SERS标记的金纳米棒探针用于免疫检测

报道了基于金纳米棒表面增强拉曼散射(SERS)的免疫检测. 将拉曼活性分子对巯基苯甲酸吸附于金纳米棒表面, 制备出SERS标记的金纳米棒探针. 该探针和蛋白抗体结合形成SERS标记抗体. 通过SERS标记抗体、待测抗原和俘获抗体(固体基底上修饰的抗体, 即俘获抗体)之间的免疫应答反应, 将金纳米棒探针组装到固体基底上, 形成SERS标记抗体-抗原-俘获抗体 “三明治”夹心复合体. 待测抗原浓度越大, 固体基底上俘获的金纳米棒探针的数目越多, 从而可通过SERS信号的强弱来检测待测抗原的浓度. 由于金纳米棒的表面等离子体共振(SPR)峰位置可以在较宽的范围内调控, 可通过激发光和SPR的耦合来提高SERS信号, 从而提高免疫检测的灵敏度. 单组分抗原可检出的浓度范围高于1×10－8 mg/mL.     

静电纺纳米复合纤维柔性表面增强拉曼散射传感基底的研究进展

表面增强拉曼散射(Surface enhanced Raman scattering,SERS)是一种分子检测光谱技术,借助SERS基底,可对生物、化学等复杂体系中的痕量分子进行分析。 其中静电纺纳米纤维SERS基底由于具有高比表面积、可透气透水、柔韧可折叠弯曲等特点,在复杂体系中提取、过滤、浓缩痕量分子等应用场景中,其表面结构具有其他刚性SERS基底不可比拟的优势。然而,静电纺纳米纤维SERS基底的发展却受到制备方法的限制,存在检测灵敏度较低、制备过程复杂等问题。 因此,目前的研究工作主要集中在新型制备方法及工艺的开发。 本文综述了静电纺纳米金银复合纤维SERS基底的几种常用制备方法,包括直接混合纺丝法、化学吸附法、静电吸附法、物理沉积法和原位化学还原法,并总结了静电纺纳米纤维SERS基底在复杂体系中提取、过滤、浓缩待测分子的应用,最后对静电纺纳米复合纤维SERS基底的发展进行了展望。     

基于自组装纳米金单层膜的全内反射SERS研究

采用静电自组装技术分别在玻璃基片和30 nm厚的金膜表面固定一层金纳米粒子(GNP)制得两种表面增强拉曼散射(SERS)基底,然后通过棱镜全内反射(TIR)激励和背向收集模式分别测试了两种基底上吸附的染料单分子层SERS光谱.实验结果表明两种SERS基底的拉曼增强效果均高度依赖于入射激光的偏振状态,对于玻璃/纳米金SERS基底,s光全内反射导致的拉曼增强因子是线偏振光(p)光的2-5倍,说明该基底上的"热点"位于纳米金单层膜内相邻粒子之间;对于玻璃/金膜/纳米金SERS基底,只有采用p光在特定的全内反射角下才能激发SERS信号,而且测得的SERS信号比玻璃/纳米金基底增强了近30倍.究其原因是p光在金膜表面共振激发的传播表面等离子体与纳米金局域表面等离子体耦合,进而导致显著场增强.实验结果指出在背向收集模式下,由p光激发的SERS信号是非偏振光,包含强度几乎相等的s和p成分.利用玻璃/金膜/纳米金基底还实现了拉曼光定向发射和收集,测得的SERS信号是p光.     

硅片表面构建的纳米金SERS基底检测雾霾颗粒物中的芴

以金纳米颗粒为基础,在硅片表面进行自组装,制备了纳米颗粒均匀密集分布的表面增强拉曼（SERS）基底,经过修饰后,实现了对雾霾颗粒物中的多环芳烃类物质—芴的分析测定。以3-氨丙基三甲氧基硅烷为偶联剂将纳米金固定到羟基化处理的硅片表面,然后将硅片在纳米金胶体和2-吡咯烷酮溶液中交替浸泡,在硅片表面制备了纳米颗粒均匀密集分布SERS基底。选择1-硫代癸烷对SERS基底进行修饰,以芴为目标物进行SERS检测,结果显示,在芴的浓度为1×10^-6～5×10^-5mol/L范围内,信号强度与浓度间具有良好的线性关系。将该基底用于雾霾颗粒物中芴的检测,在采集了雾霾样品的玻璃纤维膜表面芴的添加浓度约为5×10^-7～5×10^-6mol/g时,可以实现80%以上的回收率。     

基于自组装纳米金单层膜的全内反射SERS研究

采用静电自组装技术分别在玻璃基片和30 nm厚的金膜表面固定一层金纳米粒子（GNP）制得两种表面增强拉曼散射（SERS）基底,然后通过棱镜全内反射（TIR）激励和背向收集模式分别测试了两种基底上吸附的染料单分子层SERS光谱. 实验结果表明两种SERS基底的拉曼增强效果均高度依赖于入射激光的偏振状态,对于玻璃/纳米金SERS基底,s 光全内反射导致的拉曼增强因子是线偏振光（p）光的2-5 倍,说明该基底上的“热点”位于纳米金单层膜内相邻粒子之间;对于玻璃/金膜/纳米金SERS基底,只有采用p光在特定的全内反射角下才能激发SERS信号,而且测得的SERS信号比玻璃/纳米金基底增强了近30 倍. 究其原因是p 光在金膜表面共振激发的传播表面等离子体与纳米金局域表面等离子体耦合,进而导致显著场增强. 实验结果指出在背向收集模式下,由p 光激发的SERS信号是非偏振光,包含强度几乎相等的s 和p 成分. 利用玻璃/金膜/纳米金基底还实现了拉曼光定向发射和收集,测得的SERS信号是p光.     

作为表面增强拉曼光谱基底的高度均匀Au纳米棒的构筑及对福美双的检测

采用种子生长法制备Au纳米棒(GNRs),随后进行组装和煅烧得到单层致密堆积的GNRs薄膜。在煅烧过程中,组装所需有机物在煅烧过程中分解,从而使得GNRs表面具有较高的清洁度。研究中发现,煅烧前后金纳米棒表面的间隙进一步提高,增强了其SERS(表面增强拉曼光谱)活性。为了研究其SERS活性,选择了2种探针分子以研究其灵敏度和均匀性,发现其具有较高的灵敏度和高的信号稳定性。随后将所制备的SERS基底成功用于检测超低浓度的农药分子。     

PDMS-Au复合基底上多环芳烃分子的表面增强拉曼光谱

利用聚二甲基硅氧烷(PDMS)对有机物的富集功能,通过在金纳米粒子单层膜(Au MLF)表面旋涂薄层PDMS膜制备PDMS-Au MLF复合表面增强拉曼光谱(SERS)基底.研究了SERS增强性能与旋涂液浓度及稀释溶剂间的关系,考察了复合基底增强活性的均匀性.研究发现,采用叔丁醇为稀释溶剂,浓度为2%(质量分数)的旋涂液时所得复合基底表面多环芳烃(PAHs)的SERS信号强度最高,且此基底SERS信号强度偏差小于10%.分别以PDMS-Au MLF复合材料和Au MLF作为基底,对比研究了对萘、蒽、菲和芘4种多环芳烃的SERS检测能力.结果表明,PDMS-Au MLF复合基底对以上4种有机物的检出限分别为10~(-6),10~(-7),10~(-8)及10~(-7)mol/L,相比于单一Au MLF基底,其检测限至少降低了1个数量级,这主要源自于PDMS对PAHs的富集作用,且此类复合基底可用于多种多环芳烃混合物的特征识别.     

高透明的柔性金纳米纤维膜

通过静电纺丝技术与离子溅射镀膜法,以电纺聚乙烯吡咯烷酮(PVP)为模板,制备了高透明的柔性金(Au)纳米纤维膜.研究表明,该柔性Au纳米纤维膜呈现无规网状分布,纤维的平均直径为291~322 nm.当Au的溅射时间为75 s时,所得薄膜的可见光透过率为92%,近红外反射率为7%,电阻率为2.9×10-3Ω·cm.该Au纳米纤维膜可转移到任何柔性基底上,且显示出优异的柔韧性,在弯曲500次后其电阻率基本不变.     

Au-Ag三角纳米环单层膜的原位转化制备及 SERS效应

利用模板牺牲氧化还原反应将自组装在基片上的三角板银纳米粒子(边长约为79.2 nm)与氯金酸溶液作用进而原位转化形成三角纳米环. 通过紫外-可见(UV-Vis)光谱实时监测基片上银三角板纳米粒子在反应不同阶段的消光特性; 扫描电子显微镜(SEM)显示了银三角板纳米粒子转化过程的形貌变化; 利用X射线光电子能谱(XPS)对其成分进行分析. 表征结果表明, 三角纳米环的成分为Au-Ag合金或复合物; 随着基片与氯金酸溶液作用时间的增加, 自组装膜的表面等离子体共振峰逐渐红移; Au-Ag三角环状纳米粒子的平均壁厚度从29.3 nm缩小至16.2 nm. 以4-巯基苯胺(4-ATP)为探针分子研究了该Au-Ag三角环状纳米粒子单层膜的表面增强拉曼(SERS)活性. 自组装单层膜基底的SERS信号随着Au-Ag三角纳米环平均壁厚度的增加逐渐增强.     

室温电子还原制备金纳米颗粒与琼脂糖复合膜的表征与应用

利用室温电子还原技术合成了一种金纳米颗粒与琼脂糖复合膜。合成过程采用氩气辉光放电为廉价电子源,方便快捷,绿色环保。通过紫外-可见(UV-Vis)分光光度计、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射(XRD)仪、光电子能谱(XPS)等表征,发现可以通过改变氯金酸浓度调控复合膜中金纳米颗粒的分布,加入聚乙烯吡咯烷酮(PVP)可有效控制金纳米颗粒的形貌。由于复合膜具有金纳米颗粒密集排布的结构,可作为表面增强拉曼散射(SERS)活性基底。实验表明,以对氨基苯硫酚为探针,该复合膜作为SERS基底,SERS平均增强因子超过了106,检测限达到了10-12mol?L-1。除此之外,作为SERS基底,复合膜具有良好的均一性和稳定性。     

Novel mechanism for spinning continuous twisted composite nanofiber yarns

Highly aligned and twisted composite Nylon 6 nanofibers incorporating multiwall carbon nanotubes (MWCNTs) were successfully electrospun, using a novel mechanism. It has been found that; ultrasound combined with high speed shearing is the simplest and most convenient method to improve the dispersion of MWCNTs into a polymer matrix with a certain loading. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were conducted to characterize the morphology of nanofibers, the dispersion of MWCNTs and their alignment inside the fiber body. By manipulating the electrical forces during electrospinning and applying mechanical stretching to the electrospun nanofibers, high polymer chain orientation and better alignment of the MWCNTs particles along the fiber axis was achieved. Twist was applied to the nanofibers for providing the required inter fiber lateral cohesion interaction and friction thus, spinning a continuous twisted composite yarn. SEM images show twisted yarns with diameters ranging between 5 and 10 μm. The twist effect of the parallel bundle was investigated by controlling the twist per unit length using a motor speed controller at values of 100, 250, 500, 750 and 1000 rpm. The paper also provides a comprehensive review of various yarn spinning mechanisms of electrospun nanofibers.     

Structure and nanomechanical characterization of electrospun PS/clay nanocomposite fibers

Electrospinning has been emerging as one of the most efficient methods to fabricate polymer nanofibers. In this paper, PS/clay nanocomposite fibers with varying diameters were electrospun onto solid substrates. The fiber diameters were adjusted from 4 microm to 150 nm by changing the solution concentration. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) were used to characterize the fiber morphology. Shear modulation force microscopy (SMFM) was utilized to investigate the surface nanomechanical properties of electrospun fibers as a function of the fiber diameter and temperature. In the absence of clay, no change in T(g) was observed, even though a large increase of shear modulus below the glass transition temperature was found. This effect was postulated to result from the molecular chain alignment during electrospinning. The addition of functionalized clays to the spinning solution produced fibers with a highly aligned montmorillonite layer structure at a clay concentration of 4 wt %. Clay agglomerates were observed at higher concentrations. The existence of clay further enhanced the shear modulus of fibers and increased the glass transition temperature by nearly 20 degrees C.     

Electrospun EGNPs reinforced precursor carbon nanofibril composites by using RSM

Response surface methodology (RSM),based on five‐level, four variable Box‐Benkhen technique was investigated for modeling the average fiber diameter of electrospun polyacrylonitrile (PAN) nanofibers. The four important electrospinning parameters were studied including applied voltage (kV), Berry's number, deposition distance from nozzle to collector (cm), and spinning angle (? in degree). The measured fiber diameters were in a good agreement with the predicted results by using RSM technique. High‐regression coefficient between the variables and the response (R² = 87.74%) indicates excellent evaluation of experimental data by second‐order polynomial regression model. The optimum PAN average fiber diameters of 208 and 37‐nm standard deviation were collected at 19 kV, Berry's number = 10, 25^° spinning angle, and 16‐cm deposition distance. The PAN/N,N‐dimethylformamide (DMF) polymer solution with the optimum weight concentration (10 wt.%) was selected to study the effect of dispersing exfoliated graphite nanoplatelets (EGNPs) in PAN/DMF solution on the electrospun EGNP/PAN fibril composite diameter. Five different EGNPs weight concentrations (2, 4, 6, 8, and 10 wt.%) were dispersed in the optimized PAN/DMF polymer solution. Morphology of EGNPs/PAN fibril composites and its distribution were investigated by scanning electron microscopy (SEM) to show the minimum fiber diameter for the above‐mentioned 5 wt. % of EGNPs. A minimum fibril composite diameter of 182 nm was obtained at 10 wt.% of EGNPs. Morphological characteristics of electrospun fibers and their distribution were tested by Raman spectroscopy, SEM, differential light scattering, and high‐resolution transmission electron microscopy.     

Synthesis of Poly（N-vinylpyrrolidone） Nanofibers Containing Gold Nanoparticles via Electrospinning Technique

Poly(N-vinylpyrrolidone)(PVP)nanofibers containing gold nanoparticles were prepared by electrospinning method.This simple route was used to prepare composites on a large scale,and the syntheses are simple.The optical property of gold nanoparticles in PVP aqueous solution was investigated by UV-Visible absorption spectra.The morphology of the fibers and the distribution of particles were characterized by transmission electron microscopy.The structure of the composite was characterized by Fourier transform infrared spectroscopy.     

Preparation and characterization of coaxial electrospun thermoplastic polyurethane/collagen compound nanofibers for tissue engineering applications

Collagen functionalized thermoplastic polyurethane nanofibers (TPU/collagen) were successfully produced by coaxial electrospinning technique with a goal to develop biomedical scaffold. A series of tests were conducted to characterize the compound nanofiber and its membrane in this study. Surface morphology and interior structure of the ultrafine fibers were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM), whereas the fiber diameter distribution was also measured. The crosslinked membranes were also characterized by SEM. Porosities of different kinds of electrospun mats were determined. The surface chemistry and chemical composition of collagen/TPU coaxial nanofibrous membranes were verified by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectrometry (FTIR). Mechanical measurements were carried out by applying tensile test loads to samples which were prepared from electrospun ultra fine non-woven fiber mats. The coaxial electrospun nanofibers were further investigated as a promising scaffold for PIECs culture. The results demonstrated that coaxial electrospun composite nanofibers had the characters of native extracellular matrix and may be used effectively as an alternative material for tissue engineering and functional biomaterials.     

Synthesis and mechanical properties of para‐aramid nanofibers

Scalable, bottom‐up chemical synthesis and electrospinning of novel Cl‐substituted poly(para‐phenylene terephthalamide) (PPTA) nanofibers are herein reported. To achieve Cl‐PPTA nanofibers, the chemical reaction between the monomers was precisely controlled, and dissolution of the polymer into solvent was tailored to enable anisotropic solution formation and sufficient entanglement molecular weight. Electrospinning processing parameters were studied to understand their effects on fiber formation and mat morphology and then optimized to yield consistently high quality fibers. Importantly, the control of relative humidity during the fiber formation process was found to be critical, likely because water promotes hydrogen bond formation between the PPTA chains. The fiber and mat morphologies resulting from different combinations of chemistry and spinning conditions were observed using scanning electron microscopy, and observations were used as inputs to the optimization process. Tensile properties of single Cl‐PPTA nanofibers were characterized for the first time using a nanomanipulator mounted inside a scanning electron microscope (SEM), and fiber moduli measuring up to 70 GPa, and strengths exceeding 1 GPa were achieved. Given the excellent mechanical properties measured for the nanofibers, this chemical synthesis procedure and electrospinning protocol appear to be a promising route for producing a new class of nanofibers with ultrahigh strength and stiffness. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 563–573     

表面增强拉曼光谱检测联苯胺

采用柠檬酸钠还原法制备了具有表面增强拉曼散射(SERS)活性的银纳米溶胶, 利用透射电子显微镜、 扫描电子显微镜和紫外-可见光谱仪对银纳米溶胶进行了表征. 对水相的联苯胺进行了SERS研究, 并对联苯胺的拉曼谱带进行了归属. 考察了团聚剂氯化镁的浓度对检测的影响, 发现随着氯化镁浓度的变大, SERS信号呈现出先增大后减弱的趋势, 即氯化镁的浓度存在一个最佳值, 此时联苯胺的检测限可达到10^-8 mol/L.     

Stabilization of electrospun poly(vinyl alcohol) nanofibrous mats in aqueous solutions

<正>The stability ofpoly(vinyl alcohol)(PVA) nanofibrous mats in water media was improved by post-electrospinning treatments.Bifunctional glutaraldehyde(GA) in methanol was used as a crosslinking agent to stabilize PVA nanofiber,but fiber twinning was observed frequently,and the highly porous structure of PVA nanofibrous mats was destroyed when the crosslinked fiber was soaked in water.To overcome this shortcoming,chitosan(CS) was introduced into the PVA spinning solution to prepare PVA/CS composite nanofibers.Their treatment in GA/methanol solution could retain the fiber morphology of PVA/CS nanofibers and porous structure of PVA/CS nanofibrous mats even if they were soaked in aqueous solutions for 1 month.Scanning electron microscopy(SEM),X-ray diffraction(XRD),thermal gravimetric analysis(TGA) and differential scanning calorimetry(DSC) were applied to characterize the physicochemical structure and thermal properties of PVA nanofibers.It was found that the water resistance of PVA nanofibrous mats was enhanced because of the improvement of the degree of crosslinking and crystallinity in the electrospun PVA fibers after soaking in GA/methanol solution.