Immobilization of silver nanoparticles into POEGMA polymer brushes as SERS‐active substrates

Surface‐enhanced Raman scattering (SERS) has attracted a great deal of interest during the past four decades and emerged as an ultrasensitive optical technique for chemical and biomedical analysis. It is widely accepted that the facile fabrication of SERS substrates with high activity and good reproducibility is of crucial importance for their applications. Herein, we report on a fast and robust method for the synthesis and immobilization of silver nanoparticles (AgNPs) into poly(oligo(ethylene glycol) methacrylate) (POEGMA) brushes under mild conditions without using any reducing agents. POEGMA brushes of different chain lengths were synthesized directly on silicon wafers by surface‐initiated atom transfer radical polymerization with various reaction time. X‐ray photoelectron spectroscopy and field emission scanning electron microscope measurements indicated that the AgNPs were firmly and homogeneously embedded into POEGMA brushes. The resulting POEGMA–AgNP hybrid films were employed as SERS substrates for the detection of 4‐aminothiophenol, giving rise to an enhancement factor of up to 1.9 × 10⁶. The influence of the POEGMA's chain length on SERS performance was also investigated. Copyright © 2016 John Wiley & Sons, Ltd.     

Seed‐mediated growth method for electroless deposition of AgNPs on glass substrates for use in SERS measurements

In this work, an electroless deposition method for silver nanoparticles (AgNPs) on glass substrates was developed for use in surface‐enhanced Raman scattering (SERS) measurements. To obtain evenly distributed AgNPs of suitable size on the glass substrates, a seeding procedure was utilized as a pretreatment before the electroless deposition of AgNPs. The AgNPs thus formed were affected by both the seeding and growing procedures. To optimize the procedures for preparation of SERS substrates, several factors, including reaction time, the concentration of silver ions, and the concentration of reducing agents (glucose) for seeding and growing procedures, were varied. The morphologies of the seeds and the resulting AgNPs on the glass substrates were characterized by field‐emission scanning electron microscopy (FE‐SEM) and correlated with the SERS signals from probing with para‐nitrothiophenol (pNTP). The results indicated that only the seeding time and the concentration of silver ions significantly influenced the distribution and sizes of the Ag seeds on the substrates. In the growing procedures, both the concentration of silver nitrate and the reducing agent affected the morphologies of the resulting AgNPs and, hence, the SERS signals. The substrates prepared using this newly developed method offer 2–5 times improvement of the SERS signals compared to substrates prepared without seed treatment. Also, the AgNPs prepared by this method can be easily controlled to designated sizes with even spatial and size distributions. Copyright © 2009 John Wiley & Sons, Ltd.     

Development and analysis of cellulose nanocomposite films with in situ generated silver nanoparticles using tamarind nut powder as a reducing agent

Cellulose/Tamarind nut powder (TNP)/Silver nanoparticles (AgNPs) nanocomposites were prepared by in situ generation of AgNPs using regeneration method, followed by solution casting method. In this, TNP was used as a reducing agent. These nanocomposites were characterized using FT-IR spectroscopy, XRD and SEM and studied their mechanical properties and antibacterial activity for medical and packing applications. The FT-IR spectral studies revealed the involvement of functional groups – Polyphenols, Flavonoids and –OH in the process of reducing the metal salts into metal nanoparticles. These nanocomposites showed good antibacterial activity against five bacteria. Improved mechanical properties with good antibacterial activities make these composites suitable for medical, food and packaging applications.     

Fe3O4 – Glutathione stabilized Ag nanoparticles: A new magnetically separable robust and facile catalyst for aqueous phase reduction of nitroarenes

The heterostructured Ag nanoparticles decorated Fe₃O₄ Glutathione (Fe₃O₄‐Glu‐Ag) nanoparticles (NPs) were synthesized by sonicating glutathione (Glu) with magnetite and further surface immobilization of silver NPs on it. The ensuing magnetic nano catalyst is well characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), powder X‐ray diffraction (PXRD), thermogravimetric analysis (TGA). The prepared Fe₃O₄‐Glu‐Ag nanoparticles have proved to be an efficient and recyclable nanocatalyst with low catalyst loading for the reduction of nitroarenes and heteronitroarenes to respective amines in the presence of NaBH₄ using water as a green solvent which could be easily separated at the end of a reaction using an external magnet and can be recycled up to 5 runs without any significant loss in catalytic activity. Gram scale study for the reduction of 4‐NP has also being carried out successfully and it has been observed that this method can serve as an efficient protocol for reduction of nitroarenes on industrial level.     

Nature-inspired biogenic synthesis of silver nanoparticles for antibacterial applications

In recent decades, nanotechnology has been empowered as a new and developing interdisciplinary region of science and innovation that coordinates material science and biology. Nanoscience and nanotechnology open up new streets of examination that are helpful in synthesizing novel nanomaterials with remarkable applications. Among different metal nanomaterials, silver nanoparticles (AgNPs) attracted the attention of researchers due to their versatile antibacterial characteristics and biological properties. Biogenically synthesizing AgNPs from plants and microorganisms seems to be a highly promising alternative for developing a technology that is both environmentally benign and fast. Plants and microorganisms' ability to synthesize AgNPs has mostly remained untapped, and the lack of investigation is due to the vast variety of plants and microorganisms. This review aims to describe the current progress in various synthetic techniques for AgNPs and their potential for antibacterial applications. It discusses biogenic synthetic approaches, the role of various metabolites in the growth processes of AgNPs with antibacterial implications, bactericidal mechanisms, and the influence of operational parameters on AgNPs synthesis. Furthermore, the present status, critical challenges, and future outlook of AgNPs will be explored, which will definitely affect their present and future scenarios. We believe that by focusing readers' attention on nature-inspired, biogenically synthesized AgNPs and their bactericidal applications, this review will enable them to formulate a new perspective.     

银纳米颗粒/聚(乙撑二氧噻吩)修饰的硅纳米线阵列的合成及可见光催化性能研究

硅纳米线阵列由于其较强的光吸收能力及硅材料的丰富储量,被认为是最具大规模应用潜力的可见光光催化剂.针对硅材料在水相环境中不稳定这一瓶颈问题,本文提出了对硅纳米线阵列"先稳定、再活化"的修饰策略.通过在硅纳米线表面修饰聚(乙撑二氧噻吩)使其稳定,之后再修饰银纳米颗粒以提高光催化效率,得到了高效、稳定的可见光光催化剂.并通过研究聚(乙撑二氧噻吩)的厚度及银纳米颗粒的担载量对光催化剂性能的影响,得到了最佳的修饰条件.     

PS微球阵列的制备与表面增强拉曼散射研究

为了研究不同直径PS微球(表面溅射Ag膜)基底的表面增强拉曼散射(SERS)效应,制造了一个新的表面增强拉曼散射(SERS)基底。通过在n型(100)单晶硅片上采用旋涂的方法,得到不同直径的呈六角形有序排列的单层PS微球阵列,然后在PS微球阵列表面磁控溅射一层约30 nm的Ag膜。利用拉曼光谱仪以罗丹明R6G为探针进行了SERS光谱测定,分析比较了不同直径PS微球阵列的表面增强拉曼散射效应,结果表明,溅射有Ag膜的PS微球基底在不同直径下均有不同程度的SERS效应。随着微球直径的增加,PS微球阵列的起伏程度不断加强(粗糙度不断增加),SERS信号逐渐增强,当球直径达到600 nm时,峰的增强信号达到最大,进而获得了一个最优化的SERS基底。同时发现在基底上获得了高信噪比的R6G的SERS光谱, 与苯环相关的一系列CC双键伸缩振动特征谱以及与苯环相关的面内、面外变形振动特征谱均获得了明显增强。这种单一的大区域的拉曼散射基底,呈现出高低相间起伏分布的微观形貌,不同PS微球之间的空隙和深度有很明显的不同,能够显著改善表面Ag膜颗粒的大小和分布,进而提高了PS微球基底的SERS活性。该基底所具有的特殊阵列结构使其在利用SERS探究化学和生物等领域的单分子结构有很大的应用潜力。     

基于SERS技术的食源性致病菌芽孢拉曼光谱特征结构分析及快速识别

为了探究食源性致病菌芽孢的拉曼特征指纹图谱,实现快速识别,该研究以产气荚膜梭菌（C. perfringens）、艰难梭菌（C. difficile）和蜡样芽孢杆菌（B. cereus）的芽孢为研究对象,以柠檬酸钠还原法制备的AgNPs溶胶为基底材料,用SERS技术对芽孢进行拉曼光谱检测,解析食源性致病菌芽孢的分子结构、不同芽孢之间的异同之处。将3种食源性致病菌芽孢的SERS光谱与主成分分析（PCA）和系统聚类分析（HCA）相结合并进行对比分析,实现不同种属食源性致病菌芽孢的定性识别。结果表明,不同食源性致病菌芽孢的SERS光谱的特异性和重现性良好。芽孢光谱中Ca2+-DPA的拉曼振动峰数量和峰强度占主要地位,其拉曼振动峰位置在657～663,818～820,1 017,1 389～1 393,1 441～1 449和1 572～1 576 cm-1波段。C. difficile spores SERS光谱中Ca2+-DPA的六个特征峰峰强度均高于C. perfringens spores和B. cereus spores,C. perfringens spores次之。Ca2+-DPA在1 017 cm-1（Ca2+-DPA）处拉曼峰强度在3种芽孢的SERS光谱中均最高且差异明显,是Ca2+-DPA的主要特征峰,也是3种芽孢的主要特征峰。此外,C. perfringens spores在936 cm-1（磷脂N—C拉伸）、1 294 cm-1（脂质中的CH₂变形振动）、1 609 cm-1（蛋白质中的酪氨酸）和1 649 cm-1（蛋白质中的酰胺I）显示特有拉曼振动峰;C. difficile spores在890 cm-1（═COC═拉伸）显示特有拉曼振动峰。PCA分析结果显示PC1和PC2方差贡献率分别为51.1%和39.7%,累积贡献率达90.8%,可以将所有样本有效区分。HCA分析可以看出3种芽孢的SERS光谱被分为三个聚类,3种芽孢各自聚类无交叉干扰。结合多元统计分析不仅有效实现了3种芽孢之间的区分,也实现了梭菌属芽孢和杆菌属芽孢的区分,为食品安全控制提供有效手段。     

Antifungal,Antibacterial, and Cytotoxic Activities of Silver Nanoparticles Synthesized from Aqueous Extracts of Mace-Arils of Myristica fragrans

In the present study, mace-mediated silver nanoparticles (mace-AgNPs) were synthesized, characterized, and evaluated against an array of pathogenic microorganisms. Mace, the arils of Myristica fragrans, are a rich source of several bioactive compounds, including polyphenols and aromatic compounds. During nano synthesis, the bioactive compounds in mace aqueous extracts serve as excellent bio reductants, stabilizers, and capping agents. The UV-VIS spectroscopy of the synthesized NPs showed an intense and broad SPR absorption peak at 456 nm. Dynamic light scattering (DLS) analysis showed the size with a Z average of 50 nm, while transmission electron microscopy (TEM) studies depicted the round shape and small size of the NPs, which ranged between 5–28 nm. The peaks related to important functional groups, such as phenols, alcohols, carbonyl groups, amides, alkanes and alkenes, were obtained on a Fourier-transform infrared spectroscopy (FTIR) spectrum. The peak at 3 keV on the energy dispersive X-ray spectrum (EDX) validated the presence of silver (Ag). Mace-silver nanoparticles exhibited potent antifungal and antibacterial activity against several pathogenic microorganisms. Additionally, the synthesized mace-AgNPs displayed an excellent cytotoxic effect against the human cervical cancer cell line. The mace-AgNPs demonstrated robust antibacterial, antifungal, and cytotoxic activity, indicating that the mace-AgNPs might be used in the agrochemical industry, pharmaceutical industry, and biomedical applications. However, future studies to understand its mode of action are needed.     

Green synthesis of silver nanoparticles using aqueous extract of Stachys lavandulifolia flower,and their cytotoxicity,antioxidant, antibacterial and cutaneous wound‐healing properties

In a biological process where the herbal tea (Stachys lavandulifolia) aqueous extract was applied as a capping and reducing agent, nanoparticles (NPs) of silver (Ag) were synthesized. These AgNPs were characterized using Fourier transform‐infrared spectroscopy, field emission‐scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, transmission electron microscopy and ultraviolet–visible spectroscopy. The synthesized AgNPs had great cell viability dose‐dependently [investigating the effect of the plant on human umbilical vein endothelial cell line] and indicated this method was non‐toxic. In this study, the 2,2‐diphenyl‐1‐picrylhydrazyl (DPPH) free radical scavenging test was carried out to examine antioxidant properties, which revealed similar antioxidant properties for AgNPs and butylated hydroxytoluene. Agar diffusion tests were applied to determine the antibacterial characteristics. The macro‐broth tube test was run to determine minimum inhibitory concentration. All data of antibacterial and cutaneous wound‐healing examinations were analyzed by SPSS 21 software (Duncan post hoc test). AgNPs showed higher antibacterial property than all standard antibiotics (p ≤ 0.01). Also, AgNPs prevented the growth of all bacteria at 2–8 mg/ml concentrations and destroyed them at 2–16 mg/ml concentrations (p ≤ 0.01). For the in vivo experiment, after creating the cutaneous wound, the rats were randomly divided into six groups: untreated control; treatment with Eucerin basal ointment; treatment with 3% tetracycline ointment; treatment with 0.2% AgNO₃ ointment; treatment with 0.2% S. lavandulifolia ointment; and treatment with 0.2% AgNPs ointment. These groups were treated for 10 days. For histopathological and biochemical analysis of the healing trend, a 3 × 3‐cm section was prepared from all dermal thicknesses at day 10. Use of AgNPs ointment in the treatment groups substantially reduced (p ≤ 0.01) the wound area, total cells, neutrophil, macrophage and lymphocyte, and remarkably raised (p ≤ 0.01) the wound contracture, hydroxyl proline, hexosamine, hexuronic acid, fibrocyte and fibrocytes/fibroblast rate compared with other groups. Seemingly, AgNPs can be used as a medical supplement owing to their non‐cytotoxic, antioxidant, antibacterial and cutaneous wound‐healing properties.