An artesunate-modified half-sandwich iridium(iii) complex inhibits colon cancer cell proliferation and metastasis through the STAT3 pathway.

Colon cancer is one of the most commonly diagnosed cancers and is recognized as the most aggressive tumor of the digestive system. Aberrant activation of signal transducer and activator of transcription 3 (STAT3) is associated with proliferation, metastasis and immunosuppression of the tumor cells. Here, to inhibit the STAT3 pathway and suppress metastasis in colon cancer cells, the half-sandwich iridium complex Ir-ART containing an artesunate-derived ligand was synthesized.

A dual-locked cyclopeptide-siRNA conjugate for tumor-specific gene silencing.

Strategies allowing tumor-selective siRNA delivery while minimizing off-tumor gene silencing effects are highly demanded to advance cancer gene therapy, which however still remain challenging. We herein report a dual-locking bioconjugation approach to address this challenge. A dual-locked cyclopeptide-siRNA conjugate (DPRC) was designed to simultaneously endow siRNA with tumor-targeting properties and tumor-biomarker/visible-light dually controllable action.

Photoactivated hydride therapy under hypoxia beyond ROS.

As compared to oxidative phototherapy, studies on reactive reductive species-participating photodynamic therapy (PDT) are rare. Porphyrins are typical photosensitizers restricted by the oxygen level, but efficacy and selectivity are always incompatible in PDT. Herein, we report that phlorins are ideal hydride (H) donors and explore a water-soluble triphenylphosphonium-modified zinc-coordinated porphyrin (ZnPor) for photogeneration of zinc-cored phlorin (ZnPhl).

Regioselectivity switches between anthraquinone precursor fissions involved in bioactive xanthone biosynthesis.

Xanthone-based polyketides with complex molecular frameworks and potent bioactivities distribute and function in different biological kingdoms, yet their biosynthesis remains under-investigated. In particular, nothing is known regarding how to switch between the C-C (C-selective) and C-C bond (C-selective) cleavages of anthraquinone intermediates involved in biosynthesizing strikingly different frameworks of xanthones and their siblings. Enabled by our characterization of antiosteoporotic brunneoxanthones, a subfamily of polyketides from FB-2, we present herein the brunneoxanthone biosynthetic gene cluster and the C-selective cleavage of anthraquinone (chrysophanol) hydroquinone leading ultimately to the bioactive brunneoxanthones under the catalysis of BruN (an undescribed atypical non-heme iron dioxygenase) in collaboration with BruM as a new oxidoreductase that reduces the anthraquinone into its hydroquinone using NADPH as a cofactor.

Recent advances for enhanced photodynamic therapy: from new mechanisms to innovative strategies.

Photodynamic therapy (PDT) has been developed as a potential cancer treatment approach owing to its non-invasiveness, spatiotemporal control and limited side effects. Currently, great efforts have been made to improve the PDT effect in terms of safety and efficiency. In this review, we highlight recent advances in innovative strategies for enhanced PDT, including (1) the development of novel radicals, (2) design of activatable photosensitizers based on the TME and light, and (3) photocatalytic NADH oxidation to damage the mitochondrial electron transport chain.

Stereoselective benzylic C(sp)-H alkenylation enabled by metallaphotoredox catalysis.

Selective activation of the benzylic C(sp)-H bond is pivotal for the construction of complex organic frameworks. Achieving precise selectivity among C-H bonds with comparable energetic and steric profiles remains a profound synthetic challenge. Herein, we unveil a site- and stereoselective benzylic C(sp)-H alkenylation utilizing metallaphotoredox catalysis.

A -Ir(iii)-phenylquinazolinone complex enhances ferroptosis by selectively inhibiting metallothionein-1.

Chirality plays an indispensable role in various biological processes, and interactions between chiral enantiomers and biomolecular targets provide new perspectives in precision drug development. While ferroptosis has received increasing attention as a novel pathway to reverse drug resistance, work on the design of precise ferroptosis-targeting molecules through chiral programming was limited. In this work, we designed and synthesized a pair of chirality-dependent ferroptosis-inducing Ir(iii)-phenylquinazolinone complexes (-IrPPQ and -IrPPQ) by inhibiting ferroptosis suppressor protein-1 (FSP1), while the pair of IrPPQ complexes induced extremely different ferroptosis effects as well as distinct photodynamic therapy (PDT) responses toward pancreatic cancer cells.

Synergistic -β regulation of porphyrins: squeezing the band gap into the near-infrared I/II region.

The development of novel near-infrared (NIR) materials with extremely small energy gaps and high stability is highly desirable in bioimaging and phototherapy. Here we report an effective strategy for narrowing the energy gaps of porphyrins by synergistic regulation of /β substituents. The novel NIR absorbing/emitting -alkynyl naphthoporphyrins (Zn-TNP and Pt-TNP) are synthesized the retro-Diels-Alder reaction.

Near-infrared visualisation of single microparticle electrochemistry for batteries.

While optical microscopy of single particle electrochemistry has proven insightful for future nanoparticle-based batteries, little is explored for micron-sized particles of more practical interest. This is largely hindered by the currently limited methodology. Accordingly, we report transmission optical microscopy using near-infrared light for accessing intra-particle electrochemistry in virtue of strong light penetration as compared to visible light.

AI-assisted mass spectrometry imaging with image segmentation for subcellular metabolomics analysis.

Subcellular metabolomics analysis is crucial for understanding intracellular heterogeneity and accurate drug-cell interactions. Unfortunately, the ultra-small size and complex microenvironment inside the cell pose a great challenge to achieving this goal. To address this challenge, we propose an artificial intelligence-assisted subcellular mass spectrometry imaging (AI-SMSI) strategy with image segmentation.

SERS imaging of protein-specific glycan oxidation on living cells to quantitatively visualize pathogen-cell interactions.

Glycan oxidation on the cell surface occurs in many specific life processes including pathogen-cell interactions. This work develops a surface-enhanced Raman scattering (SERS) imaging strategy for quantitative monitoring of protein-specific glycan oxidation mediated pathogen-cell interactions by utilizing Raman reporter DTNB and aptamer co-assembled platinum shelled gold nanoparticles (Au@Pt-DTNB/Apt). Using () and MCF-7 cells as models, Au@Pt-DTNB/Apt can specifically bind to MUC1 protein on the cell surface containing heavy galactose (Gal) and -acetylgalactosamine (GalNAc) modification.

Intermittent proton bursts of single lactic acid bacteria.

Lactic acid bacteria are a kind of probiotic microorganisms that efficiently convert carbohydrates to lactic acids, thus playing essential roles in fermentation and food industry. While conventional wisdom often suggests continuous release of protons from bacteria during acidification, here we developed a methodology to measure the dynamics of proton release at the single bacteria level, and report on the discovery of a proton burst phenomenon, , the intermittent efflux of protons, of single bacteria. When placing an individual bacterium in an oil-sealed microwell, efflux and accumulation of protons consequently reduced the pH in the confined extracellular medium, which was monitored with fluorescent pH indicators in a high-throughput and real-time manner.

An AIE-based monofunctional Pt(ii) complex for photodynamic therapy through synergism of necroptosis-ferroptosis.

Side effects and drug resistance are among the major problems of platinum-based anticancer chemotherapies. Photodynamic therapy could show improved tumor targeting ability and better anticancer effect by region-selective light irradiation. Here, we report an aggregation-induced emission (AIE)-based monofunctional Pt(ii) complex (TTC-Pt), which shows enhanced singlet oxygen production by introduction of a Pt atom to elevate the intersystem crossing (ISC) rate.

Taxonomic notes on O. Pickard-Cambridge, 1894 (Araneae, Theridiidae) of China.

Background: The theridiid spider genus O. Pickard-Cambridge, 1894 includes 27 extant species and is distributed in America (23 spp.) and Asia (4 spp.

Precise activation of C-C bonds for recycling and upcycling of plastics.

The rapid accumulation of plastic waste has led to a severe environmental crisis and a noticeable imbalance between manufacturing and recycling. Fortunately, chemical upgradation of plastic waste holds substantial promise for addressing these challenges posed by white pollution. During plastic upcycling and recycling, the key challenge is to activate and cleave the inert C-C bonds in plastic waste.

Ferrocenylselenoether and its cuprous cluster modified TiO as visible-light photocatalyst for the synergistic transformation of N-cyclic organics and Cr(vi).

In this study, fcSe@TiO and [CuI(fcSe)]@TiO nanosystems based on ferrocenylselenoether and its cuprous cluster were developed and characterized by X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM), energy dispersive X-ray spectroscopy (EDX), and electron paramagnetic resonance (EPR). Under optimized conditions, 0.2 g L catalyst, 20 mM HO, and initial pH 7, good synergistic visible light photocatalytic tetracycline degradation and Cr(vi) reduction were achieved, with 92.

Cooperatively designed aptamer-PROTACs for spatioselective degradation of nucleocytoplasmic shuttling protein for enhanced combinational therapy.

Nucleocytoplasmic shuttling proteins (NSPs) have emerged as a promising class of therapeutic targets for many diseases. However, most NSPs-based therapies largely rely on small-molecule inhibitors with limited efficacy and off-target effects. Inspired by proteolysis targeting chimera (PROTAC) technology, we report a new archetype of PROTAC (PS-ApTCs) by introducing a phosphorothioate-modified aptamer to a CRBN ligand, realizing tumor-targeting and spatioselective degradation of NSPs with improved efficacy.

Photoredox-catalyzed stereo- and regioselective vicinal fluorosulfonyl-borylation of unsaturated hydrocarbons.

There has been considerable research on sulfur(vi) fluoride exchange (SuFEx) chemistry, which is considered to be a next-generation click reaction, and relies on the unique balance between reactivity and stability inherent in high valent organosulfur. The synthetic versatility of the bifunctional handles containing the fluorosulfonyl group presents great synthetic value and opportunity for drug discovery. However, the direct photoredox-catalyzed fluorosulfonyl-borylation process remains unexplored and challenging due to its system incompatibility and limited synthetic strategies.

Covalent inorganic complexes enabled zinc blende to wurtzite phase changes in CdSe nanoplatelets.

Phase changes in colloidal semiconductor nanocrystals (NCs) are essential in material design and device applications. However, the transition pathways have yet to be sufficiently studied, and a better understanding of the underlying mechanisms is needed. In this work, a complete ligand-assisted phase transition from zinc blende (ZB) to wurtzite (WZ) is observed in CdSe nanoplatelets (NPLs).

An overlooked oxidation mechanism of toluene: computational predictions and experimental validations.

Secondary organic aerosols (SOAs) influence the Earth's climate and threaten human health. Aromatic hydrocarbons (AHs) are major precursors for SOA formation in the urban atmosphere. However, the revealed oxidation mechanism dramatically underestimates the contribution of AHs to SOA formation, strongly suggesting the importance of seeking additional oxidation pathways for SOA formation.

Surface-enhanced Raman scattering sensing for detection and mapping of key cellular biomarkers.

Cellular biomarkers mainly contain proteins, nucleic acids, glycans and many small molecules including small biomolecule metabolites, reactive oxygen species and other cellular chemical entities. The detection and mapping of the key cellular biomarkers can effectively help us to understand important cellular mechanisms associated with physiological and pathological processes, which greatly promote the development of clinical diagnosis and disease treatment. Surface-enhanced Raman scattering (SERS) possesses high sensitivity and is free from the influence of strong self-fluorescence in living systems as well as the photobleaching of the dyes.