AuNRs@ZIF-8的制备及其表面增强拉曼散射光谱研究

表面增强拉曼光谱(Surface enhanced Raman spectroscopy, SERS)是一种分子光谱,具有快速、高灵敏和指纹识别的特性,在分析化学、生物医学等领域有着重要的应用。然而,在溶液样品中一些检测分子很难被SERS基底所吸附,导致分子拉曼信号增强困难。为此,本文提出了一种ZIF-8材料包覆金纳米棒(AuNRs)的核壳结构(AuNRs@ZIF-8)来实现拉曼信号增强,既可利用金纳米颗粒的表面等离激元增强特性,又可利用ZIF-8这种多孔MOFs材料的吸附性能,从而实现溶液样品的高灵敏拉曼检测。我们首先采用晶种法制备了均一性良好的AuNRs,然后对其进行聚乙烯吡咯烷酮(PVP)修饰,最后加入金属有机框架ZIF-8前驱体,得到AuNRs@ZIF-8核壳纳米结构。该结构对罗丹明(R6G)的SERS检测灵敏度很高,检测限可低至10⁻⁹ mol/L,并且线性关系和均一性均良好。此外,我们通过测试该结构吸收R6G前后的UV-Vis吸收光谱进一步证实了核壳纳米结构的生成和对目标分子的有效吸附。

     

Diagnosis of breast cancer by analysis of sialic acid concentrations in human saliva by surface-enhanced Raman spectroscopy of silver nanoparticles

Breast cancer is the most common type of malignant tumor among women and their second leading cause of cancer-related deaths.The most common method for screening and diagnosis is mammography.Nonetheless,two main problems have been identified.First,the dose of radiation received during the test prevents the method from the use on women who are ＜ 40 years old.Second,there can be mammogram failure owing to the lack of tumor contrast with the fibrous tissue.Therefore,there is a need for screening methods that will help to identify high-risk cases.We developed a biological marker test that can help to identify them.Increased levels of sialic acid (SA) in saliva are known to correlated with breast cancer.In this study,we evaluated the feasibility of Raman spectroscopy as a method for quantification of SA in saliva,using citrate-reduced silver nanoparticles (cit-Ag-NPs) as a surface-enhanced Raman spectroscopy (SERS) substrate.Quantification of SA was accomplished by measuring its intensity in saliva and comparing it with a calibration curve of SA standards.The mean SA concentration in saliva was found to be significantly higher among 100 breast cancer patients (18.3 ± 9.4 mg·dL-1;mean ± SD) than among 106 healthy controls (3.5 ± 1.0 mg·dL-1).The SERS test showed sensitivity of 94％ and specificity 98％ for detection of patients with breast cancer,assuming that SA concentration ＞ 7 mg·dL-1 is a cutoff for positive test results.Our findings prove the usefulness of this SERS technique as a simple,convenient,and highly sensitive method of quantitative analysis of SA in saliva.The simplicity of this nanotechnological test may help to substantially reduce the mortality among patients with breast cancer by providing women with a simple,noninvasive screening test that can be applied regardless of age or density of breast tissue.     

In vitro biomechanical properties,fluorescence imaging,surface-enhanced Raman spectroscopy,and photothermal therapy evaluation of luminescent functionalized CaMoO4:Eu@Au hybrid nanorods on human lung adenocarcinoma epithelial cells

Highly dispersible Eu³⁺-doped CaMoO₄@Au-nanorod hybrid nanoparticles (HNPs) exhibit optical properties, such as plasmon resonances in the near-infrared region at 790 nm and luminescence at 615 nm, offering multimodal capabilities: fluorescence imaging, surface-enhanced Raman spectroscopy (SERS) detection and photothermal therapy (PTT). HNPs were conjugated with a Raman reporter (4-mercaptobenzoic acid), showing a desired SERS signal (enhancement factor 5.0 × 10⁵). The HNPs have a heat conversion efficiency of 25.6%, and a hyperthermia temperature of 42°C could be achieved by adjusting either concentration of HNPs, or laser power, or irradiation time. HNPs were modified with antibody specific to cancer biomarker epidermal growth factor receptor, then applied to human lung cancer (A549) and mouse hepatocyte cells (AML12), and in vitro PTT effect was studied. In addition, the biomechanical properties of A549 cells were quantified using atomic force microscopy. This study shows the potential applications of these HNPs in fluorescence imaging, SERS detection, and PTT with good photostability and biocompatibility.     

双程泵浦分立式拉曼放大特性的研究

采用后向泵浦的方案,对新型双程放大分立式光纤拉曼放大器(D-DFRA)的增益特性进行了理论计算,并在双程泵浦放大条件下对增益和噪声特性及受激布里渊散射(SBS)效应进行了实验测量,计算与测量结果较好符合.本文的研究表明:对分立式拉曼放大器通过反射机制实现泵浦光的双程泵浦,可在泵浦功率不变和保持较好噪声特性的同时,大大提升放大器的增益和功率转换效率.增益的提升上限取决于系统受激布里渊散射的阈值,在双程泵浦下增益的上限可得到提高.     

Pen‐on‐Paper Approach Toward the Design of Universal Surface Enhanced Raman Scattering Substrates

The translation of a technology from the laboratory into the real world should meet the demand of economic viability and operational simplicity. Inspired by recent advances in conductive ink pens for electronic devices on paper, we present a “pen‐on‐paper” approach for making surface enhanced Raman scattering (SERS) substrates. Through this approach, no professional training is required to create SERS arrays on paper using an ordinary fountain pen filled with plasmonic inks comprising metal nanoparticles of arbitrary shape and size. We demonstrate the use of plasmonic inks made of gold nanospheres, silver nanospheres and gold nanorods, to write SERS arrays that can be used with various excitation wavelengths. The strong SERS activity of these features allowed us to reach detection limits down to 10 attomoles of dye molecules in a sample volume of 10 μL, depending on the excitation wavelength, dye molecule and type of nanoparticles. Furthermore, such simple substrates were applied to pesticide detection down to 20 ppb. This universal approach offers portable, cost effective fabrication of efficient SERS substrates at the point of care. This approach should bring SERS closer to the real world through ink cartridges to be fixed to a pen to create plasmonic sensors at will.     

Selective Surface Enhanced Raman Scattering for Quantitative Detection of Lung Cancer Biomarkers in Superparticle@MOF Structure

Surface enhanced Raman scattering (SERS) is a trace detection technique that extends even to single molecule detection. Its potential application to the noninvasive recognition of lung malignancies by detecting volatile organic compounds (VOCs) that serve as biomarkers would be a breakthrough in early cancer diagnostics. This application, however, is currently limited by two main factors: (1) most VOC biomarkers exhibit only weak Raman scattering; and (2) the high mobility of gaseous molecules results in a low adsorptivity on solid substrates. To enhance the adsorption of gaseous molecules, a ZIF‐8 layer is coated onto a self‐assembly of gold superparticles (GSPs) in order to slow the flow rate of gaseous biomarkers and depress the exponential decay of the electromagnetic field around the GSP surfaces. Gaseous aldehydes that are released as a result of tumor‐specific tissue composition and metabolism, thereby acting as indicators of lung cancer, are guided onto SERS‐active GSPs substrates through a ZIF‐8 channel. Through a Schiff base reaction with 4‐aminothiophenol pregrafted onto gold GSPs, gaseous aldehydes are captured with a 10 ppb limit of detection, demonstrating tremendous prospects for in vitro diagnoses of early stage lung cancer.     

Facile fabrication of ultrathin freestanding nanoporous Cu and Cu-Ag films with high SERS sensitivity by dealloying Mg-Cu(Ag)-Gd metallic glasses

Nanoporous metals prepared by dealloying have attracted increasing attention due to their interesting size-dependent physical,chemical,and biological properties.However,facile fabrication of metallic ultra-thin freestanding nanoporous films(UF-NPFs)by dealloying is still challenging.Herein,we report a novel strategy of facile preparation of flexible Cu,Cu3Ag,and CuAg UF-NPFs by dealloying thick Mg-Cu(Ag)-Gd metallic glass ribbons.During dealloying,the local reaction latent heat-induced glass transition of the precursor ribbons leads to the formation of a solid/liquid interface between the initially dealloyed nanoporous layer and the underlying supercooled liquid layer.Due to the bulging effect of in situ gen-erated H2 on the solid/liquid interface,Cu,Cu3Ag,and CuAg UF-NPFs with thicknesses of～200 nm can self-peel off from the outer surface of the dealloying ribbons.Moreover,it was found that the surface-enhanced Raman scattering(SERS)detection limit of Rhodamine 6G(R6G)on the Cu and CuAg UF-NPF substrates are 10-6 M and 10-11 M,respectively,which are lower than most of the Cu and Cu-Ag sub-strates prepared by other methods.This work presents a reliable simple strategy to synthesize a variety of cost effective and flexible metallic UF-NPFs for functional applications.     

几种不同改性剂对稻草/丙烯腈-丁二烯-苯乙烯复合材料性能的影响

以稻草纤维及丙烯腈-丁二烯-苯乙烯（ABS）为原料,分别以活性炭、Al₂O₃、SiO₂和硅烷偶联剂为增强改性剂,通过混炼-模压工艺制备了改性剂-稻草/ABS复合材料,对比研究了几种不同增强改性剂的增强效果及其增强机制。结果表明：硅烷偶联剂对稻草/ABS复合材料的增强效果较差,活性炭、Al₂O₃和SiO₂对稻草/ABS复合材料的增强均优于硅烷偶联剂,其中Al₂O₃的增强效果最佳。当Al₂O₃的添加量（Al₂O₃∶ABS质量比）为5%时,Al₂O₃-稻草/ABS复合材料的拉伸、弯曲及冲击强度分别达到最大值27.719 MPa、61.05 MPa和26.53 kJ/m²;当无机物添加量（无机物∶ABS质量比）为5%时,复合材料的耐水性能表现为：5% Al₂O₃ > 5%活性炭 > 5% SiO₂ > 未添加,与复合材料的力学性能梯度相符;改性剂-稻草/ABS复合材料的流变性能则表现为：5%活性炭 > 5% Al₂O₃ > 5% SiO₂ > 未添加。     

Raman spectroscopy: A technique for estimating extent of polymerization in PMMA

This work shows how laser-Raman spectroscopy can be applied in cases where a combination of an efficient, relatively inexpensive, simple, and non- destructive technique is desirable for the determination of the monomer content in poly(methylmethacrylate), PMMA. The method has been initially applied in order to investigate the optimum conditions for the in situ polymerization of PMMA in the pores of silica sol-gel for the purpose building a solid state dye laser. The calibration line which converts the ratio of two Raman intensities in the PMMA spectrum (at 1640 and 1725 cm^–1) into percentage of monomer content, under the current experimental conditions, has been achieved on the basis of NMR spectroscopy. In addition, it is shown in this work how Raman spectroscopy can allow for the estimation of the reaction enthalpies of partial monomer to polymer conversion after thermal treatment at different temperatures and periods of treatment. Received: 25 August 2000 / Reviewed and accepted: 28 August 2000     

Study of a new resin-based composites containing hydroxyapatite filler using Raman and infrared spectroscopy

The degree of conversion of polymeric matrix in hydroxyapatite-containing dental fillings by Raman and infrared spectroscopy has been determined. Resin-based dental composites are one of the most popular filling materials used in dentistry. These light-cured materials are characterized by the value of the degree of conversion, which depends on curing time and influences the quality of obtained dental filling. Distribution of the filler into polymeric matrix, which has a significant impact on the properties of the final product, has been determined by Raman mapping. The applied procedure also has allowed to present the changes of the degree of conversion on the examined surfaces. The results of the study demonstrate the versatility of the Raman spectroscopy as the analytical spectroscopic technique for determining chemical properties of dental fillings and providing insight into their organization at the microstructural level. The obtained degree of conversion values have been compared with data for the commercially available dental fillings characterized by other authors.     

Micromechanics analysis of Kevlar-29 aramid fiber and epoxy resin microdroplet composite by Micro-Raman spectroscopy

The effect of geometry on interfacial micromechanical behavior of fiber/matrix microdroplets is investigated by means of the combination of microbond test and Micro-Raman spectroscopy in this paper. Microbond test is usually employed to measure the interfacial properties of fiber/matrix composites. Since the existing method was realized through traditional microscopy technique, the test results may not satisfy those accurate analyses such as geometry influence on interfacial micromechanical behavior of composites. To overcome this problem, Micro-Raman spectroscopy is introduced into the microbond test to detect the distributions of micromechanical properties including fiber axial stress, residual stress, interfacial shear stress and stress transfer length along the interfaces between Kevlar-29 aramid fiber and epoxy resin matrix microdroplets. The obtained experimental results show that axial stress transfer will accelerate and then the shear stress concentration will be enhanced along with an increase in the interfacial edge angle. The study indicates that the geometrical characteristics can affect significantly the stress distributions in the fiber/matrix microdroplets.     

Analysis of the fragmentation test for carbon-fibre/epoxy model composites by means of Raman spectroscopy

The interfaces between high-modulus PAN-(T50) and mesophase pitch-based (P55) carbon fibres and an epoxy matrix have been studied by using the conventional fragmentation test in conjunction with polarised-light optical microscopy. Raman spectroscopy has also been used to follow stress transfer from the matrix to the fibres for the same fragmentation geometries. The level of fibre/matrix adhesion and mechanisms by which the stress is transfered from the matrix to the fibres has been determined from both the stress birefringence patterns and strain-induced Raman band shifts in the fibres. The values of interfacial shear strength have been determined by means of both the conventional analysis and the Raman technique. It is found that the Raman method gives a much more detailed picture of stress transfer in the test specimens and that the two methods give somewhat different values of the interfacial shear strength. The values of interfacial shear stress have been discussed with respect to fibre surface energy, surface chemistry and surface morphology. It was found that the surface chemical functional groups appear to have no direct correlation with interfacial shear strength. Furthermore, it appears that mechanical interlocking due to surface roughness could contribute to the higher values of interfacial shear strength determined for the PAN-based fibre.     

Preparation and photoluminescence of ZnO with nanostructure by hollow-cathode discharge

Without the use of a metal catalyst in the process, ZnO with nanostructures was successfully prepared on Si (100) substrate by simple chemical vapor-deposition method. In our work, Ar was used as the plasma forming gas, O₂ was the reactive gas and metal zinc powder (99.99% purity) vaporized by cylinder hollow-cathode discharge (HCD) acted as the zinc source. The crystal structures of the as-synthesized ZnO nanostructures were characterized by X-ray diffraction (XRD); the ZnO sample growing on the wall of the crucible showed a ‘comb-like’ nanostructure, while the other one at the bottom of the crucible showed a ‘rod-like’ structure, which can be attributed to the difference of the oxygen content. The measurement on the photoluminescence (PL) performance of the ZnO nanostructures was carried out at room temperature. The results indicated that the ‘comb-shape’ ZnO nanomaterial possessed a remarkably strong ultraviolet emission peak centered at 388 nm, while ZnO nanorods, except better ultraviolet emission, also had relatively strong blue-green emission ranging from 470 to 600 nm due to the existence of oxygen vacancies. The growth mechanism of ZnO with nanostructures is also discussed in this paper.     

Strain-sensitive Raman spectroscopy and electrical resistance of carbon nanotube-coated glass fibre sensors

This paper presents the development of glass fibres coated with nanocomposites consisting of carbon nanotubes (CNTs) and epoxy. Single glass fibres with different CNT content coating are embedded in a polymer matrix as a strain sensor for composite structures. Raman spectroscopy and electrical response of glass fibres under mechanical load are coupled for in situ sensing of deformation in composites. The results show that the fibres with nanocomposite coating exhibit efficient stress transfer across the fibre/matrix interface, and these with a higher CNT content are more prone to fibre fragmentation at the same matrix strain. A relationship between the fibre stress and the change in electrical resistance against the fibre strain is established. The major finding of this study has a practical implication in that the fibres with nanocomposite coating can serve as a sensor to monitor the deformation and damage process in composites.     

Investigation of irradiated graphene oxide/ultra-high-molecular-weight polyethylene nanocomposites by ESR and FTIR spectroscopy

Graphene oxide/ultra-high-molecular-weight polyethylene (GO/UHMWPE) nanocomposite has a potential application for artificial joints. However, free radicals and antioxidative properties of irradiated GO/UHMWPE were not clearly clarified. In this paper, GO/UHMWPE nanocomposites were prepared and irradiated by gamma-irradiation with a dose of 100 kGy. Afterward, test samples were aged in air. Free radicals and molecular structures of test samples were investigated by electron spin resonance (ESR) spectroscopy and Fourier transform infrared (FTIR) spectroscopy, respectively. These studies indicated that irradiation enhanced GO radical concentrations. And GO radicals were stable in air and even could not be quenched after accelerated aging. GO radicals were superimposed on free radicals of irradiated UHMWPE. Although GO showed free radical-scavenging capacity, the influence of GO on free radicals of irradiated UHMWPE was too weak to be observed in ESR spectroscopy. Free radicals concentrations of irradiated GO/UHMWPE nanocomposites were gradually decayed with aging time evolving in air. Observing the oxidation index values of test samples, it was proposed that irradiated GO/UHMWPE might show very weak antioxidative properties.     

Effect of oxygen plasma treatment of PPTA and PBO fibers on the interfacial properties of single fiber/epoxy composites studied by Raman spectroscopy

The interfacial micromechanics of single poly(p-phenylene terephthalamide (PPTA) and poly(p-phenylene benzobisoxazole (PBO) fibers embedded in an epoxy resin has been investigated by determining the interfacial shear stress distributions along the fiber length. The effects of an oxygen plasma treatment on the interfacial shear stress of the fiber-epoxy systems are analyzed. Raman spectroscopy was used to map the stress distributions along the fiber when the composite is subjected to a small axial tensile strain (3.5% for PPTA and 2.5% for PBO). The quality of the interface or adhesion was improved after the surface treatment, supporting the ability of plasma oxidation to enhance the adhesion of high-performance fibers to epoxy resins. The tensile behavior of fiber-reinforced systems was different in each case. PPTA reinforcements underwent fragmentation, likely by fiber microfailure, whereas debonding or bridging is the most probable fragmentation mechanism in the case of PBO.     

Analysis and classification of oral tongue squamous cell carcinoma based on Raman spectroscopy and convolutional neural networks

ABSTRACT

To detect oral tongue squamous cell carcinoma (OTSCC) using fibre optic Raman spectroscopy, we present a classification model based on convolutional neural networks (CNN) and support vector machines (SVM). 24 samples Raman spectra of OTSCC and para-carcinoma tissues from 12 patients were collected and analysed. In our proposed model, CNN is used as a feature extractor for forming a representative vector. Then the derived features are fed into an SVM classifier, which is used for OTSCC classification. Experimental results demonstrated that the area under the receiver operating characteristic curve was 99.96% and the classification error was zero (sensitivity: 99.54%, specificity: 99.54%). To show the superiority of this model, comparison results with the state-of-the-art methods showed it can obtain a competitive accuracy. These findings may pay a way to apply the proposed model in the fibre optic Raman instruments for intra-operative evaluation of OTSCC resection margins.     

Improving Rubber Mixing Performance of Hot Water Bag Compound

A rubber factory in India encountered extensive amount of rework at the rubber mixing stage for one of its medicare products, the hot water bag. The scorch time and the optimum cure time of the rubber-mixing compound were the potential product parameters for which this rework took place. Regression analysis shows that the process parameters, the temperature of the dispersion kneader and the temperature of the open mill, with adjusted R² values of 79.9 and 89.5%, respectively can predict both the scorch time and the optimum cure time. Subsequently analyzing the multiple linear regression equation for optimum cure time, which is the key process output variable, with the help of linear programming has arrived at the optimum levels of these temperatures. Besides this, analysis of variance for scorch time has shown that the mixing technique of the workers is not identical. Duncan's multiple range tests has revealed operator group 3 as the best performer for scorch time. Bartlett's test has revealed inequality of variances of four operator groups for optimum cure time. This substantiated the training need of the concerned operators. The study has resulted in reduction of the extent of rework from 80762 to 17865 PPM. Naturally this substantial reduction in rework will reduce the process cycle time and cost of production immensely.