Chloride ion refined galvanic replacement: Boosting monodispersity of Au-Ag hollow nanoparticles & their enhanced applications

In this present work, we have redesigned the well-known Turkevich protocol for promoting versatile galvanic replacement, resulting in the synthesis of hollow Au nanostructures by the sacrificial reduction of HAuCl₄ on the as-prepared Ag nanoparticles in the presence of slight excess NaCl in order to dictate their core size to cavity ratio in a highly reproducible manner. The significance of chloride ion interaction in tuning the size/shape control was corroborated with the contrasting effect of other halide ions, namely bromine and iodine. The structure-property functional relationship of these artificial hollow metal nanostructures were not only established using the systematic optical absorption and TEM measurements, but also through enhanced spectroscopy measurements such as SEIRA and SERS, elucidating the dynamic advantage of hollow nanostructures over and above their solid monometallic counterparts. Further, the familiar 4-NA to p-PDA catalytic reduction kinetics demonstrate the unusual zeroth order characteristics in the presence of hollow metal nanostructures, unequivocally distinguishing it from the common first order characteristics associated with the corresponding solid metal nanoparticles, essentially attributed to the morphology tuned accessible higher total surface area, thus exemplifying the aesthetic compliance for future technological applications.     

Emulsion Polymerization Pathway for Preparation of Polyaniline‐Sulfate Salt,using Non Ionic Surfactant

In this work, aniline was polymerized directly to the polyaniline‐sulfate salt without using a protonic acid. The polyaniline‐sulfate salt was prepared by emulsion polymerization, using a non ionic surfactant such as poly(ethylene glycol)–block poly(propylene glycol)‐block poly(ethylene glycol). In the aniline oxidation process, to give the polyaniline salt by ammonium persulfate, the sulfate ion is generated from ammonium persulfate and doped on to the polyaniline. Ammonium persulfate acts both as an oxidizing agent, as well as the protonating agent in the aniline polymerization process, to give the polyaniline salt. This result indicates that the effect of sulfate ion, generated by ammonium persulfate during oxidation of aniline to the polyaniline salt, may be taken into consideration in the polymerization process of aniline.     

Identification of reducing and nonreducing neutral carbohydrates by laser‐enhanced in‐source decay (LEISD) MALDI MS

In this work, laser‐enhanced in‐source decay (LEISD) technique of matrix‐assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI‐FT‐ICR‐MS) was used to distinguish reducing and nonreducing carbohydrates. Interestingly, easier cleavage of (1 → 2)‐linked glycosidic bonds for nonreducing carbohydrates containing D‐fructofuranosyl units was observed in MALDI‐FT‐ICR‐MS, which was in agreement with the result of theoretical calculation by the software package Gaussian 09. Importantly, no cross‐ring cleavage of fructofuranosyl residues was detected in the LEISD spectra of nonreducing carbohydrates. LEISD method therefore offers an attractive alternative for fast and efficient differentiation of reducing and nonreducing carbohydrates, and the positions of nonreducing monosaccharide residues in a carbohydrate chain could be easily speculated. Copyright © 2013 John Wiley & Sons, Ltd.     

Functional silver nanostructured surfaces applied in SERS and SIMS

Present article deals with functionality of silver nanostructured surfaces prepared by potentiostatic electrochemical deposition on the paraffin impregnated graphite electrode as template‐free substrates. The effect of the electrodeposition conditions on two silver surface functions: analytical signal enhancement in Surface‐enhanced Raman spectroscopy and pre‐ionization function, applied in secondary ion mass spectrometry (SIMS) is reported. Functional silver nanostructured substrate was prepared at a potential ?850 mV with a deposition duration of 20 min. Analytical signal enhancement factors of 3.2 ×10⁵ for Raman peak at 649 cm^?1, 3.0×10⁵ for peak at 810 cm^?1 and 2.7×10⁵ for peak at 1539 cm^?1 were determined for Rhodamine 6G at deposited surface. Slight pre‐ionization effect has been observed in SIMS, and 1.2×10⁵ fold signal enhancement was established for fragment of Rhodamine 6G with m/z 429 (M‐CH₃‐Cl). Electrochemical preparation of nanostructures represents a step towards surface integration directly into miniaturized systems and sensors. Copyright © 2013 John Wiley & Sons, Ltd.     

New SERS feature of β‐carotene: consequences for quantitative SERS analysis

While recording SERS spectra of pure β‐carotene at sub‐micromole concentrations for reference purpose, we discovered an unusual spectral response never reported before. In pre‐resonance conditions with the 532‐nm line, SERS of β‐carotene with AgNPs exhibits among the strong υ(CC) mode at 1512 cm⁻¹ unshifted from normal Raman spectrum, additional strong bands at 1649, 1575 and 1387 cm⁻¹ as well as other medium bands not observed in the Raman spectrum of the crystalline powder. Such behavior is explained in terms of selection rules relaxation upon cyclohexene terminal rings of the β‐carotene interaction with the NP surface. AFM images of the SERS system suggested dimers and trimers clustering of the nanoparticles with adsorbed β‐carotene. In light of the new SERS feature the consequences in correct interpretation of the SERS imaging from complex biosystems containing carotenoids are discussed. Relative intensity ratio of the β‐carotene band at 1512 cm⁻¹ and water against concentration allowed a reliable SERS calibration curve for 50 to 500 nmol l⁻¹ concentration range and provided quantitative SERS assessment of the carotenoid content in the sea urchin (Paracentrotus lividus) gonads extracts. Copyright © 2015 John Wiley & Sons, Ltd.     

New advancements in SERS dye detection using interfaced SEM and Raman spectromicroscopy (μRS)

In the past decade Surface Enhanced Raman Scattering (SERS) has emerged as a powerful technique for the analysis of artistic, historical and archaeological material culture. However, the identification of organic compounds in complex samples using SERS can be challenging owing to the complexity in optimizing the adsorption of target analytes onto the plasmonic substrate and the difficulty to identify proper areas on the sample for robust SERS analysis using optical systems. Scanning electron microscopy (SEM) interfaced with Raman spectromicroscopy (μRS) provides an ideal hyphenated system to overcome the last challenge by: (1) evaluating the nanoparticles coverage/distribution on the sample and (2) locating suitable areas for successful and reproducible SERS analysis. In this paper we demonstrate the potential of a system interfacing SEM and μRS for single fiber, extractionless analysis in the characterization of dyes from reference collections and archaeological textiles. Copyright © 2015 John Wiley & Sons, Ltd.     

农产品中脱氧雪腐镰刀菌烯醇的表面增强拉曼检测

利用便携式拉曼光谱仪建立了一个快速筛查与检测谷物中真菌毒素脱氧雪腐镰刀菌烯醇(DON)的表面增强拉曼散射(SERS)方法。首先利用实验室前期开发的方法制备了具有高活性的水凝胶SERS芯片。该SERS芯片是将预先制备的高SERS活性的单层碳基点(CDs)包裹的银纳米颗粒团聚体(a-AgNPs/CDs)与聚乙烯醇(PVA)水溶液混合均匀后,再利用循环冷冻-解冻的物理交联法制备而成的。实验优化了影响水凝胶SERS芯片对DON的SERS响应的实验条件,包括溶剂、浸泡温度和浸泡时间。在最佳的SERS检测条件下(溶剂为水-乙醇(1:1, v/v),浸泡温度为40 ℃,浸泡时间为5 min), DON的线性响应范围为1~10000 μg/kg(相关系数(R²)=0.9967),检出限(LOD)为0.14 μg/kg,表明该SERS基底具有较高的灵敏度。得益于水凝胶特殊的孔径结构,实际样品基质中常见的糖、蛋白质、油脂、色素等干扰物质都被阻隔在水凝胶外。因此,在复杂样品检测中仅需要简单的提取,而不需要复杂的分离处理。将该方法用于小麦粉中DON的检测,所得回收率为97.3%~103%,相对标准偏差为4.2%~5.0%。实验结果表明所建立的检测DON的SERS方法具有响应范围宽、灵敏度高、重复性好、响应迅速、操作简单、抗干扰能力强等优点,这说明本实验室所构建的水凝胶SERS芯片在粮食中生物毒素的快速筛查与检测方面具有良好的应用潜力。     

Surface-Enhanced Raman Spectroscopy (SERS) for characterization SARS-CoV-2

We used SERS with silver nanoparticles (AgNPs) as the active substrate to develop a, simple, quick, and accurate method for the detection and characterization SARS-CoV-2 without the need for RNA isolation and purification. Inactivated SARS-CoV-2 was used. The SERS signals were more than 10⁵ times enhanced than the normal Raman (NR) spectra. The SERS spectra of SARS-CoV-2 fingerprint revealed pronounced intensity signals of nucleic acids; aromatic amino acid side chains: 1007 cm^?1 (Phe marker), 1095 cm^?1 (CN and PO₂^? markers), 1580 cm^?1 (Tyr, Trp markers). Vibrations of the protein main chain: 1144 cm^?1 (CN and NH₂ markers), 1221 cm^?1 (CN and NH markers), 1270 cm^?1 (NH₂ marker), 1453 cm^?1 (CHCH₂ marker). All of these biomolecules could be adsorbed on the AgNPs surface's dense hot patches. The intensity of the SERS band varied with the concentration of SARS-CoV-2, with a virus detection limit of less than 10³ vp/mL and RSDs of 20 %.     

Sunflower-Like Nanostructure with Built-In Hotspots for Alpha-Fetoprotein Detection

In the present study, a sunflower-like nanostructure array composed of a series of synaptic nanoparticles and nanospheres was manufactured through an efficient and low-cost colloidal lithography technique. The primary electromagnetic field contribution generated by the synaptic nanoparticles of the surface array structures was also determined by a finite-difference time-domain software to simulate the hotspots. This structure exhibited high repeatability and excellent sensitivity; hence, it was used as a surface-enhanced Raman spectroscopy (SERS) active substrate to achieve a rapid detection of ultra-low concentrations of Alpha-fetoprotein (AFP). This study demonstrates the design of a plasmonic structure with strong electromagnetic coupling, which can be used for the rapid detection of AFP concentration in clinical medicine.     

Raman Imaging: An Impending Approach Towards Cancer Diagnosis

In accordance with the recent studies, Raman spectroscopy is well experimented as a highly sensitive analytical and imaging technique in biomedical research, mainly for various disease diagnosis including cancer. In comparison with other imaging modalities, Raman spectroscopy facilitate numerous assistances owing to its low background signal, immense spatial resolution, high chemical specificity, multiplexing capability, excellent photo stability and non-invasive detection capability. In cancer diagnosis Raman imaging intervened as a promising investigative tool to provide molecular level information to differentiate the cancerous vs non-cancerous cells, tissues and even in body fluids. Anciently, spontaneous Raman scattering is very feeble due to its low signal intensity and long acquisition time but new advanced techniques like coherent Raman scattering (CRS) and surface enhanced Raman scattering (SERS) gradually superseded these issues. So, the present review focuses on the recent developments and applications of Raman spectroscopy-based imaging techniques for cancer diagnosis.