Nanowire-in-bowl-shaped piezoelectric cavity structure for SERS directional detection of nanoplastics less than 50†nm.

The accurate detection of nanoplastics is crucial due to their harmful effects on the environment and human beings. However, there is a lack of detection methods for nanoplastics smaller than 50 nm. In this research, we successfully constructed an Ag/CuO nanowire (NW)/BaTiO3@Polyvinylidene fluoride (PVDF) Bowl-shaped substrate with a nanowire-in-Bowl-shaped piezoelectric cavity structure that can modulate surface-enhanced Raman scattering (SERS) by the piezoelectric effect by the virtue of the tip effect of the CuO NW and light focusing effect of the Bowl-shaped cavity. Due to its unique nanowire-in-Bowl-shaped structure and piezoelectrically modifiable ability, nanoplastics less than 50 nm were successfully detected and quantitatively analyzed. We believe that the Ag/CuO NW/BaTiO3@PVDF Bowl-shaped substrate can provide an efficient, accurate, and feasible way to achieve qualitative and quantitative detection of nanoplastics.

Review on two-dimensional material-based field-effect transistor biosensors: accomplishments, mechanisms, and perspectives.

Field-effect transistor (FET) is regarded as the most promising candidate for the next-generation biosensor, benefiting from the advantages of label-free, easy operation, low cost, easy integration, and direct detection of biomarkers in liquid environments. With the burgeoning advances in nanotechnology and biotechnology, researchers are trying to improve the sensitivity of FET biosensors and broaden their application scenarios from multiple strategies. In order to enable researchers to understand and apply FET biosensors deeply, focusing on the multidisciplinary technical details, the iteration and evolution of FET biosensors are reviewed from exploring the sensing mechanism in detecting biomolecules (research direction 1), the response signal type (research direction 2), the sensing performance optimization (research direction 3), and the integration strategy (research direction 4). Aiming at each research direction, forward perspectives and dialectical evaluations are summarized to enlighten rewarding investigations.

Plasmonic enhanced piezoelectric photoresponse with flexible PVDF@Ag-ZnO/Au composite nanofiber membranes.

The coordination of piezoelectric and plasmonic effects to regulate the separation and migration of photo-generated carriers is still a significant method to improve the performance of visible-light photoresponse. Herein, we propose the PVDF@Ag-ZnO/Au composite nanofiber membranes utilizing the piezoelectric and plasmonic effects to promote the photocatalytic degradation of organic dyes. Here, ZnO nanorods can generate a built-in electric field under vibration to separate electron-hole pairs. The Schottky junction formed by noble metal/semiconductor can not only inhibit the recombination of photo-generated carriers and accelerate the migration of carriers, but also enhance the utilization of visible light. In addition, the structure has excellent flexibility and easy recycling characteristics. We demonstrate that the plasmonic effect of noble metal can enhance the light response of membranes and broaden light absorption from ultraviolet to visible light region. With the help of the surface-enhanced Raman scattering (SERS), modulation effects of the piezoelectric effect on light response is proved. For catalytic processes, rhodamine B (98.8%) can be almost completely degraded using PVDF@Ag-ZnO/Au within 120 minutes in the piezoelectric photocatalysis process, which is 2.2 and 2.8 times higher than photocatalysis and piezoelectric catalysis, respectively. This work provides a promising strategy for harnessing solar and mechanical energy.

SERS enhancement induced by the Se vacancy defects in ultra-thin hybrid phase SnSex nanosheets.

Improving the photo-induced charge transfer (PICT) efficiency by adjusting the energy levels difference between adsorbed probe molecules and substrate materials is a key factor for boosting the surface enhanced Raman scattering (SERS) based on the chemical mechanism (CM). Herein, a new route to improve the SERS activity of two-dimensional (2D) selenium and tin compounds (SnSex, 1 ≤ x ≤ 2) by the hybrid phase materials is researched. The physical properties and the energy band structure of SnSex were analyzed. The enhanced SERS activity of 2D SnSex can be attribute to the coupling of the PICT resonance caused by the defect energy levels induced by Se vacancy and the molecular resonance Raman scattering (RRS). This established a relationship between the physical properties and SERS activity of 2D layered materials. The resonance probe molecule, rhodamine (R6G), which is used to detect the SERS performance of SnSex nanosheets. The enhancement factor (EF) of R6G on the optimized SnSe1.35 nanosheets can be as high as 2.6 × 106, with a detection limit of 10-10 M. The SERS result of the environmental pollution, thiram, shows that the SnSex nanosheets have a practical application in trace SERS detection, without the participation of metal particles. These results demonstrate that, through hybrid phase materials, the SERS sensitivity of 2D layered nanomaterials can be improved. It provides a kind of foreground non-metal SERS substrate in monitoring or detecting and provide a deep insight into the chemical SERS mechanism based on 2D layered materials.

SERS Sensing Using Graphene-Covered Silver Nanoparticles and Metamaterials for the Detection of Thiram in Soil.

Multilayer hyperbolic metamaterial (HMM)-based SERS substrates have received special consideration because they accommodate various propagation modes such as surface plasmonic polaritons (SPP). However, the SPP modes are difficult to generate in HMM due to their weak electric field enhancement. In this article, we designed novel SERS substrates consisting of graphene-covered AgNPs and HMM. The graphene-covered AgNPs work as an external coupling structure for hyperbolic metamaterials due to this structure exhibiting significant plasmonic effects as well as unique optical features. The localized surface plasmonic resonance (LSPR) of the graphene-covered AgNPs excited the SPP and thus formed a strong hot spot zone in the nanogap area of the graphene. The Raman experiment was performed using rhodamine 6G (R6G) and crystal violet (CV), which showed high stability and a maximum enhancement factor of 2.12 × 108. The COMSOL simulation further clarified that enhanced SERS performance was due to the presence of monolayer graphene and provided an atomically flat surface for organic molecules in a more controllable manner. Interestingly, the proposed SERS structure carries out quantitative detection of thiram in soil and can satisfy the basic environmental need for pesticide residue in the soil.

Preparation of a superhydrophobic AgNP/GF substrate and its SERS application in a complex detection environment.

Surface-enhanced Raman scattering (SERS) is widely considered to be a fingerprint spectrum that can realize molecular identification, and it continues to receive a lot of attention due to its high sensitivity and powerful qualitative analysis capabilities. In recent years, there has been a lot of work and reports on super-sensitive SERS substrates, but often the enhanced ability of the substrate is also effective for impurities and irrelevant molecules. Therefore, a problem that still remains to be solved is how to perform effective trace detection of specific substances in a complex detection environment. Herein, a superhydrophobic Ag nanoparticle/glass microfibre filter (AgNP/GF) substrate was designed to realize the Raman detection of complex multiphase solutions. The hydrophobic three-dimensional net-like structure provides efficient Raman enhancement, making the substrate have extremely high detection limits for dye molecules and even achieving specific detection of the hexane phase component (thiram molecule) in a multiphase solution.

Film wrap nanoparticle system with the graphene nano-spacer for SERS detection.

Film wrap nanoparticle system (FWPS) is proposed and fabricated to perform SERS effect, where the Ag nanoparticle was completely wrapped by Au film and the double-layered graphene was selected as the sub-nano spacer. In this system, the designed nanostructure can be fully rather than partly used to generate hotspots and absorb probe molecules, compared to the nanoparticle to nanoparticle system (PTPS) or nanoparticle to film system (PTFS). The optimal fabricating condition and performance of this system were studied by the COMSOL Multiphysics. The simulation results show that the strongly large-scale localized electromagnetic field appears in the whole space between the Ag nanoparticle and Au film. The experimental results show that the FWPS presents excellent sensitivity (crystal violet (CV): 10-11 M), uniformity, stability and high enhancement factor (EF: 2.23×108). Malachite green (MG; 10-10 M) on the surface of fish and DNA strands with different base sequence (A, T, C) were successfully detected. These advanced results indicate that FWPS is highly promising to be applied for the detection of environmental pollution and biomolecules.

Noble metal modified ReS2 nanocavity for surface-enhanced Raman spectroscopy (SERS) analysis.

The rhenium disulphide (ReS2) nanocavity-based surface enhanced Raman scattering (SERS) substrates ware fabricated on the gold-modified silicon pyramid (PSi) by thermal evaporation technology and hydrothermal method. In this work, the ReS2 nanocavity was firstly combined with metal nanostructures in order to improve the SERS properties of ReS2 materials, and the SERS response of the composite structure exhibits excellent performance in sensitivity, uniformity and repeatability. Numerical simulation reveals the synergistic effect of the ReS2 nanocavity and the plasmon resonance generated by the metal nanostructures. And the charge transfer between the metal, ReS2 and the analytes was also verified and plays an non-ignorable role. Besides, the plasmon-driven reaction for p-nitrothiophenol (PNTP) to p,p'-dimercaptobenzene (DMAB) conversion was successfully in-situ monitored. Most importantly, it is found for the first time that the SERS properties of ReS2 nanocavity-based substrates are strongly temperature dependent, and the SERS effect achieves the best performance at 45 °C. In addition, the low concentration detection of malachite green (MG) and crystal violet (CV) molecules in lake water shows its development potential in practical application.

MoS2-based multiple surface plasmonic coupling for enhanced surface-enhanced Raman scattering and photoelectrocatalytic performance utilizing the size effect.

MoS2-based heterostructures have received increasing attention for not only surface-enhanced Raman scattering (SERS) but also for enhanced photoelectrocatalytic (PEC) performance. This study presents a hydrothermal method for preparing vertical MoS2 nanosheets composed of in situ grown AuNPs with small size and chemically reduced AgNPs with large size to achieve the synergistic enhancement of SERS and PEC properties owing to the size effect of the plasmonic structure. Compared with pristine MoS2 nanosheets and unitary AuNPs or AgNPs composited with MoS2 nanosheets, the ternary heterostructure exhibited the strongest electromagnetic field and surface plasmon coupling, which was confirmed by finite-difference time-domain (FDTD) simulation and absorption spectra. In addition, the experimental results confirmed the outstanding SERS enhancement with an EF of 1.1×109, and the most efficient hydrogen evolution reaction (HER) activity with a sensitive photocurrent response, attributing to the multiple surface plasmonic coupling effects of the Au-Ag bimetal and efficient charge-transfer process between MoS2 and the bimetal. That is, it provides a robust method for developing multi-size bimetal-semiconductor complex nanocomposites for high-performance SERS sensors and PEC applications.

SERS substrate with wettability difference for molecular self-concentrating detection.

The surface-enhanced Raman spectroscopy (SERS) has attracted much attention due to the powerful capability of quantificational analysis. Nowadays, most of the enhancement effect by SERS substrate is provided by the 'hot spots' occupying relatively small space. When the amount of analyte is too low, it is difficult to ensure that all the probe molecules can be placed into the 'hot spots', which is a headache in SERS quatification. In order to solve this problem, we have developed a structure of CuO nanowires/Ag nanoparticles with wettability capacity difference, which can aggregate molecules in water and oil simultaneously under two different mechanisms. The limit of detection and enhancement factor of this structure are estimated as 10-15M and 1.55 × 1011respectively (for rhodamine 6G, R6G). In a proof-in-principle experiment of sewage detection, it successfully achieved the aggregation and additional enhancement of both the R6G molecules in aqueous solution and thiuram molecules in toluene, realizing efficient and accurate Raman detection.

Hierarchical Particle-In-Quasicavity Architecture for Ultratrace In Situ Raman Sensing and Its Application in Real-Time Monitoring of Toxic Pollutants.

Unstable detection environment is one of the biggest interferences for in situ surface-enhanced Raman spectroscopy (SERS) using in real-time monitoring of toxic pollutants, leading to unreliable results. To address this problem, we have designed and prepared a cavity-based particle-in-quasicavity (PIQC) architecture composed of hierarchical ZnO/Ag nanosheets and nanoprotrusions for improving the in situ SERS performance under a liquid environment. Benefitting from the special cascaded optical field mode, the PIQC ZnO/Ag exhibits excellent in situ SERS detectability, with 10-18 M of limit of detection for rhodamine 6G and 12.8% of signal relative standard deviation value. Furthermore, by means of a microfluidic chip, this PIQC structure is proved to have the quantitative analysis feasibility and realizes real-time monitoring of the 3,3',4,4'-tetrachlorobiphenyl, a representative global environmental hazard, under the flowing environment. The strategy in this paper provides a brand new idea to promote the application of in situ SERS in contaminant monitoring and is also instructive for light control in other optical fields.

Aluminum nanoparticle films with an enhanced hot-spot intensity for high-efficiency SERS.

The weak plasmonic coupling intensity in an aluminum (Al) nanostructure has limited potential applications in excellent low-cost surface-enhanced Raman scattering (SERS) substrates and light harvesting. In this report, we aim to elevate the plasmonic coupling intensity by fabricating an Al nanoparticle (NP)-film system. In the system, the Al NP are fabricated directly on different Al film layers, and the nanoscale-thick alumina interlayer obtained between neighboring Al films acts as natural dielectric gaps. Interestingly, as the number of Al film layers increase, the plasmonic couplings generated between the Al NP and Al film increase as well. It is demonstrated that the confined gap plasmon modes stimulated in the nanoscale-thick alumina region between the adjacent Al films contribute significantly to elevating the plasmonic coupling intensity. The finite-difference time-domain (FDTD) method is used to carry out the simulations and verifies this result.

CVD-Bi2Te3 as a saturable absorber for various solitons in a mode-locked Er-doped fiber laser.

In this work, we report about high energy and various solitons' operation by using high-efficiency topological insulator bismuth telluride (Bi2Te3) nanofilms as broadband saturable absorbers in the passively mode-locked Er-doped fiber laser. The Bi2Te3 film was successfully synthesized by chemical vapor deposition (CVD). Excellent characteristics of the dark-bright pulse pairs, bright pulses, and multiharmonics have been investigated experimentally by adjusting the polarization state. At the same time, the maximum average output power was 40.18 mW, and the single-pulse energy was 20.91 nJ. As we all know, it is the various solitons of the first generation with large pulse energy in an Er-doped fiber laser with Bi2Te3 as saturable absorber. The experimental results show that CVD Bi2Te3 can be used as an excellent candidate in mode-locked fiber lasers.

Toward the highly sensitive SERS detection of bio-molecules: the formation of a 3D self-assembled structure with a uniform GO mesh between Ag nanoparticles and Au nanoparticles.

We report a structure to form a hybrid system in which a mesh is sandwiched between Au nanoparticles (AuNPs) and Ag nanoparticles (AgNPs). This self-assembly method uses smaller and denser AgNPs "hot spots" that are spin-coated on a AuNPs@GO mesh nanostructure formed by the reaction of GO@MoS2 and HAuCl4 to form AuNPs@GO mesh@AgNPs SERS substrates. Sub-40-nm mesh and 10-nm gaps ensure the landing sites and spacing of the AgNPs. Consequently, the design integrates the strong plasmonic effects of AgNPs and AuNPs with the biological compatibility of the GO mesh. Crystal violet (CV) as low as 10-15 M can be detected, which confirms the ultrahigh sensitivity of AuNPs@GO mesh@AgNPs. Furthermore, the reproducibility, stability, and finite-difference time-domain (FDTD) simulations confirm the value of this SERS substrate. This material can be used for label-free DNA detection, and the AuNPs@GO mesh@AgNPs substrate facilitated single-molecule DNA detection limits.

In situ detection of trace pollutants: a cost-effective SERS substrate of blackberry-like silver/graphene oxide nanoparticle cluster based on quick self-assembly technology.

To realize fast detection of trace hazardous chemicals, a SERS substrate with the structure of a blackberry-like silver/graphene oxide nanoparticle cluster (Ag/GO NPC) has been designed and prepared through a quick capillarity-assistant self-assembly technology in this paper. Benefitting from the abundant "hot spots" and active oxygen sites brought by this Ag/GO NPC, the substrate shows good Raman performance for malachite green (MG), a common abusive germicide in aquaculture, with lowest limit of detection below 0.1 µg/L (3.48 × 10-10 mol/L). Detailed analyses are taken on both the formation process and enhancement mechanism of this SERS substrate, and the finite-difference time-domain simulations are utilized as well to prove our hypotheses. Further constructing this structure on polyethylene terephthalate (PET) film, a translucent flexible SERS substrate can be obtained, realizing a fast in situ detection of trace MG in the fishpond subsequently. In consideration of the facile preparation process, good SERS enhancement and affordable materials (PET, Cu, Ag and GO, etc.), this substrate presents high cost performance and a promising application prospect.

Graphene-Ag nanoparticles-cicada wings hybrid system for obvious SERS performance and DNA molecular detection.

In recent years, biomaterials have increasingly attracted attention on surface-enhanced Raman spectroscopy (SERS) due to their well Raman performance while metal particles are combined with biological substrates. Therefore, we propose an environmentally friendly substrate based on silver-plated cicada wings with seamless graphene layer (Gr-AgNPs-C.w.), which can be prepared with a simple and inexpensive method. Compared with AgNPs-C.w., Gr-AgNPs-C.w. hybrids show better SERS performance with high sensitivity, good uniformity and good stability with R6G detection. The minimum detected concentration can reach 10-15 M, and the value of R2 can reach 0.996, respectively. Theoretical simulation demonstrates the situation of electromagnetic field through COMSOL software. In addition, due to the affinity of graphene for biomolecules, we can successfully detect the DNA biomolecules through a simple process. Therefore, this cheap and efficient natural SERS substrate has great potential for a considerable number of biochemical SERS applications and can broaden the way in which multiple SERS platforms derived from other natural materials are prepared.

Experimental and theoretical investigation for surface plasmon resonance biosensor based on graphene/Au film/D-POF.

A D-shape plastic optical fiber (D-POF) surface plasmon resonance (SPR) biosensor based on the graphene/Au film (G/Au) was proposed and experimentally demonstrated for detection of DNA hybridization process. To improve the detection performance of SPR sensors, the Physical Vapor Deposition (PVD) method was used to evaporate the Au film directly onto the graphene grown on copper foil, and the Au film acted as a role of traditional Polymethyl Methacrylate (PMMA). The process made graphene and Au film form seamless contact. Next, the G/Au was transferred onto the D-shape fiber together. We explored the G/Au SPR sensor by using the finite element method (FEM) and obtained the optimum materials thickness to form configuration. Compared to other plastic optical fiber experiments, the proposed sensor's sensitivity was improved effectively and calculated as 1227 nm/RIU in a range of glucose solution. Meanwhile, our proposed sensor successfully distinguishes hybridization and single nucleotide polymorphisms (SNP) by observing the resonance wavelength change. It also exhibits a satisfactory linear response (R2 = 0.996) to the target DNA liquids with respective concentrations of 0.1nM to1µM, which shows this method's wide potential in medical diagnostics.

Large-energy mode-locked ytterbium-doped linear-cavity fiber laser based on chemical vapor deposition-Bi2Se3 as a saturable absorber.

We reported on the generation of pulse bunch and large-energy dark pulses in a mode-locked ytterbium-doped linear-cavity fiber laser based on Bi2Se3 as a saturable absorber (SA). Bi2Se3 nanosheets were successfully synthesized by the chemical vapor deposition (CVD) method and transferred to the end facet of a fiber connector for the proposed SA. Its saturation intensity and modulation depth were measured to be 52 MW/cm2 and 14.5%, respectively. By inserting the Bi2Se3-based SA into the Yb-doped all-fiber linear cavity, stable pulse bunches were observed. In addition, dark soliton operation with a maximum average output power of 32.6 mW and a pulse energy of 61.8 nJ were also achieved. To the best of our knowledge, this is the first demonstration of a dark soliton within a linear cavity with much larger pulse energy than previous works. Our study fully indicated that CVD-Bi2Se3 could be an excellent SA for achieving large-energy pulse operations.

Label-free diagnosis of lung cancer with tissue-slice surface-enhanced Raman spectroscopy and statistical analysis.

Despite the rapid development of medical science, the diagnosis of lung cancer is still quite challenging. Due to the ultrahigh detection sensitivity of surface-enhanced Raman spectroscopy (SERS), SERS has a broad application prospect in biomedicine, especially in the field of tumor blood detection. Although Raman spectroscopy can diagnose lung cancer through tissue slices, its weak cross sections are problematic. In this study, silver nanoparticles (AgNPs) were added to the surface of lung tissue slices to enhance the Raman scattering signals of biomolecules. The electromagnetic field distribution of AgNPs prepared was simulated using the COMSOL software. SERS obtained from the slices reflected the difference in biochemical molecules between normal (n = 23) and cancerous (n = 23) lung tissues. Principal component-linear discriminate analysis (PCA-LDA) was utilized to classify lung cancer and healthy lung tissues. The receiver operating characteristic curve gave the sensitivity (95.7%) and specificity (95.7%) of the PCA-LDA method. This study sheds new light on the general applicability of SERS analysis of tissue slices in clinical trials.

Multifunctional paper strip based on GO-veiled Ag nanoparticles with highly SERS sensitive and deliverable properties for high-performance molecular detection.

The development of paper-based SERS substrates that can allow multi-component detection in real-word scenarios is of great value for applications in molecule detection under complex conditions. Here, a multifunctional SERS-based paper sensing substrate has been developed through the uniform patterning of high-density arrays of GO-isolated Ag nanoparticles on the hydrophilic porous cellulose paper strip (GO@AgNP@paper). Wet-chemical synthesis was used to provide the cover of SERS hot spots on any part of the paper, not just limited surface deposition. In virtue of the inherent ability of paper to deliver analytes by the capillary force, the detection ability of the GO@AgNP@paper substrate was greatly promoted, allowing as low as 10-19M R6G detection from microliter-volume (50 µL) samples. For the components with different polarity, the paper substrate can be used as an all-in-one machine to achieve the integration of separation and high-sensitive detection for ultralow mixture components, which improves the practical application value of SERS-based paper devices.