A novel reactive oxygen species nano-amplifier for tumor-targeted photoacoustic imaging and synergistic therapy.

Intracellular redox homeostasis and the type of exogenous Fenton reagent play crucial roles in determining the efficacy of chemodynamic therapy (CDT). Herein, we succeeded for the first time in preparing ultrasmall copper sulfide (CuS) nanodots (1-2 nm)-embedded hollow mesoporous organosilica nanoparticle (HMON), which served as an ideal nanocarrier to load both 3-amino-1,2,4-triazole (3-AT) and disulfiram (DSF) after folate-polyethylene glycol-silane (FA-PEG-Silane) modification. The as-prepared nanoplatform (3-AT/DSF@CuS/HMON-FA, denoted as ADCuSi-FA) was found to regulate intracellular redox homeostasis once internalized by 4T1 cells, showing rapid glutathione (GSH)-responsive 3-AT, DSF and Cu ions release.

Tailoring obeticholic acid activity by iridium(III) complex conjugation to develop a farnesoid X receptor probe.

Introduction: The farnesoid X receptor (FXR) is a crucial regulator in the intestine, maintaining bile acid homeostasis. Inhibiting intestinal FXR shows promise in managing inflammatory bowel and liver diseases by reducing bile acid accumulation. Additionally, changes in FXR expression could serve as a potential biomarker for intestinal diseases.

Cyclic Ruthenium(II)-Halocarbon Complexes Derived from Ru(II)-Induced Cyclization of Homopropargylic Halopyridines: Mechanism, Bonding and Reactivity.

The activation of various homopropargylic pyridines by cis-[Ru/Os(dppm)Cl] (dppm=1,1-bis(diphenylphosphino)methane) has previously been shown to generate a diverse array of metallacycles and metalated heterocyclic complexes. However, a minor structural modification of introducing a halide onto the pyridyl group of the alkyne substrate resulted in the formation of unprecedented Ru(II)/Os(II)-haloquinolizine complexes. These complexes display (1) κ(X,C)-haloquinolizine chelates arising from the cycloisomerization of HC≡CC(OH)(CH(6-X-2-py))(Ph) on [Ru/Os(dppm)] moieties via a vinylidene pathway, (2) five-membered Ru/Os-X-C-N-C rings (X=F, Cl, Br) ortho- and peri-fused to quinolizinium skeletons, and (3) uncommon M-X-R bonding interactions that are atypical in coordination complexes.

Controlling Chemoselectivity in Ruthenium(II)-Induced Cyclization of Aniline-Functionalized Alkynes.

The cyclization of heteroatom-functionalized alkynes induced by d-transition-metal centers has traditionally been associated with the vinylidene pathway. However, recent evidence suggests that d-transition-metal centers can also activate alkynes through non-vinylidene pathways. In this study, we conducted a comprehensive experimental and theoretical investigation into the reactions between the Ru(II) complex [Ru([9]aneS3)(bpy)(OH)] and 2-alkynylanilines.

An inorganic-blended p-type semiconductor with robust electrical and mechanical properties.

Inorganic semiconductors typically have limited p-type behavior due to the scarcity of holes and the localized valence band maximum, hindering the progress of complementary devices and circuits. In this work, we propose an inorganic blending strategy to activate the hole-transporting character in an inorganic semiconductor compound, namely tellurium-selenium-oxygen (TeSeO). By rationally combining intrinsic p-type semimetal, semiconductor, and wide-bandgap semiconductor into a single compound, the TeSeO system displays tunable bandgaps ranging from 0.

A Biomineralized Bifunctional Patient-Friendly Nanosystem for Sustained Glucose Monitoring and Control in Diabetes.

Regular blood glucose monitoring and control is necessary for people with type 1 or advanced type 2 diabetes, yet diagnosing and treating patients with diabetes in an accurate, sustained and patient-friendly manner remains limited. Here, a glucose-responsive bifunctional nanosystem (PGOxMns) is constructed via one-pot biomineralisation of manganese dioxide with glucose oxidase and ε-poly-L-lysine. Under hyperglycaemic conditions, the cascade reactions that occur when glucose interacts with PGOxMns can trigger the production of Mn(II), which enhances the magnetic resonance imaging signal.

Repurposing sodium stibogluconate as an uracil DNA glycosylase inhibitor against prostate cancer using a time-resolved oligonucleotide-based drug screening platform.

Repurposing drugs can significantly reduce the time and costs associated with drug discovery and development. However, many drug compounds possess intrinsic fluorescence, resulting in aberrations such as auto-fluorescence, scattering and quenching, in fluorescent high-throughput screening assays. To overcome these drawbacks, time-resolved technologies have received increasing attention.

Pulse irradiation synthesis of metal chalcogenides on flexible substrates for enhanced photothermoelectric performance.

High synthesis temperatures and specific growth substrates are typically required to obtain crystalline or oriented inorganic functional thin films, posing a significant challenge for their utilization in large-scale, low-cost (opto-)electronic applications on conventional flexible substrates. Here, we explore a pulse irradiation synthesis (PIS) to prepare thermoelectric metal chalcogenide (e.g.

Covalent inhibition of epidermal growth factor receptor using a long-lived iridium(III)-afatinib probe.

The overexpression and overactivation of epidermal growth factor receptor (EGFR) are frequently observed in human cancers, including squamous cell carcinoma and adenocarcinoma. In this study, a covalent EGFR probe was developed by conjugating afatinib to an iridium(III) scaffold. Complex 1 showed enhanced luminescence in living epidermoid squamous carcinoma A431 cells compared to other cell lines, via engaging EGFR as confirmed via CETSA and knockdown experiments.

A glycyrrhetinic acid-iridium(III) conjugate as a theranostic NIR probe for hepatocellular carcinoma with mitochondrial-targeting ability.

Hepatocellular carcinoma (HCC) is a major contributor to global mortality rates, but current treatment options have limitations. Advanced theranostics are needed to effectively integrate diagnosis and therapeutic of HCC. Glycyrrhetinic acid (GA) has abundant binding sites with glycyrrhetinic acid receptors (GA-Rs) on the surface of HCC cells and has also been reported to possess ligands with mitochondrial-targeting capability but with limited efficacy.

A Switch-On Affinity-Based Iridium(III) Conjugate Probe for Imaging Mitochondrial Glutathione -Transferase in Breast Cancer Cells.

Glutathione -transferase is heterogeneously expressed in breast cancer cells and is therefore emerging as a potential diagnostic biomarker for studying the heterogeneity of breast cancers. However, available fluorescent probes for GSTs depend heavily on GSTs-catalyzed glutathione (GSH) nucleophilic substitution reactions, making them susceptible to interference by the high concentration of nucleophilic species in the cellular environment. Moreover, the functions of subcellular GSTs are generally overlooked due to the lack of suitable luminescence probes.

Controlling Surface Chemical Inhomogeneity of Ni P/MoNiP /MoP Heterostructure Electrocatalysts for Efficient Hydrogen Evolution Reaction.

Crystalline/amorphous phase engineering is demonstrated as a powerful strategy for electrochemical performance optimization. However, it is still a considerable challenge to prepare transition metal-based crystalline/amorphous heterostructures because of the low redox potential of transition metal ions. Herein, a facile H -assisted method is developed to prepare ternary Ni P/MoNiP /MoP crystalline/amorphous heterostructure nanowires on the conductive substrate.

Cyclization, Decyclization, and Metallacyclization of Pyridine-Substituted Homopropargylic Alcohols on Ruthenium(II) and Osmium(II) Centers.

Systematic investigations on the reactions between cis-[M(dppm) Cl ] (M=Ru/Os; dppm=1,1-bis(diphenylphosphino)methane) and pyridine/quinoline substituted homopropargylic alcohols uncovered the diverse Ru(II)/Os(II)-induced alkyne activation pathways. The alkynes underwent cyclization on M via a "non-vinylidene" pathway at lower temperatures, resulting in alkenyl intermediates which might further metallacyclize to give metallapyrroloindolizines. Conversely, reactions at higher temperatures induced alkyne cyclization on M via a "vinylidene" pathway, affording cyclic oxacarbene complexes.

Van der Waals nanomesh electronics on arbitrary surfaces.

Chemical bonds, including covalent and ionic bonds, endow semiconductors with stable electronic configurations but also impose constraints on their synthesis and lattice-mismatched heteroepitaxy. Here, the unique multi-scale van der Waals (vdWs) interactions are explored in one-dimensional tellurium (Te) systems to overcome these restrictions, enabled by the vdWs bonds between Te atomic chains and the spontaneous misfit relaxation at quasi-vdWs interfaces. Wafer-scale Te vdWs nanomeshes composed of self-welding Te nanowires are laterally vapor grown on arbitrary surfaces at a low temperature of 100 °C, bringing greater integration freedoms for enhanced device functionality and broad applicability.

Inhibition of the CDK9-cyclin T1 protein-protein interaction as a new approach against triple-negative breast cancer.

Cyclin-dependent kinase 9 (CDK9) activity is correlated with worse outcomes of triple-negative breast cancer (TNBC) patients. The heterodimer between CDK9 with cyclin T1 is essential for maintaining the active state of the kinase and targeting this protein-protein interaction (PPI) may offer promising avenues for selective CDK9 inhibition. Herein, we designed and generated a library of metal complexes bearing the 7-chloro-2-phenylquinoline CˆN ligand and tested their activity against the CDK9-cyclin T1 PPI.

Ruthenafuran Complexes Supported by the Bipyridine-Bis(diphenylphosphino)methane Ligand Set: Synthesis and Cytotoxicity Studies.

Mononuclear and dinuclear Ru(II) complexes -[Ru(κ-dppm)(bpy)Cl] (), -[Ru(κ-dppe)(bpy)Cl] () and [Ru(bpy)(μ-dpam)(μ-Cl)](Cl) ([](Cl)) were prepared from the reactions between (Cl), (S)-[Ru(bpy)(dmso-)Cl] and diphosphine/diarsine ligands (bpy = 2,2'-bipyridine; dppm = 1,1-bis(diphenylphosphino)methane; dppe = 1,2-bis(diphenylphosphino)ethane; dpam = 1,1-bis(diphenylarsino)methane). While methoxy-substituted ruthenafuran [Ru(bpy)(κ-dppe)(C^O)] ([]; C^O = anionic bidentate [(OMe)CHC(Ph)] chelate) was obtained as the only product in the reaction between and phenyl ynone HC≡C(C=O)Ph in MeOH, replacing with led to the formation of both methoxy-substituted ruthenafuran [Ru(bpy)(κ-dppm)(C^O)] ([]) and phosphonium-ring-fused bicyclic ruthenafuran [Ru(bpy)(P^C^O)Cl] ([]; P^C^O = neutral tridentate [(Ph)CHP(Ph)CHC(Ph)] chelate). All of these aforementioned metallafuran complexes were derived from Ru(II)-vinylidene intermediates.

The significance of trophic transfer in the uptake of microplastics by carnivorous gastropod Reishia clavigera.

The present study compared the relative significance of prey consumption and respiration as routes of microplastic (MP) intake in a carnivorous muricid gastropod, Reishia clavigera. The time-dependent accumulation of MPs within 14-day exposure and their removal through depuration were also investigated for two forms of MPs (fibre, fragment) at an environmentally relevant concentration (10 items L) and two higher concentrations (100 and 1000 items L). At 1000 items L, the number of MPs in R.

Tumor acidity-activatable photothermal/Fenton nanoagent for synergistic therapy.

Intracellular formation of therapeutic agents has become one of the effective ways for cancer-specific treatment. Herein, a tumor acidity-activatable photothermal/Fenton nanoagent (denoted as CoPy) was constructed based on oxidized zeolitic imidazolate framework-67 (oxZIF-67) nanosheet and pyrrole (Py) monomer for synergistic therapy. The CoPy showed negligible toxicity to normal cell models RAW264.

A bioactive ligand-conjugated iridium(III) metal-based complex as a Keap1-Nrf2 protein-protein interaction inhibitor against acetaminophen-induced acute liver injury.

Hepatotoxicity caused by an overdose of acetaminophen (APAP) is the leading reason for acute drug-related liver failure. Nuclear factor erythroid-2-related factor 2 (Nrf2) is a protein that helps to regulate redox homeostasis and coordinate stress responses via binding to the Kelch-like ECH-associated protein 1 (Keap1). Targeting the Keap1-Nrf2 interaction has recently emerged as a potential strategy to alleviate liver injury caused by APAP.

NIR-II-driven and glutathione depletion-enhanced hypoxia-irrelevant free radical nanogenerator for combined cancer therapy.

Background: Though the combination of photodynamic therapy (PDT) and chemodynamic therapy (CDT) appears to be very attractive in cancer treatment, hypoxia and overproduced glutathione (GSH) in the tumor microenvironment (TME) limit their efficacy for further application.

Results: In this work, a smart hypoxia-irrelevant free radical nanogenerator (AIPH/PDA@CuS/ZIF-8, denoted as APCZ) was synthesized in situ via coating copper sulphide (CuS)-embedded zeolitic imidazolate framework-8 (ZIF-8) on the free radical initiator 2,2'-azobis[2-(2-imidazolin-2-yl)propane]-dihydrochloride (AIPH)-loaded polydopamine (PDA). APCZ showed promising GSH-depleting ability and near-infrared (NIR)-II photothermal performance for combined cancer therapy.

One-pot synthesis of a self-reinforcing cascade bioreactor for combined photodynamic/chemodynamic/starvation therapy.

The combination of photodynamic therapy (PDT) and chemodynamic therapy (CDT) have attracted a great deal of interest, but tumor hypoxia and glutathione (GSH) overproduction still limit their further applications. Herein, an intelligent reactive oxygen species (ROS) nanogenerator Ce6/GOx@ZIF-8/PDA@MnO (denoted as CGZPM; Ce6, GOx, ZIF-8, PDA, MnO are chlorin e6, glucose oxidase, zeolitic imidazolate framework-8, polydopamine and manganese dioxide respectively) with O-generating and GSH-/glucose-depleting abilities was constructed by a facile and green one-pot method. After intake by tumor cells, the outer MnO was rapidly degraded by the acidic pH, and the overexpression of hydrogen peroxide (HO) and GSH with abundant Mn and O produced would eventually achieve multifunctionality.

Iron(ii)-induced cycloisomerization of alkynes via"non-vinylidene" pathways for iron(ii)-indolizine and -indolizinone complexes.

Reactions between pyridine-functionalized alkynes and an Fe(ii) precursor supported by 2,5,8-trithia[9](2,9)-1,10-phenanthrolinophane afforded the first Fe(ii)-indolizine and -indolizinone complexes. Structural analysis and theoretical calculations revealed the existence of unconventional "non-vinylidene" pathways and challenged the generality of vinylidene intermediacy in Fe(ii)-induced alkyne transformations.

Conventional and unconventional alkyne activations by Ru and Os for unprecedented dimetalated quinolizinium complexes.

Two types of unexpected quinolizinium complexes were obtained from the reactions between pyridine-functionalized propargylic alcohol HC[triple bond, length as m-dash]CC(OH)(Ph)(CH(2-py)) (L1) and cis-[M(L^L)Cl] (M = Ru, Os; L^L = 1,1-bis(diphenylphosphino)methane (dppm), 2,2'-bipyridine (bpy)). Their molecular structures revealed that L1 can be activated by Ru and Os via the conventional "vinylidene-involving" or unconventional "non-vinylidene-involving" pathways.

A New Tetradentate Mixed Aza-Thioether Macrocycle and Its Complexation Behavior towards Fe(II), Ni(II) and Cu(II) Ions.

A new tetradentate mixed aza-thioether macrocyclic ligand 2,6-dithia[7](2,9)-1,10-phenanthrolinophane ([13]ane(phenN)S) was successfully synthesized. Reacting metal precursors [Fe(CHCN)(OTf)], Ni(ClO)·6HO, and Cu(ClO)·6HO with one equivalent of [13]ane(phenN)S afforded [Fe([13]ane(phenN)S)(OTf)] (), [Ni([13]ane(phenN)S)](ClO) ((ClO)), and [Cu([13]ane(phenN)S)(OH)](ClO) ((ClO)), respectively. The structures of [13]ane(phenN)S and all of its metal complexes were investigated by X-ray crystallography.

Heavy metals contamination of sedimentary microplastics in Hong Kong.

This is the first study of heavy metals (As, Zn, Cd, Ni, Fe, Mn, Cu) contamination of microplastics on sandy beaches in Hong Kong. Three study sites are located in the eastern waters (Pak Lap Wan, Stanley Bay, Tung Lung Chau) and the other three in the western waters (Tai Pai Tsui, Ha Pak Nai, Shui Hau Wan). The three most abundant types of microplastics were polyethylene (42.