Significant enhancement of photoproduced reactive intermediates in liquid-like region in frozen surface water for micropollutant degradation.

Freezing enhancing the photochemistry of dissolved organic matter (DOM), yet the mechanism of reactive intermediate (RIs) generation influenced by DOM property and structure remain elusive. Here, we demonstrate that freezing induces exceptional amplification of RIs, with steady-state concentrations in ice (-10 °C) surpassing aqueous solutions by 5-41 times. Laser scanning confocal microscopy first visualized cryo-concentration of DOM and RIs in liquid-like regions (LLR).

Amino-Functionalized Lanthanide Metal-Organic Frameworks for Ratiometric Detection of Perfluorooctanoic Acid.

Perfluorooctanoic acid (PFOA) is a persistent organic pollutant with a global presence in water, air, and soil resources. Herein, a water-stable amine-functionalized lanthanide metal-organic framework () is utilized for ratiometric luminescence detection of PFOA. In the presence of PFOA, there is an increase in the emission intensity of the organic ligand, while the characteristic luminescence intensity of Eu ions decreases, accompanied by a distinct emission color change from red to blue.

Nanosecond-scale single-molecule reaction dynamics for scalable synthesis on a chip.

Reaction mechanism studies typically involve the characterization of products, and intermediates are often characterized by (sub)millisecond techniques, such as nuclear magnetic resonance, while femto/attosecond spectroscopies are used to elucidate the evolution of transition states and electron dynamics. However, due to the lack of detection techniques in the microsecond to nanosecond range, as well as the emergent complexity with increasing scale, most of the proposed intermediates have not yet been detected, which significantly hinders reaction optimization. Here, we present such a nanosecond-scale real-time single-molecule electrical monitoring technique.

Super-resolution tactile sensor arrays with sparse units enabled by deep learning.

High-resolution tactile perception is essential for humanoid robots to perform contact-based interaction tasks. However, enhancing resolution is typically accompanied by increasing the density of sensing nodes, large numbers of interconnecting wires, and complex signal processing modules. This work presents super-resolution (SR) tactile sensor arrays with sparsely distributed taxels powered by a universal intelligent framework.

A Self-Assembling Chimeric Peptide Gear-Set with "Three-in-One" Function for Precision Photodynamic Therapy.

Smart drug delivery systems that activate in response to tumor-specific signals and include real-time monitoring are highly desirable in personalized cancer treatment. Herein, a new chimeric peptide, PpIX-1-DG, is designed with an integrated "gear set" mechanism for achieving auto-activation, cascade-amplification and self-reporting features in precision photodynamic therapy. The peptide, comprised of a photosensitizer and a gemcitabine prodrug, self-assembles into nanoparticles in physiological condition.

Polyoxometalate-Containing Nanocomposite Hydrogels for Cascade-Catalytic and Photothermal Dually Enhanced Chemodynamic Therapy.

Chemodynamic therapy (CDT) has emerged as a transformative paradigm in the realm of reactive oxygen species (ROS)-mediated cancer therapies. However, the lack of endogenous hydrogen peroxide (HO) in tumors and the low catalytic efficiency of traditional Fenton catalysts limit the therapeutic effect of CDT. Herein, an injectable nanocomposite hydrogel (HA-DOPA/W-POM/-S-S-PEG@GOx) based on the hyaluronic acid-dopamine (HA-DOPA) matrix is designed to deliver tungsten-based polyoxometalates (W-POM) and peptide nanomicelles (-S-S-PEG@GOx) for achieving cascade-catalytic and photothermal dually enhanced CDT.

A core-shell structured biphasic microneedle system as an elite squad for combating melanoma with "three-in-one" therapeutic power.

Achieving optimal therapeutic outcomes with microneedle (MN) technology requires a high drug payload, tunable mechanical strength, and robust drug stability-key attributes in demand for transdermal drug delivery. This work introduces a core-shell structured biphasic MN system designed to combat melanoma with "three-in-one" therapeutic power. The MN base, made of water-insoluble poly(methyl methacrylate), forms a biphasic interface with the needle body.

A Robust Single-Molecule Diode with High Rectification Ratio and Integrability.

Advancements in molecular electronics focus on single molecules as key components to create stable and functional devices that meet the requirements of device miniaturization and molecular function exploration. However, as the pioneering concept of a molecular diode, all single-molecule rectifiers reported previously are limited by their modest rectification ratios, owing to electron transmission in the off-state, highlighting the imperative for performance enhancements. Here, we demonstrate a unique method capable of realizing a stable and reproducible high-performance single-molecule rectifier through the strategic application of an electric-field-catalyzed Fries rearrangement.

Alkaline Phosphatase and ATG4B Sequentially Activated Fluorescent Probe for Cancer Cell-Specific Live Imaging of Autophagy.

Tracking autophagy in cancer cells is crucial for enhancing cancer therapies. Existing methods are often inefficient and cannot distinguish cancer from normal cells during autophagy. Herein, a sequentially activated peptide probe, NBD-1p-Dabcyl, was developed for achieving cancer cell-specific imaging of autophagy.

Self-Reporting Ratiometric AIEgen-Peptide Nanoprobes for Activatable Chemotherapy and Noninvasive Imaging of Therapeutic Outcomes.

Efficacious chemotherapy and real-time therapeutic monitoring remain major challenges in cancer treatment. Traditional systems often lack tumor specificity, limiting efficacy, and hindering therapy optimization. Moreover, the absence of real-time monitoring can lead to missed opportunities and increased risks of side effects.

Quasi-Continuous Efficient Regulation of Single-Molecule Electronic Distribution.

The electronic distribution characteristics of molecules significantly influence the charge transport properties and the device performance of molecular electronic devices. These characteristics are closely related to subtle molecular structures, forming a formidable challenge for effective control. Here, a flexible crown ether moiety is integrated into the single-molecule junction, where its spatial structure can be regulated by an external electric field, enabling efficient tuning of the electronic characteristics.

A Photoactivated Self-Assembled Nanoreactor for Inducing Cascade-Amplified Oxidative Stress toward Type I Photodynamic Therapy in Hypoxic Tumors.

Type I photodynamic therapy (PDT) generates reactive oxygen species (ROS) through oxygen-independent photoreactions, making it a promising method for treating hypoxic tumors. However, the superoxide anion (O∙) generated usually exhibits a low oxidation capacity, restricting the antitumor efficacy of PDT in clinical practice. Herein, a photoactivated self-assembled nanoreactor (1-NBS@CeO) is designed through integration of type I PDT and cerium oxide (CeO) nanozymes for inducing cascade-amplified oxidative stress in hypoxic tumors.

Real-Time Direct Monitoring of Chirality Fixation and Recognition at the Single-Molecule Level.

Chirality, a fundamental attribute of nature, significantly influences a wide range of phenomena related to physical properties, chemical reactions, biological pharmacology, and so on. As a pivotal aspect of chirality research, chirality recognition contributes to the synthesis of complex chiral products from simple chiral compounds and exhibits intricate interplay between chiral materials. However, macroscopic detection technologies cannot unveil the dynamic process and intrinsic mechanisms of single-molecule chirality recognition.

A Dual-Responsive Morphologically-Adaptable Nanoplatform for Targeted Delivery of Activatable Photosensitizers in Precision Photodynamic Therapy.

Photodynamic therapy (PDT) is an effective approach for treating melanoma. However, the photosensitizers employed in PDT can accumulate in healthy tissues, potentially causing harm to normal cells and resulting in side effects such as heightened photosensitivity. To address this, an activatable photosensitizer (PSD) by linking PpIX with a fluorescence quencher using a disulfide bond is designed.

Real-time monitoring of reaction stereochemistry through single-molecule observations of chirality-induced spin selectivity.

Stereochemistry has an essential role in organic synthesis, biological catalysis and physical processes. In situ chirality identification and asymmetric synthesis are non-trivial tasks, especially for single-molecule systems. However, going beyond the chiral characterization of a large number of molecules (which inevitably leads to ensemble averaging) is crucial for elucidating the different properties induced by the chiral nature of the molecules.

Yiqi Chutan Formula Reverses Cisplatin-Induced Apoptosis and Ferroptosis of Skeletal Muscle by Alleviating Oxidative Stress.

Background: Cisplatin is a widely used anticancer drug in clinic, but it has a damaging effect on skeletal muscle cells. Clinical observation showed that Yiqi Chutan formula (YCF) had a alleviating effect on cisplatin toxicity.

Methods: In vitro cell model and in vivo animal model were used to observe the damage effect of cisplatin on skeletal muscle cells and verify that YCF reversed cisplatin induced skeletal muscle damage.

Ginsenoside Rh3 induces pyroptosis and ferroptosis through the Stat3/p53/NRF2 axis in colorectal cancer cells.

Ginsenoside Rh3 (GRh3) is a seminatural product obtained by chemical processing after isolation from Chinese herbal medicine that has strong antitumor activity against human tumors. However, its antitumor role remains to be elucidated. The aim of this study is to explore the mechanisms underlying the tumor suppressive activity of GRh3 from the perspective of pyroptosis and ferroptosis.

Deciphering the Molecular Mechanism of Yifei-Sanjie Pill in Cancer-Related Fatigue.

Background: The incidence of cancer-related fatigue (CRF) is increasing, but its lack of clear pathogenesis makes its prevention and treatment difficult. Therefore, it is of great significance to clarify the pathogenesis of CRF and find effective methods to treat it.

Methods: The CRF model was established by intraperitoneal injection of LLC cells in ICR mice to explore the pathogenesis of CRF and verify the therapeutic effect of the Yifei-Sanjie pill (YFSJ).

A Tunable Single-Molecule Light-Emitting Diode with Single-Photon Precision.

A robust single-molecule light-emitting diode (SM-LED) with high color purity, linear polarization, and efficiency tunability is prepared by covalently integrating one fluorescent molecule into nanogapped graphene electrodes. Furthermore, single-molecule Förster resonance energy transfer from the electroluminescent center to different accepters is achieved through rational molecular engineering, enabling construction of a multicolor SM-LED. All these characterizations are accomplished in the photoelectrical integration system with high temporal/spatial/energy resolution, demonstrating the capability of the single-photon emission of SM-LEDs.

Dipole-Modulated Charge Transport through PNP-Type Single-Molecule Junctions.

The PNP structure realized by energy band engineering is widely used in various electronic and optoelectronic devices. In this work, we succeed in constructing a PNP-type single-molecule junction and explore the intrinsic characteristics of the PNP structure at the single-molecule level. A back-to-back azulene molecule is designed with opposite ∼1.

Vibration-Assisted Charge Transport through Positively Charged Dimer Junctions.

Intermolecular charge transport plays a vital role in the fields of electronics, as well as biochemical systems. Here, we design supramolecular dimer junctions and investigate the effects of charge state and energy level alignment on charge transport under nanoconfinement. Incoherent tunneling caused by thermally-induced vibrations is enhanced in positively charged systems.

A Single-Molecule Memristor based on an Electric-Field-Driven Dynamical Structure Reconfiguration.

A robust single-molecule memristor is prepared by covalently integrating one phenol molecule with multiple binding sites into nanogapped graphene electrodes. Multilevel resistance switching is realized by the electric-field-manipulated reconfiguration of the acyl moiety on the phenol center, that is, the Fries rearrangement. In situ measurements of the reaction trajectories with an initial single substrate and an intermediate break through the limitation of macroscopic experiments, therefore unveiling both intramolecular and intermolecular mechanistic pathways (a long-term controversy) as well as comprehensive dynamic information.

Ginsenoside Rh4 Inhibits Colorectal Cancer Cell Proliferation by Inducing Ferroptosis via Autophagy Activation.

Colorectal cancer (CRC) is a severe threat to human health. Ginsenosides such as ginsenoside Rh4 have been widely studied in the antitumor field. Here, we investigated the antiproliferative activity and mechanism of Rh4 against CRC in vivo and in vitro.

Stochastic Binding Dynamics of a Photoswitchable Single Supramolecular Complex.

In this work, a real-time precise electrical method to directly monitor the stochastic binding dynamics of a single supramolecule based on the host-guest interaction between a cyclodextrin and an azo compound is reported. Different intermolecular binding states during the binding process are distinguished by conductance signals detected from graphene-molecule-graphene single-molecule junctions. In combination with theoretical calculations, the reciprocating and unidirectional motions in the trans form as well as the restrained reciprocating motion in the cis form due to the steric hindrance is observed, which could be reversibly switched by visible and UV irradiation.