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Semiconductor metal-organic frameworks (MOFs) and heterojunctions have gained increasing attention in many fields, yet their full potential remains largely unexplored. Advanced optobioelectronics are envisioned to create more opportunities for innovative biomedical applications. This study reports a UiO-66-NH

Activation of the IRE-1/XBP-1s pathway supports tumor progression. Here, we report a novel prodrug, TC-D-F07, in which a thiol-reactive dinitrobenzenesulfonyl (Dns) cage was installed onto the C8 hydroxyl of the covalent IRE-1 inhibitor D-F07. The electron-withdrawing Dns group in TC-D-F07 stabilizes the neighboring 1,3-dioxane acetal, allowing for stimulus-mediated control of its inhibitory activity. TC-D-F07 exhibits high sensitivity to intracellular thiols. Because tumor cells exhibit higher concentrations of glutathione and cysteine, treatment with TC-D-F07 results in more sustained levels of D-F07 in transformed versus normal cells. In addition, we show that a dinitrophenyl cysteine adduct resulting from cleavage of the Dns group induces endoplasmic reticulum (ER) stress, causing tumor cells to increase the expression of XBP-1s. The accumulated levels of D-F07 and its gradual decomposition into the active IRE-1 inhibitor eventually deprive tumor cells of XBP-1s, leading to more severe apoptosis than those treated with its uncaged analogue.

Hydroxyl radicals (•OH) generated in the photocatalytic process are crucial to the conversion of methane (CH4) to value-added methanol (CH3OH) at room temperature. However, utilizing noble metal-free catalysts and low-energy photons of solar light, such as visible and near-infrared light (vis-NIR), is difficult to provide more electron states to form •OH radicals. Here, we developed FeOOH/Li0.1WO3 core-shell nanorods via a two-step in/out co-modification of hexagonal tungsten oxide (h-WO3): (1) lithium ions intercalating into the hexagonal tunnels of h-WO3 to form Li0.1WO3 nanorods and (2) using FeOOH-wrapped Li0.1WO3 to obtain FeOOH/Li0.1WO3 core-shell nanorods. Introduction of lithium induces polaron transition in Li0.1WO3, enabling the absorption of vis-NIR light. Interestingly, FeOOH-based Fenton-like reaction when H2O2 is selected as an oxidant favors the generation of more •OH radicals available for CH4 oxidation to CH3OH. Meanwhile, FeOOH with FeIII as an "electron sink" highly improves the separation of photoinduced electrons and holes in Li0.1WO3. Eventually, efficient selective formation of CH4OH is achieved with remarkable generation rates up to ∼342 and ∼160 μmol g-1 at visible light (420-700 nm) and NIR light (≥800 nm), respectively. Our finding opens up new possibilities for developing noble metal-free catalysts for solar energy-driven CH4 conversion to CH3OH under ambient conditions.

Metal-organic frameworks (MOFs), which are a class of coordination polymers constructed by metal ions or clusters with organic ligands, have emerged as exciting inorganic-organic hybrid materials with the superiorities of inherent crystallinity, adjustable pore size, clear structure, and high degree of functionalization. The MOFs have attracted much attention to develop good luminescent functional materials due to their inherent luminescent centers of both inorganic and organic photonic units. Furthermore, the pores within MOFs can also be used to encapsulate a large number of luminescent guest species, which provides a broader luminescent property for MOF materials. MOFs possess the incomparable multifunctional advantages of inorganic and organic luminescent materials. A large number of luminescent MOFs (LMOFs) have been synthesized for applications in sensing, white-light-emitting diodes (LED), photocatalysis, biomedicine, etc. This paper reviews the encapsulation of various luminescent guests such as lanthanide ions, dyes, quantum dots, and luminescent complexes in metal-organic frameworks to construct luminous sensors with single- or double-emission centers, as well as the research progress of these sensors in chemical sensing. Finally, the challenges in these fields were outlined and the prospects for future development were put forward.

Herein, we describe a facile method to control the size and dispersion of CuO nanoparticles (NPs) in SBA-15 by the supercritical antisolvent (SAS) method during the depressurization process of supercritical fluid deposition (SCFD), describing the mass transfer between supercritical carbon dioxide (scCO₂) and a cosolvent. On reducing the concentration of the cupric nitrate precursor, the size of CuO NPs was decreased from 3.5 ± 1.0 to 1.0 ± 0.4 nm (Cu loading 14.2–12.1 wt %) under the depressurized rate of ∼20 MPa/min. Based on the size distribution and nucleation theory, the nucleation rate of the precursor could reach 10²⁵ cm–³·s–¹, and the calculated interface energy of cupric nitrate was less than 0.1 J/m², indicating that scCO₂ as an antisolvent caused the heterogeneous nucleation of the precursor on the surface of SBA-15 channels. Hence, the nucleation rate and growth of cupric nitrate were regulated under a given scCO₂ depressurized rate, and then the CuO NPs’ size distribution and Cu loading were controlled subsequent to calcination.

Probes are usually required for specific detection using photoelectrochemical (PEC) sensors. However, tedious probe modification and cleaning procedures reduce the efficiency of PEC sensors. To ove...

The exfoliation of graphene in organic solvents with shear has been proved to be effective and easy to scaleup. However, there are a few studies focusing on the structure of the agitator or flow ci...

The encapsulation of multiple enzyme/nanoenzyme systems within mental-organic frameworks (MOFs) shows great promise for a myriad of practical applications. Herein, two sequential biocatalysts, oxidase and hemin, were coupled together with close proximity using a bifunctional polymer, poly(1-vinylimidazole) (PVI), and encapsulated into MOFs. As a demonstration of the power of such a protocol, glucose oxidasePVI-hemin encapsulated in ZIF-8 showed significant enhancement of bioactivity for a cascade reaction compared to its counterpart without PVI. For the colorimetric assay of glucose, it showed a low limit of detection of 0.4 μM (S/N = 3), high selectivity, and excellent stability. Because there are numerous biocatalysts that can readily be coupled and encapsulated into MOFs, a myriad of interesting properties can be simply realized by encapsulating different sequential biocatalysts.

Photoelectrochemical sensing has developed rapidly in the past decade because of its inherent advantages of economic devices and low background noise. However, traditional assembly of photoelectric beacons, probes, and targets on the ITO electrode solid-liquid interface inevitably leads to time-consuming, limited selectivity, poor stability, and nonreproducibility. To overcome these drawbacks, in this work, a unique split-type PEC aptasensor for carcinoembryonic antigen (CEA) was developed in virtue of the sandwich-like structure comprised of magnetic-optical Fe3O4@SiO2@CdS-DNA1, CEA aptamer, and signal element SiO2-Au-DNA2. The sandwich-like structure is easily formed in the liquid phase and can be triggered by competition from low-abundance CEA, resulting in dissociation. By further photocurrent measurement in pure phosphate buffer saline (PBS), coexisting species can be effectively removed from the modified electrode, improving selectivity, stability, and repeatability. These advantages benefit from the preparation of uniform and monodispersed Fe3O4@SiO2@CdS and SiO2-Au particles, DNAs assembly, and an elegant design. Additionally, the as-designed signal-on PEC aptasensor is highly sensitive, short time-consuming, and economical, enabling the detection of CEA in serum specimens. It not only provides an alternative to CEA immunosensors, but also paves the way for high-performance PEC aptasensors.

Solubility of 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfanilamide] ([Bmim][NTf2]) and 1-butyl-3-methylimidazolium acetate ([Bmim][Ac]) in supercritical carbon dioxide (scCO2) using ethan...

Bimetallic Ni–Cu catalysts feature high activity in CO2 hydrogenation. However, the primary surface intermediates during reaction are still elusive, making the understanding of the reaction mechani...

Supported ionic liquid membranes (SILMs) based on [EMIM][Ac] and γ-Al2O3 membranes were prepared using a supercritical fluid deposition (SCFD) method at 12 MPa and 50 °C. The influences of the preparation time, ionic liquid loading, and ethanol content on the performance of SILMs were studied. The CO2/N2 selectivity of the as-prepared SILMs reached the ideal selectivity of [EMIM][Ac]. When the ionic liquid (IL) was dissolved in a mixture of supercritical CO2 (scCO2) and ethanol, the IL easily diffused into the small pores in supports. Moreover, the dissolved IL could transition to the liquid phase in the small pores because of the capillary phase transition, leading to the selective filling of the meso- and micropores in the supports. The surface tension of the liquid phase and the ratio of the IL concentration to the saturation IL concentration were found to be the key factors influencing the capillary phase transition of the IL.

The oxidation mechanism on one-dimensional Pt-induced nanowires on Ge(001) (NWs/Ge(001)) was investigated on the atomic scale, by scanning tunneling microscopy and density functional theory calcula...

This work reports the synthesis of dual functional molecularly imprinted polymer (MIP)-modified organometal lead halide perovskite (CH3NH3PbI3) and its application for photoelectrochemical (PEC) bioanalysis of salicylic acid (SA). Specifically, the CH3NH3PbI3 was encapsulated into the MIPs via a simple thermal polymerization process on the indium tin oxide (ITO) glass, and the as-obtained MIPs/CH3NH3PbI3/ITO electrode was characterized by various techniques, which revealed that the MIPs could not only stabilize CH3NH3PbI3 but also improve the electron-hole separation efficiency of CH3NH3PbI3 under light illumination. In the detection of model analyte SA, the PEC sensor, with numerous amounts of recognition sites to SA, exhibited desirable performance in terms of good sensitivity, selectivity, stability, and feasibility for real sample analysis. This work not only featured the use of MIPs/CH3NH3PbI3 for PEC detection of SA but also provided a new horizon for the design and implementation of functional polymers/perovskite materials in the field of PEC sensors and biosensors.

A efficient and sustainable approach for the synthesis of 3-alkylquinoxalin-2(1H)-ones has been developed through visible-light-mediated decarboxylative alkylation of quinoxalin-2(1H)-ones with phe...

Herein, via density functional theory (DFT), cluster expansion (CE), and Monte Carlo (MC) calculations, we investigate 3 binary MXene alloy systems of Ti2CO2 and M′2CO2 (M′ = V, Nb, or Ta), where T...

Oxygen adsorption on Pt-induced nanowires on Ge(001) (NWs/Ge(001)) was investigated on the atomic scale. At 77 K, we observed two disparate features based on scanning tunneling microscopy images an...

A visible-light-promoted electron-donor-acceptor (EDA) complex-initiated [5 + 1] annulation between biguanides and perfluoroalkyl halides for the construction of perfluoroalkyl- s-triazines has been developed. It was found that both visible light and dioxygen in the air are favorable for the reaction. A radical-polar crossover mechanism was proposed, in which sequential SET, radical combination, HF elimination, electrocyclization, and aromatization are involved.

A Cu(I)-catalyzed [3 + 2] intramolecular cycloaddition reaction of N-indole-tethered cyclopropenes is presented in this paper. This reaction starts from the formation of π-allyl cationic intermediate or its resonance-stabilized metal carbenoid intermediate upon activation of cyclopropene with Cu(I) catalyst and a Friedel-Crafts-type cyclization to give functionalized hydrogenated diazabenzo[ a]cyclopenta[ cd]azulenes in good to excellent yields along with moderate to good dr values. The asymmetric variant of this cycloaddition reaction can be realized, giving the desired products with moderate ee values.

Remodeling tumor immune microenvironment (TIME) is an important strategy to lift the immunosuppression and achieve immune normalization. In this work, a mannosylated lactoferrin nanoparticulate system (Man-LF NPs) is developed for dual-targeting biomimetic codelivery of shikonin and JQ1 via the mannose receptor and LRP-1 that are overexpressed in both cancer cells and tumor-associated macrophages. The Man-LF NPs can serve as multitarget therapy for inducing immune cell death in the cancer cells, repressing glucose metabolism and repolarizing tumor-associated macrophages, and consequently, lead to remodeling the TIME (e.g., promotion of dendritic cell maturation and CD8+ T cell infiltration, as well as suppression of Treg). Moreover, JQ1 is a suppressor of PD-L1, and the Man-LF NPs can also work on PD-L1 checkpoint blockage. The results reveal the synergistic combination of shikonin and JQ1 and the treatment potency of the Man-LF NPs. Importantly, it is demonstrated that the interaction between the tumor metabolism and immunity plays an essential role in immunotherapy, and the developed drug combination and nanoformulation can target the multiple components in the complicated network of TIME, providing a potential therapeutic strategy.

The filamentous fungus Fusarium fujikuroi is well-known for its production of natural plant growth hormones: a series of gibberellic acids (GAs). Some GAs, including GA1, GA3, GA4, and GA7, are biologically active and have been widely applied in agriculture. However, the low efficiency of traditional genetic tools limits the further research toward making this fungus more efficient and able to produce tailor-made GAs. Here, we established an efficient CRISPR/Cas9-based genome editing tool for F. fujikuroi. First, we compared three different nuclear localization signals (NLS) and selected an efficient NLS from histone H2B (HTB

Improvement in photocurrent performance remains the key subject to prepare a stable and efficient photocathode in photoelectrochemical cell (PEC) water splitting. Different to the ordinary methods, various annealing atmosphere gases were used to study the growth of CuO films on fluorine-doped tin oxide substrate; then, the photocurrent performance was studied when those CuO films were used as photocathodes in PEC. The scanning electron microscopy images indicate that all of the CuO films are composed of vertically arrayed CuO nanosheets, each individual nanosheet with a thickness of 100–500 nm. Those hierarchical CuO photoelectrodes in the PEC exhibit quite different photoelectrochemical activities in visible light, where the air-annealed CuO film has nearly 6 times enhancement in photocurrent (108 μA) at 0 V compared to that of film under oxygen atmosphere, and 34 times of argon. It has an acceptor concentration of 2.9 × 1021 cm–3 from Mott–Schottky analysis, which is more than 2 times larger than that of the oxygen-annealed CuO film, and 37 times larger than that of the argon-annealed film. Ultraviolet photoelectron spectroscopy measurements were carried out to explain the improved photocurrent performance of the air-annealed CuO films, where the obtained valence band of 0.44 eV and work function of 4.92 eV well match the reduction reaction of electrolyte (H2O).

A series of self-assembled monomethoxypoly(ethylene glycol)-b-poly(2-hydroxypropyl methacrylate)/poly(2-hydroxypropyl methacrylate) (mPEG113-PHPMA/PHPMA) blends are prepared by aqueous photoinitiated polymerization-induced self-assembly (photo-PISA) of HPMA at room temperature mediated by a binary mixture of mPEG113-CEPA and CEPA (CEPA = 4-cyano-4-(ethylthiocarbonothioylthio)pentanoic acid). High rates of polymerization are observed in all cases, and quantitative monomer conversions can be achieved within 15 min of 405 nm visible light irradiation. Gel permeation chromatography (GPC) measurement confirms good control is maintained under aqueous photo-PISA conditions at different [mPEG113-CEPA]/[CEPA] ratios. A morphological phase diagram is constructed for the first time by changing the degree of polymerization (DP) of PHPMA and [mPEG113-CEPA]/[CEPA] ratio. The introduction of homopolymer promotes the formation of higher order morphologies and larger spherical micelles. The obtained AB/B assemblies can be...

The solubility of the ionic liquid (IL) 1-butyl-3-methylimidazolium acetate ([Bmim]Ac) in supercritical carbon dioxide (scCO2) with cosolvents, including ethanol, acetone, dimethyl sulfoxide (DMSO), and acetonitrile, was determined at 40, 50, and 60 °C and with a pressure up to 15.0 MPa. The results showed that the addition of cosolvents has a significant effect on the solubility of [Bmim]Ac in scCO2. The ability of different cosolvents to enhance the solubility of [Bmim]Ac in scCO2 is in the following order: ethanol > DMSO > acetone > acetonitrile. The solubility of [Bmim]Ac in the scCO2/cosolvent mixture increased dramatically as the cosolvent concentration exceeded 20.0 mol %. The effect of the temperature on the solubility is more complicated. The solubility of [Bmim]Ac in scCO2/cosolvent increased slowly when using ethanol as the cosolvent, decreased slowly when using acetone or acetonitrile as the cosolvent, and increased first and then decreased when using DMSO as the cosolvent as the temperature i...

Effective treatment of metastatic (stage IV) breast cancers remains a formidable challenge. To address this issue, a cell-penetrating peptide-assisted liposomal system was developed for codelivery of doxorubicin and andrographolide. This nanomedicine-based combination therapy showed the ability to inhibit the in vitro migration and invasion of 4T1 cells through the wound healing and transwell invasion assays. Furthermore, this delivery system exhibited the enhanced accumulation in the tumor tissues and deep intratumoral penetration. The synergistic effect of doxorubicin and andrographolide led to an evident inhibition of tumor growth in an orthotopic breast tumor mouse model and efficient prevention of lung metastasis. The therapeutic mechanism was associated with the anti-angiogenesis effect. In conclusion, this nanomedicine-based combination therapy provides a potential method for overcoming metastatic breast cancers.

In this communication, we developed the first well-controlled Z-RAFT (RAFT = reversible addition–fragmentation chain transfer) mediated polymerization-induced self-assembly (PISA) formulation based on photoinitiated RAFT dispersion polymerization of tert-butyl acrylate (tBA) in ethanol/water (60/40, w/w) at room temperature using a Z-type macromolecular chain transfer agent (macro-CTA). Polymerizations proceeded rapidly via the exposure of visible-light irradiation (405 nm, 0.45 mW/cm2) with high monomer conversion (>95%) being achieved within 1 h. A variety of polymer nano-objects (spheres, worms, and vesicles) with narrow molar mass distributions were prepared by this Z-RAFT mediated PISA formulation. Silver nanoparticles were loaded with the vesicles via in situ reduction, which can be used as a catalyst for the reduction of methylene blue (MB) in the presence of NaBH4. Finally, gel permeation chromatography (GPC) analysis demonstrated that the corona block and the core-forming block could be cleaved b...

Ultrasonication is an emerging technology applied in food processing and biological experimental pretreatments. Cavitation phenomena induced during ultrasonic treatment can generate localized high temperature and pressure, which can result in glycation reaction between protein and reducing sugars. In this study, the mixture of bovine serum albumin (BSA) and d-ribose was treated under 600 W for different times. Interestingly, a large amount of carbonized black materials appeared after ultrasonication, while the UV absorbance and intrinsic fluorescence spectra reflecting conformational changes were not obvious. Only 12 sites (11 lysines and 1 arginine) of the BSA with ribose under ultrasonic treatment for 35 min were identified through liquid chromatography high-resolution mass spectrometry (LCHR-MS). K547, K548, R359/R360, and K587 were the most reactive glycated sites, with the average degree of substitution per peptide molecule (DSP) value ranging from 15 to 35%. The glycated modification was distributed not only in domain III, but also in domains I and II. The glycated modification could occur during ultrasonic treatment, thereby influencing the properties of biomacromolecule after extraction.

Thermally stable Au single-atoms supported by monolayered CuO grown at Cu(110) have been successfully prepared. The charge transfer from the CuO support to single Au atoms is confirmed to play a key role in tuning the activity for CO oxidation. Initially, the negatively charged Au single-atom is active for CO oxidation with its adjacent lattice O atom depleted to generate an O vacancy in the CuO monolayer. Afterward, the Au single-atom is neutralized, preventing further CO reaction. The produced O vacancy can be healed by exposure to O2 at 400 K and accordingly the reaction activity is restored.