Insight into the Undesired Racemization of l-Glufosinate during Heating in the Aqueous Phase.

l-glufosinate has garnered increasing attention as an ideal herbicide for weed control in agriculture. However, the underlying racemization process of l-glufosinate in the aqueous phase remains unclear. In this work, we elucidated the racemization mechanisms through heating reactions and theoretical calculations.

A sequence-activated near-infrared fluorescence probe for precisely tracking senescence.

Real-time monitoring of senescent cells is of great significance for understanding and intervening in aging. Since overexpression of endogenous β-galactosidase (β-gal) is not unique to senescent cells, probes relying solely on β-gal activity could yield inaccurate senescent cell detection. Herein, we designed a dual-mode sequential response AND logic NIR probe MFB-βgal, which contains a β-gal-cleavable unit and a morpholine unit, serving as an enzymatic activity trigger and a lysosomal targeting moiety, respectively.

Thiazolothiazole as a Multimonomer Adapting Organic Catalyst for Atom Transfer Radical Polymerization (ATRP) with Oxygen Tolerance.

Light-controlled organic atom transfer radical polymerization (O-ATRP) has emerged as a mature and advanced method for synthesizing well-defined macromolecules. However, developing a high-performance, low-loading, and oxygen-tolerant O-ATRP catalyst system remains an urgent challenge. Herein, we developed a new O-ATRP catalyst based on 2,5-bis(4-pyridinium) thiazolo[5,4-]thiazole.

Iron-Catalyzed Radical Addition Reaction of Dehydroglycine with Aliphatic Carboxylic Acids.

Iron-catalyzed ligand-to-metal charge transfer (LMCT) processes have emerged as robust strategies for diverse organic transformations. Despite this potential, their application to addition reactions of C═N unsaturated bonds remains underexplored. Herein, we report an LMCT-enabled, photoredox/iron-catalyzed radical addition to dehydroglycine derivatives.

Visualization of enantiorecognition by excited-state conformation modulation.

Chiral purity is crucial in life sciences, emphasizing the importance of precise enantiomeric identification and the development of analytical techniques. Here, we design functional dyes with visual chiral recognition capabilities by introducing recognition units 2-amino-1,2-diphenylethanol into vibration-induced emission molecules. The unambiguous differentiation in luminescent colors upon binding to enantiomers facilitates the efficient recognition of enantiomers and the analysis of enantiomeric excess.

Temperature-activated in situ hydrogel augments tumor treatment.

In situ gels with tumor-targeted therapy often struggle with precise spatiotemporal drug release, compromising their efficacy in complex and heterogenous tumors. Here, we present a temperature-activated in situ hydrogel (PTT-Br@mPEG-PLGA and Gem@TCM-TK-PEG in chitosan and PF127 gel, denoted as PP + GC gel. Therein, the photothermal compound PTT-Br is fully named 6-bromo-1-ethyl-2-(2-(6-hydroxy-2,3-dihydro-1H-xanthen-4-yl)vinyl)quinolin-1-ium, while the reactive oxygen species (ROS)-responsive polymer TCM-TK-PEG is fully named tricyano methylene pyridine-thioketal-polyethylene glycol.

Exploring the Potential of Chemically Matched Fragments as Internal Standards for Quantitative SERS with Panobinostat.

Surface-enhanced Raman spectroscopy (SERS) has great potential for therapeutic drug monitoring (TDM) due to its high sensitivity; however, achieving accurate and robust quantitative data remains challenging. The most effective approach for quantitative SERS is to use internal standards (IS). Isotopologues are particularly effective; however, these or closely related analogues of the target compound are often unavailable.

Engineering Spiropyran-Based Ratiometric F MRI Probes with Ultralarge Chemical Shift Variations.

Fluorine magnetic resonance imaging (F MRI) is a rapidly growing field with significant potential for clinical diagnostics, but it is hindered by inherently low sensitivity. Developing stimuli-responsive F MRI probes with dual-signal capabilities enhances diagnostic sensitivity but remains highly challenging. Herein, we designed pH-activatable F MRI probes based on fluorinated spiropyrans, engineered through spiro-isomerism (pH-triggered merocyanine-spiropyran interconversion) and positional-isomerism (strategically tuning F-substitution positions on the spiropyran core) strategies to achieve unprecedented ratiometric F NMR chemical shift variations (Δδ) of up to 13 ppm.

Disentangling the Effect of Key Parameters in Hydrogen Evolution for Rational Design of Metal-Semiconductor Photocatalysts via Self-Assembly.

Fabrication of high-performance metal-semiconductor photocatalysts is a challenging problem in nanoengineering since it requires development of methods, which create strong metal-semiconductor contacts and accessible catalytic surfaces while simultaneously allowing control of the physical properties of the metal nanoparticle cocatalysts. Here, we introduce a convenient self-assembly approach for preparing highly active metal-TiO photocatalysts, which meets all these requirements. More specifically, preformed Au/Pt and TiO nanoparticles were used to generate Pickering emulsions, which were converted in situ into polymer microbeads covered in a mixed surface layer of tightly packed metal and TiO nanoparticles with photocatalytic properties.

A "One-to-Multi" Activatable Near-infrared Fluorescent Probe for the Sensitive Imaging of γ‑Glutamyl Transpeptidase Activity in Living Mice.

γ-Glutamyl transpeptidase (GGT) is a membrane-bounded enzyme closely involved in a wide range of physiological and pathological processes. While numerous fluorescent probes have been developed to image GGT activity noninvasively, in vivo applications remain challenging. A key limitation lies in GGT's localization: activated fluorophores diffuse rapidly from sites of activation, significantly reducing contrast of image in living systems.

Dual-emissive self-reporting photosensitizers characterized by Kasha/-Kasha behaviors engineered a gradient donor-acceptor strategy.

Real-time monitoring of photodynamic therapy (PDT) is essential for precision medicine, yet remains hindered by microenvironmental interference and photobleaching of conventional mono-emissive photosensitizers (PSs). Herein, inspired by the energy level gradients depicted in the Jablonski diagram, we report a gradient donor-acceptor molecular design strategy to overcome Kasha's rule, achieving intrinsic dual-emissive PSs. Combining femtosecond transient absorption spectroscopy with theoretical calculations, we have verified the Kasha/-Kasha properties of the compounds: near-infrared (NIR) emission peaking at 710 nm, exhibiting viscosity dependence stems, from the S-to-S excited-state decay of the primary acceptor-donor framework, whereas visible emission at 530-590 nm, significantly enhanced upon DNA binding, originates from the S-to-S excited-state decay of the additional acceptor-donor segment.

Top-tier ranking university bring worse perception of medical learning environment to students: a cross-sectional study across 12 universities.

The medical learning environment (MLE) exerted a profound influence on students' physical, psychological, and professional development. University prestige and ranking significantly shape students' self-perception and self-esteem. Nevertheless, the relationship between university category and MLE perception remained unexplored.

Bright and stable dye-doped fluorescent polystyrene microspheres: quantitative lateral flow immunoassay for detecting serum amyloid A.

Difluoroboron is a fundamental molecular building block that enables the development of numerous highly bright fluorophores for biosensing and imaging. However, its poor stability and limited brightness in aqueous solutions are long-standing and unresolved issues in developing difluoroboron-based fluorophores, which significantly limit their widespread biosensing applicability. Herein, we report a generalizable strategy for synthesising dye-doped fluorescent polystyrene microspheres as a local hydrophobic microenvironment to "protect" difluoroboron curcuminoids from water and reactive oxygen species.

Promoting implant osseointegration via the osteoblast-selective β-amino acid polymer strategy.

Osseointegration for implants, especially bioinert implants, poses significant clinical challenges. Overcoming fibrotic encapsulation and promoting osseointegration at the implant interface are critical for successful bone repair, which highly expected biomaterials with osteoblast over fibroblast selectivity. However, few materials possess the function.

Facile fabrication of antioxidative and antibacterial hydrogel films to accelerate infected diabetic wound healing.

Diabetic wounds are accompanied with hemorrhage, excessive reactive oxygen species accumulation, microbial infection, and poor exudate management. Current dressings are insufficient to modulate the complex pathophysiological microenvironment of infected diabetic wounds. Here, we develop a facile-fabricated hydrogel film with potent antibacterial and antioxidative properties to significantly accelerate infected diabetic wounds healing.

Promoting ROS scavenging and osteogenic differentiation by metal-phenolic network nanoparticle-embedded microenvironment-responsive hydrogel for the repair of senile osteoporotic bone defects.

Senile osteoporosis (SOP) features reduced bone density and degraded trabecular structure, primarily mediated through senescent impairment of osteoblasts that disrupts coupled bone remodeling homeostasis. This pathological process induces systemic bone resorption and localized bone destruction accompanied by architectural deterioration. Existing treatments for senile osteoporosis tend to focus on a single mechanism, making it challenging to simultaneously address bone formation deficits and oxidative stress.

Synergistic Effects of Activatable Photodynamic Therapy and Crisaborole for Psoriasis through Senolysis and Immunomodulation.

Psoriasis is a multifactorial inflammatory disorder characterized by therapeutic resistance and high recurrence rates, with complex unmet clinical demands necessitating novel therapeutic strategies. Recently, emerging evidence has revealed pathological accumulation of senescent cells (SnCs) in psoriatic lesions, suggesting their critical involvement in disease persistence and relapse. Our previous studies demonstrated that precision photodynamic therapy (PDT) effectively eliminates SnCs and mitigates senescence-associated pathologies, positioning senotherapy as a potential breakthrough for psoriasis management.

A trident-like multi-cationic photosensitizer with stabilized membrane camouflage for efficient tumor-targeted photodynamic therapy.

We develop a unique trident-like multi-cationic photosensitizer (PS) with an acceptor-donor-acceptor (A-D-A) structure to enhance photodynamic therapy (PDT). The design minimizes PS leakage from membrane camouflaged nanoparticles (<1% in 24 h) hydrophilic anchoring, while boosting ROS generation (13.8-fold higher O than Rose Bengal) through excited state optimization, thus significantly improving tumor-targeted PDT efficiency.

Intersected Bicyclic N-Confused Corrole Dimers with Tunable Aromaticity and Topological Chirality.

Despite the successful syntheses of unique porphyrinoids by oxidative cyclization of oligopyrranes, the development of bicyclic variants with unprecedented topologies, aromaticity, and chirality remains challenging. Herein, we report the syntheses of a class of bicyclic porphyrinoids based on the oxidative cyclization of heptapyrrane . Thus, a nonsymmetrical intersected bicyclic N-confused corrole dimer was synthesized, wherein two terminal pyrrolic α-C atoms are linked to the β-C atoms of the middle pyrrole ring.

Mechanically tough dynamic poly(disulfide)s crosslinked by acylsemicarbazides.

Acylsemicarbazide is used to toughen a dynamic poly(disulfide) network by forming synergistic covalent and noncovalent crosslinkers. The resulting dry supramolecular network exhibits enhanced stretchability, mechanical strength and toughness while retaining dynamic reconfigurability.

Cobalt-Catalyzed Asymmetric Reductive Coupling of Isocyanates with Tertiary Alkyl Halides for Sterically Bulky Chiral Amide Synthesis.

The ubiquity of amide bonds in pharmaceuticals, agrochemicals, natural products, and peptides underscores the enduring demand for efficient amide synthesis in organic chemistry. Nevertheless, the facile construction of sterically congested chiral amides bearing α-quaternary stereogenic centers remains a formidable synthetic challenge. Herein, we report a catalytic reductive addition strategy that leverages readily accessible and stable isocyanates for stereoselective carbon-carbon bond formation.

Catalyst-modulated hydrogel dynamics for decoupling viscoelasticity and directing macrophage fate for diabetic wound healing.

Dynamic hydrogels can regulate immune responses, but decoupling bond exchange kinetics from static mechanical properties remains challenging. Here, we present a catalyst-mediated strategy to independently tune hydrogel network dynamics without altering crosslinking density or stiffness. A reversible acylhydrazone-based hydrogel system was constructed using lysozyme and PEG, with 4-amino-DL-phenylalanine (4a-Phe) as a catalyst to modulate bond exchange rates.

Sulfur-Engineered Ru/SnO Catalysts for Highly Efficient Catalytic Combustion of 1,2-Dichloroethane.

The catalytic combustion of chlorinated volatile organic compounds (CVOCs) requires catalysts with multiple active sites and excellent synergistic effects due to the complex reaction mechanisms involving both C-H and C-Cl bond cleavage as well as deep oxidation processes. Herein, Ru supported on sulfated tin oxide (STO) was designed to demonstrate excellent activity, stability, and water resistance in the catalytic combustion of 1,2-dichloroethane (EDC). The presence of various sulfate species (-OSO, -HSO, -HSO), which can undergo reversible transformations, enhanced both the acidity and the mobility of H species, thereby facilitating the cleavage of C-H and C-Cl bonds to form the intermediates of vinyl chloride.

8-Quinox Cobalt Catalyst Enables the Reductive Alkylative Addition of Sulfinylamines with Unactivated Alkyl Halides.

Sulfur-based chiral centers play a critical role in drug discovery yet pose significant challenges in achieving precise stereochemical control. Sulfinamides, serving as versatile intermediates and chiral auxiliaries, have traditionally required multistep synthesis or auxiliary-dependent strategies. Recent advances using -sulfinyltritylamine (TrNSO) enabled catalytic arylative additions; however, stereoselective alkylative approaches remain underdeveloped, likely due to the highly reactive alkyl radical intermediate.

An azo substituted quinoline-malononitrile enzyme-activable aggregation-induced emission nanoprobe for hypoxia imaging.

The development of efficient aggregation-induced emission (AIE) active probes is crucial for disease diagnosis, particularly for tumors and cardiovascular diseases. Current AIE-active probes primarily focus on improving their water solubility to resist aggregation, thereby achieving an initial fluorescence-off state. However, the complex biological environment can cause undesirable aggregation, resulting in false signals.