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High efficiency perovskite solar cells can be made through the Lewis adduct approach. The interaction between PbI2 and the Lewis base is a key factor to make high quality perovskite films. Here, we combine a two-step method with the Lewis adduct approach to fabricate high quality organometallic perovskite films by tuning the strength of the Pb–O bond in Lewis acid–base adducts via adding different Lewis base additives. By optimizing the strength of the Pb–O bond, smooth CH3NH3PbI3 films with large perovskite grains are prepared. The high quality CH3NH3PbI3 films lead to a low recombination rate, long carrier life time and highly efficient charge transfer process. As a result, the power conversion efficiency of the best perovskite solar cell increases from 12.79% to 17.26%. [ABSTRACT FROM AUTHOR]

Ordered, bimodal mesoporous CMK-5 carbon is prepared by using mesoporous SBA-15 silica as a structural mold. The carbon material is chemically modified by oxidative treatment with acidic persulfate solution. This leads to the creation of oxygen-containing functionalities at the pore walls of the carbon (up to 13 wt% oxygen), as confirmed by IR spectroscopy. The oxidative treatment is carried out before removal of the silica mold which ensures that only one of the two distinct modes of mesopores (namely, the intra-tubular pores) is affected; the other mode (inter-tubular pores) is protected from oxidation by the presence of the silica mold. This is proven by water vapor physisorption analysis. The oxidatively treated (intra-tubular) pores are significantly more polar and, hence, better wettable than the untreated (inter-tubular) pores. [ABSTRACT FROM AUTHOR]

In this work, high-performance MnO2/H-TiO2/carbon-microfiber nanowire composite electrodes were successfully synthesized. The crystalline properties and electrical conductivity of the H-TiO2 nanowires were studied by X-ray diffraction, Raman scattering and Mott–Schottky theory. To quantitatively investigate the contribution of hydrogenation to the performance of MnO2/H-TiO2 composite electrodes, their electrochemical performance and electrochemical impedance spectroscopy were quantitatively investigated. The physical mechanism is proposed based on the theory of semiconductor physics. Typically, for a composite electrode hydrogenated at 600 °C, the specific capacitance reaches 630.1 F g−1 at 10 mV s−1 and the high energy density of 46.0 W h kg−1 is obtained at the high power density of 21.8 kW kg−1. Moreover, the capacitance retention is 90% after 5000 cycles. This work provides an idea for rationally designing the high-performance supercapacitors and assembling novel nanostructures with preferable electrochemical performance. [ABSTRACT FROM AUTHOR]

The presence of abundant hydroxyl groups on the surface of Al 2 O 3 can promote the dispersion of Ni species but produce an inactive NiAl 2 O 4 phase at high temperatures. Moreover, the catalysts prepared by the conventional incipient wetness impregnation method lack the sites for the activation of CO 2 , which leads to coke deposition and thus affects the catalyst activity. The above restricts the utilization of Ni in conventional Ni/Al 2 O 3 catalysts. In this paper, Al 2 O 3 support was pre-treated by acetic acid to selectively remove hydroxyl groups without affecting the coordination environment of Al. Results revealed that the Al 2 O 3 support after hydroxyl removal not only showed moderate metal-support interaction but also produced more sites for the adsorption and activation of the reactant, which significantly improves the utilization of nickel species and the stability of the catalyst. The conversion of CH 4 and CO 2 at 700 °C was as high as 88% and 90%, respectively, and has an excellent stability of 50 h. This study provides a feasible strategy for the design of highly active methane dry-reforming catalysts., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Therapeutic approaches combining various treatments have attracted intensive interests for tumor therapy. Nevertheless, these strategies still face many obstacles, such as overexpressed GSH and hypoxia, owing to the intricate tumor microenvironment (TME). Herein, a versatile nanoplatform, CeO 2 @CuO 2 @DOX-RSL3@HA (CCDRH), was initially constructed for promoting the antitumor efficiency via regulation of the TME. The CCDRH was prepared taking mixed valence CeO 2 as the nanocarrier, followed by the attachment of CuO 2 nanodots, DOX and RSL3 and the camouflaging of hyaluronic acid. The CuO 2 could disassemble in the acidic TME to release Cu 2+ and H 2 O 2 . The POD- and CAT-mimicking activities of CeO 2 could convert H 2 O 2 to ˙OH and O 2 , leading to the enhancement of chemo-chemodynamic therapy. Meanwhile, RSL3 could effectively suppress GPX4 expression, and the overloaded Cu 2+ and Ce 4+ could deplete excess GSH, resulting in an intensive accumulation of LPO and significant nonferrous ferroptosis. Additionally, Cu + induces the oligomerization of lipoylated DLAT and downregulates iron-sulfur cluster proteins, resulting in potent cellular cuproptosis. The experimental results revealed that CCDRH exhibited high performance in tumor inhibition, which is attributed to the combined effect of enhanced chemotherapy, ferroptosis and cuproptosis. The study provides a new approach for improving anticancer efficiency via regulation of the TME.

Antibiotics are crucial for treating and preventing bacterial infections. However, the widespread use of antibiotics has led to serious antibiotic resistance issues. To address the growing threat of antibiotic-resistant bacterial infections, we designed and synthesized an antibacterial composite material, CCM@ZIF-8@PDA, through a one-pot method and surface modification strategy. This material combines the antibacterial properties of the natural product curcumin, the advantages of ZIF-8, and the photothermal conversion capability of PDA. It exhibits three antibacterial mechanisms against S. aureus : chemical antibacterial, ionic antibacterial, and photothermal antibacterial effects. At a low concentration of 100 ppm, CCM@ZIF-8@PDA achieves a 100% antibacterial rate. This multi-modal antibacterial strategy provides insights for developing new antibacterial materials to combat antibiotic resistance.

The search for suitable electrode materials for sodium storage in sodium-ion batteries (SIBs) poses significant challenges. Na 0.44 MnO 2 (NMO) has emerged as a promising candidate among various cathode materials due to its distinct three-dimensional tunnel structure, which facilitates Na + diffusion and governs structural stress fluctuations during Na + intercalation/deintercalation. However, NMO faces obstacles such as limited electronic conductivity, lattice distortion induced by the Jahn-Teller effect of Mn 3+ during cycling, and Mn 3+ disproportionation leading to material dissolution, which affects cycling durability. To overcome these problems, Na 0.44 MnO 2 /polypyrrole (NMO/PPy) composites were fabricated through surface modification of the conductive PPy using an ultrasonically assisted dispersion method. Experimental results show that NMO/PPy with a 7 wt% PPy content exhibits superior sodium storage capabilities. Specifically, at a current density of 0.5C, the initial specific discharge capacity reaches 135.2 mA h g -1 , a 12.1% increase over pristine NMO, with a capacity retention of 94.5% after 100 cycles. Of particular note is a capacity retention of 82% after 500 cycles at 1C, attributed to the PPy coating, which suppresses Mn 3+ side reactions, enhances the structural stability and electronic conductivity of NMO, and accelerates Na + diffusion. These results suggest that the use of conductive polymer coatings represents a simple and effective strategy to improve the sodium storage capacity of NMO, paving the way for the further development of high-performance SIB cathodes.

Epidemiological and animal studies have indicated that calcium and boron are essential for bone development and metabolism. However, limited information is available regarding the effects of boron supplementation on bone development and metabolism in newly weaned infants with either calcium deficiency or calcium sufficiency. This study assessed the effects of dietary boron supplementation (0 and 3 mg kg -1 ) on bone development and metabolism, in a newly weaned mouse model, under both calcium deficiency and sufficiency feeding conditions. The results show that mice fed a calcium sufficient diet exhibited lower fat percentage and final body weight than those fed a calcium deficient diet. Boron supplementation reduced the serum high-density lipoprotein cholesterol level and up-regulated the mRNA levels of FABP3 , PPAR-γ , and CaMK in the intestinal mucosa. Importantly, boron supplementation increased the tibial weight in mice on a calcium-sufficient diet and enhanced the tibial volume in those on a calcium-deficient diet. Metabolomic analysis highlighted calcium and boron's impact on metabolites like carboxylic acids and derivatives, fatty acyls, steroids and steroid derivatives, benzene and substituted derivatives, organonitrogen compounds, organooxygen compounds, and phenols, and were related to lipid metabolism and the neural signaling pathway. Transcriptomic analysis corroborated the role of calcium and boron in modulating bone metabolism via the JAK-STAT, calcium signaling, lipid metabolism, and inflammatory pathways. Multi-omics analysis indicated a strong correlation between calcium signaling pathways, lipid metabolism signaling, and dietary calcium and boron contents. This research provides insights into these complex mechanisms, potentially paving the way for novel interventions against calcium and boron deficiencies and bone metabolism abnormalities in clinical settings.

Cell condensation, linking the migration and chondrogenic differentiation of MSCs, plays a crucial role in cartilage development. Current cartilage repair strategies are inadequately concerned with this process, leading to a suboptimal quality of regenerated cartilage. Inspired by the "nest flocks" structure of Social Weavers, a degradable heterogeneous microgel assembly (F/S-MA) is developed, which can release SDF-1, to form a "micro-nest group" structure and bond with HAV peptides to promote cell recruitment, condensation and chondrogenic differentiation. First, slow-degrading microgels (S-microgels) grafted with HAV peptides and fast-degrading microgels (F-microgels) loaded with SDF-1 are fabricated by an amidation reaction and Schiff base reaction, respectively. They employ sulfhydryl-modified gelatin as assembling agents to form F/S-MA through a thiol-ene reaction, exhibiting injectability, tissue adhesion, and microporosity. F-microgels undergo rapid degradation, leading to the release of SDF-1 and the formation of a "micro-nest group" in F/S-MA. Consequently, F/S-MA exhibits cell recruitment ability, meanwhile facilitating BMSC condensation through the synergistic effects of the "micro-nest group" and HAV peptides. In vitro experiments prove that F/S-MA enhances the expression of cell-condensation-related markers, ultimately upregulating the secretion of cartilage matrix. Animal experiments show that F/S-MA optimizes the quality of regenerated cartilage by improving cell recruitment and condensation. F/S-MA enhances cell condensation through structural and component design, which will provide new insights for cartilage regeneration.

Recycling uranium (U) via adsorption and controlled conversion is crucial for the sustainable development of nuclear energy, in which photocatalytic reduction of U(vi) from aqueous solutions is considered one of the most effective strategies. The primary challenge in the photocatalytic elimination of U(vi) resides in the demand for photocatalysts with exceptional properties for effective U(vi) adsorption and charge separation. Herein, we developed the hybrids of polyoxometalate@Cu-metal-organic frameworks (POM@Cu-MOFs) through a self-assembly strategy and demonstrated the efficient removal of U(vi) via synergistic adsorption and photocatalysis. The abundant oxygen-rich groups in POM served as the adsorption sites, endowing POM@Cu-MOFs with a remarkable removal capacity (1987.4 mg g -1 under light irradiation) to remove 99.4% of UO 2 2+ . The attraction of electrons from Cu atoms within Cu-MOFs effectively accelerated the carrier dynamics due to their pronounced electronegativity. A mechanism associated with the synergetic effects of adsorption and photocatalytic reduction of U(vi) was proposed. This work provides a feasible approach for efficiently eliminating U(vi) from aqueous solutions in environmental pollution cleanup using the POM@Cu-MOF photocatalyst., Competing Interests: The authors declare no competing financial interests., (This journal is © The Royal Society of Chemistry.)

To facilitate rapid, efficient, and accurate detection of miR-96-5p associated with gastric cancer (GC), we developed a bioanalytical platform by integrating surface-enhanced Raman spectroscopy with lateral flow assay (SERS-LFA). With these SERS-LFA strips, miR-96-5p within the specimen competed with Au rhombic dodecahedron (AuRD) conjugated single-stranded DNA (ssDNA) to bond to the immobilized hairpin DNA (hpDNA) probe on the T line. Consequently, higher abundance of miR-96-5p led to reduced conjugation of AuRD on the T line, thereby resulting in diminished SERS intensity. The biosensor exhibited a detection time of approximately 30 min and demonstrated a low limit of detection (LOD) for miR-96-5p in PBS buffer solution, down to 3.7 fM. To validate its clinical utility for the early diagnosis of patients with different degrees of gastric lesions, we performed quantitative evaluations in cohorts that included healthy individuals, patients with mild intraepithelial neoplasia, patients with severe intraepithelial neoplasia, as well as patients diagnosed with GC. The results obtained from the SERS-LFA strips were in agreement with those obtained from the quantitative real-time polymerase chain reaction (qRT-PCR). Given the accomplishments, this biosensor has significant potential for the clinical diagnosis of GC, offering a promising avenue for timely detection and improved patient prognoses., Competing Interests: There are no conflicts that need to be declared., (This journal is © The Royal Society of Chemistry.)

The development of multi-resonance thermally activated delayed fluorescence (MR-TADF) materials in the deep-blue region is highly desirable. A usual approach involves constructing an extended MR-TADF framework; however, it may also intensify aggregate-caused quenching issues and thereby reduce device efficiency. In this study, we develop a molecular design strategy that fuses the MR-TADF skeleton with 9,9'-spirobifluorene (SF) units to create advanced deep-blue emitters. The SF moiety facilitates high-yield one-shot bora-Friedel-Crafts reaction towards an extended skeleton and mitigates interchromophore interactions as a steric group. Our findings reveal that orbital interactions at the fusion site significantly influence the electronic structure, and optimizing the fusion mode allows for the development of emitters with extended conjugation length while maintaining non-bonding character. The proof-of-concept emitter exhibits narrowband emission in the deep-blue region, a near-unity photoluminescence quantum yield, and a fast k RISC of 2.4 × 10 5 s -1 . These exceptional properties enable the corresponding sensitizer-free OLED to achieve a maximum external quantum efficiency (EQE max ) of 39.0% and Commission Internationale de l'Eclairage (CIE) coordinates of (0.13, 0.09). Furthermore, the hyperfluorescence device realizes an EQE max of 40.4% with very low efficiency roll-off., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

It is a big challenge to prepare thick CsPbCl 3 films using traditional solution processed approaches owing to the low solubility of precursors of PbCl 2 and CsCl in common solvents. Here, we propose an indirect solution process to prepare thick CsPbCl 3 films. In this new approach, a mother film of CsPbBr 3 is first prepared through a solution process, and then it is dipped into a diluted HCl/methanol solution. During the dipping process, it triggers a halide exchange reaction between Br - and Cl - , and it eventually produces a thick CsPbCl 3 film (∼400 nm) with high quality and purity. Afterwards, a carbon based hole transportation layer (HTL) free solar cell with a configuration of FTO/TiO 2 /CsPbCl 3 /carbon is constructed, and it delivers an average PCE of 1.23% and an outstanding PCE of 1.39% in a batch of PSCs. Meanwhile, the solar cell maintains its 82% initial PCE after storage in open air for 31 days. This work overcomes the obstacle of the traditional solution approach for the preparation of CsPbCl 3 films, which makes it promising for preparing various CsPbCl 3 film-based devices via a solution process.

BiVO 4 is an attractive photoanode material for water oxidation, but requires surface treatment to improve the energy efficiency and stability. Herein, we investigate the role of borate buffer in activating the BiVO 4 photoanode. We found that trace iron impurities in the borate buffer play a critical role in activating the photoanode. By optimizing the activation conditions, the photocurrent density attains 4.5 mA cm -2 at 1.23 V RHE without any cocatalysts, alongside a high ABPE value of 1.5% at 0.7 V RHE . Our study discloses the role of iron in the activation effect of borate buffer on the BiVO 4 photoanode, which has implications for other catalytic systems.

A series of green multi-resonance thermally activated delayed fluorescence polymeric emitters featuring conjugation-interrupted main chains were facilely prepared via metal-free superacid-catalyzed Friedel-Crafts polyhydroxyalkylation. These emitters exhibited photoluminescence quantum yields of up to 76% and small full-widths at half maximum of 35-38 nm in toluene. The corresponding solution-processed OLEDs achieved an excellent maximum external quantum efficiency of 19.4%, with CIE coordinates of (0.20, 0.62).

2D MgI 2 has a large phonon band gap and strong coupling of optical and acoustic phonons, and it is difficult to accurately predict thermal conductivity by considering only three-phonon scattering. Thus, in this study, the effect of four-phonon scattering on the thermal conductivity of a 2D MgI 2 lattice was investigated using first-principles calculations combined with Boltzmann transport theory. The results show that with increasing temperature, four-phonon scattering induces an increase in the scattering of phonons at the optical and acoustic phonon coupling (2 THz), as well as in the vicinity of the optical phonon branch (4.5 THz), which leads to the enhancement of the anharmonicity of phonon transport and results in a decrease in the thermal conductivity of the 2D material. At 700 K, the thermal conductivity of MgI 2 decreases by over half, from 0.47 W m -1 K -1 to 0.23 W m -1 K -1 , when considering both three- and four-phonon scattering, compared to considering only three-phonon scattering. This study confirms the need to consider the role of four-phonon scattering to enhance optical and acoustic phonon coupling to accurately predict the thermal conductivity of 2D materials with larger phonon band gaps.

The application of mRNA therapy is constrained by the current lipid nanoparticles' (LNPs) inability to target non-liver tissues. In this study, we demonstrate that ionizable lipids equipped with branched and biodegradable tails enhance the selective delivery of mRNA to the spleen, particularly to antigen-presenting cells. This approach offers novel insights into how the chemical structure of LNPs influences their organ-specific targeting capabilities.

Geometrical variations in a particular structure or other mechanical factors are often cited as the cause of a negative Poisson's ratio (NPR). These factors are independent of the electronic properties of the materials. This work investigates a class of two-dimensional (2D) sulfides with the chemical formula MX 2 (M = Ti, Cr, Mn, Fe, Co, X = S) using first-principles calculations. Among them, monolayered TiS 2 , CrS 2 , and MnS 2 were found to exhibit a structure-independent NPR. The strong strain response of intra-layer interactions is responsible for this unique phenomenon. This can be traced to the lone pair of electrons of the S atoms and the weak electronegativity of the central atoms in multi-orbital hybridization. Our study provides valuable insights and useful guidelines for designing innovative NPR materials.

The overuse of antibiotics in treating bacterial infections is a significant threat to the environment and human health. The utilization of visible-light-assisted peroxydisulfate (PDS) activation for eliminating organic pollutants is a promising approach. This study uses a straightforward hydrothermal method to prepare magnetically recyclable spherical Cu 2 O@Fe 3 O 4 . The efficacy of this material in removing antibiotic pollutants was assessed using simulated wastewater containing tetracycline (TC). TC removal was achieved by activating PDS with Cu 2 O@Fe 3 O 4 as the visible light photocatalyst. Experimental findings revealed that under specific conditions-a pH of 9, a Cu 2 O@Fe 3 O 4 concentration of 60 mg L -1 , and a PDS concentration of 25 mg L -1 -the removal rate of TC reached 97.67% after 30 min of irradiation. Moreover, Cu 2 O@Fe 3 O 4 exhibited excellent recyclability, maintaining a removal rate of 93.33% after five recycling rounds. X-ray diffraction characterization of the Cu 2 O@Fe 3 O 4 composite before and after cycling confirmed its robust stability and reusability. In situ X-ray photoelectron spectroscopy analysis showed that electrons migrated from Fe 3 O 4 to Cu 2 O during the photocatalytic reaction, indicating the formation of an S-type heterojunction in Cu 2 O@Fe 3 O 4 . Free radical trapping experiments demonstrated the active involvement of ·OH, ·O 2 - , SO 4 ˙ - and h + radicals in TC removal., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In this study, a laboratory-scale hybrid biofilm reactor (HBR) was constructed to treat food wastewater (FWW) before it is discharged into the sewer. The chemical oxygen demand (COD) of 29 860 mg L -1 in FWW was degraded to 200-350 mg L -1 using the HBR under the operating parameters of COD load 1.68 kg m -3 d -1 , hydraulic retention time (HRT) of 426.63 h, dissolved oxygen (DO) of 8-9 mg L -1 , and temperature of 22-23 °C. The biomass of biofilm on the surface of filler was 2.64 g L -1 for column A and 0.91 g L -1 for column O. Microbial analysis revealed richer and more diverse microorganisms in filler biofilms compared to those in suspended sludge. The hybrid filler was conducive to the development of functional microbial species, including phyla Firmicutes, Actinobacteriota, and Chloroflexi, and genus level norank_f_JG30-KF-CM45 , which will improve FWW treatment efficiency. Moreover, the microorganisms on the filler biofilm had more connections and relationships than those in the suspended sludge. The combination of an up-flow anaerobic sludge bed (UASB) and HBR was demonstrated to be an economical strategy for practical applications as a shorter HRT of 118.34 h could be obtained. Overall, this study provides reliable data and a theoretical basis for the application of HBR and FWW treatments., 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 simple aqueous complexing system of UO 2 2+ with F - is selected to systematically illustrate the application of Raman spectroscopy in exploring uranyl(VI) chemistry. Five successive complexes, UO 2 F + , UO 2 F 2 (aq), UO 2 F 3 - , UO 2 F 4 2- , and UO 2 F 5 3- , are identified, as well as the formation constants except for the 1 : 5 species UO 2 F 5 3- , which was experimentally observed here for the first time. The standard relative molar Raman scattering intensity for each species is obtained by deconvolution of the spectra collected during titrations. The results of relativistic quantum chemical first-principles and ab initio calculations are presented for the complete set of [UO 2 (H 2 O) m F n ] 2- n complexes ( n = 0-5), both for the gas phase as well as for aqueous solution modelling bulk water using the conductor-like screening model. Electronic structure calculations at the Møller-Plesset second-order perturbation theory level provide accurate geometrical parameters and in particular reveal that k water molecules in the second coordination sphere coordinating to the F - ligands in the resulting [UO 2 (H 2 O) m F n ] 2- n (H 2 O) k complexes need to be treated explicitly in order to obtain vibrational frequencies in very good agreement with experimental data. The thermodynamics and structural information obtained in this work and the developed methodology could be instructive for the future experimental and computational research on the complexation of the uranyl ion.

8-oxoguanine (o 8 G), a prevalent oxidative modification in RNA induced by reactive oxygen species (ROS), plays a pivotal role in regulating RNA functions. Accurate detection and quantification of o 8 G modifications is critical to understanding their biological significance and potential as disease biomarkers, but effective detection methods remain limited. Here, we have developed a highly specific T3 DNA ligase-dependent qPCR assay that exploits the enzyme's ability to discriminate o 8 G from guanine (G) with single-nucleotide resolution. This method can detect o 8 G in RNA at levels as low as 500 fM, with an up to 18-fold higher selectivity for discriminating o 8 G from G. By simulating oxidative stress conditions in SH-SY5Y and HS683 cell lines treated with rotenone, we successfully identified site-specific o 8 G modifications in key miRNAs associated with neuroprotective responses, including miR-124, let-7a and miR-29a. The developed assay holds significant promise for the practical identification of o 8 G, facilitating its potential for detailed studies of o 8 G dynamics in various biological contexts and diseases.

Formaldehyde adsorption on intrinsic La 2 O 3 surface, four-fold coordinated oxygen vacancy (VO 4c ), six-fold coordinated oxygen vacancy (VO 6c ), and iridium-doped La 2 O 3 (001) surface was studied by the first-principles method. The results show that formaldehyde adsorption on the Ir-doped La 2 O 3 (001) surface with VO 6c is the strongest because of the directional movement of electrons caused by the interaction of the Ir-5d orbitals and internal oxygen vacancy, wherein the adsorption energy is 3.23 eV. This model showed a significant increase in adsorption energy, indicating that Ir doping improves the formaldehyde adsorption capacity of the La 2 O 3 (001) surface. The energy band analysis shows that iridium doping introduces impurity energy levels into the intrinsic La 2 O 3 energy band, which enhances the interaction between the La 2 O 3 (001) surface and formaldehyde molecules. Density of state analysis indicated that the adsorption of formaldehyde molecules on the La 2 O 3 (001) surface is mainly due to the interaction between the O-2p, C-2p orbitals of formaldehyde and the Ir-5d orbital of iridium atoms. Furthermore, the existence of VO 4c and VO 6c defects has no effect on the position and shape of the valence and conduction bands. The effects of oxygen vacancy and iridium doping on the optical properties mainly appeared in the low-energy infrared and visible regions, making the O-2p, C-2p orbitals of formaldehyde and the Ir-5d, O-2p orbitals of the La 2 O 3 (001) surface become hybridized near the Fermi level and the electronic transition from the valence band to conduction band more likely to occur. The La 2 O 3 material can be used as an ideal photocatalytic material for formaldehyde degradation., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The development of nanomedicines with simplified compositions and synergistic theranostic functionalities remains a great challenge. Herein, we develop a simple method to integrate both atovaquone (ATO, a mitochondrial inhibitor) and cisplatin within tannic acid (TA)-iron (Fe) networks coated with hyaluronic acid (HA) for targeted magnetic resonance (MR) imaging-guided chemo-chemodynamic synergistic therapy. The formed TFP@ATO-HA displayed good colloidal stability with a mean size of 95.5 nm, which could accumulate at tumor sites after circulation and be specifically taken up by metastatic 4T1 cells overexpressing CD44 receptors. In the tumor microenvironment, TFP@ATO-HA could release ATO/cisplatin and Fe 3+ in a pH-responsive manner, deplete glutathione, and generate reactive oxygen species with endogenous H 2 O 2 for chemodynamic therapy (CDT). Additionally, ATO could enhance chemotherapeutic efficacy by inhibiting mitochondrial respiration, relieving hypoxia, and amplifying the CDT effect by decreasing intracellular pH and elevating Fenton reaction efficiency. In vivo experiments demonstrated that TFP@ATO-HA could effectively inhibit tumor growth and suppress lung metastases without obvious systemic toxicity. Furthermore, TFP@ATO-HA exhibited a r 1 relaxivity of 2.6 mM -1 s -1 and targeted MR imaging of 4T1 tumors. Dual drug-loaded metal-phenolic networks can be easily prepared and act as effective theranostic nanoplatforms for targeted MR imaging and synergistic chemo-chemodynamic therapy.

Food proteins are considered an ideal source for the identification of bioactive peptides with the potential to intervene in nutrition-related chronic diseases such as cardiovascular disease, obesity, and diabetes. Egg white-derived peptides (EWPs) have been shown to improve glucose tolerance in insulin-resistant rats. However, underlying mechanisms are to be elucidated. Therefore, we hypothesized that EWP exerts a hypoglycemic effect by regulating hepatic glucose homeostasis. Our results showed that 7 weeks of EWP treatment reduced the fasting blood glucose in T2DM mice and the inhibition of the liver gluconeogenic pathway was involved in the mechanisms of actions. Using the untargeted metabolomics technique, we found that EWP treatment also altered the hepatic metabolic profile in T2DM mice, in which, the role of fatty acid esters of hydroxy fatty acids in mediating the hypoglycemic effect of EWPs might be pivotal.

Constructing Z-scheme heterojunctions incorporating an exquisite hollow structure is an effective performance regulation strategy for the realization of high quantum efficiency and a strong redox ability over photocatalysts. Herein, we report the delicate design and preparation of a core-shell hollow CdS@CoTiO 3 Z-scheme heterojunction with a CdS nanoparticle (NP)-constructed outer shell supported on a CoTiO 3 nanorod (NR) inner shell. The in situ growth synthetic method led to a tightly connected interface for the heterojunction between CdS and CoTiO 3 , which shortened the transport distance of photoinduced charges from the interface to the surface. The promoted charge carrier separation efficiency and the retained strong redox capacity caused by the Z-scheme photoinduced charge-transfer mechanism were mainly responsible for the boosted photocatalytic performance. Additionally, the well-designed core-shell structure afforded a larger interfacial area by the multiple direction contact between CdS and CoTiO 3 , ensuring sufficient channels for efficient charge transfer, and thus further boosting the photocatalytic activity. As an efficient photocatalyst, the optimized CdS@CoTiO 3 nanohybrids displayed excellent 2,4-dichlorophenol (2,4-DCP) and tetracycline (TC) degradation efficiencies of 91.3% and 91.8%, respectively. This study presents a Z-scheme heterojunction based on ecofriendly CoTiO 3 , which could be valuable for the development of metal perovskite photocatalysts for application in environmental remediation, and also demonstrated the tremendous potential of integrating a Z-scheme heterojunction with the morphology design of photocatalyts.

Herein, we develop innovative p-block Bi-doped Co 3 O 4 nanoflakes (Bi-Co 3 O 4 NFAs) on nickel foam, which exhibit excellent electrocatalytic activity for both glucose oxidation (GOR) and H 2 evolution reactions (HER). The two-electrode GOR-HER electrolyzer using Bi-Co 3 O 4 NFAs as both the cathode and anode shows a remarkable reduced operation voltage of 1.48 V at 10 mA cm -2 , superior to the 1.66 V of the OER-HER electrolyzer, demonstrating promising potential for advanced H 2 production featuring energy saving and simultaneously produced value-added chemicals.

The request for both high catalytic selectivity and high catalytic activity is rather challenging, particularly for catalysis systems with the primary and side reactions having comparable energy barriers. Here in this study, we simultaneously optimized the selectivity and activity for acetylene semi-hydrogenation by rationally and continuously varying the doping ratio of Zn atoms on the surface of Pd particles in Pd/ZnO catalysts. In the reaction temperature range of 40-200 °C, the conversion of acetylene was close to ∼100%, and the selectivity for ethylene exceeded 90% (the highest ethylene selectivity, ∼98%). Experimental characterization and density functional theory calculations revealed that the Zn promoter could alter the catalyst's potential energy surface, resulting in a "confinement" effect, which effectively improves the selectivity yet without significantly impairing the catalytic activity. The mismatched impacts on activity and selectivity resulting from continuous and controllable alteration in the catalyst structure provide a promising parameter space within which the two aspects could both be optimized., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Despite the rapid development of computational methods, including density functional theory (DFT), predicting the performance of a catalytic material merely based on its atomic arrangements remains challenging. Although quantum mechanics-based methods can model 'real' materials with dopants, grain boundaries, and interfaces with acceptable accuracy, the high demand for computational resources no longer meets the needs of modern scientific research. On the other hand, Machine Learning (ML) method can accelerate the screening of alloy-based catalytic materials. In this study, an ML model was developed to predict the CO 2 and CO adsorption affinity on single-atom doped binary alloys based on the thermochemical properties of component metals. By using a greedy algorithm, the best combination of features was determined, and the ML model was trained and verified based on a data set containing 78 alloys on which the adsorption energy values of CO 2 and CO were calculated from DFT. Comparison between predicted and DFT calculated adsorption energy values suggests that the extreme gradient boosting (XGBoost) algorithm has excellent generalization performance, and the R -squared ( R 2 ) for CO 2 and CO adsorption energy prediction are 0.96 and 0.91, respectively. The errors of predicted adsorption energy are 0.138 eV and 0.075 eV for CO 2 and CO, respectively. This model can be expected to advance our understanding of structure-property relationships at the fundamental level and be used in large-scale screening of alloy-based catalysts., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

Hypochlorous acid (HOCl) released from activated leukocytes plays a significant role in the human immune system, but is also implicated in numerous diseases due to its inappropriate production. Chlorinated nucleobases induce genetic changes that potentially enable and stimulate carcinogenesis, and thus have attracted considerable attention. However, their multiple halogenation sites pose challenges to identify them. As a good complement to experiments, quantum chemical computation was used to uncover chlorination sites and chlorinated products in this study. The results indicate that anion salt forms of all purine compounds play significant roles in chlorination except for adenosine. The kinetic reactivity order of all reaction sites in terms of the estimated apparent rate constant k obs-est (in M -1 s -1 ) is heterocyclic NH/N (10 2 -10 7 ) > exocyclic NH 2 (10 -2 -10) > heterocyclic C8 (10 -5 -10 -1 ), but the order is reversed for thermodynamics. Combining kinetics and thermodynamics, the numerical simulation results show that N9 is the most reactive site for purine bases to form the main initial chlorinated product, while for purine nucleosides N1 and exocyclic N 2 / N 6 are the most reactive sites to produce the main products controlled by kinetics and thermodynamics, respectively, and C8 is a possible site to generate the minor product. The formation mechanisms of biomarker 8-Cl- and 8-oxo-purine derivatives were also investigated. Additionally, the structure-kinetic reactivity relationship study reveals a good correlation between lg  k obs-est and APT charge in all purine compounds compared to FED 2 (HOMO), which proves again that the electrostatic interaction plays a key role. The results are helpful to further understand the reactivity of various reaction sites in aromatic compounds during chlorination.

Arachidonic acid metabolites are a family of bioactive lipids derived from membrane phospholipids. They are involved in cancer progression, but arachidonic acid metabolite profiles and their related biosynthetic pathways remain uncertain in colorectal cancer (CRC). To compare the arachidonic acid metabolite profiles between CRC patients and healthy controls, quantification was performed using a liquid chromatography-mass spectrometry-based analysis of serum and tissue samples. Metabolomics analysis delineated the distinct oxidized lipids in CRC patients and healthy controls. Prostaglandin (PGE2)-derived metabolites were increased, suggesting that the PGE2 biosynthetic pathway was upregulated in CRC. The qRT-PCR and immunohistochemistry analyses showed that the expression level of PGE2 synthases, the key protein of PGE2 biosynthesis, was upregulated in CRC and positively correlated with the CD68+ macrophage density and CRC development. Our study indicates that the PGE2 biosynthetic pathway is associated with macrophage infiltration and progression of CRC tumors.

Herein, a photoinduced direct C(sp 2 )-H alkylation of N -heteroaromatics by using commercially available tetrabutylammonium tribromide (TBATB) as a HAT reagent is described. The method uses O 2 as the oxidant, and features metal-free, mild reaction conditions and good functional group compatibility.

Immunosuppressive tumor microenvironments challenge the effectiveness of protein-based biopharmaceuticals in cancer immunotherapy. Reestablishing tumor cell immunogenicity by enhancing calreticulin (CRT) exposure is expected to improve tumor immunotherapy. Given that CRT translocation is inherently modulated by phosphorylated eIF2α, the selective inhibition of protein phosphatase 1 (PP1) emerges as an effective strategy to augment tumor immunogenicity. To harness the PP1-disrupting potential of GADD34-derived motifs and address their limited intracellular delivery, we integrated these sequences into an enzyme-triggered, cell-penetrating peptide-mediated chimeric protein scaffold. This design not only facilitates efficient cytoplasmic delivery of these immunostimulatory motifs to induce "eat-me" signaling, but also provides a versatile platform for combination immunotherapy. Fabrication of biomodulators with cytotoxic BLF1 provides additional "eat-me" signaling through phosphatidylserine exposure or that with an immunomodulatory designed ankyrin repeat protein disables "don't-find-me" signaling by antagonizing PD-L1. Notably, these bifunctional biomodulators exhibit remarkable ability to induce macrophage phagocytosis, dendritic cell maturation, and CD8 + T activation, ultimately substantially inhibiting tumor growth. This study presents a modular genetic coding strategy for PP1-centered therapies that enables seamless integration of immunostimulatory sequences into protein-based anti-tumor cocktail therapies, thereby offering novel alternatives for improving antitumor efficacy.

The electrochemiluminescence (ECL) behavior of a tri(2,2'-bipyridyl)ruthenium(ii) (Ru(bpy) 3 2+ )/tripropylamine (TPrA) system was investigated in sensor chips with two kinds of integrated two-electrode systems, which included screen-printed electrodes (SPE) and physical vapor deposition (PVD) electrodes. Firstly, under excitation with an optimal transient potential (TP) within 100 ms, the ECL assay could be carried out on the microchips using an Au & Au electrode system, emitting strong and stable light signal. Secondly, on the PVD chip, the ECL intensity initiated by optimal TP was eight times stronger than the peak light signal emitted by the linear sweep voltammetry model. Finally, the logarithmic ECL intensities exhibited a linear increase with the logarithmic concentrations of Ru(bpy) 3 2+ in both the SPE and PVD chips without any reference electrode (RE). Typically, the integration of an interdigital two-electrode system in the microchip significantly enhanced the ECL sensitivity of Ru(bpy) 3 2+ because the large relative area between the working electrode (WE) and counter electrode (CE) achieved a highly efficient mass transfer. This improvement enabled the establishment of a reliable linear relationship across a wide concentration range, spanning from 1 pM to 1 μM ( R 2 = 0.998). Therefore, the exceptional ECL response of the Ru(bpy) 3 2+ /TPrA system on microfluidic chips using a two-electrode system and the TP excitation model has been demonstrated. This suggests that ECL chips without a RE have broad potential for the rapid and sensitive detection of multiple targets., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Two-dimensional ferromagnets with a long-range ferromagnetic ordering at finite temperature present a bright prospect for their potential applications in nanoscale spintronic devices. The tuning of their intrinsic ferromagnetism and Curie temperature is essential for the development of next-generation data storage and spintronic devices. In this work, the electronic structures, ferromagnetism and Curie temperature of two-dimensional MnS 2 monolayer are controlled by charge doping and electric field using first principles calculations. The results show that the dynamic and thermal stability of monolayer MnS 2 for all of the cases can be still maintained. Moreover, there is no existence of phase transition and all MnS 2 monolayers at any charge doping concentrations and electric field intensities favor ferromagnetic coupling. For the manipulation of electron doping, the calculated total magnetic moment M tot of the MnS 2 monolayer exhibits an increase from 3.112 to 3.491 μ B per unit cell. Further analysis indicates that a transition from half-metal to metal occurs by introducing the charge doping and vertical electric field, and the Mn 3d electronic states are the major determinants of ferromagnetism. Additionally, the charge doping enables the magnetic anisotropy energy to transform from an in-plane easy axis to the magnetization direction out of the plane. The Curie temperature T c of the MnS 2 monolayer can be moderately enhanced above room temperature by hole doping and application of a vertical electric field. Remarkably, T c reaches its peak at 767 K at a hole doping concentration of -0.8 e . This work enriches the microscopic understanding of the tuning mechanism of ferromagnetism and supplies a sound theoretical basis for subsequent experimental studies.

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

The first dual nickel/photoredox-catalyzed enantioselective reductive cross-coupling of racemic α-chloro thioesters with aryl iodides has been developed. This strategy avoids the need for organometallic reagents or stoichiometric metal reductants. This reaction could tolerate a wide range of substrate scope with excellent reactivity and high enantioselectivities (up to 91% ee) to access a variety of chiral α-aryl thioesters. The synthetic utility of the corresponding α-aryl thioesters is demonstrated. Furthermore, we explored the mechanism of such an enantioselective radical cross-coupling process.

Despite numerous studies having reported the effects and mechanisms of antihypertensive peptides including peptides derived from egg white proteins, the role of peptides in a female hypertensive animal model is unknown. On the other hand, the role of epigenetic modulation by peptide treatment has rarely been investigated. This study sought to investigate the effect of egg white protein hydrolysate (EWH) in female spontaneously hypertensive rats (SHRs) as well as to explore the underlying mechanisms from the perspectives of the transcriptome and the profiles of non-coding RNAs. Young (12-14-week-old) female SHRs were orally administered 250 mg per kg body weight (low-dose) or 1000 mg per kg body weight (high-dose) EWH daily for 10 weeks. The blood pressure of the rats was monitored weekly. The mRNA and non-coding RNAs (miRNA, lncRNA, and circRNA) in the aorta were profiled by the high-throughput RNA-seq technique. Differentially expressed (DE) RNAs in the aorta were identified for the construction of the competing endogenous RNA (ceRNA) networks and key molecules were validated by qRT-PCR. The treatment of the high-dose EWH showed a significant effect on reducing blood pressure in female SHRs. Bioinformatic analyses revealed 813, 90, 347 and 869 DE-mRNAs, DE-miRNAs, DE-lncRNAs and DE-circRNAs, respectively. The CNTN5-LncRNA-XR_001835895.1-miR-384-5p was identified as the central network which was validated in the aorta and circulation of female SHRs. The results from this study demonstrated that the treatment with EWH reduced blood pressure via regulating the ceRNA networks in female SHRs, which provided novel insights into the mechanisms of food protein-derived antihypertensive peptides.

Exposing the photocatalyst's highly active facets and hybridizing the photocatalyst with suitable cocatalysts in the proper spot have been recognized as strong methods for high-performance photocatalysts. Herein, Ag 2 NCN/TiO 2 -Ti 3 C 2 composites were synthesized by applying simple calcination and physically weak interaction deposition processes to obtain an excellent photocatalyst for Rhodamine B (Rh B) degradation when exposed to visible light. The findings from the experiments reveal that the Ag 2 NCN/TiO 2 -Ti 3 C 2 400 composite exhibited an outstanding photocatalytic rate in 80 min, with the highest Rh B degradation rate ( k = 0.03889 min -1 ), which was 16 times higher than that of pure Ag 2 NCN ( k = 0.00235 min -1 ) and 2.2 times higher than that of TiO 2 -Ti 3 C 2 400 ( k = 0.01761 min -1 ). The results from the following factors: (i) the powerful interfacial contact created by the in situ formation of TiO 2 , and the superior electrical conductivity of Ti 3 C 2 that makes carrier separation possible; (ii) TiO 2 with electron-rich (101) facets are deposited on the surface of Ag 2 NCN, significantly reducing charge carrier recombination by trapping photoelectrons; (iii) a Z-type heterojunction is constructed between nanosize aggregate Ti 3 C 2 -TiO 2 and Ag 2 NCN with non-metal Ti 3 C 2 as the solid medium, improving the transfer and separation of photogenerated charges and inhibiting the recombination of electrons and holes. Additionally, the redox ability of the composite photocatalyst is enhanced. Furthermore, the analyses of active species showed that photogenerated superoxide radicals and holes were the principal active agents inside the photodegradation of Rh B. Moreover, the composite exhibited outstanding photo-stability.

Poly(vinyl alcohol) (PVA)/modified porous starch (MPS) gel beads were prepared through in situ chemical cross-linking by incorporating with MPS, which was obtained by modifying porous starch (PS) with polyethyleneimine (PEI) and glutaraldehyde (GA). Addition of MPS could improve the storage modulus and the effective crosslinking density ( v e ) of the gel beads, and the mechanical properties were enhanced. The PVA-MPS gel beads were preserved as immobilized microbial carriers for 40 d and reactivated in wastewater. Scanning electron microscope (SEM) observations showed that the beads were highly porous and conducive for microorganism adhesion. The PVA-MPS gel beads were able to remove 97% of ammonia nitrogen and 80% of chemical oxygen demand (COD) after reactivation under all four preservation conditions. The abundance of Hydrogenophaga as denitrifying bacteria on PVA-MPS gel beads increased, with abundance of 8.44%, 5.55%, 8.90% and 9.48%, respectively. It proved that the carrier provided a partial hypoxic environment for microorganisms., 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.)

Carboxylic acid-modified materials are a common means of achieving efficient NH 3 adsorption. In this study, we report that improved NH 3 adsorption capacity and easier desorption can be achieved through the introduction of substances containing Lewis basic groups into carboxylic acid-modified materials. Easily synthesized mesoporous acid-base hybrid polymers were constructed with polymers rich in carboxylic acid and Lewis base moieties through cooperative hydrogen bonding interactions (CHBs). The hybrid polymer PAA-P4VP presented higher NH 3 capacity (18.2 mmol g -1 at 298 K and 1 bar NH 3 pressure) than PAA (6.0 mmol g -1 ) through the acid-base reaction and the assistance from CHBs with NH 3 , while the NH 3 desorption from PAA-P4VP was easier for the reformation of CHBs. Based on the introduction of CHBs, a series of mesoporous acid-base hybrid polymers was synthesized with NH 3 adsorption capacity of 15.8-19.3 mmol g -1 and high selectivity of NH 3 over CO 2 ( S NH 3 /CO 2 = 25.4-56.3) and N 2 ( S NH 3 /N 2 = 254-1068), and the possible co-existing gases, such as SO 2 , had a lower effect on NH 3 uptake by hybrid polymers. Overall, the hybrid polymers present efficient NH 3 adsorption owing to the abundant acidic moieties and CHBs, while the concomitant Lewis bases promote NH 3 desorption., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)