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Chiral Electrodeposition

机译:手性电沉积

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摘要

Chirality is ubiquitous in Nature. One enantiomer of a molecule is often physiologically active, while the other enantiomer may be either inactive or toxic. For example, S-ibupro-fen is up to 100 times more active than R-ibuprofen. R-thalidomide is a sedative, but S-thalidomide causes birth defects. Worldwide sales of single-enan-tiomer drugs reached 159 billion dollars in 2003.! The industrial synthesis of chiral compounds presently utilizes solution-phase, homogeneous catalysts and enzymes. Chiral surfaces offer the possibility of developing heterogeneous enantiospecific catalysts that can more readily be separated from the products and reused. In addition, such surfaces may serve as electrochemical sensors for chiral molecules, perhaps even implantable chiral sensors that could be used to monitor drug levels in the body. Another application would be post-chromatographic chiral electrochemical detectors, which would obviate the need for chiral separation of analyte molecules before chemical detection. Chiral surfaces have been produced previously by adsorbing chiral molecules on achiral substrates,~(2-8) or by slicing single crystals so that they exhibit high-index faces with chiral kink sites. ~(9-17) These high index single crystals have been shown to act as enantioselective heterogeneous catalysts. ~(15) Recently, we showed that chiral films of metal oxides such as CuO can be electrodeposited on achiral surfaces, using chiral molecules such as tartaric or amino acids to direct the chirality. ~(18-20) In this respect, elec-trodeposition resembles biomineraliza-tion in that organic molecules adsorbed on surfaces may have profound effects on the morphology of the inorganic deposits. ~(17,21-25) The reduction of symmetry of surfaces by the adsorption of chiral molecules is known in biominer-alization to produce chiral crystal habits on minerals such as calcite and gypsum which have achiral space groups. Enantioselective adsorption on the surfaces of minerals such as calcite has also been invoked to explain the genesis of biogenic homochirality. ~(26)
机译:手性在自然界无处不在。分子的一种对映体通常具有生理活性,而另一种对映体可能是无活性的或有毒的。例如,S-布洛芬的活性是R-布洛芬的100倍。 R-沙利度胺是镇静剂,但是S-沙利度胺会导致先天性缺陷。 2003年,全球单烯基-替丁药物的销售额达到1590亿美元。手性化合物的工业合成目前利用溶液相,均相催化剂和酶。手性表面提供了开发异构对映体特异性催化剂的可能性,该催化剂可以更容易地与产物分离并重新使用。另外,这种表面可以用作手性分子的电化学传感器,甚至可以用作可植入的手性传感器,其可以用于监测体内的药物水平。另一个应用是色谱后手性电化学检测器,它将避免化学检测之前手性分离分析物分子的需要。先前已经通过将手性分子吸附在非手性底物上(〜(2-8))或通过切片单晶来制备手性表面,从而使它们表现出具有手性扭结位点的高折射率面。 〜(9-17)已证明这些高折射率单晶可用作对映选择性非均相催化剂。 〜(15)最近,我们证明了使用手性分子(例如酒石酸或氨基酸)指导手性,可以将金属氧化物(如CuO)的手性膜电沉积在非手性表面上。 〜(18-20)在这方面,电沉积类似于生物矿化,因为吸附在表面上的有机分子可能会对无机沉积物的形态产生深远的影响。 〜(17,21-25)在生物矿化中,通过手性分子的吸附降低表面的对称性是众所周知的,这种方法会在方解石和石膏等具有非手性空间群的矿物上产生手性晶体习性。在方解石等矿物表面上的对映选择性吸附也被用来解释生物手性的成因。 〜(26)

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