Red/orange dual-emissive carbon dots for pH sensing and cell imaging

The dual-emissive N, S co-doped carbon dots (N, S-CDs) with a long emission wavelength were synthesized via solvothermal method. The N, S-CDs possess relatively high photoluminescence (PL) quantum yield (QY) (35.7%) towards near-infrared fluorescent peak up to 648 nm. With the advanced characterization techniques including X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), etc. It is found that the doped N, S elements play an important role in the formation of high QY CDs. The N, S-CDs exist distinct pH-sensitive feature with reversible fluorescence in a good linear relationship with pH values in the range of 1.0–13.0. What is more, N, S-CDs can be used as an ultrasensitive Ag⁺ probe sensor with the resolution up to 0.4 μM. This finding will expand the application of as prepared N, S-CDs in sensing and environmental fields.

     

Au nanoring arrays with tunable morphological features and plasmonic resonances

Gold nanoring arrays are widely applied in various fields benefitting from their localized surface plasmon resonance (LSPR) properties. A key advantage of gold nanoring arrays is that the dipole resonance peak can be systematically tuned by changing the dimensions of gold nanoring arrays. However, most of the currently reported methods for preparing gold nanoring arrays cannot conveniently control the heights of the nanorings at a low cost. Here we introduce a facile method for preparing gold nanoring arrays with tunable plasmonic resonances using colloidal lithography. The dimensions of the nanorings including diameters, lattice constants, even the heights of the nanorings can be conveniently varied. Fourier transform near-infrared (FT-NIR) absorption spectroscopy was used to obtain the plasmonic resonance spectra of the nanoring arrays. All the prepared gold nanoring arrays exhibited a strong NIR or infrared (IR) plasmonic resonance which can be tuned by varying the nanoring dimensions. This versatile method can also be used to fabricate other types of plasmonic nanostructures, such as gold nanocone arrays. The obtained gold nanoring arrays as well as nanocone arrays may have potential applications in surface-enhanced spectroscopy or plasmonic sensing.

     

Integrated hetero-nanoelectrodes for plasmon-enhanced electrocatalysis of hydrogen evolution

Hetero-nanostructures of plasmonic metals and semiconductors have attracted increasing attention in the field of photocatalysis.However,most of the hetero-nanostructured catalysts are randomly arranged and therefore require comprehensive structural design for optimizing their properties.Herein,we report the robust construction of hierarchical hetero-nanostructures where gold(Au)nanorods and molybdenum disulfide(Mo S₂)quantum sheets(QSs)are integrated in highly ordered arrays.Such construction is achieved through porous anodic alumina(PAA)template-assisted electrodeposition.The as-fabricated hetero-nanostructures demonstrate exciting electrocatalysis towards hydrogen evolution reaction(HER).Both plasmon-induced hot-electron injection and plasmonic scattering/reabsorption mechanisms are determinative to the enhanced electrocatalytic performances.Notably,broadband photoresponses of HER activity in the visible range are observed,indicating their superiority compared with random systems.Such integrated hetero-nanoelectrodes could provide a powerful platform for conversion and utilization of solar energy,meanwhile would greatly prompt the production and exploration of ordered nanoelectrodes.     

Rational design of hierarchically porous Fe-N-doped carbon as efficient electrocatalyst for oxygen reduction reaction and Zn-air batteries

The rational design and construction of hierarchically porous nanostructure for oxygen reduction reaction (ORR) electrocatalysts is crucial to facilitate the exposure of accessible active sites and promote the mass/electron transfer under the gas-solid-liquid triple-phase condition. Herein, an ingenious method through the pyrolysis of creative polyvinylimidazole coordination with Zn/Fe salt precursors is developed to fabricate hierarchically porous Fe-N-doped carbon framework as efficient ORR electrocatalyst. The volatilization of Zn species combined with the nanoscale Kirkendall effect of Fe dopants during the pyrolysis build the hierarchical micro-, meso-, and macroporous nanostructure with a high specific surface area (1,586 m²·g⁻¹), which provide sufficient exposed active sites and multiscale mass/charge transport channels. The optimized electrocatalyst exhibits superior ORR activity and robust stability in both alkaline and acidic electrolytes. The Zn-air battery fabricated by such attractive electrocatalyst as air cathode displays a higher peak power density than that of Pt/C-based Zn-air battery, suggesting the great potential of this electrocatalyst for Zn-air batteries.

     

Mechanical force-induced assembly of one-dimensional nanomaterials

There have been intensive and continuous research efforts in large-scale controlled assembly of one-dimensional (1D) nanomaterials, since this is the most effective and promising route toward advanced functional systems including integrated nano-circuits and flexible electronic devices. To date, numerous assembly approaches have been reported, showing considerable progresses in developing a variety of 1D nanomaterial assemblies and integrated systems with outstanding performance. However, obstacles and challenges remain ahead. Here, in this review, we summarize most widely studied assembly approaches such as Langmuir-Blodgett technique, substrate release/stretching, substrate rubbing and blown bubble films, depending on three types of external forces: compressive, tensile and shear forces. We highlight the important roles of these mechanical forces in aligning 1D nanomaterials such as semiconducting nanowires and carbon nanotubes, and discuss each approach on their effectiveness in achieving high-degree alignment, distinct characteristics and major limitations. Finally, we point out possible research directions in this field including rational control on the orientation, density and registration, toward scale-up and cost-effective manufacturing, as well as novel assembled systems based on 1D heterojunctions and hybrid structures.

     

Continuous mechanical tuning of plasmonic nanoassemblies for tunable and selective SERS platforms

The continuous tuning of plasmonic nanoassembly's structure is the key to manipulate their optical and catalytic properties.Herein,we report a strategy of using macroscopic deformation to continuously tune the structure and optical activity of massive plasmonic nanoassemblies that are embedded in elastic polymer matrix.Plasmonic gold nanoparticles(Au NPs)are assembled to nanochains(Au NCs)with defined length and further embedded into polyvinylpyrrolidone(PVP)matrix.The nanostructure and plasmonic properties of massive Au NCs in this Au NCs-PVP film can be simultaneously and continuously tuned,simply by reversible mechanical deformation of this elastic film.In this way,the surface-enhanced Raman scattering(SERS)enhancement factor of this film as a SERS substrate can be mechanically modulated in the range of 10⁰to 6.8×10⁷.Meanwhile,the PVP matrix also serves as a selective diffusion barrier to eliminate the fluorescence interference of large biomolecules,which enables the Au NCs-PVP film as a convenient SER S substrate for quick and direct analysis of small molecule analytes in biological samples and food,avoiding the complicate and time-consuming sample pretreatment process.     

Synergistic effect enhances the peroxidase-like activity in platinum nanoparticle-supported metal—organic framework hybrid nanozymes for ultrasensitive detection of glucose

The metal—organic frameworks (MOFs) are expected as ideal biomimetic enzymes for colorimetric glucose detection because of their large surface areas, well defined pore structures, tunable chemical composition, and multi-functional sites. However, the intrinsically chemical instability and low mimetic enzyme activity of MOFs hinder the application of them in imitating the enzyme reactions. In this work, we demonstrated a metal-MOF synergistic catalysis strategy, by loading Pt nanoparticles (Pt NPs) on MIL-88B-NH₂ (Fe-MOF) to increase peroxidase-like activity for the detection of glucose. The induced electrons transfer from Pt atom to Fe atom accelerated the redox cycling of Fe³⁺/Fe²⁺, improved the overall efficiency of the peroxidase-like reaction, and enabled the efficient and robust colorimetric glucose detection, which was proved by both experiments and density functional theory (DFT) calculation. Additionally, the sensitivity and chemical stability of this synergistic effect strategy to detect the glucose are not affected by the complex external factors, which represented a great potential in fast, easy, sensitive, and specific recognition of clinical diabetes.

     

Adaptive nanopores:A bioinspired label-free approach for protein sequencing and identification

Single molecule protein sequencing would tremendously impact in proteomics and human biology and it would promote the development of novel diagnostic and therapeutic approaches.However,its technological realization can only be envisioned,and huge challenges need to be overcome.Major difficulties are inherent to the structure of proteins,which are composed by several different amino-acids.Despite long standing efforts,only few complex techniques,such as Edman degradation,liquid chromatography and mass spectroscopy,make protein sequencing possible.Unfortunately,these techniques present significant limitations in terms of amount of sample required and dynamic range of measurement.It is known that proteins can distinguish closely similar molecules.Moreover,several proteins can work as biological nanopores in order to perform single molecule detection and sequencing.Unfortunately,while DNA sequencing by means of nanopores is demonstrated,very few examples of nanopores able to perform reliable protein-sequencing have been reported sofar.Here,we investigate,by means of molecular dynamics simulations,how a re-engineered protein,acting as biological nanopore,can be used to recognize the sequence of a translocating peptide by sensing the MshapeH of individual amino-acids.In our simulations we demonstrate that it is possible to discriminate with high fidelity,9 different amino-acids in a short peptide translocating through the engineered construct.The method,here shown for fluorescence-based sequencing,does not require any labelling of the peptidic analyte.These results can pave the way for a new and highly sensitive method of sequencing.     

An electrodeposition approach to metal/metal oxide heterostructures for active hydrogen evolution catalysts in near-neutral electrolytes

Neutral water splitting is attractive for its use of non-corrosive and environmentally friendly electrolytes. However, catalyst development for hydrogen and oxygen evolution remains a challenge under neutral conditions. Here we report a simple electrodeposition and reductive annealing procedure to produce a highly active Ni-Co-Cr metal/metal oxide heterostructured catalyst directly on Ni foam. The resulting electrocatalyst for hydrogen evolution reaction (HER) requires only 198 mV of overpotential to reach 100 mA/cm² in 1 M potassium phosphate (pH = 7.4) and can operate for at least two days without significant performance decay. Scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) imaging reveals a Ni-Co alloy core decorated with blended oxides layers of NiO, CoO and Cr₂O₃. The metal/metal oxide interfaces are suggested to be responsible for the high HER activity.

     

Layer-by-layer assembled dual-ligand conductive MOF nano-films with modulated chemiresistive sensitivity and selectivity

In this paper,a dual-ligand design strategy is demonstrated to modulate the performance of the electronically conductive metalorganic frameworks(EC-MOFs)thin film with a spray layer-by-layer assembly method.The thin film not only can be precisely prepared in nanometer scale(20-70 nm),but also shows the pin-hole-free smooth surface.The high quality nano-film of 2,3,6,7,10,11-hexaiminotriphenylene(HITP)doped Cu-HHTP enables the precise modulation of the chemiresistive sensitivity and selectivity.Selectivity improvement over 220%were realized for benzene vs.NH3>as well as enhanced response and recovery properties.In addition,the selectivity of the EC-MOF thin film sensors toward other gases(e.g.triethylamine,methane,ethylbenzene,hydrogen,butanone,and acetone)vs.NH3 at room temperature is also discussed.     

Direct aerobic oxidation of monoalcohol and diols to acetals using tandem Ru@MOF catalysts

The aerobic oxidation of monoalcohols and diols to acetals is an important academic and industrial challenge for the production of fine chemicals and intermediates.The existing methods usually rely on a two-step process in which alcohols are first oxidized to aldehydes over metal catalysts(Ru,Pt,Pd)and then acetalized using acids.Due to the instability of aldehydes,how to avoid over-oxidation to their respective carboxylic acids and esters is a long-standing challenge.For this reason,certain non-conjugated dialdehydes have never been successfully produced from diol oxidation.Hereby we report a Ru@metal-organic framework(MOF)tandem catalyst containing ultra-fine Ru nanoparticles(<2 nm)for direct alcohol to acetal conversion of monoalcohol and diols with noformation of carboxylic acids.Mechanistic study reveals that the presence of Lewis acid sites in the MOF work in concert with Ru active sites to promptly convert aldehydes to acetals thereby effectively suppressing the formation of over-oxidation byproducts.     

Nanovilli electrode boosts hydrogen evolution:A surface with superaerophobicity and superhydrophilicity

Although tremendous efforts have been paid on electrocatalysts toward efficient electrochemical hydrogen generation,breakthrough is still highly needed in the design and synthesis of wonderful non-precious-metal electrocatalyst.Herein,a nanovilli Ni2P electrode,which with superaerophobic and superhydropholic can significantly facilitate the mass and electron transfer was constructed via a facial morphology control strategy.Meanwhile,the substitution of sluggish oxygen evolution with urea oxidation,lowering the two-electrode cell voltage to only 1.48 volts to achieve a current density of 10 mA·cm^-2.Thus,the as-constructed electrode achieves the operation of hydrogen generation by an AA battery.This work sheds new light on the exploration of other high-efficient electrocatalysts for hydrogen generation by using intermittent clean energy.     

Highly efficient multi-metal catalysts for carbon dioxide reduction prepared from atomically sequenced metal organic frameworks

The precise control on the combination of multiple metal atoms in the structure of metal-organic frameworks(MOFs)endowed by reticular chemistry,allows the obtaining of materials with compositions that are programmed for achieving enhanced reactivity.The present work illustrates how through the transformation of MOFs with desired arrangements of metal cations,multi-metal spinel oxides with precise compositions can be obtained,and used as catalyst precursor for the reverse water-gas shift reaction.The differences in the spinel initial composition and structure,determined by neutron powder diffraction,influence the overall catalytic activity with changes in the process of in s itu formation of active,metal-oxide supported metal nanoparticles,which have been monitored and characterized with in situ X-ray diffraction and photoelectron spectroscopy studies.     

Regulating surface state of WO3 nanosheets by gamma irradiation for suppressing hydrogen evolution reaction in electrochemical N2 fixation

Realizing the reduction of N₂ to NH₃ at low temperature and pressure is always the unremitting pursuit of scientists and then electrochemical nitrogen reduction reaction offers an intriguing alternative. Here, we develop a feasible way, gamma irradiation, for constructing defective structure on the surface of WO₃ nanosheets, which is clearly observed at the atomic scale by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The abundant oxygen vacancies ensure WO₃ nanosheets with a Faradaic efficiency of 23% at −0.3 V vs. RHE. Moreover, we start from the regulation of the surface state to suppress proton availability towards hydrogen evolution reaction (HER) on the active site and thus boost the selectivity of nitrogen reduction.

     

Graphitic nanorings for super-long lifespan lithium-ion capacitors

Porous graphitic carbon nanorings (PGCNs) are proposed by smart catalytic graphitization of nano-sized graphene quantum dots (GQDs). The as-prepared PGCNs show unique ring-like morphology with diameter around 10 nm, and demonstrate extraordinary mesoporous structure, controllable graphitization degree and highly defective nature. The mechanism from GQDs to PGCNs is proven to be a dissolution-precipitation process, undergoing the procedure of amorphous carbon, intermediate phase, graphitic carbon nanorings and graphitic carbon nanosheets. Further, the relationship between particles size of GQDs precursor and graphitization degree of PGCNs products is revealed. The unique microstructure implies PGCNs a broad prospect for energy storage application. When applied as negative electrode materials in dual-carbon lithium-ion capacitors, high energy density (77.6 Wh·kg⁻¹) and super long lifespan (89.5% retention after 40,000 cycles at 5.0 A·g⁻¹) are obtained. The energy density still maintains at 24.5 Wh·kg⁻¹ even at the power density of 14.1 kW·kg⁻¹, demonstrating excellent rate capability. The distinct microstructure of PGCNs together with the strategy for catalytic conversion from nanocarbon precursors to carbon nanorings opens a new window for carbon materials in electrochemical energy storage.

     

A robust bifunctional catalyst for rechargeable Zn-air batteries:Ultrathin NiFe-LDH nanowalls vertically anchored on soybeanderived Fe-N-C matrix

ABSTRACT NiFe layered double hydroxide(NiFe-LDH)nanosheets and metal-nitrogen-carbon materials(M-N-C,M=Ni,Fe,Co,etc.)are supreme catalysts in the oxygen evolution reaction(OER)and oxygen reduction reaction(ORR)process,respectively.Nevertheless,the monotonic performance and insufficient stability severely hamper their practical application in rechargeable batteries.Herein,we simultaneously combine ultrathin NiFe-LDH nanowalls with renewable soybean-derived Fe-N-C matrix to obtain a hybrid materials(NiFe-LDH/FeSoy-CNSs-A),which exhibits robust catalytic activities for OER(E_j=10=1.53 V vs.RHE)and ORR(E_1/2=0.91 V vs.RHE),with a top-notch battery parameters and stability in assembled rechargeable Zn-air batteries.Intensive investigations indicate that the vertically dispersed NiFe-LDH nanosheets,Fe-N-C matrix derived from soybean and the strong synergy between them are responsible for the unprecedented OER and ORR performances.The key role of intrinsic N defects involved in the hybrid materials is firstly specified by ultrasoundassisted extraction of soy protein from soybean.The exquisite design can facilitate the utilization of sustainable biomass-derived catalysts,and the mechanism investigations of N defects and oxygenic groups on the structure-activity relationship can stimulate the progress of other functional hybrid electrocatalysts.     

Panorama of boron nitride nanostructures via lamp ablation

A diverse range of remarkable boron nitride (BN) nanostructures subsuming nano-horns, nano-rods, nano-platelets, and clusters of hollow nanospheres (nano-onions, arguably of greatest applied and fundamental interest) have been produced exclusively from crystalline BN precursor powder via lamp ablation. The procedure is safe, devoid of toxic reagents, simple, rapid and scalable—generating some genres of nanoparticles that had previously proved elusive. Product structure and composition were unambiguously assessed by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy.

     

Nanomaterials for radiotherapeutics-based multimodal synergistic cancer therapy

Over the past decade, numerous studies have attempted to enhance the effectiveness of radiotherapy (external beam radiotherapy and internal radioisotope therapy) for cancer treatment. However, the low radiation absorption coefficient and radiation resistance of tumors remain major critical challenges for radiotherapy in the clinic. With the development of nanomedicine, nanomaterials in combination with radiotherapy offer the possibility to improve the efficiency of radiotherapy in tumors. Nanomaterials act not only as radiosensitizers to enhance radiation energy, but also as nanocarriers to deliver therapeutic units in combating radiation resistance. In this review, we discuss opportunities for a synergistic cancer therapy by combining radiotherapy based on nanomaterials designed for chemotherapy, photodynamic therapy, photothermal therapy, gas therapy, genetic therapy, and immunotherapy. We highlight how nanomaterials can be utilized to amplify antitumor radiation responses and describe cooperative enhancement interactions among these synergistic therapies. Moreover, the potential challenges and future prospects of radio-based nanomedicine to maximize their synergistic efficiency for cancer treatment are identified.

     

Shape-controlled synthesis of liquid metal nanodroplets for photothermal therapy

The capping agents for liquid metal (LM) nanodroplets in aqueous solutions are restricted to thiol-containing and positively-charged molecules or macromolecules. However, both thiolate-metal complex and electrostatic interaction are liable to detachment upon strong mechanical forces such as sonication, leading to limited stability and applications. To address this, we utilized ultrasmall water soluble melanin nanoparticles (MNPs) as the capping agent, which exhibited strong metal binding capability with the oxide layer of gallium based LMs and resulted in enhanced stability. Interestingly, shape-controlled synthesis of LM nanodroplets can be achieved by the incorporation of MNPs. Various EGaIn nanostructures including nanorice, nanosphere and nanorod were obtained by simply tuning the feed ratio, sonication time, and suspension temperature. Among these shapes, EGaIn nanorice has the best photothermal conversion efficiency, which could be leveraged for photothermal therapy.

     

Atomistic modeling and rational design of optothermal tweezers for targeted applications

Optical manipulation of micro/nanoscale objects is of importance in life sciences,colloidal science,and nanotechnology.Optothermal tweezers exhibit superior manipulation capability at low optical intensity.However,our implicit understanding of the working mechanism has limited the further applications and innovations of optothermal tweezers.Herein,we present an atomistic view of opto-thermo-electro-mechanic coupling in optothermal tweezers,which enables us to rationally design the tweezers for optimum performance in targeted applications.Specifically,we have revealed that the non-uniform temperature distribution induces water polarization and charge separation,which creates the thermoelectric field dominating the optothermal trapping.We further design experiments to systematically verify our atomistic simulations.Guided by our new model,we develop new types of optothermal tweezers of high performance using low-concentrated electrolytes.Moreover,we demonstrate the use of new tweezers in opto-thermophoretic separation of colloidal particles of the same size based on the difference in their surface charge,which has been challenging for conventional optical tweezers.With the atomistic understanding that enables the performance optimization and function expansion,optothermal tweezers will further their impacts.