Acid triggering highly-efficient release of reactive oxygen species to block mitochondrial-mediated homeostasis maintenance for accelerating cell death.

A pivotal pathway of photodynamic therapy (PDT) is to prompt mitochondrial damage by reactive oxygen species (ROS) generation, thus leading to cancer cell apoptosis. However, mitochondrial autophagy is induced during such a PDT process, which is a protective mechanism for cancer cell homeostasis, resulting in undermined therapeutic efficacy. Herein, we report a series of meticulously designed donor (D)-π-acceptor (A) photosensitizers (PSs), characterized by the strategic modulation of thiophene π-bridges, which exhibit unparalleled mitochondrial targeting proficiency.

Photocatalytic Direct Borylation of Benzothiazole Heterocycles via a Triplet Activation Strategy.

Boron compounds are widely employed in organic chemistry, pharmaceuticals, and materials science. Among them, borylated heterocycles serve as versatile synthons for the construction of new C-C or C-heteroatom bonds via coupling or radical processes. Such methods for direct C-H borylation reactions are of high synthetic value to reduce the number of synthetic steps and the amount of waste and to improve efficiency.

NHC-BH-CH: synthesis, characterization and electrochemical properties of the N-heterocyclic-carbene-stabilized fullerene-borane complex.

NHC-[60]fullereborane (NHC-BH-CH) has been synthesized, isolated in pure form, and characterized. The reaction of C with NHC-borane produced NHC-BH-CH as the first air-stable and separatable fullerene-borane compound. The formation of a N-heterocyclic carbene stabilized this borane complex of C, and the structure of the complex was unambiguously determined throughsingle-crystal X-ray analysis.

Modulating the bandgap of Cr-intercalated bilayer graphene combining the 18-electron rule and the 2D superatomic-molecule theory.

Bandgap engineering of graphene is of great significance for its potential applications in electronic devices. Herein, we used a sandwich compound Cr(CH) as the building block to construct Cr-intercalated bilayer graphene (BLG), namely a CCr monolayer. Chemical bonding analysis reveals that strong d-π interaction ensures π electrons of the graphene layers and d orbitals of the Cr atoms localized in CCrC units to achieve the favored 18-electron rule, thus leading to a bandgap of 0.

Chiral Amphiphilic Au Cluster and Its Specific Recognition to Remote Di-amines.

The atomic precision of metal nanoclusters and variability of surface ligands pave the way for their rational design and functionalization, whereas the property strengthening in multiple ways has been long challenging. Herein, improved amphiphilicity, chirality, thermostability, and strong CPL (circularly polarized luminescence) properties have been accomplished by facile ligand exchange of [Au(CHT)] with HCapt (HCHT and HCapt denote cyclohexanethiol and captopril). In addition, the obtained chiral [Au(SR)] (short for [Au(CHT)(Capt)]) clusters show specific binding affinity to remote-diamines (such as arginine and single/double strand DNA), originating from the hydrogen bonding and Van der Waals interaction among the surface Capt ligands and the di-amine groups.

self-assembled near-infrared phototherapeutic agent: unleashing hydrogen free radicals and coupling with NADPH oxidation.

Investigation of electron transfer (ET) between photosensitizers (PSs) and adjacent substrates in hypoxic tumors is integral to highly efficient tumor therapy. Herein, the oxygen-independent ET pathway to generate hydrogen free radicals (H˙) was established by the self-assembled phototherapeutic agent -S under near-infrared (NIR)-light irradiation, coupled with the oxidation of reduced coenzyme NADPH, which induced ferroptosis and effectively elevated the therapeutic performance in hypoxic tumors. The higher surface energy and longer exciton lifetimes of the fine crystalline -S nanofibers were conducive to improving ET efficiency.

One-Step Wet-Spinning of High-Energy Density Coaxial Fibrous Supercapacitors Based on In Situ Carbon-Modified Nitrogen-Doped MXene Nanosheets.

Fibrous supercapacitors (SCs) are emerging promising power sources for flexible/wearable electronics and have attracted an extensive amount of attention from researchers. However, the low energy density has always hindered their further development. Here, a coaxial fibrous SC (CFSC) was fabricated by one-step wet-spinning combined with an electrodeposition strategy.

Molecular engineering to elevate reactive oxygen species generation for synergetic damage on lipid droplets and mitochondria.

Photodynamic therapy (PDT), characterized by high treatment efficiency, absence of drug resistance, minimal trauma, and few side effects, has gradually emerged as a novel and alternative clinical approach compared to traditional surgical resection, chemotherapy and radiation. Whereas, considering the limited diffusion distance and short lifespan of reactive oxygen species (ROS), as well as the hypoxic tumor microenvironment, it is crucial to design photosensitizers (PSs) with suborganelle specific targeting ability and low-oxygen dependence for accurate and highly efficient photodynamic therapy. In this study, we have meticulously designed three PSs, namely CIH, CIBr, and CIPh, based on molecular engineering.

Regulation of Charge Transfer Pathway in Ag-ZnInS Nanowires for Visible Photodynamic Therapy on Candida Albicans Infections.

Photodynamic therapy (PDT) is receiving extensive attention as an antimicrobial strategy that does not cause drug resistance by reactive oxygen species (ROS). Herein, hierarchical Ag-ZnInS (Ag-ZIS) core-shell nanowires are synthesized by in situ Metal-Organic Framework derived method for efficient PDT of Candida albicans (C. albicans).

Bimetallic AgCu Nanocluster, Structure Determination, and Nonlinear Optical Properties.

The atomic precision of the subnanometer nanoclusters has provided sound proof on the structural correlation of metal complexes and larger-sized metal nanoparticles. Herein, we report the synthesis, crystallography, structural characterization, electrochemistry, and optical properties of a 133-atom intermetallic nanocluster protected by 57 thiolates (3-methylbenzenethiol, abbreviated as -MBTH) and 3 chlorides, with the formula of AgCu(-MBT)Cl. This is the largest Ag-Cu bimetallic cluster ever reported.

Photocatalytic Synthesis of Indanone, Pyrone, and Pyridinone Derivatives with Diazo Compounds as Radical Precursors.

We disclose herein a photocatalytic radical cascade cyclization of diazoalkanes for the divergent synthesis of important carbocycles and heterocycles. Under the optimal reaction conditions, various indanone, pyrone, and pyridinone derivatives can be obtained in moderate to good yields. Mechanistic experiments support the formation of carbon-centered radicals from diazoalkanes through the proton-coupled electron transfer process.

Metal-Determined Explosive Characteristics of M(NO)(1-AT) of Thermal and Laser Ignition (M = Cr, Mn, Fe, Co, Ni, Cu, and Zn; = 2 or 3).

Optical and thermal ignition are two common pathways to initiate the explosion of primary explosives, where laser ignition is a more reliable and safer initiation method. Caused by the current-applied laser igniter with the wavelength of 1064 or 915 nm, the energetic complexes with strong absorption in the near-infrared (NIR) region are possibly applied as laser-ignited explosives. Recently, [Cu(NO)(1-AT)] complex has been synthesized with excellent NIR absorption properties, where 1-amino-5H-tetrazole (1-AT) has been proved to be a promising laser-ignited energetic ligand.

Achieving Long-Lived Charge Separated State through Ultrafast Interfacial Hole Transfer in Redox Sites-Isolated CdS Nanorods for Enhanced Photocatalysis.

As opposed to natural photosynthesis, a significant challenge in a semiconductor-based photocatalyst is the limited hole extraction efficiency, which adversely affects solar-to-fuel efficiency. Recent studies have demonstrated that photocatalysts featuring spatially isolated dual catalytic oxidation/reduction sites can yield enhanced hole extraction efficiencies. However, the decay dynamics of excited states in such photocatalysts have not been explored.

Effect of Specific Heavy Doping of Silver Atoms into the Icosahedral Au on Electronic Structure and Catalytic Performance.

The exploration of specific heavy doping of silver atoms into icosahedral Au clusters and their electronic structures and properties has been somewhat limited. Herein, we report two heavily Ag doped nanoclusters, [AuAg(CHNOS)(Dppf)Cl] and [AuAg(CHNOS)(Dppf)Cl](SbF) (AuAg-0 and AuAg-1, respectively) [CHNOSH = 2-mercaptobenzoxazole, and Dppf = 1,1'-bis(diphenylphosphino)ferrocene]. The electronic structures and superatomic orbitals of nanoclusters were determined by density functional theory (DFT) calculations, and the energy degeneracy of the superatomic orbitals of AuAg-1 is higher than that of AuAg-0.

A new methodology for studying vortex dynamics based on point-contact spectroscopy.

Vortex dynamics has attracted tremendous attention for both fundamental physics and applications of type-II superconductors. However, methods to detect local vortex motion or vortex jump with high sensitivity are still scarce. Here, we fabricated soft point contacts on the clean layered superconductor 2H-NbSe2, which are demonstrated to contain multiple parallel micro-constrictions by scanning electronic microscopy.

Synthesis of spiro[indolenine]-methanofullerenes Deoxofluor promoted deoxygenative cyclopropanation of 1,2-(3-indole)-fullerenols.

Deoxofluor-promoted intramolecular cyclopropanation of 1,2-(3-indole)fullerenols has been developed as a straightforward and efficient protocol for the synthesis of various spiro[indolenine]-methanofullerenes. This approach exhibits low cost, operational simplicity, and convenient conditions, and thus has potential application value.

Temperature-modulated sensing characteristics of ultrafine Au nanoparticle-loaded porous ZnO nanobelts for identification and determination of BTEX.

The identification and determination of benzene, toluene, ethylbenzene, and xylene (BTEX) has always been a formidable challenge for chemiresistive metal oxide sensors owing to their structural similarity and low reactivity, as well as the intrinsic cross sensitivity of metal oxides. In this paper, a temperature-modulated sensing strategy is proposed for the identification and determination of BTEX using a high-performance chemiresistive sensor. Ultrafine Au nanoparticle-loaded porous ZnO nanobelts as sensing materials were synthesized through an exchange reaction followed by thermal oxidation, which exhibited high response toward BTEX.

Theoretical study of the saturation and nature of the hydrogen bonds to gold.

Traditional hydrogen bonds are well-known to exhibit directionality and saturation. By contrast, gold involved hydrogen bonds (GHBs) have been extensively studied but remain lack of in-depth understanding towards the intrinsic nature and saturation property. This work exemplifies three series of complexes: [L-Au-L]-⋯(HF)n (L = H, CH3, (CH3)3; n = 1-8) containing GHBs to dig into the intrinsic nature with the aid of multiple theoretical analysis methods, finding that the formation of GHB is highly subject to orbital interactions along with steric hindrance.

MXene-Mediated Cellulose Conductive Hydrogel with Ultrastretchability and Self-Healing Ability.

Constructing natural polymers such as cellulose, chitin, and chitosan into hydrogels with excellent stretchability and self-healing properties can greatly expand their applications but remains very challenging. Generally, the polysaccharide-based hydrogels have suffered from the trade-off between stiffness of the polysaccharide and stretchability due to the inherent nature. Thus, polysaccharide-based hydrogels (polysaccharides act as the matrix) with self-healing properties and excellent stretchability are scarcely reported.

Fabricating -collidine-derived vinylene-linked covalent organic frameworks for photocatalysis.

Research into vinyl-linked covalent organic frameworks (COFs) has grown significantly in recent years due to various attractive properties. Herein, we design and synthesize two highly crystalline and stable 2,4,6-collidine-derived vinylene-linked 2D COFs. Both COFs can act as efficient photocatalysts to facilitate visible-light-driven aerobic oxidation.

Motif-to-Core Nucleation in a Decahedral Evolution Pattern.

The atomic precision of ultrasmall metal nanoclusters has opened the door to elucidating the structural evolution principles of metal nanomaterials at the molecular level. Here, we report a novel set of super-atomic Ag clusters, including [Ag(TBBT)(DPPP)] (Ag), [Ag(DMAT)(DPPM)Cl] (Ag), Ag(SPhCF)(DPPF)Cl (Ag), and [Ag(DMAT)(DPPP)Cl] (Ag). The core structures of these clusters correspond to one decahedral Ag, perpendicular bi-decahedrons, three-dimensional penta-decahedrons, and hexa-decahedrons, respectively.

Unraveling the Aromatic Rule of Cyclic Superatomic Molecules in π-Conjugated Compounds.

The aromaticity of π-conjugated compounds has long been a confusing issue. Based on a recently emerged two-dimensional (2D) superatomic-molecule theory, a unified rule was built to decipher the aromaticity of cyclic superatomic molecules of π-conjugated compounds from the chemical bonding perspective. Herein, a series of planar []helicenes and []circulenes, composed of benzene, thiophene, or furfuran, are systemically studied and seen as superatomic molecules OF or O, where superatoms F and O denote π-conjugated units with 5 and 4 π electrons, respectively.

Enhanced pH-Responsive Chemo/Chemodynamic Synergistic Cancer Therapy Based on In Situ Cu Di-Chelation.

Considering the chemodynamic therapy and chemotherapy independent of external stimulus witnessing great advantage in the clinical translation, developing a smart nanoplatform that can realize enhanced chemo/chemodynamic synergistic therapy in the tumor microenvironment (TME) is of great significance. Herein, we highlight the enhanced pH-responsive chemo/chemodynamic synergistic cancer therapy based on in situ Cu di-chelation. The alcohol-withdrawal drug disulfiram (DSF) and chemotherapeutic drug mitoxantrone (MTO) were embedded into PEGylated mesoporous CuO (denoted as PEG-CuO@DSF@MTO NPs).

A multifunctionally reversible detector: Photoacoustic and dual-channel fluorescence sensing for SO/HO.

In this work, the phenothiazine fragment with powerful electron-donating ability was specifically selected to construct a multifunctional detector (noted as T1) in double-organelle with near-infrared region I (NIR-I) absorption. The changes of SO/HO content in mitochondria and lipid droplets were observed through red/green channels respectively, which was due to the reaction between benzopyrylium fragment of T1 and SO/HO to achieve red/green fluorescence conversion. Additionally, T1 was endowed with photoacoustic properties deriving from NIR-I absorption to reversibly monitor SO/HOin vivo.