Herein, we present a photoinduced, CeCl3-catalyzed three-component decarboxylative reaction that couples carboxylic acids, alkenes and tert-butyl hydroperoxide for the formation of various organic peroxides. The ligand-to-metal charge transfer (LMCT) excitation mode allows the decarboxylative alkylation-peroxidation reaction to occur under mild conditions, and is well applicable to primary, secondary and tertiary carboxylic acids and styrene derivatives.
Metal-organic frameworks (MOFs) are crystalline porous architectures formed by the coordination of organic ligands with metal ions or clusters. MOFs are notable for their vast surface area, abundant active sites, high porosity, and tunable properties. However, their application in energy storage and catalysis is impeded by limited conductivity and chemical stability. A promising approach to mitigating these constraints is the integration of MOFs with other functional or conductive materials. MXenes, with their distinctive layered structure, exceptional electrical conductivity, and rich surface functional groups, provide numerous advantages when combined with MOFs. This review encapsulates the synthesis methodologies of MXene/MOF composites and explores their applications across various domains, including lithium-ion batteries, supercapacitors, lithium-sulfur batteries, zinc-ion batteries, electrocatalysts, and photocatalysts.
The energy density and lifespan of prototype Li-S batteries under high sulfur loading and lean electrolyte have been mainly restricted by the incomplete interconversion between insulating S8 and Li2S. The introduction of an electrocatalyst has been preserved as an effective way to breakthrough the bottleneck of the interconversion rate. Herein, we demonstrate a novel bidirectional redox mediator, insoluble dithiobisphthalimide (DTPI), as the electrocatalyst for both S8 reduction and Li2S oxidation. Due to the dual-functional role of both electron/Li+ donor and acceptor, DTPI can efficiently accelerate the redox reactions during charge/discharge and significantly alleviate the incomplete conversion of sulfur species. Consequently, the Li-S batteries with DTPI deliver superior specific capacity and cycling stability in comparison with those without DTPI. Especially, the redox mediator is scalable for synthesis and the DTPI-based 5 A·h pouch cell delivers a specific discharge capacity of around 870 mA·h·g−1 at 0.1 C (1 C=1675 mA/g) without capacity fading over 80 cycles. The bidirectional catalysis mechanism has been studied through theoretical calculation and ex-situ characterization of the cathode materials. This work approves the effectiveness of bidirectional organic redox mediator in the construction of practical Li-S batteries.
Non-invasive bioelectronics, especially organic electrochemical transistors (OECTs), have drawn extensive attentions of academical and medical communities by virtue of their efficient bio-electronic interfacing, water-involved ionic transport, excellent ionic-electronic coupling, ultralow power consumption, wide detectable range, and outstanding detection sensitivity. Designable structure diversity, low-temperature solution processability, facile bio/chemical functionalization, and excellent biocompatibility of organic mixed ionic-electronic conductors (OMIECs) render OECTs particularly suitable for non-invasive or minimally invasive healthcare analytical platform. Here, we comprehensively review recent advances of the non-invasive analytical healthcare applications based on OECTs, especially on the detection of biomarkers or metabolites in the excretory biofluids, as well as the recording of electrophysiological signals. A brief introduction of OECT and its comparison with other organic thin-film transistors upon device configuration and working mechanism are firstly discussed. State-of-the-art non-invasive OECT-based biosensors are summarized on their detection of ionic and molecular biomarkers, following with circuit design strategies of OECTs for real-time and in-situ electrophysiological recording from skin surface. In conclusion, remaining barriers and future challenges of non-invasive OECT-based bioelectronics towards lower detection limit, more accurate quantitative relationship between analyte concentrations and measured parameters, more intimate device-tissue interface, and long-term operation stability are deeply analyzed with a critical outlook.
Nb-based tungsten bronze oxides have emerged as attractive materials in various fields, owing to the structural openings and simple synthesis method. In this work, the tetragonal tungsten bronze (TTB) NaWNbO6 was prepared by solid state reaction at a relatively low temperature of 775 °C. The local structure was systematically studied by solid state nuclear magnetic resonance (SSNMR) with the aid of transition electronic microscopy (TEM). The analysis indicates that NaWNbO6 has pentagonal, square, and triangular tunnels. Notably, square tunnels were partly occupied (50%) by Na, which creates the ability for the Li-ion storage with a volumetric capacity of 210 A·h·L−1 at 0.2 C. The 2D 23Na-23Na EXSY results further suggest the ability of ions to fast exchange between the tetragonal and pentagonal tunnels, resulting in a high-rate performance 20 C.
Although glucose electrochemical sensors based on enzymes play a dominant role in market, their stability remains a problem due to the inherent nature of enzymes. Therefore, glucose sensors that are independent on enzymes have attracted more attention for the development of stable detection devices. Here we present an enzyme-free glucose sensor based on Ni(OH)2 and reduced graphene oxide (rGO). The as-fabricated sensor still exhibits excellent electrocatalytic activity for detecting glucose under enzyme independent conditions. The enhanced catalytic performance may due to synergistic effect as follows: (i) the interaction between the Ni2+ and π electron of graphene induces the formation of the β-phase Ni(OH)2 with higher catalytic activity; (ii) the frozen dry process works as a secondary filtration, getting rid of poorly formed Ni(OH)2 particles with low catalytic activity; (iii) the rGO network with good conductivity provides a good electronic pathway for promoting electron transfer to reduce the response time. Based on the synergistic effect, the sensor exhibits a wide linear detection range from 0.2 µmol/L to 1.0 µmol/L and a low detection limit (0.1 µmol/L, S/N=3). The excellent detection performance, as well as the easy and low-cost preparation method, suggests the promising applicability of the sensor in the glucose detection market.
Chemiluminescence, a phenomenon emitting light from chemical reactions rather than photon absorption, has gained significant interest for applications in bioimaging and biosensing due to its high sensitivity and low background interference. Now there is a growing interest in near-infrared (NIR) chemiluminescent probes for improved tissue penetration and reduced autofluorescence. This review summarizes NIR emissive chemiluminescent probes based on 1,2-dioxetane and discusses their chemical structures and applications. Structure modification strategies for red-shifting wavelength and enhancing brightness include incorporating electron-withdrawing groups, designing chemiluminophore-fluorophore cassettes, and exploring alternative chemiluminescent scaffolds. This review aims to inspire the exploration of NIR chemiluminescent probes in disease detection and treatment.
Dynamic photoresponsive molecular crystals are promising candidates for making intelligent devices and materials in the future. Here, we synthesized a new photoactive molecule (E)-2,2-dimethyl-5-[3-(naphthalen-1-yl)allylide]-1,3-dioxane-4,6-dione [(E)-DNADD] that undergoes an E-to-Z photoisomerization in both liquid solution and solids when exposed to visible light (405 nm). Compared to the bulk crystals, the photoresponsive behavior in microcrystals was profoundly improved. Highly crystalline (E)-DNADD microplate crystals exhibit robust motions, including bending, curling, and coiling under light irradiation. The photoproduct conversion of the photochemical reaction in the microplate is no more than 20%, while the large bending curvature of the coiled illuminated samples was estimated at approximately 150–300 mm−1, comparable to some photoactive nanowires. Our results indicate that shrinking crystal dimensions can boost the photoresponses in molecular crystals and provide a facile strategy for developing dynamic molecular crystals at the microscopic scale.
Perovskite quantum dots (PQDs) have demonstrated great promise in bioimaging applications owing to their outstanding photophysical properties. Nonetheless, their practicality is seriously limited by the instability of PQDs against moisture. Here we develop a post-synthetic ligand exchange strategy to construct silica-coated PQD (PQD@SiO2) nanocrystals, which results in the simultaneous improvement of photoluminescence efficiency and moisture stability. More importantly, compared to the classical in-situ ligand exchange method of fabricating PQD@SiO2, the issues of chemical etching and resultant photoluminescence degradation are judiciously overcome. Employing the proposed PQD@SiO2, we showcase their robust usefulness in labeling chlorella, paving the way for PQD-based in-vivo photoluminescence bioimaging methodology.
In this work, melanin nanoparticle-resveratrol (MNP-RES) nanosystem was excogitated and constructed for the treatment and imaging of folate-induced renal fibrosis (RF) mice model to fulfill the combination of diagnosis and therapeutic. Physicochemical characterization indicated that MNP-RES was a monodisperse spherical framework with a uniform diameter of (18.6±2.7) nm and the drug loading content of RES was 44.8%. The inhibition ratios of reactive oxygen species, such as ·OH, ·O2−, ABTS’ and DPPH were all greater than 80%. After systemic therapy with MNP-RES, the levels of serum creatinine (SCr) and blood urea nitrogen (BUN) were decreased, and the extent of renal fibrosis was considerably relieved, which was verified by H&E, Masson and terminal-deoxynucleoitidyl transferase mediated nick end labeling (TUNEL) staining. The MNP-RES nanosystem can diagnose and monitor the therapeutic efficacy of RF in real time and noninvasively via photoacoustic/magnetic resonance imaging (PA/MRI) dual-modality imaging, and the MNP-RES diagnostic-therapeutic nanosystem had satisfactory biocompatibility in vivo, which facilitated its future bio-transformation for RF treatment in clinical application.
This brief review highlights the techniques and diverse applications of time-resolved electron paramagnetic resonance (TREPR) spectroscopy, underscoring its essential role in elucidating the structures, spin dynamics, and reactivities of open-shell systems. Furthermore, we discuss the limitations of traditional TREPR methodologies, particularly their challenges in directly observing reactive radical intermediates under real-world reaction conditions. Lastly, we present the latest advancements in TREPR technology developed in our laboratory, specifically ultrawide single-sideband phase-sensitive detection (U-PSD) TREPR, highlighting its significant impact and tremendous potential in advancing free radical chemistry research. We envision promising future applications of TREPR and its pivotal role in enhancing our understanding of mechanisms involved in complex radical processes and photocatalysis.
Recently, metal-organic framework (MOF)@enzyme composites have attracted increasing research interest. However, the fabrication of polymers-modified MOF@enzyme composites with high bio-catalytic performance remains challenging. Herein, a stimulus-responsive polymer, poly(acrylate-3′,3′-dimethyl-6-nitro-spiro-2H-1-benzopyran-2,2′ indoline-1′-ester-co-N-isopropyl acrylamide) (PSPN), was in-situ polymerized in UiO-66-NH2 (UN). The dual-responsive PSPN-UN@L-ASNase composites were constructed following L-asparaginase (L-ASNase) covalently attached to the UN surface. Interestingly, under 365 nm UV irradiation at 45 °C, the PSP moiety in PSPN underwent a trans-to-cis conformational change and the PN moiety in PSPN transferred from a stretched- to a coiled-state, generating a confinement effect that significantly enhanced the bio-catalytic performance of the composites. Compared with free L-ASNase, the composites showed a 42.0-folds increase in maximum catalytic reaction velocity. Furthermore, the PSPN-UN@L-ASNase composites demonstrated high toxicity for Jurkat leukaemia cells. The stimulus-responsive polymer-MOF@enzyme composites provide a novel avenue for controlled bio-catalysis with great potential for targeted leukaemia therapy.
Sensing materials possessing intrinsic color perception are indispensable prerequisites for the development of filterless photosensors, which could eliminate the need for complex device designs and avoid color distortion in post-processing. Traditional materials are constrained by complex processing methods and limited stability. Herein, a color-photosensitive array based on ionic liquid with selective photothermal conversion (ILSPC) has been developed for intrinsic color perception. Relying on the selective absorption, photothermal conversion, and thermosensitivity of ILSPC, a photo-thermo-electric sensing system has been constructed. Besides, the versatility of the two algorithms has been validated in color reconstruction and electrical signal prediction. As an exploration, the photosensitive array showcases promising color recognition capabilities, potentially propelling the evolution of flexible photosensors.
Due to their precise atomic structures, photoluminescent copper nanoclusters (Cu NCs) have promising applications in basic research and technical applications, such as bioimaging, cell labeling, phototherapy, and photoactivation catalysis. In this work, we report a simple strategy for synthesizing novel CuNCs co-protected by alkynyl and phosphine ligands with the molecular formula [Cu7(PPh3)10(PE)3(CH3O)] (Cu4@Cu3). Single-crystal X-ray crystallography reveals that the NC core exhibits an open square structure and an overall pyramid shape. Two Cu4@Cu3 units are connected through weak interactions to form dimers in crystals, creating a molecular cage that looks like two tightly closed bowls. Cu4@Cu3 exhibits dual emission in the visible region. It is also an aggregation-induced emission (AIE)-active luminescent substance, which exhibits strong emission in the visible light region when aggregated. Besides, it has the properties of radioluminescent (RL) and could be a potential scintillator material. This study not only enriches the types of atomically accurate AIE clusters, but also holds significant importance for the development of a new generation of high-performance and environmentally friendly X-ray scintillators.