g-C3N4/Pt/BiVO4 nanocomposites for highly efficient visible-light photocatalytic removal of contaminants and hydrogen generation.

Inspired by natural photosynthesis, artificial heterojunction photocatalysts have been extensively studied. Herein, a novel ternary graphitic carbon nitride/platinum/bismuth vanadate (g-C3N4/Pt/BiVO4) photocatalytic system was successfully synthesized, where Pt/BiVO4 nanosheet is anchored on the surface of layered g-C3N4, as evidenced by structural observations. Ultraviolet photoelectron spectroscopy and ultraviolet-visible diffuse reflectance spectroscopy are carried out to identify the position of the conduction band and valence band. A Z-scheme is used to interpret the superior photocatalytic performance of g-C3N4/Pt/BiVO4 and further verified by the capture of free radicals and terephthalic acid photoluminescence experiments. Compared with the g-C3N4/BiVO4 binary system, the Z-scheme g-C3N4/Pt/BiVO4 photocatalyst not only possesses enhanced carrier separation efficiency but also maintains sufficient redox properties, thus inducing superior photocatalytic activity. More importantly, the novel Z-scheme photocatalyst exhibits excellent recycle stability, which could provide inspiration for the rational design of efficient and practical photocatalysts for environmental pollution treatment. The ternary photocatalyst also exhibits significantly enhanced visible-light photocatalytic hydrogen production performance.

Al-based metal organic framework derived self-assembled carbon nanosheets as innovative anodes for Li- and Na-ion batteries.

Functional modification and structural design of carbon electrode materials are considered as a cost-effective method to improve their electrochemical performance. In this study, a solvothermal method is applied to realize self-assembly of the metal-organic framework. After simple carbonization and acid treatment, carbon nanosheets with 2D adjustable defective sub-units are successfully prepared for the first time. It is found that carbonization temperature has a significant effect on the carbon skeleton structure. The optimal nanostructures with large specific surface area and appropriate pore size distribution make self-assembled carbon nanosheets having excellent Li/Na-ion storage properties. In addition, the adjustable carbon skeleton structure can effectively avoid irreversible damage when charge-discharge cycles. For Li-ion batteries, a specific capacity of 825 mAh g-1 is achieved after 100 cycles at 100 mA g-1, while for Na-ion batteries a specific capacity of 193 mAh g-1 is observed after 100 cycles at 100 mA g-1. Moreover, for Na-ion batteries, even at a high rate of 1000 mA g-1 the material delivers a specific capacity of 109.5 mAh g-1 after 3500 cycles.

Plasmonic Interferometer Array Biochip as a New Mobile Medical Device for Cancer Detection.

We report a plasmonic interferometer array (PIA) sensor and demonstrate its ability to detect circulating exosomal proteins in real-time with high sensitivity and low cost to enable the early detection of cancer. Specifically, a surface plasmon wave launched by the nano-groove rings interferes with the free-space light at the output of central nano-aperture and results in an intensity interference pattern. Under the single-wavelength illumination, when the target exosomal proteins are captured by antibodies bound on the surface, the biomediated change in the refractive index between the central aperture and groove rings causes the intensity change in transmitted light. By recording the intensity changes in real-time, one can effectively screen biomolecular binding events and analyze the binding kinetics. By integrating signals from multiple sensor pairs to enhance the signal-to-noise ratio, superior sensing resolutions of 1.63×10-6 refractive index unit (RIU) in refractive index change and 3.86×108 exosomes/mL in exosome detection were realized, respectively. Importantly, this PIA sensor can be imaged by a miniaturized microscope system coupled with a smart phone to realize a portable and highly sensitive healthcare device. The sensing resolution of 9.72×109 exosomes/mL in exosome detection was realized using the portable sensing system building upon a commercial smartphone.

Flat metallic surface gratings with sub-10 nm gaps controlled by atomic-layer deposition.

Atomic layer lithography is a recently reported new technology to fabricate deep-subwavelength features down to 1-2 nm, based on combinations of electron beam lithography (EBL) and atomic layer deposition (ALD). However, the patterning area is relatively small as limited by EBL, and the fabrication yield is not very high due to technical challenges. Here we report an improved procedure to fabricate flat metallic surfaces with sub-10 nm features based on ALD processes. To demonstrate the scalability of the new manufacturing method, we combine the ALD process with large area optical interference patterning, which is particularly promising for the development of practical applications for nanoelectronics and nanophotonics with extremely strong confinement of electromagnetic fields.

Nanocavity absorption enhancement for two-dimensional material monolayer systems.

Here we propose a strategy to enhance the light-matter interaction of two-dimensional (2D) material monolayers based on strong interference effect in planar nanocavities, and overcome the limitation between optical absorption and the atomically-thin thickness of 2D materials. By exploring the role of spacer layers with different thicknesses and refractive indices, we demonstrate that a nanocavity with an air spacer layer placed between a graphene monolayer and an aluminum reflector layer will enhance the exclusive absorption in the graphene monolayer effectively, which is particularly useful for the development of atomically-thin energy harvesting/conversion devices.

Simultaneous Detection of Tumor Derived Exosomal Protein-MicroRNA Pairs with an Exo-PROS Biosensor for Cancer Diagnosis.

Tumor derived exosomes (TEXs) have emerged as promising biomarkers for cancer liquid biopsy. Conventional methods (such as ELISA and qRT-PCR) and emerging biosensing technologies mainly detect a single type of exosomal biomarker due to the distinct properties of different biomolecules. Sensitive detection of two different types of TEX biomarkers, i.e., protein and microRNA combined biomarkers, may greatly improve cancer diagnostic accuracy. We developed an exosome protein microRNA one-stop (Exo-PROS) biosensor that not only selectively captured TEXs but also enabled in situ, simultaneous detection of TEX protein-microRNA pairs via a surface plasmon resonance mechanism. Exo-PROS assay is a fast, reliable, low sample consumption, and user-friendly test. With a total of 175 cancer patients and normal controls, we demonstrated that TEX protein-microRNA pairs measured by Exo-PROS assay detected lung cancer and breast cancer with 99% and 96% accuracy, respectively. Exo-PROS assay also showed superior diagnostic performance to conventional ELISA and qRT-PCR methods. Our results demonstrated that Exo-PROS assay is a potent liquid biopsy assay for cancer diagnosis.

A Compact Surface Plasmon Resonance Biosensor for Sensitive Detection of Exosomal Proteins for Cancer Diagnosis.

Exosomes are nanosized (50-150 nm) extracellular vesicles released by all types of cells in the body. They transport various biological molecules, such as DNAs, RNAs, proteins, and lipids from parent cells to recipient cells for intercellular communication. Exosomes, especially those from tumor cells, are actively involved in caner development, metastasis, and drug resistance. Recently, many studies have shown that exosomal proteins are promising biomarkers for cancer screening, early detection and prognosis. Among many detection techniques, surface plasmon resonance (SPR) is a highly sensitive, label-free, and real-time optical detection method. Commercial prism-based wavelength/angular-modulated SPR sensors afford high sensitivity and resolution, but their large footprint and high cost limit their adaptability for clinical settings. We have developed an intensity-modulated, compact SPR biosensor (25 cm × 10 cm × 25 cm) for the detection of exosomal proteins. We have demonstrated the potential application of the compact SPR biosensor in lung cancer diagnosis using exosomal epidermal growth factor receptor (EGFR) and programmed death-ligand 1 (PD-L1) as biomarkers. The compact SPR biosensor offers sensitive, simple, fast, user-friendly, and cost-effective detection of exosomal proteins, which may serve as an in vitro diagnostic test for cancer.

Super-Resolution Displacement Spectroscopic Sensing over a Surface "Rainbow".

Subwavelength manipulation of light waves with high precision can enable new and exciting applications in spectroscopy, sensing, and medical imaging. For these applications, miniaturized spectrometers are desirable to enable the on-chip analysis of spectral information. In particular, for imaging-based spectroscopic sensing mechanisms, the key challenge is to determine the spatial-shift information accurately (i.e., the spatial displacement introduced by wavelength shift or biological or chemical surface binding), which is similar to the challenge presented by super-resolution imaging. Here, we report a unique "rainbow" trapping metasurface for on-chip spectrometers and sensors. Combined with super-resolution image processing, the low-setting 4× optical microscope system resolves a displacement of the resonant position within 35 nm on the plasmonic rainbow trapping metasurface with a tiny area as small as 0.002 mm2. This unique feature of the spatial manipulation of efficiently coupled rainbow plasmonic resonances reveals a new platform for miniaturized on-chip spectroscopic analysis with a spectral resolution of 0.032 nm in wavelength shift. Using this low-setting 4× microscope imaging system, we demonstrate a biosensing resolution of 1.92 × 109 exosomes per milliliter for A549-derived exosomes and distinguish between patient samples and healthy controls using exosomal epidermal growth factor receptor (EGFR) expression values, thereby demonstrating a new on-chip sensing system for personalized accurate bio/chemical sensing applications.

Polyvinyl Alcohol/Graphene Oxide Interlayer for Enhancing Adhesive Performance of HA Coating on C/C Composites Prepared by Hydrothermal Electrodeposition/Hydrothermal Treatment.

Hydroxyapatite (HA) coatings directly deposited by hydrothermal electrochemical technology (HET) onto carbon/carbon (C/C) composites exhibited a catastrophic failure occurring at the interface of the HA and C/C. To overcome this problem, a polyvinyl alcohol (PVA)/graphene oxide (GO) interlayer (P/G interlayer) was applied on the (NH4)2S2O8-pretreated C/C substrate (named P/G-C/C) by using a dipping method. Subsequently, a calcium phosphate coating was deposited on P/G-C/C, shortened as M-P/G-C/C, by HET, and then converted into HA coating (abbreviated as HA-P/G-C/C) through posthydrothermal treatment. For comparison, HA coating was prepared onto C/C without a P/G interlayer through the same process, which was denoted as HA-C/C. The composition, microstructure, and morphology of the samples were characterized by X-ray diffractometry (XRD), energy-dispersive spectroscopy (EDS), scanning electron microscopy (SEM), Raman spectra, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS). The adhesive performance of the coatings on C/C was measured by a scratch test. Finally, an in vitro bioactivity of the coatings was evaluated in a simulated body fluid solution at 37 °C. Results showed no apparent differences in the morphology and phase of the posttreated coatings, both of which are composed of a dense structure containing needle-like HA crystals. However, the HA-P/G-C/C sample possessed a higher Ca/P ratio and denser interface, thereby exhibiting higher adhesive performance and better bioactivity. The adhesive strength of the HA-P/G coating was observed at a critical load of 41.04 N, which increased by 29.3% relative to the HA coating. Moreover, the failure site was on the HA-P/G coating rather than at the interface. The enhanced adhesive performance was ascribed to the PVA/GO-repairing pits on C/C and PVA and GO toughening effects on the HA coating. In vitro and in vivo tests revealed no statistical significance for the two HA-coated C/C samples, although the HA-P/G coating exhibited better bioactivity, inducing the growth of bonelike apatite than the HA coating.

A Novel Bi2MoO6/ZIF-8 Composite for Enhanced Visible Light Photocatalytic Activity.

A series of novel Bi2MoO6/zeolitic imidazolate framework-8 (ZIF-8) photocatalysts have been successfully fabricated through a facile self-assembly process. X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-vis spectrophotometry, and X-ray photoelectron spectroscopy (XPS) characterized pure Bi2MoO6, pure ZIF-8, and a series of Bi2MoO6/ZIF-8 composites. The result indicated that, when compared with pure Bi2MoO6, the composite of Bi2MoO6/ZIF-8 exhibited excellent photocatalytic performance for the degradation of methylene blue (MB) under visible light. Moreover, the Bi2MoO6/ZIF-8-3 composite (the molar ratio of Bi2MoO6 to 2-MI is 3:3) has optimum photocatalytic performance because of the suitable amount of ZIF-8 decorated on the flower-like Bi2MoO6. The enhanced photocatalytic activity is probably due to the introduction of ZIF-8, which will promote the separation of electron-hole pair and the surface morphology. Benefitting from the diversity of the MOF species (ZIF-8 is one of them), this composing strategy of Bi2MoO6/MOF composite would provide new insight into the design of highly efficient visible light photocatalysts.

Intensity-modulated nanoplasmonic interferometric sensor for MMP-9 detection.

To elucidate the secretary function of immune cells, we develop a nanoplasmonic circular interferometric biosensor based on intensity interrogation for label-free and dynamic sensing of molecular secretion. Exceptional sensitivity has been demonstrated through coupling free light and surface plasmon polariton (SPPs) waves, which generates a constructive and deconstructive interference pattern with high contrast and narrow linewidth when illuminated by white light. Alternatively, by adopting a narrow-band LED source and a CCD camera in this work, the transmission intensity of multiple sensing units is monitored simultaneously with a simple collinear optical setup. This intensity-modulated sensing platform yields a resolution of 4.1 × 10-5 refractive index unit (RIU) with a high temporal resolution of 1 s and a miniaturized footprint as small as 9.8 × 9.8 µm2 for a single sensing unit. By integrating the signals from multiple sensor units, the resolution of a 12 × 12 sensor array was found to reach 7.3 × 10-6 RIU. We apply this sensor array to detect matrix metalloproteinase 9 (MMP-9) secretion from human monocytic cells, THP-1, at different time points after lipopolysaccharide (LPS) simulation and the results are in good agreement with enzyme-linked immunosorbent assay (ELISA) tests, but without the need for labeling. The spatial, temporal and mass resolutions of the sensor array are found to exceed other label-free technologies. These biomolecular arrays, incorporated in a microfluidic sensor platform, hold great potential for the study the dynamics and interplay of cell secretion signals and achieving a better understanding of single cell functions.

Enhanced Visible Light Driven Photocatalytic Behavior of BiFeO3/Reduced Graphene Oxide Composites.

BiFeO3/Reduced Graphene Oxide (BFO/RGO) composites have been fabricated by a simple hydrothermal method. The X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman, and X-ray photoelectron spectroscopy (XPS) analysis reveal that graphene oxide was reduced in hydrothermal process and BFO/RGO composites were successfully synthesized. UV-visible absorption and photoluminescence properties show that the introduction of RGO can effectively reduce the recombination of photogenerated electron and hole pairs. Compared to the pristine BFO, the photocatalytic performance of BiFeO3 Graphene Oxide (BGO) composites is enhanced for the degradation of Methylene blue (MB) solution under visible light irradiation, and the result shows that the optimal amount of Graphene Oxide (GO) in the composites is 60 mg (BGO60). The excellent photocatalytic performance is mainly ascribed to improved light absorption, increased reactive sites, and the low recombination rate of electron-hole pairs. This work can provide more insights into designing advanced photocatalysts for wastewater treatment and environmental protection.

Cold Vapor Generation beyond the Input Solar Energy Limit.

100% efficiency is the ultimate goal for all energy harvesting and conversion applications. However, no energy conversion process is reported to reach this ideal limit before. Here, an example with near perfect energy conversion efficiency in the process of solar vapor generation below room temperature is reported. Remarkably, when the operational temperature of the system is below that of the surroundings (i.e., under low density solar illumination), the total vapor generation rate is higher than the upper limit that can be produced by the input solar energy because of extra energy taken from the warmer environment. Experimental results are provided to validate this intriguing strategy under 1 sun illumination. The best measured rate is ≈2.20 kg m-2 h-1 under 1 sun illumination, well beyond its corresponding upper limit of 1.68 kg m-2 h-1 and is even faster than the one reported by other systems under 2 sun illumination.

Sensitive Detection of Exosomal Proteins via a Compact Surface Plasmon Resonance Biosensor for Cancer Diagnosis.

Exosomes are small extracellular vesicles released by cells for cell-cell communication. They play important roles in cancer development, metastasis, and drug resistance. Exosomal proteins have been demonstrated by many studies as promising biomarkers for cancer screening, diagnosis, and monitoring. Among many detection techniques, surface plasmon resonance (SPR) is a highly sensitive, label-free, and real-time optical detection method. Commercial prism-based wavelength/angular-modulated SPR sensors afford high sensitivity and resolution, but their large footprint and high cost limit their adaptability for clinical settings. Recently, a nanoplasmonic exosome (nPLEX) assay was developed to detect exosomal proteins for ovarian cancer diagnosis. However, comparing with conventional SPR biosensors, the broad applications of nanoplasmonic biosensors are limited by the difficult and expensive fabrication of nanostructures. We have developed an intensity-modulated, compact SPR biosensor (25 cm × 10 cm × 25 cm) which uses a conventional SPR sensing mechanism and does not require nanostructure fabrication. Calibration from glycerol showed that the compact SPR biosensor offered sensitivity of 9.258 × 103%/RIU and resolution of 8.311 × 10-6 RIU. We have demonstrated the feasibility of the compact SPR biosensor in lung cancer diagnosis using exosomal epidermal growth factor receptor (EGFR) and programmed death-ligand 1 (PD-L1) as biomarkers. It detected a higher level of exosomal EGFR from A549 nonsmall cell lung cancer (NSCLC) cells than BEAS-2B normal cells. With human serum samples, the compact SPR biosensor detected similar levels of exosomal EGFR in NSCLC patients and normal controls, and higher expression of exosomal PD-L1 in NSCLC patients than normal controls. The compact SPR biosensor showed higher detection sensitivity than ELISA and similar sensing accuracy as ELISA. It is a simple and user-friendly sensing platform, which may serve as an in vitro diagnostic test for cancer.

Conducting polymer-coated MIL-101/S composite with scale-like shell structure for improving Li-S batteries.

Lithium-sulfur batteries are regarded as a promising energy storage system. However, they are plagued by rapid capacity decay, low coulombic efficiency, a severe shuttle effect and low sulfur loading in cathodes. To address these problems, effective carriers are highly demanded to encapsulate sulfur in order to extend the cycle life. Herein, we introduced a doped-PEDOT:PSS-coated MIL-101/S multi-core-shell structured composite. The unique structure of MIL-101, large specific area and conductive shell ensure high dispersion of sulfur in the composite and minimize the loss of polysulfides to the electrolyte. The doped-PEDOT:PSS-coated sulfur electrodes exhibited an increase in initial capacity and an improvement in rate characteristics. After 192 cycles at the current density of 0.1C, a doped-PEDOT:PSS-coated MIL-101/S electrode maintained a capacity of 606.62 mA h g-1, while the MIL-101/S@PEDOT:PSS electrode delivered a capacity of 456.69 mA h g-1. The EIS measurement revealed that the surface modification with the conducting polymer provided a lower resistance to the sulfur electrode, which resulted in better electrochemical behaviors in Li-S battery applications. Test results indicate that the MIL-101/S@doped-PEDOT:PSS is a promising host material for the sulfur cathode in the lithium-sulfur battery applications.

Frozen "Tofu" Effect: Engineered Pores of Hydrophilic Nanoporous Materials.

Frozen tofu is a famous Asian food made by freezing soft bean curds, which are naturally porous to store flavor and nutrients. When the narrow pores of the soft bean curd are saturated with water and then frozen, pore widths expand to generate a completely new porous structure-frozen tofu has visibly wider pores than the initial bean curd. Intriguingly, this principle can be generalized and applied to manipulate micro/nanopores of functional porous materials. In this work, we will manipulate the pore size of nanoporous polymeric photonic crystals based on the phase change between water and ice. Wet-drying and freeze-drying methods were applied to shrink or expand the pore size intentionally. This principle is validated by directly observing the optical reflection peak shift of the material. Owing to the change in pore size, the reflection peak of the polymeric photonic crystal structure can be permanently, and intentionally, tuned. This simple but elegant mechanism is promising for the development of smart materials/devices for applications ranging from oil/water membrane separations, health monitoring, and medical diagnostics to environmental monitoring, anticounterfeiting, and smart windows.

Ultra-broadband enhancement of nonlinear optical processes from randomly patterned super absorbing metasurfaces.

Broadband light trapping and field localization is highly desired in enhanced light-matter interaction, especially in harmonic generations. However, due to the limited resonant bandwidth, most periodic plasmonic nanostructures cannot cover both fundamental excitation wavelength and harmonic generation wavelength simultaneously. Therefore, most previously reported plasmonic nonlinear optical processes are low in conversion efficiency. Here, we report a strong enhancement of second harmonic generation based on a three-layered super absorbing metasurface structure consisting of a dielectric spacer layer sandwiched by an array of random metallic nanoantennas and a metal ground plate. Intriguingly, the strong light trapping band (e.g. >80%) was realized throughout the entire visible to near-infrared spectral regime (i.e., from 435 nm to 1100 nm), enabling plasmonically enhanced surface harmonic generation and frequency mixing across a broad range of excitation wavelengths, which cannot be achieved with narrow band periodic plasmonic structures. By introducing hybrid random antenna arrays with small metallic nanoparticles and ultra-thin nonlinear optical films (e.g. TiO2) into the nanogaps, the nonlinear optical process can be further enhanced. This broadband light-trapping metastructure shows its potential as a building block for emerging nonlinear optical meta-atoms.

Extremely Cost-Effective and Efficient Solar Vapor Generation under Nonconcentrated Illumination Using Thermally Isolated Black Paper.

Passive solar vapor generation represents a promising and environmentally benign method of water purification/desalination. However, conventional solar steam generation techniques usually rely on costly and cumbersome optical concentration systems and have relatively low efficiency due to bulk heating of the entire liquid volume. Here, an efficient strategy using extremely low-cost materials, i.e., carbon black (powder), hydrophilic porous paper, and expanded polystyrene foam is reported. Due to the excellent thermal insulation between the surface liquid and the bulk volume of the water and the suppressed radiative and convective losses from the absorber surface to the adjacent heated vapor, a record thermal efficiency of ≈88% is obtained under 1 sun without concentration, corresponding to the evaporation rate of 1.28 kg (m2 h)-1. When scaled up to a 100 cm2 array in a portable solar water still system and placed in an outdoor environment, the freshwater generation rate is 2.4 times of that of a leading commercial product. By simultaneously addressing both the need for high-efficiency operation as well as production cost limitations, this system can provide an approach for individuals to purify water for personal needs, which is particularly suitable for undeveloped regions with limited/no access to electricity.

Phase change dispersion of plasmonic nano-objects.

Phase is an inherent and important feature for coherent processes, which, unfortunately, has not been completely understood for surface plasmon polariton (SPP) and matter interactions. Here we propose a practical approach to extract the phase change dispersion during the interaction between free-space light, SPPs and nanogroove/slit based on far-field information only. Numerical simulation and experimental validation were both presented using nanoslit-groove plasmonic interferometers, agreeing well with theoretical near-field analysis. This approach is generally feasible to extract the intrinsic phase dispersion of other plasmonic nanostructures and can reveal more fundamental features of SPP-matter interactions.

Holographic photopolymer linear variable filter with enhanced blue reflection.

A single beam one-step holographic interferometry method was developed to fabricate porous polymer structures with controllable pore size and location to produce compact graded photonic bandgap structures for linear variable optical filters. This technology is based on holographic polymer dispersed liquid crystal materials. By introducing a forced internal reflection, the optical reflection throughout the visible spectral region, from blue to red, is high and uniform. In addition, the control of the bandwidth of the reflection resonance, related to the light intensity and spatial porosity distributions, was investigated to optimize the optical performance. The development of portable and inexpensive personal health-care and environmental multispectral sensing/imaging devices will be possible using these filters.