Evolution of structural and electronic properties standardized description in rhenium disulfide at the bulk-monolayer transition.

The structural and electronic properties of ReS2 different forms - three-dimensional bulk and two-dimensional monolayer - were studied within density functional theory and pseudopotentials. A method for standardizing the description of bulk unit cells and "artificial" slab unit cells for DFT research has been proposed. The preference of this method for studying zone dispersion has been shown. The influence of the vacuum layer thickness on specified special high-symmetry points is discussed. Electron band dispersion in both classical 3D Brillouin zones and transition to 2D Brillouin zones in the proposed two-dimensional approach using the Niggli form of the unit cell was compared. The proposed two-dimensional approach is preferable for low-symmetry layered crystals such as ReS2. It was established that the bulk ReS2 is a direct gap semiconductor (band gap of 1.20 eV), with the direct transition lying in the X point of the first Brillouin zone, and it is in good agreement with published experimental data. The reduction in material dimension from bulk to monolayer was conducted with an increasing band gap up to 1.45 eV, with a moving direct transition towards the Brillouin zone center. The monolayer of ReS2 is a direct-gap semiconductor in a wide range of temperatures, excluding only a narrow range at low temperatures, where it comes as a quasi-direct gap semiconductor. The transition, situated directly in the Γ-point, lies 3.3 meV below the first direct transition located near this point. The electronic density of states of ReS2 in the bulk and monolayer cases of ReS2 were analyzed. The molecular orbitals were built for both types of ReS2 structures as well as the electron difference density maps. For all types of ReS2 structures, an analysis of populations according to Mulliken and Voronoi was carried out. All calculated data is discussed in the context of weak quantum confinement in the 2D case.

Phospholipid-inspired alkoxylation induces crystallization and cellular uptake of luminescent COF nanocarriers.

The porous nature and structural variability of covalent organic frameworks (COFs) make them preferred for drug loading and delivery applications. However, most COF materials suffer from poor luminescent properties and inefficiency for cell uptake. Herein, we experimentally demonstrate the crucial role of long alkoxy chains in the synthesis of crystalline COF nanostructures with high cellular uptake efficiency. After luminescence integration through band engineering, the semiconducting COF exhibits an optical bandgap of 2.05 eV, an emission wavelength of 632 nm, a high quantum yield of 37 %, and excellent fluorescence stability (100 % at 3 h). Such excellent optical properties of the designed COF nanocarriers enable quantitative evaluations of cellular uptake and visual tracking of drug delivery. It was demonstrated that the cellular uptake efficiency was enhanced by orders of magnitude for the COF after the introduction of long n-octyloxy chains, which firstly delivered the anticancer camptothecin (CPT) to cell lysosomes, and then underwent "endo/lysosomal escape" to induce cell apoptosis. In vivo assay evidenced a significant enhancement in the therapeutic effect with a 96 % inhibition of tumor growth after 14 days of treatment. This progress sheds light on designing cutting-edge drug delivery nanosystems based on COF materials with integrated diagnostic and therapeutic functions.

Red-Fluorescent Covalent Organic Framework Nanospheres for Trackable Anticancer Drug Delivery.

Covalent organic frameworks (COFs) have emerged as promising drug carriers due to their structural variability, inherent porosity, and customizable functions. However, most COFs used in drug delivery suffer from low cellular bioavailability and poor luminescence properties. In this study, we designed a series of size-tunable, crystalline, and red-fluorescent COF nanospheres (COFNSs) for trackable anticancer drug delivery. The semiconducting COFNSs were prepared by condensations of 1,3,5-triformylbenzene (TFB) with various dihydrazide blocks through the Schiff-base reaction, resulting in red emission at 647 nm and excellent fluorescence stability (∼100% for 1 h). Such fluorescence property allowed for systematic investigation of the cellular endocytosis pathway of COFNSs, visualization of drug delivery, and observation of the cell apoptosis process. The COFNSs exhibited high cell viability (>90%), a loading capacity of 183 wt % for the anticancer drug camptothecin (CPT), and significant enhancement in inhibiting 4T1 cancers both in vitro and in vivo as the CPT nanocarrier. This progress presents a valuable approach to design COF nanocarriers with integrated fluorescent and drug delivery functions.

Flower-like porous BCN assembled by nanosheets for paclitaxel delivery.

Developing smart drug delivery systems has become a feasible solution to overcome the challenges in cancer chemotherapeutics. In this work, porous boron carbon nitride (ZBCN) nanomaterials with flower-like structures assembled with BCN nanosheets were synthesized by using ZIF-L as a template. The rich hydroxyl groups on the BCN surfaces make it highly dispersible and stable in aqueous solutions. Additionally, ZBCN exhibits stable photoluminescence properties that can be utilized for cellular uptake and tracking of drug delivery. Furthermore, the flower-like ZBCN structure contributes to a large specific surface area of up to 340 m2 g-1 and a pore volume of 1.03 cm3 g-1; and the presence of rich macropores results in a high drug loading capacity of 116 wt% for paclitaxel. In vitro and in vivo anticancer experiments demonstrated that ZBCN exhibits excellent performance in delivering anticancer drugs, with in vivo tumor inhibition of 58%. This study presents a novel template method for preparing porous BCN nanomaterials, offering a promising platform for high-performance anticancer drug delivery.

Boron Dopants in Red-Emitting B and N Co-Doped Carbon Quantum Dots Enable Targeted Imaging of Lysosomes.

Lysosomes are of great significance to cell growth, metabolism, and survival, as they independently maintain acidity and regulate various balances in cells. Therefore, it is essential to develop advanced probes for lysosome visualization and live tracking. Herein, a type of lysosome-targeting probe based on boron (B) and nitrogen (N) co-doped carbon quantum dots (B/N-CQDs) is presented, which exhibits red emission at 618 nm, high quantum yield (28%), and excellent fluorescence stability (97% at 1 h). These B/N-CQDs are prepared by a novel and green solid-state reaction and purified using a simple extraction process without additional chemical modifications. It is found that the boron dopants in the structure play a crucial role in the resultant lysosome-specific targeting property through borate esterification between boronic acid groups in the sample and diol structures in glycoproteins. This can be applied as a powerful tool for cell apoptosis, necrosis, and endosomal escape tracking. This work not only offers a new concept for targeted subcellular probe designs via chemical doping but also demonstrates the feasibility of these tools for analyzing complex cellular physiological activities.

Design of size uniform and controllable covalent organic framework nanoparticles for high-performance anticancer drug delivery.

Covalent organic frameworks (COFs) receive much attention in biomedicine because of their unique adsorption, optical and biological properties, as well as highly variable structures. However, preparation of nanosized COFs with uniform and controllable size is still a challenge. Herein, we develop a facile interfacial method to prepare the COF nanoparticles (COFNPs) with the uniform size of 30-50 nm from p-benzoquinone (BQ) and 4-[1,2,2-tris(4-aminophenyl)ethenyl]aniline (TPEA) by Michael addition. The TPEA-BQ COFNPs show positive zeta potential and effectively load the hydrophobic anticancer drug camptothecin (CPT) with the capacity of up to 127wt%, and remarkably improved the CPT dispersibility in water due to the retention of quinone structure. In vitro assay reveals CPT@ TPEA-BQ significantly reduced cell viability to 29% after 24 h incubation, much lower than that of free CPT (51%) at the same concentration of 10 µg mL-1. Further in vivo experiment confirms the high anticancer drug delivery performance of the designed TPEA-BQ COFNPs. After 20 days of injection treatment, the CPT loaded in TPEA-BQ COFNPs inhibits the tumor growth by 60%, much higher than that of free CPT group (23%). This work demonstrates the feasibility to design advanced drug delivery systems based on highly structure-tunable COF system.

Microbatteries with twin-Swiss-rolls redefine performance limits in the sub-square millimeter range.

To maintain the downscaling of microelectronic devices with footprints less than one square millimeter, next-generation microbatteries should occupy the same area and deliver adequate energy for running a new generation of multi-functional microautonomous systems. However, the current microbattery technology fails in accomplishing this task because the micrometer-sized electrodes are not compatible with on-chip integration protocols and technologies. To tackle this critical challenge, an on-chip Swiss-roll microelectrode architecture is employed that exploits the self-assembly of thin films into ultra-compact device architectures. A twin-Swiss-roll microelectrode on a chip occupies a footprint of 0.045 mm2 and delivers an energy density up to 458 µW h cm-2. After packaging, the footprint of a full cell increases to 0.11 mm2 with a high energy density of 181 µW h cm-2. The volumetric energy density excluding the chip thickness is 16.3 mW h cm-3. These results open opportunities for deploying microbatteries as energy and power sources to drive smart dust microelectronics and microautonomous systems.

Flexible and Wearable Zinc-Ion Hybrid Supercapacitor Based on Double-Crosslinked Hydrogel for Self-Powered Sensor Application.

The rapidly growing Internet of Things (IoT) has brought about great demand for high-performance sensors as well as power supply devices for those sensors. In this respect, the integration of sensors and energy storage devices, or the development of multifunctional devices having both energy storage and sensing properties, is of great interest in the development of compact sensing systems. As a proof of concept, a zinc-ion hybrid supercapacitor (ZHS) based on a double-crosslinked hydrogel electrolyte is developed in this work, which can be employed not only as an energy storage device, but also as a self-powered sensor for human movement and breathing detection. The ZHS delivers a capacitance of 779 F g-1 and an energy density of 0.32 mWh cm-2 at a power density of 0.34 mW cm-2, as well as sensitive resistance response to strain. Our work provides a useful basis for future designs of self-powered sensing devices and function-integrated systems.

Biodegradable and Peroxidase-Mimetic Boron Oxynitride Nanozyme for Breast Cancer Therapy.

Nanomaterials having enzyme-like activities are recognized as potentially important self-therapeutic nanomedicines. Herein, a peroxidase-like artificial enzyme is developed based on novel biodegradable boron oxynitride (BON) nanostructures for highly efficient and multi-mode breast cancer therapies. The BON nanozyme catalytically generates cytotoxic hydroxyl radicals, which induce apoptosis of 4T1 cancer cells and significantly reduce the cell viability by 82% in 48 h. In vivo experiment reveals a high potency of the BON nanozyme for breast tumor growth inhibitions by 97% after 14-day treatment compared with the control, which are 10 times or 1.3 times more effective than the inert or B-releasing boron nitride (BN) nanospheres, respectively. This work highlights the BON nanozyme and its functional integrations within the BN nanomedicine platform for high-potency breast cancer therapies.

Fabrications of High-Performance Planar Zinc-Ion Microbatteries by Engraved Soft Templates.

Miniaturized energy storage devices (MESDs) provide future solutions for powering dispersive electronics and small devices. Among them, aqueous zinc ion microbatteries (ZIMBs) are a type of promising MESDs because of their high-capacity Zn anode, safe and green aqueous electrolytes, and good battery performances. Herein, for the first time, a simple and powerful strategy to fabricate flexible ZIMBs based on tailored soft templates is reported, which are patterned by engraving and enables to design the ZIMBs featured with arbitrary shapes and on various substrates. The assembled ZIMBs employing α-MnS as the cathode materials and guar gum gel as the quasi-solid-state electrolyte exhibited very high areal specific capacity of up to 178 µAh cm-2 , a notable areal energy density of 322 µWh cm-2 and power density of 710 µW cm-2 . Footprint areas of the manufactured ZIMBs as small as 40 mm2 can be achieved. The proposed method based on the engraved soft templates provides a practical route for ZIMB and other MESD designs, which is critical for portable and wearable electronics development.

Miniaturized Energy Storage Devices Based on Two-Dimensional Materials.

A growing demand for miniaturized biomedical sensors, microscale self-powered electronic systems, and many other portable, wearable, and integratable electronic devices is continually stimulating the rapid development of miniaturized energy storage devices (MESDs). Miniaturized batteries (MBs) and supercapacitors (MSCs) were considered to be suitable energy storage devices to power microelectronics uninterruptedly with reasonable energy and power densities. However, in addition to similar challenges encountered with electrode materials in conventional energy storage devices, their performances are also greatly affected by microfabrication technologies, as well as the challenges of how to realize stable and high-performance MESDs in such a limited footprint area. Benefiting from the unique architectural engineering of two-dimensional materials and the emergence of precise and controllable microfabrication techniques, the output electrochemical performances of MSCs and MBs are improving rapidly. This minireview summarizes recent advances in MSCs and MBs built from two-dimensional materials, including electrode/device configuration designs, material synthesis, microfabrication processes, smart function incorporations, and system integrations. An introduction to configurations of the MESDs, from linear fibrous shapes, planar sandwich thin-film or interdigital structures, to three-dimensional configurations, is presented. The fundamental influences of the electrode material and configuration designs on the exhibited MB/MSC electrochemical performances are also highlighted.

Pairing of Luminescent Switch with Electrochromism for Quasi-Solid-State Dual-Function Smart Windows.

Smart window is a promising green technology with feature of tunable transparency under external stimuli to manage light transmission and solar energy. However, more functions based on the intelligent management of the solar spectrum need to be integrated into present smart windows. In this work, a dual-function smart window is fabricated by pairing the luminescent switch with the electrochromic window. The dual function is based on a single fluorine doped tin oxide coated glass functionalized with tungsten oxide and copper nanocluster, among which tungsten oxide serves as an electrochromic material and copper nanocluster provides photoinduced luminescence. Along with the regulation of the visible light based on the electrochromism of the window, the luminescence can be finely switched on and off, which establishes a pair of reversible states ("on" and "off") for the dual-function smart window. The contrast between two states reaches 88%. Furthermore, the manipulation of dual-function smart window is highly reversible with a short response time of 12.6 s. This prototype of dual-function smart window paves the way for developing multifunctional smart windows by integrating different functional materials into one smart window based on the rational management of the solar spectrum.

Electronic and Optical Properties of 2D Materials Constructed from Light Atoms.

Boron, carbon, nitrogen, and oxygen atoms can form various building blocks for further construction of structurally well-defined 2D materials (2DMs). Both in theory and experiment, it has been documented that the electronic structures and optical properties of 2DMs are well tunable through a rational design of the material structure. Here, the recent progress on 2DMs that are composed of B, C, N, and O elements is introduced, including borophene, graphene, h-BN, g-C3 N4 , organic 2D polymers (2DPs), etc. Attention is put on the band structure/bandgap engineering for these materials through a variety of methodologies, such as chemical modifications, layer number and atomic structure control, change of conjugation degree, etc. The optical properties, such as photoluminescence, thermoluminescence, single photon emission, as well as the associated applications in bioimaging and sensing, are discussed in detail and highlighted.

Construction of Polarized Carbon-Nickel Catalytic Surfaces for Potent, Durable, and Economic Hydrogen Evolution Reactions.

Electrocatalytic hydrogen evolution reaction (HER) in alkaline solution is hindered by its sluggish kinetics toward water dissociation. Nickel-based catalysts, as low-cost and effective candidates, show great potentials to replace platinum (Pt)-based materials in the alkaline media. The main challenge regarding this type of catalysts is their relatively poor durability. In this work, we conceive and construct a charge-polarized carbon layer derived from carbon quantum dots (CQDs) on Ni3N nanostructure (Ni3N@CQDs) surfaces, which simultaneously exhibit durable and enhanced catalytic activity. The Ni3N@CQDs shows an overpotential of 69 mV at a current density of 10 mA cm-2 in a 1 M KOH aqueous solution, lower than that of Pt electrode (116 mV) at the same conditions. Density functional theory (DFT) simulations reveal that Ni3N and interfacial oxygen polarize charge distributions between originally equal C-C bonds in CQDs. The partially negatively charged C sites become effective catalytic centers for the key water dissociation step via the formation of new C-H bond (Volmer step) and thus boost the HER activity. Furthermore, the coated carbon is also found to protect interior Ni3N from oxidization/hydroxylation and therefore guarantees its durability. This work provides a practical design of robust and durable HER electrocatalysts based on nonprecious metals.

Reinforcing Germanium Electrode with Polymer Matrix Decoration for Long Cycle Life Rechargeable Lithium Ion Batteries.

Germanium is a promising anode material for lithium ion batteries because of its high theoretical specific capacity and low operation voltage. However, a significant challenge in using Ge-based anodes is the large volume variation during cycling that causes pulverization and capacity fade. Despite intense studies in the past decade, unsatisfactory cycling stability of the Ge-based electrodes still impedes their widespread applications. In this study, we demonstrate a high-performance electrode through the synergistic combination of a high-capacity Ge film grown on a three-dimensional current collector and an in situ formed poly(vinylidene fluoride)-hexafluoropropene/SiO2 protective layer. Specifically, the polymer matrix is in continuous contact with the surface of the Ge shell, which provides improved mechanical and ionic transport properties. As a highlight, we present impressive cycling stability over 3000 cycles at 1 C rate with a capacity retention as high as 95.7%. Furthermore, the LiCoO2-Ge full battery operates at an average voltage of 3.3 V at 0.5 C and maintains good electrochemical performance, suggesting great potential for applications in energy storage and conversion devices.

Advances on Microsized On-Chip Lithium-Ion Batteries.

Development of microsized on-chip batteries plays an important role in the design of modern micro-electromechanical systems, miniaturized biomedical sensors, and many other small-scale electronic devices. This emerging field intimately correlates with the topics of rechargeable batteries, nanomaterials, on-chip microfabrication, etc. In recent years, a number of novel designs are proposed to increase the energy and power densities per footprint area, as well as other electrochemical performances of microsized lithium-ion batteries. These advances may guide the pathway for the future development of microbatteries.

Tuning of the Optical, Electronic, and Magnetic Properties of Boron Nitride Nanosheets with Oxygen Doping and Functionalization.

Engineering of the optical, electronic, and magnetic properties of hexagonal boron nitride (h-BN) nanomaterials via oxygen doping and functionalization has been envisaged in theory. However, it is still unclear as to what extent these properties can be altered using such methodology because of the lack of significant experimental progress and systematic theoretical investigations. Therefore, here, comprehensive theoretical predictions verified by solid experimental confirmations are provided, which unambiguously answer this long-standing question. Narrowing of the optical bandgap in h-BN nanosheets (from ≈5.5 eV down to 2.1 eV) and the appearance of paramagnetism and photoluminescence (of both Stokes and anti-Stokes types) in them after oxygen doping and functionalization are discussed. These results are highly valuable for further advances in semiconducting nanoscale electronics, optoelectronics, and spintronics.

Hollow boron nitride nanospheres as boron reservoir for prostate cancer treatment.

High global incidence of prostate cancer has led to a focus on prevention and treatment strategies to reduce the impact of this disease in public health. Boron compounds are increasingly recognized as preventative and chemotherapeutic agents. However, systemic administration of soluble boron compounds is hampered by their short half-life and low effectiveness. Here we report on hollow boron nitride (BN) spheres with controlled crystallinity and boron release that decrease cell viability and increase prostate cancer cell apoptosis. In vivo experiments on subcutaneous tumour mouse models treated with BN spheres demonstrated significant suppression of tumour growth. An orthotopic tumour growth model was also utilized and further confirmed the in vivo anti-cancer efficacy of BN spheres. Moreover, the administration of hollow BN spheres with paclitaxel leads to synergetic effects in the suppression of tumour growth. The work demonstrates that hollow BN spheres may function as a new agent for prostate cancer treatment.

Multifunctional Superelastic Foam-Like Boron Nitride Nanotubular Cellular-Network Architectures.

Construction of cellular architectures has been expected to enhance materials' mechanical tolerance and to stimulate and broaden their efficient utilizations in many potential fields. However, hitherto, there have been rather scarce developments in boron nitride (BN)-type cellular architectures because of well-known difficulties in the syntheses of BN-based structures. Herein, cellular-network multifunctional foams made of interconnective nanotubular hexagonal BN (h-BN) architectures are developed using carbothermal reduction-assisted in situ chemical vapor deposition conversion from N-doped tubular graphitic cellular foams. These ultralight, chemically inert, thermally stable, and robust-integrity (supporting about 25,000 times of their own weight) three-dimensional-BN foams exhibit a 98.5% porosity, remarkable shape recovery (even after cycling compressions with 90% deformations), excellent resistance to water intrusion, thermal diffusion stability, and high strength and stiffness. They remarkably reduce the coefficient of thermal expansion and dielectric constant of polymeric poly(methyl methacrylate) composites, greatly contribute to their thermal conductivity improvement, and effectively limit polymeric composite softening at elevated temperatures. The foams also demonstrate high-capacity adsorption-separation and removal ability for a wide range of oils and organic chemicals in oil/water systems and reliable recovery under their cycling usage as organic adsorbers. These created multifunctional foams should be valuable in many high-end practical applications.

Improved Li+ Storage through Homogeneous N-Doping within Highly Branched Tubular Graphitic Foam.

A novel carbon structure, highly branched homogeneous-N-doped graphitic (BNG) tubular foam, is designed via a novel N, N-dimethylformamide (DMF)-mediated chemical vapor deposition method. More structural defects are found at the branched portions as compared with the flat tube domains providing abundant active sites and spacious reservoirs for Li+ storage. An individual BNG branch nanobattery is constructed and tested using in situ transmission electron microscopy and the lithiation process is directly visualized in real time.