Resonance Raman assignment and evidence for noncoupling of individual 2- and 4-vinyl vibrational modes in a monomeric cyanomethemoglobin.
Resonance Raman assignment and evidence for noncoupling of individual 2- and 4-vinyl vibrational modes in a monomeric cyanomethemoglobin.
复制标题
单体氰基高铁血红蛋白中单个 2- 和 4- 乙烯基振动模式不耦合的共振拉曼分配和证据。
DOI：
10.1021/bi00435a050
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发表时间：
1989
期刊：
影响因子：
2.9
通讯作者：
Parish,DW
中科院分区：
文献类型：
--
作者：
Gersonde,K;Yu,NT;Lin,SH;Smith,KM;Parish,DW
8月19日，……九百八十八; 1989年1月9日收到的修订版摘要：研究了单体昆虫氰高铁血红蛋白的共振拉曼光谱（CTT III和CTT IV）用（1）在4-乙烯基以及2，4-二乙烯基上选择性氘代的血红素IX，（2）单乙烯基截短的血红素如天青素（2-氢，4-乙烯基）和异-天血红素（2-乙烯基，4-氢），（3）对称血红素，如原血红素III（与2-和3-乙烯基）和血红素XIII（具有1-和4-乙烯基）和（4）不具有2-和4-乙烯基的血红素，例如中血红素IX、次血红素IX、2，4-二甲基次血红素IX和2，4-二溴次血红素IX。有证据表明，在这些cyanomet CTT血红蛋白中血红素的2-和4-位置处的高度局部化的乙烯基C= C伸缩振动是非耦合的和不等价的;即，1631-和1624-cm-1线已分别被分配给2-乙烯基和4-乙烯基。2-乙烯基（在pemptoheme中）或4-乙烯基（在isopemptoheme中）的消除不影响剩余乙烯基的C= C伸缩频率。此外，两个低频乙烯基弯曲模式位于412处，强度介于2-乙烯基和4-乙烯基之间。而所观察到的591-cm-1线仅由这两种弯曲模式的2-乙烯基和4-乙烯基产生。血红蛋白中的铁原卟啉IX（原血红素IX）的2-和4-乙烯基在通过蛋白质-血红素相互作用调节血红素反应性中起重要作用（Gersonde，1983; Gersonde等人，1986年）。每个乙烯基的取向（相对于血红素平面）和蛋白质-乙烯基相互作用的性质已经通过核磁共振（NMR）光谱进行了探测（La Mar等人，1978年）。另一方面，共振拉曼光谱提供了关于各种连接和未连接的血红蛋白中乙烯基的电子和键合性质的有用信息（Kerr等人，1985; Gersonde等人，1986，1987; Tanaka等人，1987年）。
August 19,¡ 988; Revised Manuscript Received January 9, 1989 abstract: We have investigated the resonance Raman spectra of monomeric insect cyanomethemoglobins (CTT III and CTT IV) reconstituted with (1) protohemes IX selectively deuterated at the 4-vinyl as well as the 2, 4-divinyls,(2) monovinyl-truncated hemes such as pemptoheme (2-hydrogen, 4-vinyl) and iso-pemptoheme (2-vinyl, 4-hydrogen),(3) symmetric hemes such as protoheme III (with 2-and 3-vinyls) and protoheme XIII (with 1-and 4-vinyls), and (4) hemes without 2-and 4-vinyls such as mesoheme IX, deuteroheme IX, 2, 4-dimethyldeuteroheme IX, and 2, 4-dibromodeuteroheme IX. Evidence is presented that the highly localized vinyl C= C stretching vibrations at the 2-and 4-positions of the heme in these cyanomet CTT hemoglobins are noncoupled and inequivalent; ie, the 1631-and 1624-cm" 1 lines have been assigned to 2-vinyl and 4-vinyl, respectively. The elimination of the 2-vinyl (in pemptoheme) or the 4-vinyl (in isopemptoheme) does not affect the C= C stretching frequency of the remaining vinyl. Furthermore, two low-frequencyvinyl bending modesat 412 and intensities between 2-vinyl and 4-vinyl. The observed whereas the 591-cm'1 line results exclusively from the 2-vinyl and 4-vinyl for these twobending modes.The 2-and 4-vinyl groups of iron protoporphyrin IX (pro-toheme IX) in hemoglobins play an important role in modulating heme reactivity through protein-heme interactions (Gersonde, 1983; Gersonde et al., 1986). The orientation of each vinyl (relative to the heme plane) and the nature of protein-vinyl interactions have been probed by nuclear mag-netic resonance(NMR) spectroscopy (La Mar et al., 1978). On the other hand, resonance Raman spectroscopy provides useful information pertaining to the electronic and bonding nature of the vinyl groups in various ligated and unligated hemoglobins (Kerr et al., 1985; Gersonde et al., 1986, 1987; Tanaka et al., 1987).