Huber Klaus, Witte Thomas, Hollmann Jutta, Keuker-Baumann Susanne
Department Chemie, Universität Paderborn, Fakultät für Naturwissenschaften, Warburger Strasse 100, D-33098 Paderborn, Germany.
J Am Chem Soc. 2007 Feb 7;129(5):1089-94. doi: 10.1021/ja063368q.
A new tool is presented to control formation of Ag nanoparticles. Small amounts of silver ions were added to dilute solutions of long-chain sodium polyacrylates (NaPA). Four NaPA samples covering a molar mass regime of 97 kD < or = Mw < or = 650 kD have been used. With amounts of added Ag(+) as low as 1-2% of the COO(-) groups of the polyanionic chains, significant changes could already be induced in the NaPA coils with 650 kD. If the NaPA concentration was kept below 0.1 g/L, the coils with 650 kD exhibited a significant coil shrinking in stable solutions. At larger NaPA concentrations, addition of Ag+ initiates an aggregation of the polyacrylate coils toward compact structures. Coil shrinking and aggregation was revealed by means of time-resolved static light scattering. If exposed to UV-radiation, small Ag particles formed within the shrunken anionic polyacrylate coils. The Ag nanoparticles were identified by means of an enhanced light scattering and a characteristic plasmon absorption band around 410 nm. No such Ag particle formation could be observed even at 5 times larger concentrations of Ag(+) and NaPA if the two smallest polyacrylate samples have been used under otherwise equal conditions. This molar mass sensitive response of NaPA to Ag(+)-addition suggests an interesting phenomenon: if the coil size of the NaPa chains, which act as Ag(+) collectors, is large enough, local Ag(+) concentration in these coil-shaped Ag(+) containers exceeds a critical value, and irradiation with UV generates Ag nanoparticles.
提出了一种用于控制银纳米颗粒形成的新工具。将少量银离子添加到长链聚丙烯酸钠(NaPA)的稀溶液中。使用了四个覆盖摩尔质量范围为97 kD≤Mw≤650 kD的NaPA样品。当添加的Ag(+)量低至聚阴离子链中COO(-)基团的1 - 2%时,对于650 kD的NaPA线圈已经可以诱导出显著变化。如果NaPA浓度保持在0.1 g/L以下,650 kD的线圈在稳定溶液中会表现出显著的线圈收缩。在较高的NaPA浓度下,添加Ag+会引发聚丙烯酸酯线圈聚集形成致密结构。通过时间分辨静态光散射揭示了线圈收缩和聚集现象。如果暴露于紫外线辐射下,在收缩的阴离子聚丙烯酸酯线圈内会形成小的银颗粒。通过增强光散射和410 nm左右的特征等离子体吸收带来鉴定银纳米颗粒。在其他条件相同的情况下,如果使用两个最小的聚丙烯酸酯样品,即使Ag(+)和NaPA浓度增大5倍,也观察不到这种银颗粒的形成。NaPA对添加Ag(+)的这种摩尔质量敏感响应表明了一个有趣的现象:如果作为Ag(+)收集器的NaPa链的线圈尺寸足够大,这些线圈状Ag(+)容器中的局部Ag(+)浓度会超过临界值,并且紫外线照射会产生银纳米颗粒。