3D printing design in the device architecture, battery configuration, performance improvement, and system integration. Finally, the future challenges and perspectives concerning high-performance 3D-printed micro-batteries are adequately highlighted and discussed. This comprehensive discussion aims at providing a blueprint for the design and construction of next-generation 3D-printed micro-batteries., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Although plant-derived cancer therapeutic products possess great promise in clinical translations, they still suffer from quick degradation and low targeting rates. Herein, based on the oxygen vacancy (OV)-immobilization strategy, an OV-enriched biodegradable silicate nanoplatform with atomically dispersed Fe/Mn active species and polyethylene glycol modification was innovated for loading gallic acid (GA) (noted as FMMPG) for intratumoral coordination-enhanced multicatalytic cancer therapy. The OV-enriched FMMPG nanozymes with a narrow band gap (1.74 eV) can be excited by a 650 nm laser to generate reactive oxygen species. Benefiting from the Mn-O bond in response to the tumor microenvironment (TME), the silicate skeleton in FMMPG collapses and completely degrades after 24 h. The degraded metal M (M = Fe, Mn) ions and released GA can in situ produce a stable M-GA nanocomplex at tumor sites. Importantly, the formed M-GA with strong reductive ability can transform H 2 O 2 into the fatal hydroxyl radical, causing serious oxidative damage to the tumor. The released Fe 3+ and Mn 2+ can serve as enhanced contrast agents for magnetic resonance imaging, which can track the chemodynamic and photodynamic therapy processes. The work offers a reasonable strategy for a TME-responsive degradation and intratumoral coordination-enhanced multicatalytic therapy founded on bimetallic silicate nanozymes to achieve desirable tumor theranostic outcomes.

Lactic acid bacterial fermentation helps reduce the immunoreactivity of soy protein. Nevertheless, the effect of lactic acid bacterial fermentation on a particular soy allergen and the consequent dynamic change of epitopes during gastrointestinal digestion are unclear. In this study, soy glycinin was isolated and an in vitro dynamic gastrointestinal model was established to investigate the dynamic change in the immunoreactivity and peptide profile of unfermented (UG) and fermented glycinin (FG) digestates. The results demonstrated that the FG intestinal digestate had a lower antigenicity (0.08%-0.12%) and IgE-binding capacity (1.49%-3.61%) towards glycinin at the early (I-5) and middle (I-30) stages of gastrointestinal digestion, especially those prepared at 2% (w/v) protein concentration. Peptidomic analysis showed that the glycinin subunits G1 and G2 were the preferred ones to release the most abundant peptides, whereas G2, G4, and G5 had an elevated epitope-cleavage rate in FG at stages I-5 and I-30. Three-dimensional modeling revealed that fermentation-induced differential degradation epitopes in gastrointestinal digestion were predominantly located in the α-helix and β-sheet structures. They were closely correlated with the reduced immunoreactivity of soy glycinin.

Two carbonyl and o -NH 2 -NO 2 -containing energetic materials and their analogues were effectively designed, synthesized and fully characterized with multinuclear NMR, IR and elemental analyses. Their structures were also further confirmed via X-ray diffraction. Among them, compound 7 exhibits good potential for application as a secondary explosive with extremely high density (2.04 g cm -3 ), good sensitivity (IS > 40 J, FS > 360 N), and excellent calculated detonation performance ( D v = 8943 m s -1 , P = 35.0 GPa). Furthermore, a detailed comparative study based on X-ray diffraction, Hirshfeld surfaces and 2D fingerprint plots among compounds 4, 7 and 9 has demonstrated that the density and detonation performance could be effectively improved via introducing a carbonyl group into fused-ring compounds. More importantly, the sensitivity of the resulting energetic materials did not deteriorate. Obviously, this strategy via introducing carbonyl, o -NH 2 -NO 2 and nitroamino groups into fused-ring energetic compounds will help in the design of next-generation high-energy and insensitive fused-ring energetic materials.

This perspective article describes a new dual carbon fiber battery, where both the cathode and anode are made of carbon fiber. The dual carbon fiber battery combines the advantages of carbon fiber and dual graphite batteries, including a higher working potential compared to lithium-ion batteries, a high areal capacity, and easy access due to the mature manufacturing technology of carbon fibers. In this article, we discuss the mechanism, current status and potential application areas of dual carbon fiber batteries. Additionally, we highlight the challenges and prospects of these batteries., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Prepubertal male patients with cancer have decreased fertility after treatment, but there are currently no suitable means for fertility rescue. Testicular transplantation seems to be a promising treatment. The short-term insufficiency of blood supply after transplantation is the key problem that needs to be solved. In this research, nitric oxide (NO), a gas and small molecule transmitter with the effect of promoting angiogenesis, acted at the site of testicular transplantation. Herein, poloxamer-407 (P407) and lipid microbubble materials served as transport carriers for NO and helped NO to function at the transplant site. P407 hydrogel loaded with NO microbubbles (PNO) slowly released NO in vitro . The three-dimensional space of the hydrogel provided a stable environment for NO microbubbles, which is conducive to the continuous release of NO. In this study, 25% PNO (w/v) was selected, and the gelling temperature was 19.47 °C. The gelling efficiency was relatively high at body temperature. Rheological experiments showed that PNO, at this concentration, had stable mechanical properties. The results from in vivo experiments demonstrated that testicular grafts in the PNO group exhibited a notably accelerated blood flow recovery compared to the other groups. Additionally, the PNO group displayed a significant improvement in reproductive function recovery. In conclusion, PNO exhibited slow release of NO, and a small amount of NO promoted angiogenesis in testicular grafts and restored reproductive function.

Drug delivery systems based on nanoparticles still face challenges of low efficacy and an inability to track treatment effects in tumor therapy due to biological barriers. This limitation hinders clinicians' ability to determine treatment effects and proper drug dosages, thus, ultimately impeding the further application and transformation of nanoplatforms. To address this challenge, an all-in-one nanoplatform for therapy and imaging is proposed. The nanoplatform is constructed by using nanoparticles through the co-encapsulation of the photothermal therapeutic agent IR780, the passively targeted drug OA@Fe 3 O 4 , and the chemotherapeutic drug paclitaxel. Under the guidance of magnetic navigation, the nanoparticles can enhance local enrichment of the drug, while the luminescence properties of IR780 enable drug tracking at the same time. Remarkably, the nanoparticles exhibit improved photothermal-chemotherapy synergy under magnetic targeting guidance, demonstrating antitumor effects in both in vitro and in vivo experiments. It is demonstrated that the use of these polymeric nanoparticles has significant potential for future biomedical applications and clinical decisions., Competing Interests: The authors have declared that no competing interest exists., (This journal is © The Royal Society of Chemistry.)

To tackle the obstacles related to tumor targeting and overcome the limitations of single treatment models, we have developed a nanoplatform that is both tumor-targeted and enzyme-responsive. This nanoplatform integrates photothermal gold nanorods (AuNRs) and protein drugs into a single system. This nanosystem, known as AuNRs@HA-mPEG-Deta-LA, was fabricated by modifying gold nanorods (AuNRs) with a polymeric ligand called hyaluronic acid-grafted-(mPEG/diethylenetriamine-conjugated-lipoic acid). The purpose of this fabrication was to load cytochrome c (CC) and utilize it for the synergetic protein-photothermal therapy of cancer. The resulting nanoplatform exhibited a high efficiency in loading proteins and demonstrated excellent stability in different biological environments. Additionally, CC-loaded AuNRs@HA-mPEG-Deta-LA not only enabled localized hyperthermia for photothermal therapy (PTT) with laser irradiation but also facilitated the release of CC under the action of hyaluronidase, an enzyme known to be overexpressed in tumor cells. The confocal imaging results demonstrated that the presence of a specific polymeric ligand on this nanoparticle enhances the internalization of CD44-positive cancer cells, accelerates endo/lysosomal escape, and facilitates the controlled release of CC within the cells. Furthermore, the results of the MTT assay also showed that AuNRs@HA-mPEG-Deta-LA as a protein nanocarrier demonstrated excellent biocompatibility. Importantly, this synergistic therapeutic strategy effectively induced apoptosis in A549 cancer cells by increasing the intracellular concentration of CC and utilizing the photothermal conversion of AuNRs, which was observed to be more effective compared to using only protein therapy or PTT. Therefore, this study showcased a nanoplatform based on AuNRs that has great potential for tumor-targeted protein delivery in combination with PTT in cancer treatment.

Skin injuries and drug-resistant bacterial infections pose serious challenges to human health. It is essential to establish a novel multifunctional platform with good anti-infection and wound-healing abilities. In this study, a new MXene-doped composite microneedle (MN) patch with excellent mechanical strength and photothermal antibacterial and ROS removal properties has been developed for infected wound healing. When the MN tips carrying the MXene nanosheets are inserted into the cuticle of the skin, they will quickly dissolve and subsequently release the nanomaterials into the subcutaneous infection area. Under 808 nm NIR irradiation, the MXene, as a "nano-thermal knife", sterilizes and inhibits bacterial growth through synergistic effects of sharp edges and photothermal antibacterial activity. Furthermore, ROS caused by injury and infection can be cleared by MXene-doped MNs to avoid excessive inflammatory responses. Based on the synergistic antibacterial and antioxidant strategy, the MXene-doped MNs have demonstrated excellent wound-healing properties in an MRSA-infected wound model, such as promoting re-epithelialization, collagen deposition, and angiogenesis and inhibiting the expression of pro-inflammatory factors. Therefore, the multifunctional MXene-doped MN patches provide an excellent alternative for clinical drug-resistant bacteria-infected wound management.

An efficient synthesis of α-sulfenylated carbonyl compounds from propargylic alcohols and aryl thiols under heating conditions is described. The method is characterized by mild conditions, simple operation, metal-free catalysis and good functional group tolerance. Mechanistic studies suggest that the reaction involves a radical pathway and an isomerization process.

Transition metal-catalyzed asymmetric nitrene transfer is a powerful method to generate enantioenriched amines found in natural products and bioactive molecules. A highly chemo- and enantioselective intramolecular silver-catalysed aziridination of 2,2,2-trichloroethoxysulfonyl (Tces)-protected carbamimidates gives [4.1.0]-bicyclic aziridines in good yields and up to 99% ee.

Electrocatalytic hydrogenation of benzoic acid (BA) to cyclohexanecarboxylic acid (CCA) at ambient temperature and pressure has been recognized as a promising alternative to thermal hydrogenation since water is required as the hydrogen source. So far, only a few Pt-based electrocatalysts have been developed in acidic electrolyte. To overcome the limitations of reactant solubility and catalyst corrosion, herein, carbon fiber-supported Ru electrocatalysts with abundant Ru/RuO 2 heterojunctions were fabricated via cyclic electrodeposition between -0.8 and 1.1 V vs. Ag/AgCl. In an alkaline environment, a Ru/RuO 2 catalyst achieves an excellent ECH reactivity in terms of high BA conversion (100%) and selectivity towards CCA (100%) within 180 min at a current density of 200/3 mA cm -2 , showing exceptional reusability and long-term stability. 1-Cyclohexenecarboxylic acid (CEA) was identified as the reaction intermediate, whose the selectivity is governed by the applied potential. Kinetic studies demonstrate that ECH of BA over Ru/RuO 2 follows a Langmuir-Hinshelwood (L-H) mechanism. In situ Raman spectroscopy and theoretical calculations reveal that the Ru/RuO 2 interface enhances the adsorption strength of CEA, thereby facilitating the production of fully hydrogenated CCA. This work provides a deep understanding of the ECH pathway of BA in alkaline media, and gives a new methodology to fabricate heterostructure electrocatalysts., 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.)

A novel Pd-catalyzed assembly of N -substituted phthalimides by merging of [4+1] cycloaddition and difluorocarbene transfer carbonylation from 2-iodo- N -phenylbenzamides and difluorocarbene precursors is disclosed. Difluorocarbene acts as a carbonyl source and simultaneously forms one C-C bond, one C-N bond and one CO bond to produce N -substituted phthalimides in high yields.

This paper initially contrasts the solvent-based and solventless molding processes, subsequently optimizing a sustainable and efficient solventless molding route for both STP and SLTP. Key physicochemical parameters such as extrusion rate, residual volatile solvents, moisture content, and apparent density of both propellant types are meticulously compared. Furthermore, the orientation of crystal particles and the structure of the matrix-bound interface are analyzed. Comprehensive examination of triaxial progressive failure phenomena-including static thermal mechanical responses, quasi-static structural deformation, and dynamic structural damage-is conducted, leading to the formulation of a damage mechanism and model. Subsequently, a structural mechanics model for nitroguanidine micrometer rod-reinforced triple base propellants is established, quantitatively evaluating the influence of nitroguanidine crystal arrangement angles on the structural strength of both propellant types. This study furnishes a theoretical foundation for specialized internal structural and mechanical behaviors through theoretical computations., Competing Interests: The authors have no competing financial interests or personal relationships that could have influenced the work. They have no professional or personal interest in any product, service, or company that could affect the position presented in the manuscript. All authors have approved the manuscript for publication., (This journal is © The Royal Society of Chemistry.)

Hard-Soft Acid-Base (HSAB) principle plays an important guiding role in the design and synthesis of novel clusters and coordination compounds, in which "soft acids prefer to react with soft bases, while hard acids have an affinity for hard bases". Based on HSAB principle, four Ag/Ti heterometallic clusters, including Ag2Ti10, Ag2Ti11 with "Ti-encapsulated Ag" configurations, and two "Ag-encapsulated Ti" structures Ag2Ti2 and Ag2Ti12, were synthesized under solvothermal conditions. In addition, Ag2Ti12 exhibited an efficient and stable catalytic activity for sulfide oxidation. This work provides not only a new structural model for the modulation of the catalytic oxidative desulfurization properties of Ag/Ti heterometallic clusters but also a new insight of the utilization of phosphine-containing ligands to regulate the structure of Ag/Ti heterometallic clusters.

Recently, surface plasmon resonance (SPR) biosensors have been widely used in environmental monitoring, food contamination detection and diagnosing medical conditions due to their superior sensitivity, label-free detection and rapid analysis speed. This paper briefly elaborates on the development history of SPR technology and introduces SPR signal sensing principles. A summary of recent applications of SPR sensors in different fields is highlighted, including their figures of merit and limitations. Finally, the personal perspectives and future development trends about sensor preparation and design are discussed in detail, which may be critical for improving the performance of SPR sensors.

Protein-protein interactions (PPIs) between the B-cell lymphoma 2 (Bcl-2) family are considered a major driving force in cell cycle regulation and signaling. However, how this interfacial noncovalent interaction is achieved molecularly remains poorly understood. Herein, anti-apoptotic protein (Bcl-2) and pro-apoptotic protein (BAX) were used as models and their PPIs were explored for the first time using atomic force microscopy-based single-molecule force spectroscopy (SMFS) and in silico approaches. In addition, we used advanced analytical models, including multiple kinetic models, thermodynamic models, Poisson distributions, and contact angle molecular recognition to fully reveal the complexity of the BAX/Bcl-2 interaction interfaces. We propose that the binding kinetics between BAX/Bcl-2 are mainly mediated by specific (hydrogen bonding) and non-specific forces (hydrophobic interactions and electrostatic interactions) and show that the complicated multivalent binding interaction induces stable BAX/Bcl-2 complexes. This study enriches our understanding of the molecular mechanisms by which BAX interacts with Bcl-2. It provides valuable insights into the physical factors that need to be considered when designing PPI inhibitors.

Osteoporosis, one of the serious public health problems worldwide, can lead to degeneration of the bone structure and increased risk of fractures. Epigallocatechin gallate (EGCG) is a natural product with potential efficacy in inhibiting bone loss. However, the specific mechanism remains unclear. This study first investigated the role of EGCG in preventing dexamethasone (DEX)-induced osteoporosis by regulating intestinal microbiota and serum metabolites. We detected the bone density, bone microstructure, and changes in intestinal microorganisms and serum metabolites. According to our results, EGCG inhibited the decline of bone density, protected the bone microstructure, increased microbial diversity, promoted the abundance of beneficial bacteria such as Prevotellaceae and Ruminococcus , and inhibited the abundance of pathogenic bacteria such as Peptostreptococcaceae. There were also significant changes in serum metabolites among different treatments. Differential metabolites were mainly involved in sphingolipid metabolism and glycerophospholipid metabolism pathways, especially ceramide (d18:0/16:0(2OH)), phosphatidylserine (P-20:0/20:4(5 Z ,8 Z ,11 Z ,14 Z )), phosphatidylserine (18:2(9 Z ,12 Z )/12:0), and phosphatidylethanolamine (O-16:0/0:00), which were increased after EGCG treatment. Notably, most of the above metabolites were positively correlated with bone mineral density, BV/TV and Tb·Th, and negatively correlated with Tb·Sp. In summary, EGCG can prevent bone damage, promote the production of beneficial bacteria and metabolites, and enhance immune function. This study provides a basis and reference for the prevention and treatment of osteoporosis, as well as the application of EGCG in maintaining body health.