用于核酸的振动斯塔克效应探针。
Vibrational stark effect probes for nucleic acids.
作者信息
Silverman Lisa N, Pitzer Michael E, Ankomah Peter O, Boxer Steven G, Fenlon Edward E
机构信息
Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA.
出版信息
J Phys Chem B. 2007 Oct 11;111(40):11611-3. doi: 10.1021/jp0750912. Epub 2007 Sep 18.
The vibrational Stark effect (VSE) has proven to be an effective method for the study of electric fields in proteins via the use of infrared probes. To explore the use of VSE in nucleic acids, we investigated the Stark spectroscopy of nine structurally diverse nucleosides. These nucleosides contained nitrile or azide probes in positions that correspond to both the major and minor grooves of DNA. The nitrile probes showed better characteristics and exhibited absorption frequencies over a broad range; that is, from 2253 cm-1 for 2'-O-cyanoethyl ribonucleosides 8 and 9 to 2102 cm(-1) for a 13C-labeled 5-thiocyanatomethyl-2'-deoxyuridine 3c. The largest Stark tuning rate observed was |Deltamu| = 1.1 cm(-1)/(MV/cm) for both 5-cyano-2'-deoxyuridine 1 and N2-nitrile-2'-deoxyguanosine 7. The latter is a particularly attractive probe because of its high extinction coefficient (epsilon = 412 M-1cm-1) and ease of incorporation into oligomers.
振动斯塔克效应（VSE）已被证明是一种通过使用红外探针来研究蛋白质中电场的有效方法。为了探索VSE在核酸中的应用，我们研究了九种结构各异的核苷的斯塔克光谱。这些核苷在与DNA的大沟和小沟相对应的位置含有腈或叠氮化物探针。腈探针表现出更好的特性，并在很宽的范围内呈现吸收频率；即，对于2'-O-氰基乙基核糖核苷8和9为2253 cm-1，对于13C标记的5-硫氰酸甲酯-2'-脱氧尿苷3c为2102 cm(-1)。观察到的最大斯塔克调谐率|Δμ| = 1.1 cm-1/(MV/cm)，对于5-氰基-2'-脱氧尿苷1和N2-腈-2'-脱氧鸟苷7均如此。后者是一种特别有吸引力的探针，因为它具有高消光系数（ε = 412 M-1cm-1）且易于掺入寡聚物中。
Zotero 插件