在Alkynyl-Protected金纳米集群中的异体化
Zong-Jie Guan1,2, Feng Hu1, Jiao-Jiao Li1
1Department of Chemistry , Tsinghua University , Beijing 100084 , P.R. China.
研究人员合成了两种异构金纳米集群,Au23(CCBut) 15,首次揭示了基保护的金纳米集群中的异构性. 这些异构体具有独特的光学特性和独特的金属对联体比率.
科学领域:
- 无机化学
- 纳米技术
- 材料科学
背景情况:
- 黄金纳米集群 (AuNC) 是具有可调节性质的有希望的纳米材料.
- 基尼对AuNC具有独特的表面被动性和电子特性.
- 了解 AuNC 的同位素对于控制它们的结构-属性关系至关重要.
研究的目的:
- 报告同位素黄金纳米集群的受控合成和结构特征.
- 研究异构对AuNC的光学特性的影响.
- 探索这些同位素系统的电子结构和潜在的转换.
主要方法:
- 单晶X射线衍射用于精确的结构确定.
- 用于组合分析的矩阵辅助激光脱离离子飞行时间质谱 (MALDI-TOF MS).
- 电子结构研究的时间依赖密度函数理论 (TD-DFT) 计算.
主要成果:
- 两个同位素黄金纳米集群,Au23(CCBut) 15 (Au-1和Au-2),已成功合成并从结构上阐明.
- 金属与配体的比率不同于之前报告的AuNC系统.
- 同位体具有不同的光学特性,具有不同的HOMO-LUMO过渡特性,Au-2可以自发转化为Au-1.
结论:
- 这项研究呈现了基保护黄金纳米集群中的第一个异构实例.
- 这些发现提供了对全烯保护黄金纳米集群的合成,结构和异构的见解.
- 这项工作鼓励对异构金属纳米集群及其应用进行进一步研究.
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相关概念视频
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Preparation of Alkynes: Alkylation Reaction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Isomerism in Alkenes
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