Laboratory of Organic Chemistry, Wageningen University, Dreijenplein 8, 6703 HB Wageningen, The Netherlands.
Chem Asian J. 2011 Oct 4;6(10):2776-86. doi: 10.1002/asia.201100375. Epub 2011 Aug 24.
The preparation and characterization of butylene-terminated silicon nanoparticles (SiNPs) and their functionalization using thiol-ene chemistry is described, as well as the coupling of DNA strands. Bromide-terminated SiNPs were prepared by means of the oxidation of magnesium silicide and functionalized with butylene chains through treatment with the corresponding Grignard reagent. The successful coupling was confirmed by NMR and FTIR spectroscopy. TEM measurements revealed a silicon-core diameter of (2.4±0.5) nm. The fluorescence emission maximum is at λ(max)=525 nm when excited at λ(exc)=430 nm. The conjugation of these alkene-terminated SiNPs by means of thiol-ene chemistry is described for a variety of functional thiols. Efficient coupling was evidenced by NMR and FTIR spectroscopy. Moreover, the characteristic fluorescence properties of the SiNPs remained unaltered, thus demonstrating the value of this approach towards functional oxide-free SiNPs. Activation of the attached carboxylic acid moieties allowed for conjugation of NH(2)-terminated oligo-ssDNA (ss=single strand) to the SiNPs. Successful coupling was confirmed by a characteristic new UV absorption band at 260 nm, and by the still-present distinctive fluorescence of the SiNPs at 525 nm. Gel electrophoresis confirmed coupling of 2 to 3 DNA strands onto the SiNPs, whereas no uncoupled DNA was observed.
描述了丁烯封端的硅纳米粒子（SiNPs）的制备和表征，以及它们通过硫醇-烯反应的功能化，以及 DNA 链的偶联。溴封端的 SiNPs 通过镁硅化物的氧化制备，并通过相应的格氏试剂处理与丁烯链功能化。通过 NMR 和 FTIR 光谱证实了成功的偶联。TEM 测量显示硅核直径为（2.4±0.5）nm。当在 λ（exc）=430nm 处激发时，荧光发射最大值为 λ（max）=525nm。通过硫醇-烯反应描述了这些烯封端的 SiNPs 与各种功能化硫醇的偶联。通过 NMR 和 FTIR 光谱证实了高效偶联。此外，SiNPs 的特征荧光性质保持不变，因此证明了这种方法对于无氧化物功能化 SiNPs 的价值。附着的羧酸部分的活化允许 NH（2）-封端的寡 ssDNA（ss=单链）与 SiNPs 偶联。通过在 260nm 处出现特征新的紫外吸收带以及 SiNPs 在 525nm 处仍存在的独特荧光来证实成功偶联。凝胶电泳证实了 2 到 3 个 DNA 链偶联到 SiNPs 上，而没有观察到未偶联的 DNA。
