Anantharaj S, Sakthikumar K, Elangovan Ayyapan, Ravi G, Karthik T, Kundu Subrata
Electrochemical Materials Science (ECMS) Division, CSIR-Central Electrochemical Research Institute (CECRI), Karaikudi 630006, Tamil Nadu, India.
Electrochemical Materials Science (ECMS) Division, CSIR-Central Electrochemical Research Institute (CECRI), Karaikudi 630006, Tamil Nadu, India; Department of Chemistry, Kansas State University, Manhattan, KS 66506, USA.
J Colloid Interface Sci. 2016 Dec 1;483:360-373. doi: 10.1016/j.jcis.2016.08.046. Epub 2016 Aug 21.
Highly Sensitive and ultra-small Rhenium (Re) metal nanoparticles (NPs) were successfully stabilized in water by the staging and fencing action of the versatile biomolecule DNA that resulted in two distinct aggregated chain-like morphologies with average grain sizes of 1.1±0.1nm and 0.7±0.1nm for the very first time within a minute of reaction time. Re NPs are formed by the borohydride reduction of ammonium perrhenate (NH4ReO4) in the presence of DNA at room temperature (RT) under stirring. The morphologies were controlled by carefully monitoring the molar ratio of NH4ReO4 and DNA. The synthesized material was employed in two potential applications: as a substrate for surface enhanced Raman scattering (SERS) studies and as a catalyst for the reduction of aromatic nitro compounds. SERS study was carried out by taking methylene blue (MB) as the probe and the highest SERS enhancement factor (EF) of 2.07×10(7) was found for the aggregated chain-like having average grain size of 0.7±0.1nm. Catalytic reduction of 4-nitro phenol (4-NP), 2-nitro phenol (2-NP) and 4-nitroaniline (4-NA) with a rate constant value of 6×10(-2)min(-1), 33.83×10(-2)min(-1) and 37.4×10(-2)min(-1) have testified the excellent catalytic performance of our Re NPs immobilized on DNA. The overall study have revealed the capability of DNA in stabilizing the highly reactive Re metal at nanoscale and made them applicable in practice. The present route can also be extended to prepare one dimensional (1-D), self-assembled NPs of other reactive metals, mixed metals or even metal oxides for specific applications in water based solutions.
通过多功能生物分子DNA的分级和围栏作用,高灵敏度和超小铼(Re)金属纳米颗粒(NPs)成功地在水中稳定下来,在反应时间的一分钟内首次形成了两种不同的聚集链状形态,平均粒径分别为1.1±0.1nm和0.7±0.1nm。在室温(RT)搅拌条件下,通过硼氢化钠还原高铼酸铵(NH4ReO4)并在DNA存在的情况下形成Re NPs。通过仔细监测NH4ReO4与DNA的摩尔比来控制形态。合成的材料被用于两个潜在应用:作为表面增强拉曼散射(SERS)研究的基底以及作为还原芳香族硝基化合物的催化剂。以亚甲基蓝(MB)为探针进行SERS研究,发现平均粒径为0.7±0.1nm的聚集链状形态具有最高2.07×10(7)的SERS增强因子(EF)。对4-硝基苯酚(4-NP)、2-硝基苯酚(2-NP)和4-硝基苯胺(4-NA)的催化还原速率常数分别为6×10(-2)min(-1)、33.83×10(-2)min(-1)和37.4×10(-2)min(-1),证明了固定在DNA上的Re NPs具有优异的催化性能。整体研究揭示了DNA在纳米尺度上稳定高活性Re金属的能力,并使其在实际中得到应用。目前的方法也可以扩展到制备一维(1-D)、自组装的其他活性金属、混合金属甚至金属氧化物的纳米颗粒,用于水基溶液中的特定应用。