Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications.

Transition metal dichalcogenides (TMDs) are a promising class of layered materials in the post-graphene era, with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior. Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties, providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs. The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable (opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts (0-100%). Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase, band alignment/structure, carrier density, and surface reactive activity, enabling novel and promising applications. This review comprehensively elaborates on atomically substitutional engineering in TMD layers, including theoretical foundations, synthetic strategies, tailored properties, and superior applications. The emerging type of ternary TMDs, Janus TMDs, is presented specifically to highlight their typical compounds, fabrication methods, and potential applications. Finally, opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.

Intrinsic Optical Properties and Emerging Applications of Gold Nanostructures.

The collective oscillation of free electrons at the nanoscale surface of gold nanostructures is closely modulated by tuning the size, shape/morphology, phase, composition, hybridization, assembly, and nanopatterning, along with the surroundings of the plasmonic surface located at a dielectric interface with air, liquid, and solid. This review first introduces the physical origin of the intrinsic optical properties of gold nanostructures and further summarizes stimuli-responsive changes in optical properties, metal-field-enhanced optical signals, luminescence spectral shaping, chiroptical response, and photogenerated hot carriers. The current success in the landscape of nanoscience and nanotechnology mainly originates from the abundant optical properties of gold nanostructures in the thermodynamically stable face-centered cubic (fcc) phase. It has been further extended by crystal phase engineering to prepare thermodynamically unfavorable phases (e.g., kinetically stable) and heterophases to modulate their intriguing phase-dependent optical properties. A broad range of promising applications, including but not limited to full-color displays, solar energy harvesting, photochemical reactions, optical sensing, and microscopic/biomedical imaging, have fostered parallel research on the multitude of physical effects occurring in gold nanostructures.

Thermoelectric Silver-Based Chalcogenides.

Heat is abundantly available from various sources including solar irradiation, geothermal energy, industrial processes, automobile exhausts, and from the human body and other living beings. However, these heat sources are often overlooked despite their abundance, and their potential applications remain underdeveloped. In recent years, important progress has been made in the development of high-performance thermoelectric materials, which have been extensively studied at medium and high temperatures, but less so at near room temperature. Silver-based chalcogenides have gained much attention as near room temperature thermoelectric materials, and they are anticipated to catalyze tremendous growth in energy harvesting for advancing internet of things appliances, self-powered wearable medical systems, and self-powered wearable intelligent devices. This review encompasses the recent advancements of thermoelectric silver-based chalcogenides including binary and multinary compounds, as well as their hybrids and composites. Emphasis is placed on strategic approaches which improve the value of the figure of merit for better thermoelectric performance at near room temperature via engineering material size, shape, composition, bandgap, etc. This review also describes the potential of thermoelectric materials for applications including self-powering wearable devices created by different approaches. Lastly, the underlying challenges and perspectives on the future development of thermoelectric materials are discussed.

BSA-assisted hydrothermal conversion of MoS2 nanosheets into quantum dots with high yield and bright fluorescence for constructing a sensing platform via dual quenching effects.

With large surface-responsive and excitation-dependent fluorescence, two-dimensional fluorescent quantum dots (QDs) have been receiving tremendous attention to develop their facile synthetic approaches and/or expand their promising applications. Here, a two-step strategy is demonstrated for high-yield production of MoS2 QDs from MoS2 powder through first sonication-driven exfoliation and subsequent hydrothermal splitting with the assistance of bovine serum albumin (BSA). Experimentally, ∼100 nm-sized MoS2 nanosheets are ultrasonically exfoliated from MoS2 powder in a BSA solution, and further hydrothermally split into âˆ¼ 8.2 nm-sized QDs (NQDs) at 200 °C. In addition to their excellent stability/dispersibility in aqueous solution, the resultant MoS2 NQDs also exhibit much brighter blue fluorescence than those synthesized by other methods. The strong fluorescence is significantly quenched by p-nitrophenol for constructing a sensitive sensor with high selectivity, which is attributed to dual quenching effects from inner filter effect (IFE) and fluorescence resonance energy transfer (FRET). Interestingly, with the increment of pH from 5 to 10, the ratio of IFE in fluorescence quenching gradually decreases accompanied by an increment of FRET ratio, resulting in the high sensitivity and responsivity for detecting p-nitrophenol at a wide range of pH. Clearly, the MoS2 NQD-based sensing approach demonstrates a promising potential for selective detection and fast analysis of pollutants in environment monitoring and security screening.

One-step synthesized amphiphilic carbon dots for the super-resolution imaging of endoplasmic reticulum in live cells.

Stimulated emission depletion (STED) microscopy provides a powerful tool for visualizing the ultrastructure and dynamics of subcellular organelles, however, the photobleaching of organelle trackers have limited the application of STED imaging in living cells. Here, we report photostable and amphiphilic carbon dots (Phe-CDs) with bright orange fluorescence via a simple one-pot hydrothermal treatment of o-phenylenediamine and phenylalanine. The obtained Phe-CDs not only had high brightness (quantum yield ∼18%) but also showed excellent photostability under ultraviolet irradiation. The CDs can quickly penetrate into cells within 2 min and are specific for intracellular ER. The further investigations by Phe-CDs revealed the reconstitution process of ER from loosely spaced tubes into a continuously dense network of tubules and sheets during cell division. Importantly, compared with the standard microscopy, STED super-resolution imaging allowed the tracking of the ER ultrastructure with a lateral resolution less than 100 nm and the pores within the ER network are clearly visible. Moreover, the three dimensional (3D) structure of ER was also successfully reconstructed from z-stack images due to the excellent photostability of Phe-CDs.

Size Effects of Electrocatalysts: More Than a Variation of Surface Area.

The efficiency of electrocatalytic reactions has been continuously improved in recent years due to the great effort in the development of electrocatalysts. A popular strategy is engineering the size of electrocatalysts for better electrochemical performance and lower cost. Nanosized electrocatalysts with high specific surface area have been widely used in state-of-the-art electrochemical devices such as fuel cells. From an engineering aspect, nanosizing electrocatalysts increases the surface area of the electrode and improves the electrode/device performance. Beyond an engineering scope, this perspective highlights the size effects of certain scientific fundamentals in electrocatalytic reactions. The paper summarizes the representative examples in studying the size effects of electrocatalysts and sheds light on the change of intrinsic properties of electrocatalysts caused by the size variation. The size effects of electrocatalysts should be investigated in terms of both engineering and fundamental aspects; that is, the observed activity change is more than a result of surface area variation, and it is interesting to investigate the link between the intrinsic activity and the properties of the catalysts.

Aqueous Synthesis, Doping, and Processing of n-Type Ag2Se for High Thermoelectric Performance at Near-Room-Temperature.

Herein, we have successfully synthesized binary Ag2Se, composite Ag0:Ag2Se, and ternary Cu+:Ag2Se through an ambient aqueous-solution-based approach in a one-pot reaction at room temperature and atmospheric pressure without involving high-temperature heating, multiple-processes treatment, and organic solvents/surfactants. Effective controllability over phases and compositions/components are demonstrated with feasibility for large-scale production through an exquisite alteration in reaction parameters especially pH for enhancing and understanding thermoelectric properties. Thermoelectric ZT reaches 0.8-1.1 at near-room-temperature for n-type Ag2Se and Cu+ doping further improves to 0.9-1.2 over a temperature range of 300-393 K, which is the largest compared to that reported by wet chemistry methods. This improvement is related to the enhanced electrical conductivity and the suppressed thermal conductivity due to the incorporation of Cu+ into the lattice of Ag2Se at very low concentrations (x%Cu+:Ag2Se, x = 1.0, 1.5, and 2.0).

Machine Learning-Driven Biomaterials Evolution.

Biomaterials is an exciting and dynamic field, which uses a collection of diverse materials to achieve desired biological responses. While there is constant evolution and innovation in materials with time, biomaterials research has been hampered by the relatively long development period required. In recent years, driven by the need to accelerate materials development, the applications of machine learning in materials science has progressed in leaps and bounds. The combination of machine learning with high-throughput theoretical predictions and high-throughput experiments (HTE) has shifted the traditional Edisonian (trial and error) paradigm to a data-driven paradigm. In this review, each type of biomaterial and their key properties and use cases are systematically discussed, followed by how machine learning can be applied in the development and design process. The discussions are classified according to various types of materials used including polymers, metals, ceramics, and nanomaterials, and implants using additive manufacturing. Last, the current gaps and potential of machine learning to further aid biomaterials discovery and application are also discussed.

Biomaterials by design: Harnessing data for future development.

Biomaterials is an interdisciplinary field of research to achieve desired biological responses from new materials, regardless of material type. There have been many exciting innovations in this discipline, but commercialization suffers from a lengthy discovery to product pipeline, with many failures along the way. Success can be greatly accelerated by harnessing machine learning techniques to comb through large amounts of data. There are many potential benefits of moving from an unstructured empirical approach to a development strategy that is entrenched in data. Here, we discuss the recent work on the use of machine learning in the discovery and design of biomaterials, including new polymeric, metallic, ceramics, and nanomaterials, and how machine learning can interface with emerging use cases of 3D printing. We discuss the steps for closer integration of machine learning to make this exciting possibility a reality.

Advances in photothermal nanomaterials for biomedical, environmental and energy applications.

Materials that exhibit photothermal effect have attracted enormous research interests due to their ability to strongly absorb light and effectively transform it into heat for a wide range of applications in biomedical, environmental and energy related fields. The past decade has witnessed significant advances in the preparation of a variety of photothermal materials, mainly due to the emergence of many nano-enabled new materials, such as plasmonic metals, stoichiometric/non-stoichiometric semiconductors, and the newly emerging MXenes. These photothermal nanomaterials can be hybridized with other constituents to form functional hybrids or composites for achieving enhanced photothermal performance. In this review, we present the fundamental insight of inorganic photothermal materials, including their photothermal conversion mechanisms/properties as well as their potential applications in various fields. Emphasis is placed on strategic approaches for improving their light harvesting and photothermal conversion capabilities through engineering their nanostructured size, shape, composition, bandgap and so on. Lastly, the underlying challenges and perspectives for future development of photothermal nanomaterials are proposed.

Metal-facilitated Photocatalytic Nanohybrids: Rational Design and Promising Environmental Applications.

As a promising technique to potentially address the energy crisis and environmental issues, photocatalysis has been reported widely to exhibit various outstanding behaviors in production of new fuels/chemicals and treatment of contaminants. The photocatalytic performance is extremely dependent on the used photocatalysts, so that the design and preparation of efficient photocatalysts are critically important for significantly improving the photocatalytic activity. Among various strategies, the hybridization of metal with semiconductors has recently been attracting more and more research interest owing to their expended spectral absorption, promoted transferring rate of charge carriers and Plasmon-enhanced effect. In this minireview, the metal-facilitated hybrid photocatalysts are overviewed comprehensively to first reveal unique functions of metals in improvement of photoactivity and summarize the emerging metal-involved hybrid systems. Subsequently, the synthetic methods towards hybrid photocatalysts are introduced and their practical applications are emphasized in environmental remediation including degradation of organic pollutants, conversion of harmful gases, treatment of heavy metal ions and sterilization of bacteria. At the end, the challenges for industrializing these hybrid photocatalysts are discussed carefully and future development is suggested rationally.

Revealing the signaling regulation of hydrogen peroxide to cell pyroptosis using a ratiometric fluorescent probe in living cells.

A ratiometric fluorescent probe with a large emission shift was developed for the accurate measurement of hydrogen peroxide (H2O2) in sophisticated pyroptosis signaling pathways. The results reported here demonstrate that H2O2, as a principal member of ROS, is a critical upstream signaling molecule in regulating pyroptosis.

Synthesis and optical and electronic properties of one-dimensional sulfoxonium-based hybrid metal halide (CH3)3SOPbI3.

We report the synthesis and optical and electronic properties of a one-dimensional sulfoxonium-based hybrid metal halide in an orthorhombic crystal system with a Pnma space group. To provide direct insights, a method is developed to calculate tolerance factors with the ionic radii of non-spherical cations from X-ray crystallographic data.

Plasmonically Modulated Gold Nanostructures for Photothermal Ablation of Bacteria.

With the wide utilization of antibiotics, antibiotic-resistant bacteria have been often developed more frequently to cause potential global catastrophic consequences. Emerging photothermal ablation has been attracting extensive research interest for quick/effective eradication of pathogenic bacteria from contaminated surroundings and infected body. In this field, anisotropic gold nanostructures with tunable size/morphologies have been demonstrated to exhibit their outstanding photothermal performance through strong plasmonic absorption of near-infrared (NIR) light, efficient light to heat conversion, and easy surface modification for targeting bacteria. To this end, this review first introduces thermal treatment of infectious diseases followed by photothermal therapy via heat generation on NIR-absorbing gold nanostructures. Then, the usual synthesis and spectral features of diversified gold nanostructures and composites are systematically overviewed with the emphasis on the importance of size, shape, and composition to achieve strong plasmonic absorption in NIR region. Further, the innovated photothermal applications of gold nanostructures are comprehensively demonstrated to combat against bacterial infections, and some constructive suggestions are also discussed to improve photothermal technologies for practical applications.

An azacyclo-localizing fluorescent probe for the specific labeling of lysosome and autolysosome.

Understanding lysosome-related physiology needs specific lysosome probes to track the biological processes of lysosome in living cells. Here, we report an azacyclo-modified fluorescent probe that has a large Stokes shift, good photostability and negligible cytotoxicity for highly specific labeling of lysosome and autolysosome in living cells. The probes with different kinds of azacyclo groups on parent dye dansyl are screened to show that dansyl-cycleanine (DNS-C) with four nitrogen atoms possesses the best lysosome-localized ability. And DNS-C as a universal tracker exhibits excellent ability for lysosome labeling in different cell lines with high overlap coefficients (≥0.90). Different from a commercially available LysoTracker, the Stokes shift of DNS-C up to 240 nm (λex/em = 330/570 nm), is much larger than that of LysoTracker ~20 nm (λex/em = 573/595 nm). More importantly, the fluorescence of DNS-C keeps still high brightness after a time-lapsed imaging for 40 min in living cells, implying its remarkable photostability for long-term tracking. In addition, DNS-C can also clearly image the autolysosome, a critical subcellular compartment, forming by the fusion of lysosome with autophagosome in autophagy. These results suggest the promising utility of our probe as a powerful tool to real-time trace physiological processes of lysosomes.

Functionalized Hybridization of 2D Nanomaterials.

The discovery of graphene and subsequent verification of its unique properties have aroused great research interest to exploit diversified graphene-analogous 2D nanomaterials with fascinating physicochemical properties. Through either physical or chemical doping, linkage, adsorption, and hybridization with other functional species into or onto them, more novel/improved properties are readily created to extend/expand their functionalities and further achieve great performance. Here, various functionalized hybridizations by using different types of 2D nanomaterials are overviewed systematically with emphasis on their interaction formats (e.g., in-plane or inter plane), synergistic properties, and enhanced applications. As the most intensely investigated 2D materials in the post-graphene era, transition metal dichalcogenide nanosheets are comprehensively investigated through their element doping, physical/chemical functionalization, and nanohybridization. Meanwhile, representative hybrids with more types of nanosheets are also presented to understand their unique surface structures and address the special requirements for better applications. More excitingly, the van der Waals heterostructures of diverse 2D materials are specifically summarized to add more functionality or flexibility into 2D material systems. Finally, the current research status and faced challenges are discussed properly and several perspectives are elaborately given to accelerate the rational fabrication of varied and talented 2D hybrids.

Graphene Oxide: From Tunable Structures to Diverse Luminescence Behaviors.

Since the first discovery of luminescent graphene oxide (GO), exponentially increasing investigations on the tunable structures and surfaces for modulating its optical properties have struggled to expand applications in imaging, sensing, biomedical diagnostics, and so on. Here, the latest works on reconstructing or modifying the structures and surfaces of GO to achieve diverse luminescence are systematically reviewed, including fluorescence, electroluminescence, and chemiluminescence. Moreover, the fundamental difficulties of the investigations and applications of luminescent GO nanomaterials are clarified to inspire more constructive thoughts for expanding their application boundaries.

Membrane-Penetrating Carbon Quantum Dots for Imaging Nucleic Acid Structures in Live Organisms.

The dynamics of DNA and RNA structures in live cells are important for understanding cell behaviors, such as transcription activity, protein expression, cell apoptosis, and hereditary disease, but are challenging to monitor in live organisms in real time. The difficulty is largely due to the lack of photostable imaging probes that can distinguish between DNA and RNA, and more importantly, are capable of crossing multiple membrane barriers ranging from the cell/organelle to the tissue/organ level. We report the discovery of a cationic carbon quantum dot (cQD) probe that emits spectrally distinguishable fluorescence upon binding with double-stranded DNA and single-stranded RNA in live cells, thereby enabling real-time monitoring of DNA and RNA localization and motion. A surprising finding is that the probe can penetrate through various types of biological barriers in vitro and in vivo. Combined with standard and super-resolution microscopy, photostable cQDs allow time-lapse imaging of chromatin and nucleoli during cell division and Caenorhabditis elegans (C. elegans) growth.

Morphological Growth and Theoretical Understanding of Gold and Other Noble Metal Nanoplates.

For the last decades, the chemical reduction of Au3+ to Au0 has been widely employed to produce various gold nanostructures. In comparison with the fast reduction, the slow reduction is systematically investigated in this research to provide more insights to reveal intermediary process and further disclose the underlying mechanism for growing gold nanostructures by using a series of simple ligands with aldehyde groups as weak reducing agents. The different binding energies of ligands to Aun+ (n=3, 1 and 0) exhibit variable binding affinities in starting, intermediate, and final gold species. For example, formic acid has much stronger binding affinity to Au+ than Au3+ , and thus Au+ intermediate is able to be stabilized/captured during slow reduction of Au3+ . Upon the disproportionation of Au+ to Au0 and Au3+ , formic acid has much stronger binding affinity to the newly formed Au0 than other ligands for the controlled formation of gold nanostructures. Meanwhile, the adsorption of ligands causes substantially decreased surface energies on different gold planes. There are much higher energies on {110} planes compared to the other two {111} and {100} planes with certain ratios in these energies, leading to morphological growth of gold nanosheets. In this paper, we experimentally demonstrate anisotropic growth of gold nanosheets by using various ligands with weak reducing and appropriate coordination capabilities, and further provide insights to understand their morphological growth mechanism behind. This synthetic strategy is successfully extended to prepare silver, palladium, and platinum nanoplates.