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Social Determinants of Health, including marital status, are becoming increasingly identified as key drivers of health care utilization. This paper describes a robust method to determine the marital status of patients using structured and unstructured electronic healthcare data from a single academic institution in the United States. We developed and validated a natural language processing pipeline (NLP) for the ascertainment of marital status from clinical notes and compared the performance against two baseline methods: a machine learning n-gram model, and structured data obtained from the electronic health record. Overall our NLP engine had excellent performance on both document-level (F1 0.97) and patient-level (F1 0.95) classification. The NLP Engine had superior performance compared with a baseline machine learning n-gram model. We also observed a good correlation between the marital status obtained from our NLP engine and the baseline structured electronic healthcare data (κ 0.6).

A novel modification route integrating the copolymers of positive charged quaternary amines and polyethylene glycol (PEG) units using a combination of reversible addition–fragmentation chain-transfer polymerization (RAFT) and “Graft From” strategy, has been proposed and developed, for the first time, to decorate the surface of mesoporous silica nanoparticles (MSNs). These MSNs are shown to have a greatly reduced hydrodynamic particle size in physiological solution. It is demonstrated that such an efficient copolymer surface modification strategy, resulting in PEG coating with high positive zeta potential, can achieve a nearly 2-fold enhanced permeability and retention (EPR) effect, and longer blood half-life compared to coating with PEG only. Besides, the in vivo results demonstrated that this surface modification strategy could lead to a higher efficacy of doxorubicin (DOX) drug delivery and greater suppression of side effects compared to the free drug. Based on this novel strategy of combining “RAFT” and “Graft From” polymerization, it is anticipated that this efficient modification of tumor-specific targeting of MSNs can be widely used in future nanomedicine research.

Macromolecules responsive to both electric field and pH are modified on the outlets of mesoporous silica nanospheres to form a novel dual-mode drug delivery system. Dual drug delivery modes are indicated by the release patterns obtained by simulating the body's gastric and intestinal fluid ex vivo. In a pH 1.4 release medium (simulated gastric fluid, SGF) without an alternating electric field, only 8.5% of the total payload is found to leach in 8 h, whereas 50.3% and 60.2% of the total payload are released in the same time period by elevating the pH of the release medium or applying an alternating electric field. The two stimuli signals can work independently or corporately to regulate the release kinetics to form a dual-mode drug delivery mechanism, which makes it more flexible for use in certain complicated situations.

Natural antibodies are used widely for various applications such as in biomedical analysis, protein separation, and targeted-drug delivery, but they suffer from high cost and low stability. In this study, we developed a facile approach for the construction of antibody-like binding sites in a porous silica solid for efficient separation of bovine serum albumin (BSA) based on large-pore silica particles (LPSPs). This was accomplished by grafting two types of organosilane monomers, 3-aminopropyltriethoxylsilane (APTES) and octyltrimethoxysilane (OTMS), to provide hydrogen bonds or hydrophobic interactions with BSA through molecular imprinting technology. The resulting molecularly imprinted, large-pore silica particles (MI-LPSPs) were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG), X-ray diffraction (XRD) and N2 sorption analysis. Results showed that the as-synthesized MI-LPSPs exhibited a spherical morphology, favorable stability and large pore structure. The kinetic adsorption experiments showed that the MI-LPSPs could reach equilibrium within one hour and were described well by the pseudo second-order model, indicating that chemical adsorption might be the rate-limiting step. Meanwhile, the MI-LPSPs had a large binding capacity up to 162.82 mg g−1 and high selectivity for the recognition of BSA. Moreover, such a high binding capacity and selectivity was retained after six runs, indicating a good stability and reusability of MI-LPSPs. Thus, it is expected that a simple synthetic methodology in the present study provides a promising pathway to prepare novel imprinted materials for efficient purification and separation of target proteins.

The accurate characterization of low abundance phosphopeptides based on mass spectrometry (MS) techniques remains a challenge due to signal suppression by the large excess of interfering proteins and non-phosphopeptides. This demands better methods to effectively enrich phosphopeptides prior to MS analysis. In the current work, facilely synthesized Zr-based metal–organic frameworks (MOFs) of UiO-66 and UiO-67 have been successfully exploited as novel affinity materials for the enrichment and analysis of phosphopeptides. Thanks to their abundantly existent and naturally exposed Zr–O clusters, intrinsically large surface areas and highly ordered open cavities, UiO-66 and UiO-67 exhibited sensitive and specific enrichment of phosphopeptides with an interesting molecular sieving effect. An optimized protocol for loading, washing and elution was developed. Under these most optimized conditions, specific accumulation was demonstrated by the selective enrichment of phosphopeptides in the presence of abundant non-phosphorylated species. Meanwhile, high-abundance interfering proteins could be effectively excluded during the enrichment process. Additionally, the MOFs have also been successfully used to enrich phosphopeptides from human serum. These merits combined with their high chemical and thermal stabilities, make UiO-66 and UiO-67 highly promising for applications in phosphopeptidome research.

A salt-assisted acid etching (SAAE) strategy has been developed to construct rattle/hollow mesoporous silica/organosilica nanovehicles (R/HMSVs or R/HMOVs), which settles the drawbacks of traditional silica etching approaches, such as undesirable by-products, by alkaline etching and strong corrosion of the HF etching process. The hollow structure and phenylene-bridged framework of HMOVs were found to be responsible for the high cargo-loading capacity and pH-responsive drug releasing behavior, respectively, based on the special cargo-framework interaction. Especially, the molecularly organic–inorganic hybrid HMOVs have been, for the first time, successfully engineered to concurrently deliver anticancer drugs and P-gp-associated shRNA molecules for enhancing the intracellular drug concentrations and reversing the multidrug resistance (MDR) of cancer cells. On the basis of this special SAAE strategy, a wide range of mesoporous silica-based hollow nanostructures are anticipated to be synthesized to satisfy the strict requirements in various nano-catalytic and biomedical applications.

A highly sensitive and selective near-infrared excited potassium nanosensor has been developed for brain activity monitoring., Potassium ion (K+) concentration fluctuates in various biological processes. A number of K+ probes have been developed to monitor such fluctuations through optical imaging. However, the currently available K+ probes are far from being sensitive enough in detecting physiological fluctuations in living animals. Furthermore, the monitoring of deep tissues is not applicable because of short-wavelength excitation prevailingly used so far. Here, we report a highly sensitive and selective nanosensor for near-infrared (NIR) K+ imaging in living cells and animals. The nanosensor is constructed by encapsulating upconversion nanoparticles (UCNPs) and a commercial K+ indicator in the hollow cavity of mesoporous silica nanoparticles, followed by coating a K+-selective filter membrane. The membrane adsorbs K+ from the medium and filters out interfering cations. The UCNPs convert NIR to ultraviolet light, which excites the K+ indicator, thus allowing the detection of the fluctuations of K+ concentration in cultured cells and intact mouse brains.

The oxidation of intracellular biomolecules by reactive oxygen species (ROS) forms the basis for ROS-based tumor therapy. However, the current therapeutic modalities cannot catalyze H2 O2 and O2 concurrently for ROS generation, thereby leading to unsatisfactory therapeutic efficacy. Herein, it is reported a bioinspired hollow N-doped carbon sphere doped with a single-atom copper species (Cu-HNCS) that can directly catalyze the decomposition of both oxygen and hydrogen peroxide to ROS, namely superoxide ion (O2 •- ) and the hydroxyl radical (•OH), respectively, in an acidic tumor microenvironment for the oxidation of intracellular biomolecules without external energy input, thus resulting in an enhanced tumor growth inhibitory effect. Notably, the Fenton reaction turnover frequency of Cu species in Cu-HNCS is ≈5000 times higher than that of Fe in commercial Fe3 O4 nanoparticles. Experimental results and density functional theory calculations reveal that the high catalytic activity of Cu-HNCS originates from the single-atom copper, and the calculation predicts a next-generation Fenton catalyst. This work provides an effective paradigm of tumor parallel catalytic therapy for considerably enhanced therapeutic efficacy.

Ultrasound theranostics features non-invasiveness, minor energy attenuation, and high tissue-penetrating capability, and is playing ever-important roles in the diagnosis and therapy of diseases in clinics. Herein, ultrasound is employed as a microscopic pressure resource to generate reactive oxygen species (ROS) for piezocatalytic tumor therapy under catalytic mediation by piezoelectric tetragonal BaTiO

The spontaneous reaction between Zn and H

MXenes, a new family of multifunctional two dimensional (2D) solid crystals integrating high electroconductivity and rich surface chemistries, are promising candidates for electrolysis, which, however, have rarely been reported. Herein, free-standing ultrathin 2D MXene nanosheets were successfully fabricated from bulky and rigid MAX phase ceramics by liquid exfoliation with HF etching (delamination) and TPAOH intercalation (disintegration). The high oxygen reduction reaction (ORR) performance has been obtained, due to the extremely small thickness of the as-fabricated Ti3C2 around 0.5–2.0 nm, equivalent to the dimensions of single-layer or double-layer Ti3C2 nanosheets in thickness. The ORR performance of the obtained Ti3C2 MXene-based catalyst exhibits desirable activity and stability in alkaline media. This study demonstrates the potential of earth-abundant 2D MXenes for constructing high-performance and cost-effective electrocatalysts.

With the booming of non-noble-metal electrocatalysts for efficient oxygen reduction reaction under alkaline conditions, corresponding anodic catalysts for methanol oxidation are urgently needed especially for direct methanol fuel cells with alkaline membranes. Here, we report the facile synthesis of a CuO/Co(OH)2-nanosheet composite as a novel kind of high-performance electrochemical methanol oxidation reaction (MOR) catalyst. The obtained material with an optimized Cu/Co ratio shows much enhanced mass activity and area-specific activity, as well as excellent stability. The electronic structure interaction between Cu and Co, which results in the Co ion binding-energy elevation, is considered to be the origin of high MOR performance. This work promises the great potential of cobalt hydroxide as a novel kind of MOR catalyst and may arouse much interest in exploring more hydroxides as efficient nonprecious-metal electrocatalysts for MOR.

Creating active and stable electrocatalysts remains a highly desirable and critical goal in the fields of catalysis and clean energy conversion. Single-atom catalyst (SAC), as a new research frontier in heterogeneous catalysis, has demonstrated emerging prospects for many electrocatalytic reactions. Support-assisted pyrolysis approaches are widely used in the synthesis of single-atom electrocatalysts. While extensive efforts have been devoted to increase the loading of the atomically dispersed metal sites, the role of the support in creating these active metal sites remains largely unexplored. Herein, we compare catalysts created by support-free and support-assisted pyrolysis of vitamin B12 and cobalt tetramethoxyphenylporphyrin, respectively, and demonstrate an important effect of support-induced structural reconstruction that directly controls the activation of SAC. Electrochemical studies show support-free catalysts are inactive for oxygen reduction reaction whereas the support-assisted pyrolysis yield...

The photocatalytic activity enhancement of graphitic carbon nitride (g-C3N4) in water splitting were commonly achieved by introducing various functional groups onto/into its planar structure. Herein, oxidized g-C3N4 (CNO) was prepared via an extremely facile K2CO3 activation approach. The high-resolution XPS spectra and solid-state 13C NMR spectra confirmed the successful introduction of O-containing groups and O atoms were inherited the original molecular framework of g-C3N4, but exhibited effectively enlarged bonded with C atoms rather than N atoms in the tri-s-triazine structure of g-C3N4. CNO inherited the original molecular framework of g-C3N4, but exhibited effectively enlarged surface area and enhanced visible light absorption, and more attrractively, the band structure of g-C3N4 could be well-tuned with the introduction of oxygen species. Importantly, the surface O-containing moieties could strongly interact with cocatalyst Pt and thus remarkably promote interfacial electron transfer and consequent photo-generated charge carrier separation. Consequently, the as-obtained CNO exhibited the remarkably enhanced photocatalytic performance with a H2 evolution rate of 199.7 μmol h−1, which is 9 times that of g-C3N4 (22.2 μmol h−1).

Hydrogen (H2) is presently one of the most promising clean and renewable energy sources, but the conventional hydrogen production by electrochemical water-splitting, though of great potential and extensively studied, is seriously obstructed especially by the anodic oxygen evolution reaction because of its sluggish kinetics. Herein, we report the efficient hydrogen production from methanol solution using facile-synthesized ultrathin 2D bi-metal–organic framework nanosheets (UMOFNs) as a precious metal-free anodic catalyst. The prepared UMOFNs showed a much lowered anodic potential of 1.365 (V vs reversible hydrogen electrode) at 10 mA cm–2, which was markedly 232 mV lower than that in conventional water splitting, and moreover, the average turnover frequency reached 19.62 s–1. Benefiting from nearly 100% Faraday efficiency of H2 production on the counter graphite carbon electrodes without additional electrocatalysts, high-purity hydrogen was produced with enhanced efficiency. More importantly, the anodic e...

Cerebral vasculature and neuronal networks will be largely destroyed due to the oxidative damage by overproduced reactive oxygen species (ROS) during a stroke, accompanied by the symptoms of ischemic injury and blood-brain barrier (BBB) disruption. Ceria nanoparticles, acting as an effective and recyclable ROS scavenger, have been shown to be highly effective in neuroprotection. However, the brain access of nanoparticles can only be achieved by targeting the damaged area of BBB, leading to the disrupted BBB being unprotected and to turbulence of the microenvironment in the brain. Nevertheless, the integrity of the BBB will cause very limited accumulation of therapeutic nanoparticles in brain lesions. This dilemma is a great challenge in the development of efficient stroke nanotherapeutics. Herein, we have developed an effective stroke treatment agent based on monodisperse ceria nanoparticles, which are loaded with edaravone and modified with Angiopep-2 and poly(ethylene glycol) on their surface (E-A/P-CeO2). The as-designed E-A/P-CeO2 features highly effective BBB crossing via receptor-mediated transcytosis to access brain tissues and synergistic elimination of ROS by both the loaded edaravone and ceria nanoparticles. As a result, the E-A/P-CeO2 with low toxicity and excellent hemo/histocompatibility can be used to effectively treat strokes due to great intracephalic uptake enhancement and, in the meantime, effectively protect the BBB, holding great potentials in stroke therapy with much mitigated harmful side effects and sequelae.

Summary Recent advances in two-dimensional (2D) chemistry have led to the rapid development of research on the emerging 2D inorganic nanomaterials in various fields, such as condensed matter physics, material science, chemistry, biology, and nanotechnology. As a special cross-disciplinary research frontier, 2D inorganic nanosheets for oncological applications, which are capable of accomplishing desirable theranostic performance, have attracted great attention from the scientific community in recent years. In this review, we summarize the underlying fundamental principles for the material chemistry of the 2D inorganic family in cancer theranostics and nano-enabled amalgamation of material chemistry and oncology on the basis of the recent progress in theranostic platforms based on 2D inorganic nanosheets. Moreover, current challenges and perspectives on the development of 2D inorganic nanosheets for further clinical translations are also discussed. It is expected that this emerging 2D inorganic family will play a vital role in next-generation cancer theranostics.

With a growing demand for clean and renewable energy associated with water splitting, regenerative fuel cells, metal-air batteries, etc., exploring an efficient and cost-effective electrocatalyst with superior durability for oxygen evolution reaction (OER) is of great significance. In this study, a unique CoOx embedded nanoflower microstructure (Co0.6-PyNa) has been synthesized via an extremely facile one-step, highly scalable aqueous method under mild conditions, by using Co(COOH)2 as the precursor and pyrrole as the structure-directing agent. The Co0.6-PyNa exhibits the excellent electrocatalytic activity toward OER in 1 M KOH solution with an overpotential of as low as 299 mV and a small Tafel slope of 67 mV dec−1, which is comparable to the commercial RuO2, along with superior operational stability to RuO2. The high OER catalytic performance of Co0.6-PyNa has been reasoned to originate from the exposure of abundant CoOx active species uniformly dispersed on the nanoflakes due to its high specific surface area and the intrinsic extraordinarily high activity of CoOx active species. This work provides a promising strategy to fabricate efficient, stable and low-cost OER electrocatalyst, which is expected to promote the development of OER-related energy storage and conversion technologies.

"Smart" bioresponsive materials, which are sensitive to biological signals or pathological abnormalities, are appealing therapeutic platforms for the development of next-generation cancer theranostics. In this work, a novel "stepwise extraction" strategy has been proposed and demonstrated in constructing injectable bioresponsive composite implant, which features unique theranostic responsivenesses to exogenous and external triggers. The as-designed implant exhibits theranostic functions and biodegradability for cancer treatment based on the change of intratumoral microenvironment and the needs of therapeutic process. This "stepwise extraction" process, that is, "solvent extraction", "manganese extraction" and "phosphorus extraction", significantly promoted the biodegradation and disintegration of the bioresponsive implant step by step, accompanied by the corresponding component releases from the PLGA framework and furthermore, accomplished different specific theranostic functions needed at different treatment stages. This is the first demonstration of bioresponsive organic-inorganic hybrid implant with marked theranostic functions and excellent biodegradability by a "stepwise extraction" approach, paving the way to the solutions of unsatisfactory therapeutic efficacy and strong side effects in current cancer therapeutic modalities.

A novel dual-emitting metal–organic framework based on Zr and Eu, named as UiO-66(Zr&Eu), was built using a clever strategy based on secondary building units. With the use of polymers, the obtained UiO-66(Zr&Eu) was subsequently deposited as thin films that can be utilized as smart thermometers. The UiO-66(Zr&Eu) polymer films can be used for the detection of temperature changes in the range of 237–337 K due to the energy transfer between the lanthanide ions (Eu in clusters) and the luminescent ligands, and the relative sensitivity reaches 4.26% K–1 at 337 K. Moreover, the sensitivity can be improved to 19.67% K–1 by changing the film thickness. In addition, the temperature-sensing performance of the films is superior to that of the powders, and the sensor can be reused 3 times without loss of performance.

A facile strategy is established for constructing composite nanostructure with ultrasmall Pt nanoparticles (NPs) of ~2 nm in diameter being homogeneously embedded in N-doped carbon nanosheets. The strong coordination between Pt atoms in cisplatin and N atoms in pyrrole contributes to the robust embedding of Pt NP into the N-doped carbon nanosheets after annealing. Such a unique partially-embedding structure facilitates the active site exposure while stabilizing the ultrasmall Pt NPs, leading to the comparable electrochemical activities for hydrogen evolution and oxygen reduction reactions, and substantially improves durability performance compared to that of the state-of-the-art Pt/C (20 wt%) .

Ultrasound (US)-triggered sonodynamic therapy (SDT) can solve the critical issue of low tissue-penetrating depth of traditional phototriggered therapies, but the SDT efficacy is still not satisfactorily high in combating cancer at the current stage. Here we report on augmenting the SDT efficacy based on catalytic nanomedicine, which takes the efficient catalytic features of nanoenzymes to modulate the tumor microenvironment (TME). The multifunctional nanosonosensitizers have been successfully constructed by the integration of a MnOx component with biocompatible/biodegradable hollow mesoporous organosilica nanoparticles, followed by conjugation with protoporphyrin (as the sonosensitizer) and cyclic arginine-glycine-aspartic pentapeptide (as the targeting peptide). The MnOx component in the composite nanosonosensitizer acts as an inorganic nanoenzyme for converting the tumor-overexpressed hydrogen peroxide (H2O2) molecules into oxygen and enhancing the tumor oxygen level subsequently, which has been demonst...

Beyond mesoporous silica nanoparticles (MSNs), mesoporous organosilica nanoparticles (MONs) have been becoming an even more attractive alternative to the traditional organic or inorganic nanomaterials in biomedical applications, especially for drug delivery, due to its high surface area, stable physicochemical properties, low toxicity, high biocompatibility, and particularly the devisable features decided by the incorporated organic fragments. However, it is still challenging to fabricate uniform ultrasmall MONs with tunable composition, morphology and fine biodegradability. Herein, we report, on the large-scale fabrication of monodispersed and molecularly organic-inorganic hybrid MONs with framework-incorporated physiologically active thioether bonds, controllable nanostructure, composition and morphology, which provides the material foundation for exploring the versatile biomedical applications of organosilica nanosystems. The hybrid MONs of less than 50 nm in particle size exhibit the unique reduction-responsive biodegradation behavior, and the biodegradation rate is significantly higher than that of traditional mesoporous silica nanoparticles with pure inorganic Si O Si framework. The reductive microenvironment-triggered biodegradation of MONs induces the concurrent reduction-responsive anticancer drug releasing from MONs, enabling tumor-specific drug delivery. Importantly, these biocompatible and biodegradable MONs exhibit significantly improved drug-delivery efficiency and enhanced tumor-suppressing effect for combating cancer. Based on the facile and large-scale fabrication of MONs with controllable key structure/composition/morphology parameters, unique tumor microenvironment-responsive biodegradation behavior and high performance for drug delivery, the MONs therefore show more promising potentials for clinical translation as compared to traditional MSNs.

In this work, a novel kind of magnetic, core-shell structured and surface molecularly imprinted polymers (MMIPs) for the recognition of salicylic acid (SA) was facilely synthesized through a surface imprinting and sol-gel polymerization approach. The as-synthesized MMIPs exhibit uniform core-shell structure and favorable magnetic properties with a saturation magnetization of 22.8 emu g−1. The binding experiments demonstrated that MMIPs possessed high binding and specific recognition capacity, as well as fast binding kinetics and phase separation rate. The maximum binding capacity of MMIPs is around 36.8 mg g−1, nearly 6 times that of the magnetic non-imprinted polymers (MNIPs). Moreover, the selectivity experiments show that all the relative selectivity coefficients towards SA over its structure analogs are higher than 18, further indicating the markedly enhanced binding selectivity of MMIPs. Furthermore, the MMIPs were successfully applied for the determination of SA in environmental water samples with the recovery rates ranging from 94.0 to 108.0 %. This strategy may provide a versatile approach for the fabrication of well-defined molecularly imprinted polymers on nanomaterials for the analysis of complicated matrixes.

Based on the theory of mixing enthalpy of i,j element pairs (ΔHij) and atomic-size difference δ, we designed a uranium-containing equiatomic UHfNbTi high-entropy alloy with a single-phase bcc structure. The alloy showed good room-temperature compressive plastic properties. They with stood at least 60% of compression strain without fracture. We investigated the effect of average valence electron concentration (VEC) on the mechanical properties of the alloy. Reducing the VEC number is expected to produce uranium-containing high-entropy alloys with high ductility.

Doping hetero-metal ions in semiconductors, especially metal oxides, is a common practice to elevate their photocatalytic reduction activity. However, the underlying enhancement mechanism of doping different metal ions into the host lattice on photocatalytic CO2 reduction has been rarely explored and thus remains unclear. In this work, CeO2 nanoparticles doped with three different metal ions (CeM, M = Y, La, Mo) have been synthesized, which exhibited significantly improved photo-reduction CO2 activity. According to the analysis of Electron paramagnetic resonance (EPR) and X-ray photoelectron spectroscopy (XPS), Y and Mo doping results in increased oxygen vacancy concentration in CeO2, which promotes the absorption of UV–visible light and the separation/transfer of electrons and holes, consequently elevating the catalytic activity. More importantly, through in-situ FT-IR, CO2 adsorption/activation and the intermediates generated on catalyst surface during CO2 photoreduction reaction were investigated and discussed in-depth. Similar carbonates and hydrocarbonates, such as HCO3−, b-CO32− and m-CO32−, have been found to be produced on CeO2 and CeM, while these intermediates accumulated and strongly covered on the catalyst surface have been revealed to be responsible for the gradually declined CO2 reduction activity and stability.

Due to the strong bonding between Ti and O atoms, creating oxygen vacancy in stable TiO2 usually involves harsh synthetic conditions. In this work, inspired by DFT calculation results that much lower energy is required to dissociate Ti-OH bond than Ti-O bond, we report a facile approach by simply calcining TiOx(OH)y precursor in inertia atmosphere, to effectively create oxygen vacancy in titania (Ti-N2-600). During CO2 photoreduction, CH4 and CO are the major products on Ti-N2-600, whose evolution rates are about 2.8 times and 3.6 times those on commercial TiO2 (P25), respectively. The in-situ Fourier-transform infrared spectroscopy (FTIR) results indicate the oxygen vacancy in Ti-N2-600 favors 1) CO2 activation and photoreduction since CO2·- is generated but not detected on P25; 2) the *COL formation and further transformation. This Ti-OH breakage strategy presents a new insight into oxygen vacancy generation in TiO2 and more generically other metal oxide semiconductors.

Temperature plays a crucial role in both scientific research and industry. However, traditional temperature sensors, such as liquid-filled thermometers, thermocouples, and transistors, require contact to obtain heat equilibrium between the probe and the samples during the measurement. In addition, traditional temperature sensors have limitations when being used to detect the temperature change of fast-moving samples at smaller scales. Herein, the carbon quantum dots (C-QDs) functionalized metal–organic framework (MOF) composite film, a novel contactless solid optical thermometer, has been prepared via electrophoretic deposition (EPD). Instead of terephthalic acid (H2BDC), 1′,2′,4′,5′-benzenetetracarboxylic (H4BTEC) acid was employed to construct a UiO-66 framework to present two uncoordinated carboxylic groups decorated on the pore surface. The uncoordinated carboxylic groups can generate negative charges, which facilitates the deposition of film on the positive electrode during the EPD process. Moreover,...

With ever-increasing severe environment pollutions and energy demand, it is becoming greatly important to develop sustainable energy resources as alternatives to traditional fossil fuels. As one of the ultimate clean energy sources, hydrogen (H2) energy produced by water splitting using electricity from solar radiation, wind, tide, and nuclear fusion, among other sources, has attracted more and more public attention since the late 18th century. Although noble-metal-based electrocatalysts perform well, they suffer severely from the high cost and rarity from the viewpoint of practical applications. Recently, various kinds of non-noble-metal electrocatalysts based on low cost and earth-abundant transition metals have been developed for both hydrogen evolution reaction (HER) and oxygen (O2) evolution reaction (OER). Among them, non-noble-metal bifunctional electrocatalysts (NHOBEs), showing high performances in both HER and OER, are therefore of great significance and importance in future applications. With N...

Engineering novel dual-emitting metal–organic frameworks (MOFs) with wide emission ranges for application as ratiometric temperature sensors is still a challenge. In this paper, two novel dual-emitting MOFs with intergrated lanthanide metals and luminescent ligand in a UiO-66-type structure, named Ln@UiO-66-Hybrid, were prepared via the combination of postsynthetic modification and postsynthetic exchange methods. Subsequently, the as-synthesized MOFs were deposited onto fluorine tin oxide substrates through electrophoretic deposition by taking advantage of the charges from the unmodified carboxylic groups of the MOFs. The as-prepared Tb@UiO-66-Hybrid and Eu@UiO-66-Hybrid films were applied to detect temperature changes. The resulting Tb@UiO-66-Hybrid film exhibited good temperature-sensing properties with a relative sensitivity of up to 2.76% K–1 in the temperature range of 303–353 K. In addition, the Eu@UiO-66-Hybrid film showed excellent temperature-sensing performance based on the energy transfer betwe...

Tumour chemotherapy employs highly cytotoxic chemodrugs, which kill both cancer and normal cells by cellular apoptosis or necrosis non-selectively. Catalysing/triggering the specific chemical reactions only inside tumour tissues can generate abundant and special chemicals and products locally to initiate a series of unique biological and pathologic effects, which may enable tumour-specific theranostic effects to combat cancer without bringing about significant side effects on normal tissues. Nevertheless, chemical reaction-initiated selective tumour therapy strongly depends on the advances in chemistry, materials science, nanotechnology and biomedicine. This emerging cross-disciplinary research area is substantially different from conventional cancer-theranostic modalities in clinics. In response to the fast developments in cancer theranostics based on intratumoural catalytic chemical reactions, this tutorial review summarizes the very-recent research progress in the design and synthesis of representative nanoplatforms with intriguing nanostructures, compositions, physiochemical properties and biological behaviours for versatile catalytic chemical reaction-enabled cancer treatments, mainly by either endogenous tumour microenvironment (TME) triggering or exogenous physical irradiation. These unique intratumoural chemical reactions can be used in tumour-starving therapy, chemodynamic therapy, gas therapy, alleviation of tumour hypoxia, TME-responsive diagnostic imaging and stimuli-responsive drug release, and even externally triggered versatile therapeutics. In particular, the challenges and future developments of such a novel type of cancer-theranostic modality are discussed in detail to understand the future developments and prospects in this research area as far as possible. It is highly expected that this kind of unique tumour-specific therapeutics by triggering specific in situ catalytic chemical reactions inside tumours would provide a novel but efficient methodology for benefiting personalized biomedicine in combating cancer.

Hydrogen energy, which is environmentally friendly and sustainable, has attracted significant attention from researchers worldwide for its promising future applications. Water electrolysis in conjunction with renewable electricity (from wind, photovoltaics, tides, etc.) can provide a “zero emission” source of hydrogen. However, water electrolysis is severely hampered by its slow kinetics, especially that of the oxygen evolution reaction (OER) at the cathode. Recently, an alternative strategy for water splitting, the chemical-assisted hydrogen electrocatalytic evolution reaction (CAHER), has been developed and shows promising activity. This strategy enables the substitution of a relatively facile chemical oxidation reaction (COR) for the sluggish cathodic OER. The COR is not only kinetically faster, but also can produce high value products. Efforts have been made to identify suitable chemicals and correspondingly efficient catalysts. Understanding the mechanisms of CAHER is highly beneficial for system design, chemical selection and catalyst optimization. Therefore, the most recent progress in CAHER is introduced in this mini-review from the aspects of basic principles, the diverse auxiliary reductive chemicals and the development of electrocatalysts. Possible mechanisms for the hydrogen evolution at the cathode and oxidation/degradation of chemicals at the anode are proposed to elucidate the CAHER process. Finally, promising strategies for improving CAHER performance with regard to future developments are outlined.

Solar-driven photoelectrochemical (PEC) technology has been widely recognized as a green and sustainable approach to produce fossil-fuel-alternative energy sources, whereas currently its feasibility is still a great challenge due to the lack of high-performance photoanodes. Herein, two-dimensional trimetallic CoNiFe-layered double hydroxides (CoNiFe-LDHs) nanosheets were uniformly anchored on one-dimensional Ta3N5 nanotube arrays used as a novel integrated photoanode. Serving as a hole collector, CoNiFe-LDHs can accelerate hole extraction from photo-excited Ta3N5 towards surface water oxidation reaction (WOR), thus promoting the separation of electron-hole pairs and ultimately markedly improving PEC water-splitting performance. Moreover, the trimetallic CoNiFe-LDHs were more effective in boosting the PEC performance than the three sets of bimetallic LDHs. By further replacing WOR with glycerol oxidation reaction (GOR), the composite photoanode achieved a ten-fold enhancement of solar energy conversion efficiency reaching 0.56% with nearly 100% Faradaic efficiency for concurrent generation of formate and hydrogen. Importantly, the stability of Ta3N5 was dramatically enhanced due to the synergy of CoNiFe-LDHs loading and anodic GOR. The significantly enhanced PEC properties can be mainly attributed to the increased surface active sites, promoted hole extraction and utilization, and particularly the improved charge separation efficiency. This work provides a reference for the fabrication of high-performance Ta3N5-based photoanodes towards efficient and stable PEC hydrogen generation and the green conversion of biomass derivatives into valuable chemicals.

Oxygen evolution reaction (OER) is a pivotal electrochemical reaction process for many renewable energy technologies. Due to the sluggish OER kinetics, searching for efficient low-cost non-precious metal catalysts is one of the crucial but very challenging steps. Herein, V2C MXene synergistically coupled with hypophosphite-intercalated FeNi (oxy)hydroxide (H2PO2−/FeNi-LDH-V2C) electrocatalyst is synthesized. The H2PO2−/FeNi-LDH-V2C exhibits excellent OER performance with an overpotential of 250 mV (η10) and small Tafel slope of 46.5 mV dec−1 in 1.0 M KOH electrolyte, and excellent rechargeable Zn-air battery performance with superior open circuit potential (1.42 eV), power density (137 mW cm−2) and well durability. The strong interaction and electronic coupling with prominent charge-transfer between FeNi-LDHs and V2C MXene endow the composite significant OER performance and structural stability, and the adsorption/desorption balance for the OER reaction pathway, eventually promoting the intrinsic activity. This work demonstrates the great promise of MXene-based nanohybrids as advanced electrocatalysts for renewable energy applications.

Silicon, a highly biocompatible and ubiquitous chemical element in living systems, exhibits great potentials in biomedical applications. However, the silicon-based nanomaterials such as silica and porous silicon have been largely limited to only serving as carriers for delivery systems, due to the lack of intrinsic functionalities of silicon. This work presents the facile construction of a two-dimensional (2D) hydrogen-bonded silicene (H-silicene) nanosystem which is highlighted with tunable bandgap and selective degradability for tumor-specific photodynamic therapy facilely by surface covalent modification of hydrogen atoms. Briefly, the H-silicene nanosheet material is selectively degradable in normal neutral tissues but rather stable in the mildly acidic tumor microenvironment (TME) for achieving efficient photodynamic therapy (PDT). Such a 2D hydrogen-bonded silicene nanosystem featuring the tunable bandgap and tumor-selective degradability provides a new paradigm for the application of multi-functional two-dimensional silicon-based biomaterials towards the diagnosis and treatments of cancer and other diseases.

Cardiovascular diseases caused by ischemia are attracting considerable attention owing to its high morbidity and mortality worldwide. Although numerous agents with cardioprotective benefits have been identified, their clinical outcomes are hampered by their low bioavailability, poor drug solubility, and systemic adverse effects. Advances in nanoscience and nanotechnology provide a new opportunity to effectively deliver drugs for treating ischemia-related diseases. In particular, cardiac ischemia leads to a characteristic pathological environment called an ischemic microenvironment (IME), significantly different from typical cardiac regions. These remarkable differences between ischemic sites and normal tissues have inspired the development of stimuli-responsive systems for the targeted delivery of therapeutic drugs to damaged cardiomyocytes. Recently, many biomaterials with intelligent properties have been developed to enhance the therapeutic benefits of drugs for the treatment of myocardial ischemia. Strategies for stimuli-responsive drug delivery and release based on IME include reactive oxygen species, pH-, hypoxia-, matrix metalloproteinase-, and platelet-inspired targeting strategies. In this review, state-of-the-art IME-responsive biomaterials for the treatment of myocardial ischemia are summarized. Perspectives, limitations, and challenges are also discussed for the further development of innovative and effective approaches to treat ischemic diseases with high effectiveness and biocompatibility.