纳米银形状控制合成与聚合物纳米银复合材料

纳米银(Ag NPs)由于其独特的物理、化学和生物学特性备受研究人员的关注.纳米银应用性能除了受到粒子尺寸、分布、纯度等因素影响,还与纳米银的形状密切相关.纳米银的形状对纳米银的抗菌性能、光学性能以及聚合物纳米银复合材料的综合性能都会产生重要影响.纳米银的形状控制合成可以进一步发挥聚合物纳米银复合材料的性能潜力.因此,不断发展纳米银新的合成方法,研究纳米银形状控制的机理就显得尤为重要.本文综述了纳米银合成方法和不同形状纳米银的最新研究进展,合成方法重点介绍了辐射法、激光烧蚀法、电化学法、光化学法和生物合成法,评述了这些方法的优缺点;同时从模板法、动力学、热力学以及氧化刻蚀4个方面介绍了纳米银形状控制的机理.介绍了聚合物纳米银复合材料的研究进展.     

聚合物存在下纳米银复合材料的制备与表征

以聚丙烯腈聚乙二醇嵌段共聚物PAN-b-PEG-b-PAN为稳定剂, 在超声辐照下成功地制备了分散性较好、尺寸均匀的纳米银颗粒. 用X射线衍射(XRD)、红外光谱(FTIR)、透射电镜(TEM)、紫外-可见吸收光谱(UV-Vis)和热分析(TGA)等对制备的纳米银复合材料进行了表征. 红外结果表明超声辐照并没有破坏聚合物的链结构. 聚合物的引入, 对纳米银颗粒起到了很好的分散保护作用. 用低浓度的硝酸银溶液, 得到粒径较小的纳米银颗粒; 随着硝酸银浓度增大, 纳米银颗粒粒径也增大. 而聚合物的浓度增大时, 所得银纳米颗粒粒径减小. 对银纳米颗粒的形成机理进行了讨论.     

乙二胺溶剂热还原法制备碳纳米管

以乙二胺作为溶剂和碳源,用KBH4还原NiCl2得到的镍作为催化剂,于300℃制备碳纳米管。X-射线衍射(XRD)、透射电子显微镜(TEM)、选区电子衍射(SAED)和Raman光谱分析证明,产品为多壁碳纳米管,直径约为100nm,长度达几微米。该方法具有反应温度低、反应时间短、操作简便等特点。     

超声化学法制备树枝状纳米银的研究

Nanostructured silver dendrites were synthesized by using sonochemical method from an aqueous solution of AgNO₃ in the presence of isopropanol as reducing agent and polyethylene glycol (PEG) as disperser. The silver nanostructures were characterized by using TEM， XRD and EDS analysis. The effects of reducing agents， dispersers， concentration of AgNO₃ on the silver dendrites nanostructures were also invetigated. A well-defined nanostructured silver dendrite was prepared by ultrsonic irradiation of the aqueous solution of 0.04 mol·L^-1 silver nitrate， 4.00 mol·L^-1 isopropanol and 0.04 mol·L^-1 PEG400 for 1 h.     

以乙二胺为手臂分子制备的DNA修饰电极及其伏安性能

Carboxyl was formed on the surface of glassy carbon electrode(GCE) by electrochemical oxidation. Ethylenediamine(En) was used as the arm molecule to link carboxyl with dsDNA using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide hydrochloride (EDC) and N- hydroxysuccinimide (NHS) as the activators to prepare dsDNA modified electrode(dsDNA/En/GCE). It was shown that dsDNA couM be covalently immobilized on the surface of GCE. ssDNA modified electrode(ssDNA/En/GCE) was obtained via the thermal denaturation of dsDNA/En/GCE. The dsDNA/En/GCE and ssDNA/En/GCE were characterized by voltammetry with methylene blue(MB) as the indicator. The results indicated that the currents of the redox peaks of MB at ssDNA/En/GCE were larger than those at dsDNA/En/GCE, and the currents of the redox peaks at En/GCE were the smallest. The peak-currents of MB at the DNA modified electrode had good reproducibility after multi-denaturation and hybridization cycles.     

葡聚糖为载体的双亲型LDL吸附剂吸附动力学研究

合成了以葡聚为载体，同时具有亲水性磺酸基和疏水性胆固醇两类配基的新型低密度脂蛋白（LDL）吸附剂。通过对LDL纯溶液中吸附等温线的测试，比较了以Dextran G-75为载体的双亲型LDL吸附剂与单一亲水型磺酸基配基，单一疏水型胆固醇基吸附剂吸附量和亲和吸附系数的关系。对双亲型LDL吸附剂的吸附动力学进行了初步研究，在LDL溶液中，亲水型磺酸基，疏水型胆固醇配基，双亲型LDL吸附剂对LDL的吸附曲线基本上符合Langmuir吸附方程，另外通过高离子强度NaCl洗脱实验，测定了双亲型LDL吸附剂上具有的磺酸基与胆固醇两类基在对低密脂蛋白吸附过程中所起的配合效果，为下一步作用力机制研究提供了参考依据。     

纳米银粒子的制备方法进展

综述了纳米银粒子的制备方法,包括物理方法和化学方法。     

气相色谱法测定羟乙基乙二胺中的乙二胺含量

采用毛细管气相色谱内标法测定羟乙基乙二胺中的乙二胺含量．结果表明。乙二胺在0．12．0ms／mL范围内的线性关系良好（r=0．9997）,检出限为0．02m/mL,方法的精密度RSD为1．7％（n=6）,加标回收率在95％～101％．     

葡聚糖免疫磁性毫微粒的制备及作为复合靶向载体研究

用共沉淀法制备出具有超顺磁性的葡聚糖磁性毫微粒.研究了制备过程中葡聚糖浓度、铁盐用量、搅拌速度、氨水浓度和Fe～(3+)/Fe～(2+)摩尔比对葡聚糖磁性毫微粒有效粒径的影响.抗人乳腺癌单抗与高碘酸钠氧化的葡聚糖磁性毫微粒反应形成葡聚糖免疫磁性毫微粒,并对它的磁化率、形态和抗体保留活性等性质进行了研究.通过放射免疫实验考察葡聚糖免疫磁性毫微粒体外结合肿瘤抗原的能力,同时研究了放射性标记的葡聚糖免疫磁性毫微粒在动物体内的磁性和抗体导向能力.     

树枝状纳米银颗粒的制备与电活性

在Ag(NH3)2+溶液中,在钛基体上电沉积出树枝状纳米银颗粒,研究了沉积电位对树枝状纳米银颗粒形成的影响,探讨了这种树枝状纳米银颗粒形成的机理,并研究了这种钛基树枝状纳米银电极(Ag/Ti)在碱性溶液中对甲醛氧化的电催化活性。结果表明,在30 mmol/LAg(NH3)2+以及沉积电位在-1.8～-1.2 V(vsAg)时,形成了形态为树枝状的纳米银颗粒。在沉积电位为-1.6 V(vs Ag),Ag(NH3)2+浓度为30 mmol/L的溶液中,电沉积制备的这种树枝状纳米银电极(Ag/Ti)对甲醛氧化具有强的电催化活性。循环伏安曲线表明,在0.1 mol/LNaOH溶液中以及甲醛的浓度范围在0～40 mmol/L,甲醛浓度和它的氧化峰电流密度呈现良好的线性关系,检测下限达到0.662 mmol/L,这种新型的树枝状纳米银电极有望作为甲醛检测的传感器。     

三角形纳米银颗粒的制备及其热稳定性的研究

具有独特的光学和化学性质的纳米三角形银纳米颗粒在光电、催化和生物传感器等领域中有广泛的应用.提供一种简单的方法制备三角银纳米颗粒,对其进行表征研究,且详细讨论了其热力学稳定性.     

天然松香用于制备球型纳米银的研究

以AgNO3为原料,利用天然松香中的还原性物质枞酸还原银氨络离子得到银纳米颗粒,利用油酸等与纳米颗粒的相互作用在表面形成一层保护层来防止纳米颗粒的聚集。并用UV-vis、TEM和XRD对其进行检测和表征。通过控制反应条件,可制得粒度分布较均匀、结晶性能良好的银纳米颗粒。     

Biofunctionalized silver and gold nanoparticles as potential curative agents

In this study, the bark of an important medicinal plant, Indigofera aspalathoides is utilized as a bioreductant for the synthesis of silver nanoparticles (AgNPs) and gold nanoparticles (AuNPs). The formation of nanoparticles was monitored, and the reaction parameters were optimized by UV–Vis spectroscopy. The attachment of biocomponents as stabilizer was proved employing Fourier‐transform infrared (FT‐IR) studies. Through transmission electron microscopy (TEM), the morphology was found to be predominantly spherical and a mixture of triangle and hexagon in the case of AgNPs and AuNPs, respectively. The crystallite size of AgNPs and AuNPs was affirmed through X‐ray diffraction (XRD) studies using Sherrer formula as 22.03 and 47.70 nm, respectively. DPPH method was adopted to analyse the free‐radical quenching ability, and the AgNPs, AuNPs and extract showed inhibition of 76%, 89% and 59% at a concentration of 200 μg ml^?1, and the corresponding IC₅₀ values were 86.49, 55.20 and 149.19 μg ml^?1. The binding of nanoparticles to calf‐thymus DNA (CT‐DNA) was through groove and the high binding constants (8.49 × 10⁶ M^?1 and 2.34 × 10⁷ M^?1 for AgNPs and AuNPs) point out the potential of these nanoparticles as curative drugs. The MTT assay showed that AgNPs were 100% toxic, and the low IC₅₀ value suggests that this can be used in the medicinal field as a safe drug.     

Synthesis of amphiphilic graft copolymer brush and its use as template film for the preparation of silver nanoparticles

A microphase‐separated, amphiphilic graft copolymer consisting of a poly (vinyl chloride) (PVC) backbone and poly(oxyethylene methacrylate) (POEM) side chains, (PVC‐g‐POEM at 62:38 wt %) was synthesized via atom transfer radical polymerization (ATRP). Nuclear magnetic resonance (¹H NMR), FTIR spectroscopy, and transmission electron microscopy (TEM) clearly revealed that the “grafting from” method using ATRP was successful and that the graft copolymer molecularly self‐assembled into discrete nanophase domains of continuous PVC and isolated POEM regions. The self‐assembled graft copolymer film was used to template the growth of silver nanoparticles in solid state by introducing a AgCF₃SO₃ precursor and a UV irradiation process. The in situ formation of silver nanoparticles in the graft copolymer template film was confirmed by TEM, UV–visible spectroscopy, and wide angle X‐ray scattering. FTIR spectroscopy and X‐ray photoelectron spectroscopy also demonstrated the selective incorporation and in situ formation of silver nanoparticles within the hydrophilic POEM domains, presumably due to strong interactions between the silver and the ether oxygen in POEM. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3911–3918, 2008     

Synthesis of aza-crown ether-modified silver nanoparticles as colorimetric sensors for Ba2+

In this paper, we have demonstrated a facile strategy of preparing aza-crown ether (ACE)-modified silver nanoparticles (Ag NPs) by an efficient nano-conjugate technology named dithiocarbamate. This is the first report of using ACE to modify Ag NPs. ACE-modified Ag NPs have a good recognition of Ba²⁺, with the detection limit of 10^? 8 mol/l. It is reasonable to believe that Ba²⁺ induced the self-assembly of Ag NPs by the formation of the sandwich structure with ACE.

     

Synthesis of silver nanoparticles in mesoporous high-aluminum aluminosilicate matrices

A new method for the synthesis of Ag/Al_xSi_1–x O_2–0.5x nanocomposite materials was proposed. The method is based on the use of charged mesoporous aluminosilicate matrices as nanoreactors. The porous structure of the matrices was characterized by ²⁷Al NMR spectroscopy and nitrogen capillary sorption at 77 K. An increase in the aluminum loading destroys the matrix structure and decreases the specific surface area. The resulting aluminosilicates were used as matrices for the synthesis of silver nanoparticles. The nanocomposites were examined by transmission electron microscopy and chemical analysis to estimate the silver percentage in specimens. Silver nanowires (20% Ag) are formed in the low-aluminum (<10 mol.%) matrices, whereas an increase in the aluminum percentage affords both nanowires and spherical particles 3–10 nm in size and decreases the total amount of silver in the nanocomposite.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2391–2393, November, 2004.     

Paramagnetic behaviour of silver nanoparticles generated by decomposition of silver oxalate

Silver oxalate Ag₂C₂O₄, was already proposed for soldering applications, due to the formation when it is decomposed by a heat treatment, of highly sinterable silver nanoparticles. When slowly decomposed at low temperature (125 °C), the oxalate leads however to silver nanoparticles isolated from each other. As soon as these nanoparticles are formed, the magnetic susceptibility at room temperature increases from −3.14 10⁻⁷ emu.Oe⁻¹.g⁻¹ (silver oxalate) up to −1.92 10⁻⁷ emu.Oe⁻¹.g⁻¹ (metallic silver). At the end of the oxalate decomposition, the conventional diamagnetic behaviour of bulk silver, is observed from room temperature to 80 K. A diamagnetic-paramagnetic transition is however revealed below 80 K leading at 2 K, to silver nanoparticles with a positive magnetic susceptibility. This original behaviour, compared to the one of bulk silver, can be ascribed to the nanometric size of the metallic particles.     

Toward a comprehensive understanding of textiles functionalized with silver nanoparticles

This article provides a comprehensive understanding of development of textiles functionalized with silver nanoparticles (AgNPs). There are three established methods to fabricate textiles functionalized with AgNPs, namely, solution‐immersion, layer‐by‐layer deposition, and sonochemical. In addition, several textile types such as cotton, wool, polyester, silk, cotton/polyester blend, polyamide, and regenerated cellulose have been used for the fabrication. The AgNP deposition mechanism on textiles is mainly due to electrostatic interaction between AgNPs and textile constituents. It was exhibited that the deposition of AgNPs on textiles can transform their textiles colors. In addition, it was demonstrated that the deposition of AgNPs on textiles is not permanent, particularly against washing treatment. Textiles modified with AgNPs have several promising applications such as antibacterial, antifungal, catalyst, electronic devices, water treatment, sun protection, air treatment, and surface‐enhanced Raman scattering, which are comprehensively discussed in this article. Future challenges in fabricating textiles functionalized with AgNPs remain on how this can be carried out to improve long‐term stabilization of AgNPs on textiles to achieve their permanent deposition by employing greener approaches.     

Ionic liquids-assisted greener preparation of silver nanoparticles

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