Latest ArticlesEnantioselective enamine catalysis has enriched asymmetric synthesis by enabling precise stereochemical control. While classically thermal/photochemical strategies have expanded reaction diversity, electrochemical enantiocontrol remains underexplored despite its potential for tunable redox manipulation. This review systematically evaluates electrochemical enantioselective enamine catalysis through polar/radical mediated chemical bond formation pathways, aiming to delineate current mechanistic paradigms and highlight electrochemistry's unique role on asymmetric enamine catalysis beyond thermodynamic and photochemical conditions. Future efforts including developing enhanced compatibility of chiral catalysts and intermediates with electrochemical systems, as well as exploiting transformative techniques for mechanistic elucidation could be promising to unlock more novel transformations and stereoselectivity models.
The stability of cathode catalyst layers (CCLs) in proton exchange membrane fuel cells (PEMFCs) is critically undermined by Pt dissolution and the loss of effective gas-water management associated with carbon support corrosion. In this work, we develop a porous TiN nanotube−supported Pt (i.e., Pt/TiN NTs) CCL that integrates robust Pt–Ti interfacial bonding with a highly accessible nanotube network to address these persistent challenges. The formation of abundant Pt–Ti bonds at the interface markedly strengthens Pt anchoring, resulting in a 2.3−fold reduction in Pt dissolution and minimal particle coarsening after accelerated durability testing compared to nanoflows-based controls dominated by Pt–N−Ti interactions. The membrane electrode assembly fabricated with this CCL achieves a peak power density of 0.81 W/cm2 and demonstrates exceptional durability, retaining 77% of its initial mass activity and 87.3% of its power density following aggressive square-wave potential cycling, meeting the 2025 U.S. Department of Energy benchmarks. Computational fluid dynamics simulation further reveal that the unique porous architecture facilitates efficient oxygen transport and rapid water removal, sustaining high catalytic utilization under operational conditions. This strategy establishes TiN NTs scaffolds as a generalizable solution for the next generation of carbon-free, high-stability catalyst layers, offering practical guidance for durable and efficient fuel cell design.
The management of breast cancer remains clinically intractable, driven by its highly invasive behavior and limited susceptibility to conventional treatments. In this study, we engineered an innovative cyclodextrin-porphyrin co-assembled nanoplatform (CT NPs) to enable multimodal breast cancer therapy. By successfully encapsulating camptothecin (CPT) within this nanocarrier, the system (CTC NPs) achieved synergistic chemo-phototherapeutic efficacy through dual-modality action. The highly biocompatible cyclodextrin carrier significantly improved the physicochemical characteristics of CPT. In vivo studies revealed that CTC NPs effectively evaded clearance by the reticuloendothelial system, overcame the defect of premature drug leakage, and exhibited superior tumor targeting and infiltration capabilities. Under near-infrared (NIR) laser irradiation, CTC NPs can simultaneously induce localized hyperthermia and produce reactive oxygen species (ROS), thereby achieving efficient tumor ablation. In 4T1 tumor-bearing mice, CTC NPs exhibited targeted, safe, and highly potent anti-tumor efficacy, significantly suppressing both primary tumor progression (tumor suppression rate > 95%) and metastatic dissemination. In summary, this integrated nanoplatform establishes a novel theranostic paradigm for synergistic chemo-phototherapy against triple-negative breast cancer (TNBC), achieving precise tumor ablation through NIR-triggered drug release and real-time imaging guidance.
Two pairs of potent analgesic alkaloid enantiomers with unprecedented chemical architectures, named pyrethalkalines A (1) and B (2), were isolated from the roots of Anacyclus pyrethrum. Pyrethalkaline A (1) is an unprecedented 6/6/6/6/5-fused pentacyclic triamino alkaloid featuring a unique 8,15-diaza-pentacyclo[12.3.1.11,9.05,19.010,14]nonadecane core, and pyrethalkaline B (2) is a novel 6/6/6/6/5/6-fused hexacyclic triamino alkaloid possessing an unprecedented 8,13,19-triazahexacyclo[16.3.1.11,9.05,23.010,18.011,16]tricosane motif. Their structures were elucidated by comprehensive spectroscopic data analysis, quantum 13C nuclear magnetic resonance (NMR) DP4+ and electronic circular dichroism (ECD) calculations, and single-crystal X-ray diffraction analysis, and their plausible biosynthetic pathways were proposed. Alkaloids (±)-1 and (−)-1 at three lower doses of 1, 0.2, and 0.04 mg/kg, and (+)-2 at two lower doses of 1 and 0.2 mg/kg showed more potent analgesic activity than the positive control morphine. Further investigation revealed that (+)-1 and (−)-1 are dual transient receptor potential melastatin 8 (TRPM8) (half-maximal inhibitory concentration (IC50) = 1.90 ± 0.09 and 1.40 ± 0.17 µmol/L, respectively) and Kv1.2 inhibitors. Molecular dockings of 1 provide a novel structural model to develop potent analgesics dual targeting TRPM8 and Kv1.2 ion channels, and (±)-1 have the potential for the development of a non-opioid potent analgesic to treat neurogenic pains.
Traditional cancer therapies are limited by side effects and damage to healthy tissues, while modern targeted treatments face challenges such as drug resistance and restricted applicability across cancer types. Early diagnosis also remains difficult, as many methods lack the sensitivity and specificity needed to reliably detect small, early-stage tumors. This review explores hybrid nanomaterial-based delivery systems, such as lipid–gold nanoparticle composites combined with polymeric nanocarriers, to improve the precision and efficacy of gene therapy. Advances in nanotechnology are highlighted for their ability to augment gene-editing tools including RNA interference and clustered regularly interspaced short palindromic repeats/CRISPR-associated protein 9 (CRISPR/Cas9), supported by techniques like optical tweezers, plasmonics, fluorescence imaging, and metamaterials. Nanophotonics in particular offers ultra-sensitive molecular imaging and real-time biomarker detection, underscoring its value for early cancer diagnosis. Artificial intelligence further strengthens these approaches by optimizing nanocarrier design, predicting therapeutic outcomes, and guiding personalized treatment strategies. Machine learning and deep learning platforms enable efficient analysis of complex genomic and clinical datasets, improving predictive accuracy and therapeutic customization. The review also outlines molecular mechanisms of gene therapy, from editing to expression, and addresses barriers to clinical translation, such as data integration, model validation, and regulatory considerations. Combining nanotechnology, artificial intelligence (AI), and gene-editing advances holds promise for more effective, targeted, and minimally invasive cancer treatments. These integrated strategies support earlier detection, enhance therapeutic precision, and provide a framework for translating experimental breakthroughs into clinical applications that better align with the goals of personalized medicine.
Organic fluorescence-phosphorescence dual-emitting materials based on tunable single chromophores have attracted much attention for their broad application prospects in information technology, display media and other fields due to their high luminescence stability, simple preparation process and excellent reproducibility. Herein, we constructed a novel LP-activated fluorescence-phosphorescence dual-light-harvesting (FPRET) supramolecular assembly based on LP with orthogonal charges, the phosphorescent molecule G and the NIR dye NIB through a supramolecular non-covalent strategy. The energy transfer efficiency of fluorescence is 54.68% when the molar ratio of G/LP to NIB is 10:1, while the energy transfer efficiency and antenna effect of phosphorescence are 48.75% and 241.43 respectively when the molar ratio of G/LP to NIB is 50:1. In addition, by co-assembling with carbon dots (CDs) and adjusting the ratio of donor to acceptor components, the full-color spectral regulation including white light (CIE chromaticity coordinates x, y = 0.31, 0.33) was realized. Utilizing this LP to promote the supramolecular full-color FPRET assembly of single fluorophore G and showing the multi-level anti-counterfeiting of intelligent logic gates through pattern, time, and color editing, it provides a new insight and direction for the development of a new generation of high-performance optical functional materials.
In contrast to conventional cancer treatment modalities, cancer immunotherapy has increasingly emerged as one of the most promising therapeutic approaches for cancer, owing to its capacity to elicit long-lasting immune memory and its favorable safety profile. However, the immunosuppressive tumor microenvironment (ITME) significantly hinders its progression. While tumor stromal cells play a crucial role in the formation of the ITME, they also offer several potential targets for interventions aimed at reshaping this suppressive milieu. In clinical practice, the modulating of tumor stromal cells overcomes resistance mechanisms, exhibits broader therapeutic potential, and allows for more manageable toxicity profiles. Owing to the capacity of nanodrug delivery systems (nano-DDS) to facilitate accurate targeting and integrate multiple functions, a growing number of researchers are employing nano-DDS in the immunotherapy modulated to tumor stromal cells. This review begins by elucidating the roles played by different tumor stromal cells in the formation of the ITME. Subsequently, we provide the nanodelivery strategies modulating distinct tumor stromal cells. Finally, we propose the current challenges and discuss potential future development directions in this field.
The development of efficient and cost-effective non-precious-metal single-atom catalysts (SACs) is crucial for advancing the practical application of electrocatalytic CO2 reduction (CO2RR). However, identifying highly active metal atoms and designing catalysts with uniform active center structures remain significant challenges. To address this, we developed a generic pyrolysis method to synthesize a series of transition metal-based SACs with atomically dispersed metal anchored on carbon nitride support (M-C3N4, M = Fe, Ni, Cu). Benefiting from the unique electronic structure of the Fe-N4 sites supported on C3N4, the Fe-C3N4 catalyst demonstrated exceptional performance, achieving a CO Faradaic efficiency of 99.6% and maintaining excellent stability. Theoretical calculations indicate that the Fe site exhibits a relatively stronger interaction with the *COOH intermediate, thereby helping to lower the energy barrier of the CO2 protonation process. This study provides valuable theoretical insights and practical synthesis strategies for designing high-performance non-precious-metal SACs for CO2RR.
Inspired by the natural synthesis of biomolecules, the artificial production of therapeutic agents within cells has emerged as a powerful and versatile approach for disease treatment. Performing artificial chemical reactions within living cells to achieve various physiological goals remains both an intriguing and highly challenging endeavor. This review summarizes recent advancements and future trends in the field of chemical reactions inside living cells, organized by different reaction mechanisms. We also provide an in-depth discussion of their chemical designs, reaction mechanisms, and functional applications. Furthermore, we explore the underlying chemical principles of these reactions and discuss strategies for these materials to enhance their therapeutic efficacy. As researchers continue to expand the repertoire of intracellular synthesis techniques, it is anticipated that these advancements will provide valuable tools for probing biological systems and developing innovative therapeutic strategies.