2D TiS2-Nanosheet-Coated Concave Gold Arrays with Triple-Coupled Resonances as Sensitive SERS Substrates.

Herein, a hybrid substrate for surface-enhanced Raman scattering (SERS) is fabricated, which couples localized surface plasmon resonance (LSPR), charge transfer (CT) resonance, and molecular resonance. Exfoliated 2D TiS2 nanosheets with semimetallic properties accelerate the CT with the tested analytes, inducing a remarkable chemical mechanism enhancement. In addition, the LSPR effect is coupled with a concave gold array located underneath the thin TiS2 nanosheet, providing a strong electromagnetic enhancement. The concave gold array is prepared by etching silicone nanospheres assembled on larger polystyrene nanospheres, followed by depositing a gold layer. The LSPR intensity near the gold layer can be adjusted by changing the layer thickness to couple the molecular and CT resonances, in order to maximize the SERS enhancement. The best SERS performance is recorded on TiS2-nanosheet-coated plasmonic substrates, with a detectable methylene blue concentration down to 10-13 m and an enhancement factor of 2.1 × 109 and this concentration is several orders of magnitude lower than that of the TiS2 nanosheet (10-11 m) and plasmonic substrates (10-9 m). The present hybrid substrate with triple-coupled resonance further shows significant advantages in the label-free monitoring of curcumin (a widely applied drug for treating multiple cancers and inflammations) in serum and urine.

Atomically Thin TaSe2 Film as a High-Performance Substrate for Surface-Enhanced Raman Scattering.

An atomically thin TaSe2 sample, approximately containing two to three layers of TaSe2 nanosheets with a diameter of 2.5 cm is prepared here for the first time and applied on the detection of various Raman-active molecules. It achieves a limit of detection of 10-10  m for rhodamine 6G molecules. The excellent surface-enhanced Raman scattering (SERS) performance and underlying mechanism of TaSe2 are revealed using spectrum analysis and density functional theory. The large adsorption energy and the abundance of filled electrons close to the Fermi level are found to play important roles in the chemical enhancement mechanism. Moreover, the TaSe2 film enables highly sensitive detection of bilirubin in serum and urine samples, highlighting the potential of using 2D SERS substrates for applications in clinical diagnosis, for example, in the diagnosis of jaundice caused by excess bilirubin in newborn children.

Dopamine Imaging in Living Cells and Retina by Surface-Enhanced Raman Scattering Based on Functionalized Gold Nanoparticles.

Retinal dopamine is believed to be involved in the development of myopia, which is projected to affect almost half of the world population's visual health by 2050. Direct visualization of dopamine in the retina with high spatial precision is essential for understanding the biochemical mechanism during the development of myopia. However, there are very few approaches for the direct detection of dopamine in the visual system, particularly in the retina. Here, we report surface-enhanced Raman scattering (SERS)-based dopamine imaging in cells and retinal tissues with high spatial precision. The surface of gold nanoparticles is modified with N-butylboronic acid-2-mercaptoethylamine and 3,3'-dithiodipropionic acid di(N-hydroxysuccinimide ester), which shows excellent specific reaction with dopamine. The existence of dopamine triggers the aggregation of gold nanoparticles that subsequently form plasmonic hot spots to dramatically increase the Raman signal of dopamine. The as-synthesized SERS nanoprobes have been evaluated and applied for dopamine imaging in living cells and retinal tissues in form-deprivation (FD) myopia guinea pigs, followed by further investigation on localized dopamine levels in the FD-treated mice. The results suggest a declined dopamine level in mice retina after 2-week FD treatment, which is associated with the development of myopia. Our approach will greatly contribute to better understanding the localized dopamine level associated with myopia and its possible treatments. Furthermore, the imaging platform can be utilized to sensing other important small molecules within the biological samples.

Smart Contact Lenses for Healthcare Monitoring and Therapy.

The eye contains a wealth of physiological information and offers a suitable environment for noninvasive monitoring of diseases via smart contact lens sensors. Although extensive research efforts recently have been undertaken to develop smart contact lens sensors, they are still in an early stage of being utilized as an intelligent wearable sensing platform for monitoring various biophysical/chemical conditions. In this review, we provide a general introduction to smart contact lenses that have been developed for disease monitoring and therapy. First, different disease biomarkers available from the ocular environment are summarized, including both physical and chemical biomarkers, followed by the commonly used materials, manufacturing processes, and characteristics of contact lenses. Smart contact lenses for eye-drug delivery with advancing technologies to achieve more efficient treatments are then introduced as well as the latest developments for disease diagnosis. Finally, sensor communication technologies and smart contact lenses for antimicrobial and other emerging bioapplications are also discussed as well as the challenges and prospects of the future development of smart contact lenses.

On-mask detection of SARS-CoV-2 related substances by surface enhanced Raman scattering.

We have developed a convenient surface-enhanced Raman scattering (SERS) platform based on vertical standing gold nanowires (v-AuNWs) which enabled the on-mask detection of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) related substances such as the Spike-1 protein and the corresponding pseudo-virus. The Spike-1 protein was clearly distinguished from BSA protein with an accuracy above 99 %, and the detection limit could be achieved down to 0.01 µg/mL. Notably, a similar accuracy was achieved for the pseudo-SARS-CoV-2 (pSARS-2) virus as compared to the pseudo-influenza H7N9 (pH7N9) virus. The sensing strategy and setups could be easily adapted to the real SARS-CoV-2 virus and other highly contagious viruses. It provided a promising way to screen the virus carriers by a fast evaluation of their wearing v-AuNWs integrated face-mask which was mandatory during the pandemic.

Rapid, label-free histopathological diagnosis of liver cancer based on Raman spectroscopy and deep learning.

Biopsy is the recommended standard for pathological diagnosis of liver carcinoma. However, this method usually requires sectioning and staining, and well-trained pathologists to interpret tissue images. Here, we utilize Raman spectroscopy to study human hepatic tissue samples, developing and validating a workflow for in vitro and intraoperative pathological diagnosis of liver cancer. We distinguish carcinoma tissues from adjacent non-tumour tissues in a rapid, non-disruptive, and label-free manner by using Raman spectroscopy combined with deep learning, which is validated by tissue metabolomics. This technique allows for detailed pathological identification of the cancer tissues, including subtype, differentiation grade, and tumour stage. 2D/3D Raman images of unprocessed human tissue slices with submicrometric resolution are also acquired based on visualization of molecular composition, which could assist in tumour boundary recognition and clinicopathologic diagnosis. Lastly, the potential for a portable handheld Raman system is illustrated during surgery for real-time intraoperative human liver cancer diagnosis.

Noninvasive Diagnosis of Gastric Cancer Based on Breath Analysis with a Tubular Surface-Enhanced Raman Scattering Sensor.

SERS-based breath analysis as an emerging technique has attracted increasing attention in cancer screening. Here, eight aldehydes and ketones in the human breath are reported as the VOC biomarkers identified by gas chromatography-mass spectrometry (GC-MS) and applied further for the noninvasive diagnosis of gastric cancer (GC) with a tubular SERS sensor. The tubular SERS sensor is prepared with a glass capillary loaded with ZIF-67-coated silver particles (Ag@ZIF-67), which offers Raman enhancement from the plasmonic nanoparticles and gas enrichment from the metal-organic framework (MOF) shells. The composite materials are modified with 4-aminothiophenol (4-ATP) to capture different aldehyde and ketone compounds. The tubular sensor is served simultaneously as a gas flow channel and a detection chamber, bringing a higher gas capture efficiency than the planar SERS sensor. As a proof-of-concept, the tubular SERS sensor is successfully employed to screen gastric cancer patients with an accuracy of 89.83%, based on the noninvasive, rapid, and easily operated breath analysis. The results demonstrate that the established breath analysis method provides an excellent alternative for the screening of GC and other diseases.

Smart Contact Lens with Dual-Sensing Platform for Monitoring Intraocular Pressure and Matrix Metalloproteinase-9.

Contact lenses have become a popular health-monitoring wearable device due to their direct contact with the eyes. By integrating biosensors into contact lenses, real-time and noninvasive diagnoses of various diseases can be realized. However, current contact lens sensors often require complex electronics, which may obstruct the user's vision or even damage the cornea. Moreover, most of the reported contact lens sensors can only detect one analyte. Therefore, an optical-based dual-functional smart contact lens sensor has been introduced to monitor intraocular pressure (IOP) and detect matrix metalloproteinase-9 (MMP-9), both of which are key biomarkers in many eye-related diseases such as glaucoma. Specifically, the elevated IOP is continuously monitored by applying an antiopal structure through color changes, without any complex electronics. Together with the peptide modified gold nanobowls (AuNBs) surface-enhanced Raman scattering (SERS) substrate, the quantitative analysis of MMP-9 at a low nanomolar range is achieved in real tear samples. The dual-sensing functions are thus demonstrated, providing a convenient, noninvasive, and potentially multifunctional sensing platform for monitoring health and diagnostic biomarkers in human tears.

A miniaturized electrochemical device based on the nitrogen, carbon-codoped bimetal for real-time monitoring of acetaminophen and dopamine in urine.

In-situ real-time detection of drug metabolites and biomolecules in hospitalized patients' urine helps the doctors to monitor their physiological indicators and regulate the use of drug doses. In this work, nitrogen-doped carbon-supported bimetal was prepared into the screen-printed electrodes (SPEs) and applied for real-time monitoring of acetaminophen (AC) and dopamine (DA) in urine. Via one-step pyrolysis of the core-shell cubic precursor (Cu3[Co(CN)6]2@Co3[Co(CN)6]2, CuCo@CoCo), the nitrogen-doped carbon-supported bimetal (CuCo-NC) was formed. The bimetal composites presented twice higher catalytic activity than the counterparts with single metal. In addition, the nanocomposites exhibited strong conductivity after pyrolysis, promoting electron transport efficiency as indicated by impedance measurements. Accordingly, the CuCo-NC based sensor offered excellent sensitivity with the detection limits down to 50 nM and 30 nM at the detection range of 0.1-400 µM and 0.2-200 µM for detection of AC and DA, respectively. Finally, in combination with a miniaturized electrochemical device, the sensor was applied for in-situ real-time monitoring of AC and DA in the urinary bag for up to 12h. As compared with other techniques such as high-performance liquid chromatography, UV-spectrophotometry and fluorescence spectrometer, the biosensor demonstrated the advantages of real-time monitoring, easy operation and excellent portability. However, the multi-component detection and self-calibration function need to be further developed. This method paves a way for the continuous monitoring of drug metabolites and biomolecules of hospitalized patients.

Nesting Co3Mo Binary Alloy Nanoparticles onto Molybdenum Oxide Nanosheet Arrays for Superior Hydrogen Evolution Reaction.

Transition-metal alloys have attracted a great deal of attention as an alternative to Pt-based catalysts for hydrogen evolution reaction (HER) in alkaline. Herein, a facile and convenient strategy to fabricate Co3Mo binary alloy nanoparticles nesting onto molybdenum oxide nanosheet arrays on nickel foam is developed. By modulating the annealing time and temperature, the Co3Mo alloy catalyst displays a superior HER performance. Owing to substantial active sites of nanoparticles on nanosheets as well as the intrinsic HER activity of Co3Mo alloy and no use of binders, the obtained catalyst requires an extremely low overpotential of only 68 mV at 10 mA cm-2 in alkaline, with a corresponding Tafel slope of 61 mV dec-1. At the same time, the catalyst demonstrates excellent stability during the long-term measurements. The density functional theory calculation provides a deeper insight into the HER mechanism, unveiling that the active sites on the Co3Mo-based catalyst are Mo atoms. This strategy of combining catalytic active species with hierarchical nanoscale materials can be extended to other applications and provides a candidate of nonnoble metal catalysts for practical electrochemical water splitting.

Dual-Functional Starfish-like P-Doped Co-Ni-S Nanosheets Supported on Nickel Foams with Enhanced Electrochemical Performance and Excellent Stability for Overall Water Splitting.

Dual-functional electrocatalysts have recently been reported to improve the conversion and storage of energy generated from overall water splitting in alkaline electrolytes. Herein, for the first time, a shape-controlled synthesis of starfish-like Co-Ni-S nanosheets on three-dimensional (3D) hierarchically porous nickel foams (Co-Ni-S/NF) via a one-step hydrothermal method was developed. The influence of reaction time on the nanosheet structure and properties was intensively studied. After 11 h reaction, the Co-Ni-S/NF-11 sample displays the most regular structure of nanosheets and the most outstanding electrochemical properties. As to water splitting, hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) required overpotentials of 284.3 and 296 mV, respectively, to provide a current density of 100 mA cm-2. The marvelous electrochemical performance can be attributed to the conductive networks of 3D layered porous nickel skeletons that are highly interconnected, which provided a large specific area and highly active sites. To further enhance the electrochemical performances of the electrocatalyst, the influence of the doping of the P element was also studied. The results proved that the P-doped Co-Ni-S/NF maintains the starfish structure and demonstrates outstanding properties, providing a current density of 100 mA cm-2 with only 187.4 and 292.2 mV overpotentials for HER and OER, respectively. It exhibited far more excellent properties than reported dual-functional electrocatalysts. Additionally, when used as an overall water-splitting catalyst, P-Co-Ni-S/NF can provide a 10 mA cm-2 current density at a given cell voltage of 1.60 V in 1 M KOH, which is competitive to the best-known electrocatalysts, with high long-term stability.

A general strategy for the functionalization of two-dimensional metal chalcogenides.

Two-dimensional (2D) metal chalcogenides (MC) such as MoS2 have been recognized as promising materials for near future applications. However, general strategies to functionalize them are still scarce, while the nature of functionalization still remains unclear. Herein, we demonstrate a simple and universal functionalization route through complexation reaction between the amino-containing organic agents and MCs. Degrees of functionalization are tunable by adjusting the organic group types and ratios. No further defects are introduced and the functionalized 2D MCs are dispersible in corresponding typical solvents. Both experimental results and geometry optimization calculations indicate that the grafting of functional groups through the coordination effect truly exist, while the surface properties and resulting photoelectric properties of 2D MCs are greatly altered. More intriguingly, our proposed functionalization process is demonstrated to be universal and can be applied to different MCs, thus opening new avenues for the application of 2D MCs.

Large-scale controlled synthesis of porous two-dimensional nanosheets for the hydrogen evolution reaction through a chemical pathway.

Molybdenum disulfide (MoS2) is an extensively studied promising non-noble catalyst because of its remarkable performance for the hydrogen evolution reaction (HER). However, the primary factors that affect its catalytic activity have not been analysed comprehensively and quantitatively; this impedes the further design and development of MoS2-based electrocatalysts. Herein, using novel porous MoS2 nanosheets prepared via a controlled and scalable KOH-assisted exfoliation pathway, we methodically studied the contributions of bore edge active sites to the catalytic activity towards the HER. To make the preparation safer, 2H-MoS2 instead of 1T-MoS2 that needs to be prepared with butyllithium has been chosen to synthesize porous MoS2 nanosheets. A comparative study revealed that the overpotential of porous MoS2 nanosheets exhibited an extreme point, which was predominantly due to the different densities of bore edge active sites derived from different quantities of KOH. Amazingly, the HER performance of MoS2 nanosheets experienced the most obvious improvement after these nanosheets were treated with 37.5 wt% KOH. A series of tests and density functional theory calculations were conducted to explain the experimental results, which were consistent with each other. Furthermore, this method has been proven to be universal since porous WS2 and SnS2 nanosheets have been prepared by the same route. This study presents novel insights and reveals a new, controlled, and scalable chemical avenue for programming electrocatalysts based on MoS2 or other layered materials.

Anion-exchange engineering of cookie-like Bi2S3/Bi2MoO6 heterostructure for enhanced photocatalytic activities and gas-sensing properties.

Developing efficient visible-light-driven photocatalysts will advance alternative energy technologies, ultimately curbing the environmental pollution associated with fossil fuels. In this work, Bi2S3/Bi2MoO6 photocatalysts with a heterogeneous cookie-like structure were prepared for the first time by in-situ anion exchange at relatively low temperatures. The catalysts exhibited enhanced photocatalytic activity, which we attributed to the photocurrent response, a diminished recombination rate of photogenerated electron-hole pairs, and the existence of a large heterojunction interface. These governing factors were discerned by photoelectrochemical measurements, calculated energy band positions and photoluminescence spectra. Bi2S3/Bi2MoO6 nanocomposites also exhibit better performance in response to gas than bare Bi2MoO6 according to gas sensing tests. Our work, in relaying a feasible method to synthesize Bi2S3/Bi2MoO6-based heterojunction superstructures, and documents a universal preparation method of synthetic heterogeneous complexes, and provides necessary groundwork for the development of next generation semiconductor photocatalytic technology and gas sensor.

Surface Tension Components Ratio: An Efficient Parameter for Direct Liquid Phase Exfoliation.

Direct liquid phase exfoliation (LPE) is generally regarded as an effective and efficient methodology for preparing single- to few-layered nanosheets on a large scale. Based on a previous finding that the polar and dispersive components of surface tension can be used as critical parameters for screening suitable solvents for LPE, in this study, we conducted in-depth research on direct LPE of two-dimensional (2D) materials by the extensive LPE of a series of 2D materials and the thorough comparison of their surfaces properties and LPE efficiencies. We rationally developed the surface tension component matching (STCM) theory, and in nature, its key point lies in the close ratio of polar to dispersive components (P/D) between the solvents and the aimed 2D materials. To this end, the surface tension components ratio is demonstrated to be an effective parameter for screening LPE solvents. In addition to the optimization of the LPE process for these 2D materials, this work has further greatly enlarged the comprehensive library for the solvent and 2D material matching pairs based on the improved STCM theory.

Insight into the hydrogen evolution reaction of nickel dichalcogenide nanosheets: activities related to non-metal ligands.

Transition metal dichalcogenides, MX2 (M = Fe, Co, Ni, X = S, Se, Te), have been proven to be promising substitutes for noble metals in hydrogen evolution reactions (HERs). However, forthright comparisons of metal sulfides, metal selenides, and metal tellurides are rarely conducted, let alone the mechanism of the important role of their non-metal ligands. In this paper, we report the pilot study of a controllable method for the preparation of a series of NiX2 (X = S, Se, Te) nanosheets via a facile anion-exchange reaction. Consequently, the HER activities and stabilities of NiS2, NiSe2, and NiTe2 nanosheets were tested in both acid and alkaline solutions. The required overpotentials to reach 10 mA cm-2 in 0.5 M H2SO4 for NiS2, NiSe2, and NiTe2 were 213, 156, and 276 mV, respectively. The best performance of NiSe2 was also confirmed in 1 M KOH. Besides NiS2 and NiTe2 nanosheets, the HER properties of NiSe2 nanosheets are superior to most of the available nickel catalysts. Interestingly, the results from electrochemical measurements were found to be fully consistent with the data based on density function theory calculation. Among various factors that might influence the HER activities of nickel dichalcogenides, the free energies of hydrogen adsorption and conductivities have played important roles.

Controlled Electrodeposition Synthesis of Co-Ni-P Film as a Flexible and Inexpensive Electrode for Efficient Overall Water Splitting.

Synthesis of highly efficient and robust catalysts with earth-abundant resources for overall water splitting is essential for large-scale energy conversion processes. Herein, a series of highly active and inexpensive Co-Ni-P films were fabricated by a one-step constant current density electrodeposition method. These films were demonstrated to be efficient bifunctional catalysts for both H2 and O2 evolution reactions (HER and OER), while deposition time was deemed to be the crucial factor governing electrochemical performance. At the optimal deposition time, the obtained Co-Ni-P-2 catalyst performed remarkably for both HER and OER in alkaline media. In particular, it requires -103 mV overpotential for HER and 340 mV for OER to achieve the current density of 10 mA cm-2, with corresponding Tafel slopes of 33 and 67 mV dec-1. Moreover, it outperforms the Pt/C//RuO2 catalyst and only needs -160 mV (430 mV) overpotential for HER (OER) to achieve 200 mA cm-2 current density. Co-Ni-P electrodes were also conducted for the proof-of-concept exercise, which were proved to be flexible, stable, and efficient, further opening a new avenue for rapid synthesis of efficient, flexible catalysts for renewable energy resources.

Facile synthesis of CuCo2S4 as a novel electrode material for ultrahigh supercapacitor performance.

CuCo2S4 nanoparticles demonstrating outstanding electrochemical performances were firstly synthesized through a simple solvothermal approach without using any templates. CuCo2S4 synthesized in glycerol (CuCo2S4-glycerol) fulfills an ultrahigh capacitance of 5030 F g(-1) at 20 A g(-1) in a polysulfide electrolyte.

Cobalt-Doped FeSe2-RGO as Highly Active and Stable Electrocatalysts for Hydrogen Evolution Reactions.

Herein, we describe the preparation and testing of Co-doped FeSe2 hybridized with graphene (Fe1-xCoxSe2/RGO), a high-active yet stable electrocatalyst for hydrogen evolution reactions (HERs) in acidic solutions. First, we systematically analyze the composition and morphology of Fe1-xCoxSe2/RGO and attribute its excellent electrochemical performance to its unique architecture-a base of highly conductive graphene with fully exposed active edges that enhances conductivity and facilitates ion/electron transfer. Our experimental measurements indicate elevated HER activity with a moderate overpotential of ∼166 mV at a hydrogen production current density of 10 mA cm(-2), a small Tafel slope of ∼36 mV dec(-1), and long cycling lifespan more than 20 h. The promising results, in addition to the fact that Fe1-xCoxSe2/RGO is a high-performance, precious-metal-free electrocatalyst, pave the way for exciting opportunities in renewable hydrogen production applications.

Insight into In Situ Amphiphilic Functionalization of Few-Layered Transition Metal Dichalcogenide Nanosheets.

A facile route toward functionalized amphiphilic layered transition-metal dichalcogenide nanosheets through in situ polymerization of polystyrene-polyacrylamide copolymers is established. The attachment of copolymers greatly affects their dispersibility in different kinds of solvents. Surface-tension components, polarity, and coordination effects of the copolymer are found to be the main factors affecting the dispersibility.