Science China Chemistry最新文献

Phototherapy has emerged as a promising modality in modern medicine, attracting significant attention due to its non-invasiveness, exceptional spatiotemporal controllability, and reduced side effects. Advanced technologies have been developed in phototherapy, encompassing three main approaches: photodynamic therapy, photothermal therapy, and photoactivatable prodrug-based therapy. In this review, we present photosensitizers, photothermal agents, and photoactivatable prodrugs, along with photo-responsive carriers used in therapy. Subsequently, we discuss the advantages of phototherapy in combating cancer, infections, and other diseases. Additionally, we highlight the benefits of combining phototherapy with other treatments, as single-mode therapeutic modalities often fail to achieve satisfactory efficiency. Finally, we address the current challenges in developing effective phototherapy agents, particularly regarding their clinical applications. We believe that advancements in phototherapy will promote non-invasive theranostic techniques for clinical studies.

Gastric cancer (GC) is a prevalent and lethal malignancy worldwide, and the 5-year survival rate is less than 30%. The absence of distinctive symptoms often leads to late-stage diagnosis, contributing to a grim prognosis. Early detection is pivotal for improving the survival rates and outcomes of GC patients. Traditional diagnostic methods, including gastroscopy and histopathological examination, are restricted in the early diagnosis of GC. Conventional protein biomarkers, such as carcinoembryonic antigen (CEA), carbohydrate antigen 19-9 (CA19-9), and carbohydrate antigen 72-4 (CA72-4), exhibit insufficient sensitivity and specificity for GC screening, which diminishes their clinical value. Recently, novel circulating biomarkers, such as circulating tumor cells (CTCs), circulating tumor cell DNA (ctDNA), and circulating free RNA (cfRNA), have emerged as promising candidates in the burgeoning field of liquid biopsy due to their superior sensitivity and specificity. This review focuses on the latest research on blood-based biomarkers for GC diagnosis and examines the clinical potentials and challenges associated with these emerging biomarkers.

The aqueous zinc ions hybrid capacitors (ZHCs) have great potential for future energy storage devices by their high safety and low cost merits, more importantly, it could combine the advantages of batteries and supercapacitors with high energy density and power output, respectively. However, the development of reliable cathodes is still a challenge with the unsatisfactory cycling stability and limited reaction kinetic, severely restricting its further commercial applications. Herein, we present phosphorus functionalized nitrogen-doped hierarchical porous carbon nanosheets (PN-HPCNS), where the P incorporation could effectively enhance the electronic transfer kinetics and ion adsorption capability to achieve superior zinc-ion storage properties. The as-prepared PN-HPCNS cathode-based ZHC exhibits a high energy and power density (169.1 Wh kg⁻¹/68 W kg⁻¹, 15,840 W kg⁻¹/30.8 Wh kg⁻¹) and long cycling lifespans more than 20,000 cycles with 92.0% capacity retention. Systematic characterizations coupled with kinetics studies indicate that phosphorus modification is crucial to superior zinc ion storage, enabling PN-HPCNS with favorable reaction kinetics, promoting ion adsorption by providing more active sites. Moreover, the theoretical calculation reveals that the phosphorus modification could enhance the adsorption ability, contributing to the superior ZHCs performance of PN-HPCNS.

Rational design of single atom nanozymes (SAzymes) could be achieved through the accurate configuration regulation of metal coordination sites, nevertheless, the un-defined carbon environment of traditional SAzymes synthesized by high-temperature pyrolysis makes it difficult to unveil the influence of carbon skeletons with enzyme mimicking activities of SAzymes. Herein, we investigated the relationship between the carbon skeletons and the enzyme mimicking activities through the construction of a series of fully π-conjugated covalent organic polymer (COP)-based SAzymes with analogous Fe-N₄ sites. The experimental results and theoretical calculations demonstrated that carbon skeletons bonded to the Fe-N₄ catalytic sites strongly affect the enzyme mimicking activities of COP SAzymes. When the number of benzene rings in carbon skeletons was 1, the COP SAzyme possessed much more remarkable oxidase (OXD) and peroxidase (POD) mimicking activities, and further reducing or increasing the benzene rings would dramatically inhibit the enzyme mimicking activity. Additionally, the fantastic enzyme mimicking activity of COP-1 could be applied to colorimetric detection of biological molecules and degradation of pollutants. These results provide a new perspective for the rational fabrication of SAzymes with high catalytic efficiency.

White light-emitting diodes (WLEDs) as energy-saving light sources are widely used to alleviate the rising electric consumption. Most commercial WLEDs are blue/yellow-mixed emitting devices, which have some disadvantages, such as physiological damages of rich blue light, complex device structure and color aging. It is essential to develop single-component WLEDs with quasi-solar spectrum to overcome these problems. Here we demonstrate a high-performance single-component WLED based on donor-acceptor integrated carbon nitride (DACN) material. The donor-acceptor simultaneously increases the photoluminescence efficiency and the carrier mobility of graphitic carbon nitride (g-CN), hence, the DACN-based WLED reaches a milestone in maximum luminance of 2,045 cd m⁻² and maximum external quantum efficiency of 2.2%, which are one order of magnitude higher than pristine g-CN-based LED. Furthermore, the DACN-based WLED emits broadband white light with color coordinates of (0.34, 0.44) and a color temperature of 5,163 K. Our works open a way to boost optoelectronic properties of g-CN materials and show their promising application in single-component WLEDs.

Achieving color-tunable room-temperature phosphorescence (RTP), especially including blue RTP from a single-component polymer still faces a formidable challenge. Herein, we wisely choose conformation-dependent phenothiazine with trifluoromethyl substituent as the side group of the phosphor monomer (CzPT) and then copolymerize it with N-isopropylacrylamide (NIPAM) through photopolymerization to obtain polymers PPCzPTs. Time-dependent color-tunable phosphorescence from unusual quasi-equatorial (eq) to quasi-axial (ax) conformers are obtained, and the RTP color changes from orange (550 nm) to blue (470 nm) with phosphorescence lifetime up to 0.96 s. The theoretical calculations confirm that the quasi-axial conformer is the preferred structure that facilitates the formation of intramolecular hydrogen bonds on the trifluoromethyl group. The EPR spectra illustrate that the persistent UV irradiation generates radical cations to induce the conformational transitions first, followed by photopolymerization immobilizing the ax conformation in PPCzPTs. Applications of data encryption and anti-counterfeiting are fabricated to show prompt and delayed multicolor information. This work affords a simple and feasible avenue for two-dimensional color tunable room temperature phosphorescence from a single-component polymer.

Photoactive complexes of nonprecious transition metals, mainly including those in the first-row and partially the second-row of the Periodic table of elements, have received increasing attention in view of their low cost and long-term sustainability. They are recognized as promising alternatives to noble transition metal complex congeners that have been extensively studied in optoelectronic devices, artificial photosynthesis, photocatalysis, biodiagnostics, and therapeutics, etc. This review is devoted to a comprehensive summary on the classical and recent advances on photoactive nonprecious transition metal complexes, including photoactive Zr, V, Cr, Mo, and W complexes, Mn complexes and hybrids, Fe, Co, Ni, and Cu complexes, and Zn and Cd complexes and hybrids. A particular focus is given on the molecular design, modulation of photophysical and photochemical properties, and applications of the representative and lately-developed nonprecious metal complexes. In addition, a perspective on the future development in this field is provided at the end of this review.

Dinuclear metal synergistic catalysis (DMSC) has been evidenced to be effective in enhancing the catalytic activity for CO₂ reduction. However, the reaction kinetics of CO₂ reduction is still limited by the local CO₂ concentration around the dinuclear catalytic centers. Inspired by the structure of carbonic anhydrase, we have designed and synthesized a dinuclear cobalt(II) complex with an –OH group. This complex not only exhibits DMSC for CO₂ reduction but also possesses excellent capture capacity for CO₂ molecules. Consequently, the complex demonstrates high efficiency for the photocatalytic reduction of CO₂ to CO, with turnover number reaching as high as 43,400 and a selectivity of 97%. Even in 10% CO₂, the complex still shows state-of-the-art catalytic activity. The results of experiments and theoretical calculations reveal that besides the DMSC contributing to the enhanced catalytic activity, the –OH group in the dinuclear cobalt(II) complex facilitates the capture of CO₂ by the formation of HCO₃⁻ intermediates, thereby enhancing the affinity towards CO₂ and boosting the catalytic activity for CO₂-to-CO conversion.

Gene expression must be precisely regulated in cells and functional nucleic acids are the most widely utilized tools for gene manipulation. Photocontrol of how these nucleic acid tools work in the cellular environment can precisely manipulate gene expression through a non-invasive way. Here we report a methodology on multiplex photocontrol of functional nucleic acids to achieve totally temporal and orthogonal regulation of gene expression in living cells. We select two functional nucleic acid systems as examples, DNAzyme and CRISPR/Cas9, and demonstrate the power of light control for precise gene manipulation by rational design of chemically modified oligonucleotides through introduction of two photocleavable linkers. Unlike the previous modulation of functional nucleic acids by simply activating or deactivating, we successfully achieve versatile controlling patterns using light as the governing factor. This design represents a generalized pathway towards the photo-controllable functional nucleic acids, which greatly enriches the toolbox for optogenetic studies.