Facile Preparation of WO3−x Dots with Remarkably Low Toxicity and Uncompromised Activity as Co-reactants for Clinical Diagnosis by Electrochemiluminescence

The exceptional nature of WO_3−x dots has inspired widespread interest, but it is still a significant challenge to synthesize high-quality WO_3−x dots without using unstable reactants, expensive equipment, and complex synthetic processes. Herein, the synthesis of ligand-free WO_3−x dots is reported that are highly dispersible and rich in oxygen vacancies by a simple but straightforward exfoliation of bulk WS₂ and a mild follow-up chemical conversion. Surprisingly, the WO_3−x dots emerged as co-reactants for the electrochemiluminescence (ECL) of Ru(bpy)₃²⁺ with a comparable ECL efficiency to the well-known Ru(bpy)₃²⁺/tripropylamine (TPrA) system. Moreover, compared to TPrA, whose toxicity remains a critical issue of concern, the WO_3−x dots were ca. 300-fold less toxic. The potency of WO_3−x dots was further explored in the detection of circulating tumor cells (CTCs) with the most competitive limit of detection so far.     

Single-Atom Electrocatalysts from Multivariate Metal–Organic Frameworks for Highly Selective Reduction of CO2 at Low Pressures

Single-atom catalysts (SACs) are of great interest because of their ultrahigh activity and selectivity. However, it is difficult to construct model SACs according to a general synthetic method, and therefore, discerning differences in activity of diverse single-atom catalysts is not straightforward. Herein, a general strategy for synthesis of single-atom metals implanted in N-doped carbon (M₁-N-C; M=Fe, Co, Ni and Cu) has been developed starting from multivariate metal–organic frameworks (MOFs). The M₁-N-C catalysts, featuring identical chemical environments and supports, provided an ideal platform for differentiating the activity of single-atom metal species. When employed in electrocatalytic CO₂ reduction, Ni₁-N-C exhibited a very high CO Faradaic efficiency (FE) up to 96.8 % that far surpassed Fe₁-, Co₁- and Cu₁-N-C. Remarkably, the best-performer, Ni₁-N-C, even demonstrated excellent CO FE at low CO₂ pressures, thereby representing a promising opportunity for the direct use of dilute CO₂ feedstock.     

Divergent Total Synthesis of Euphoranginol C,Euphoranginone D,ent-Trachyloban-3β-ol,ent-Trachyloban-3-one,Excoecarin E,and ent-16α-Hydroxy-atisane-3-one

A divergent synthetic approach to biogenetically related diterpenoids such as ent-kauranes, ent-trachylobanes, ent-beyerane, and ent-atisane has been developed. The unified synthetic route involves the De Mayo reaction to rapidly generate the bicyclo[3.2.1]-octane moiety of ent-kaurane. The key reactions also include bioinspired nucleophilic cyclopropanation generating the [3.2.1.0^2,7]-tricyclic core of ent-trachylobane and regioselective cyclopropane fragmentation furnishing ent-beyerane and ent-atisane through the nucleophilic attack and protonation of the cyclopropane ring. This strategy enables the asymmetric total syntheses of six diterpenoids from the commercially available geraniol.     

Smart Magnetic and Fluorogenic Photosensitizer Nanoassemblies Enable Redox-Driven Disassembly for Photodynamic Therapy

Stimuli-responsive smart photosensitizer (PS) nanoassemblies that allow enhanced delivery and controlled release of PSs are promising for imaging-guided photodynamic therapy (PDT) of tumors. However, the lack of high-sensitivity and spatial-resolution signals and fast washout of released PSs from tumor tissues have impeded PDT efficacy in vivo. Herein, we report tumor targeting, redox-responsive magnetic and fluorogenic PS nanoassemblies ( NP-RGD ) synthesized via self-assembly of a cRGD- and disulfide-containing fluorogenic and paramagnetic small molecule ( 1-RGD ) for fluorescence/magnetic resonance bimodal imaging-guided tumor PDT. NP-RGD show high r₁ relaxivity but quenched fluorescence and PDT activity; disulfide reduction by glutathione (GSH) promotes efficient disassembly into a small-molecule probe ( 2-RGD ) and an organic PS (PPa-SH), which could further bind with intracellular albumin, allowing prolonged retention and cascade activation of fluorescence and PDT to ablate tumors.     

Photoassisted Selective Steam and Dry Reforming of Methane to Syngas Catalyzed by Rhodium–Vanadium Bimetallic Oxide Cluster Anions at Room Temperature

Photoassisted steam reforming and dry (CO₂) reforming of methane (SRM and DRM) at room temperature with high syngas selectivity have been achieved in the gas-phase catalysis for the first time. The catalysts used are bimetallic rhodium–vanadium oxide cluster anions of Rh₂VO_1–3⁻. Both the oxidation of methane and reduction of H₂O/CO₂ can take place efficiently in the dark while the pivotal step to govern syngas selectivity is photo-excitation of the reaction intermediates Rh₂VO_2,3CH₂⁻ to specific electronically excited states that can selectively produce CO and H₂. Electronic excitation over Rh₂VO_2,3CH₂⁻ to control the syngas selectivity is further confirmed from the comparison with the thermal excitation of Rh₂VO_2,3CH₂⁻, which leads to diversity of products. The atomic-level mechanism obtained from the well-controlled cluster reactions provides insight into the process of selective syngas production from the photocatalytic SRM and DRM reactions over supported metal oxide catalysts.     

A Fully Non-fused Ring Acceptor with Planar Backbone and Near-IR Absorption for High Performance Polymer Solar Cells

Fused-ring electron acceptors have made significant progress in recent years, while the development of fully non-fused ring acceptors has been unsatisfactory. Here, two fully non-fused ring acceptors, o-4TBC-2F and m-4TBC-2F, were designed and synthesized. By regulating the location of the hexyloxy chains, o-4TBC-2F formed planar backbones, while m-4TBC-2F displayed a twisted backbone. Additionally, the o-4TBC-2F film showed a markedly red-shifted absorption after thermal annealing, which indicated the formation of J-aggregates. For fabrication of organic solar cells (OSCs), PBDB-T was used as a donor and blended with the two acceptors. The o-4TBC-2F-based blend films displayed higher charge mobilities, lower energy loss and a higher power conversion efficiency (PCE). The optimized devices based on o-4TBC-2F gave a PCE of 10.26 %, which was much higher than those based on m-4TBC-2F at 2.63 %, and it is one of the highest reported PCE values for fully non-fused ring electron acceptors.     

Host Differential Sensitization toward Color/Lifetime-Tuned Lanthanide Coordination Polymers for Optical Multiplexing

Optical multiplexing based on luminescent materials with tunable color/lifetime has potential applications in information storage and security. However, the available tunable luminescent materials reported so far still suffer from several drawbacks of low efficiency or poor stability, thus restraining their further applications. Herein, we demonstrate a strategy to develop efficient and stable lanthanide coordination polymers (LCPs) with tunable luminescence as a new option for optical multiplexing. Their multicolor emission from green to red and naked-eye-sensitive green emission with tunable lifetime (from ca. 300 to ca. 600 μs) can be controlled by host differential sensitization and energy transfer between lanthanide ions. The quantum efficiencies of developed samples range from around 20 % to 46 % and the luminescence intensity/lifetime appear quite stable in polar solvents up to ten weeks. Furthermore, with the aid of inkjet printing and concepts of luminescence lifetime imaging and time-gated imaging, we illustrate their promising applications of information storage and security in spatial and temporal domains.     

Characterization of sequence variation at 30 autosomal STRs in Chinese Han and Tibetan populations

Massively parallel sequencing (MPS) technologies have the ability to reveal sequence variations within STR alleles as well as their nominal allele lengths, which have traditionally been detected by CE instruments. Recently, Thermo Fisher Scientific has updated the MPS-STR panel, named the Precision ID GlobalFiler next-generation sequencing (NGS) STR Panel version 2, with primers redesigned to add two pentanucleotide tandem repeat loci and profile interpretation supported by the Converge software. Using the Ion Chef System, the Ion S5XL System, and the Converge software, genetic variations were characterized within STR repeat and flanking regions of 30 autosomal STR markers in 115 unrelated individuals from two Chinese population groups (58 Tibetans and 57 Hans). Nineteen STRs demonstrated a relative increase in diversity with the variant sequence alleles compared with those of traditional nominal length alleles. In total, 390 alleles were identified by their sequences compared with 258 alleles that were identified by length. Of these 92 sequence variants found within the STR repeat regions, 40 variants were located in STR flanking regions. Additionally, the agreement of the results with CE data was evaluated, as was the ability of this new MPS panel to analyze case-type (11 samples) and artificially degraded samples (seven samples in triplicate). The results generated from this study illustrate that extensive sequence variation exists in commonly used STR markers in the selected population samples and indicate that this NGS STR panel has the potential to be used as an effective tool for human forensics.     

Anisotropic charge carrier transport of optoelectronic functional selenium-containing organic semiconductor materials

Organic semiconductors (OSCs) materials are currently under intense investigation because of their potential applications such as organic field-effect transistors, organic photovoltaic devices, and organic light-emitting diodes. Inspired by the selenization strategy can promote anisotropic charge carrier migration, and selenium-containing compounds have been proved to be promising materials as OSCs both for hole and electron transfer. Herein, we now explore the anisotropic transport properties of the series of selenium-containing compounds. For the compound containing Se Se bond, the Se Se bond will break when attaching an electron, thus those compounds cannot act as n-type OSCs. About the different isomer compounds with conjugated structure, the charge transfer will be affected by the stacking of the conjugated structures. The analysis of chemical structure and charge transfer property indicates that Se-containing materials are promising high-performance OSCs and might be used as p-type, n-type, or ambipolar OSCs. Furthermore, the symmetry of the selenium-containing OSCs will affect the type of OSCs. In addition, there is no direct relationship between the R groups with their performance, whether it or not as p-type OSCs or n-types. This work demonstrates the relationship between the optoelectronic function and structure of selenium-containing OSCs materials and hence paves the way to design and improve optoelectronic function of OSCs materials.     

A Dual-Ligand Porous Coordination Polymer Chemiresistor with Modulated Conductivity and Porosity

Single-ligand-based electronically conductive porous coordination polymers/metal–organic frameworks (EC-PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π-conjugated EC-MOF containing copper units with mixed trigonal ligands was developed: Cu₃(HHTP)(THQ) (HHTP=2,3,6,7,10,11-hexahydrotriphenylene, THQ=tetrahydroxy-1,4-quinone). The modulated conductivity (σ≈2.53×10⁻⁵ S cm⁻¹ with an activation energy of 0.30 eV) and high porosity (ca. 441.2 m² g⁻¹) of the Cu₃(HHTP)(THQ) semiconductive nanowires provided an appropriate resistance baseline and highly accessible areas for the development of an excellent chemiresistive gas sensor.