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161.
Inchul Shin Ian Davis Karinel Nieves-Merced Yifan Wang Stanton McHardy Aimin Liu 《Chemical science》2021,12(11):3984
SfmD is a heme-dependent enzyme in the biosynthetic pathway of saframycin A. Here, we present a 1.78 Å resolution de novo crystal structure of SfmD, which unveils a novel heme cofactor attached to the protein with an unusual HxnHxxxC motif (n ∼ 38). This heme cofactor is unique in two respects. It contains a single thioether bond in a cysteine–vinyl link with Cys317, and the ferric heme has two axial protein ligands, i.e., His274 and His313. We demonstrated that SfmD heme is catalytically active and can utilize dioxygen and ascorbate for a single-oxygen insertion into 3-methyl-l-tyrosine. Catalytic assays using ascorbate derivatives revealed the functional groups of ascorbate essential to its function as a cosubstrate. Abolishing the thioether linkage through mutation of Cys317 resulted in catalytically inactive SfmD variants. EPR and optical data revealed that the heme center undergoes a substantial conformational change with one axial histidine ligand dissociating from the iron ion in response to substrate 3-methyl-l-tyrosine binding or chemical reduction by a reducing agent, such as the cosubstrate ascorbate. The labile axial ligand was identified as His274 through redox-linked structural determinations. Together, identifying an unusual heme cofactor with a previously unknown heme-binding motif for a monooxygenase activity and the structural similarity of SfmD to the members of the heme-based tryptophan dioxygenase superfamily will broaden understanding of heme chemistry.The de novo crystal structure of SfmD reveals a novel c-type heme cofactor for promoting a monooxygenation reaction in the biosynthetic pathway of saframycin A. 相似文献
162.
J. Ren H. -D. Ließ R. Mäckel H. Baumgärtner 《Fresenius' Journal of Analytical Chemistry》1995,353(3-4):303-306
Based on the well known Kelvin probe for work function measurements a new microstructure analysis system – the Scanning Kelvin Microscope – has been developed. It allows to measure simultaneously with high lateral resolution the distribution of the contact potential difference (CPD) between a conductive sample and a reference probe together with the topographical structure of the sample surface. The measurement is contact free and non-destructive and can be carried out in natural environments. At present the lateral resolution of the measurement approaches 5 m. The results can be displayed on a computer in three dimensional colour pictures. 相似文献
163.
Based on the well known Kelvin probe for work function measurements a new microstructure analysis system - the Scanning Kelvin Microscope - has been developed. It allows to measure simultaneously with high lateral resolution the distribution of the contact potential difference (CPD) between a conductive sample and a reference probe together with the topographical structure of the sample surface. The measurement is contact free and non-destructive and can be carried out in natural environments. At present the lateral resolution of the measurement approaches 5 microm. The results can be displayed on a computer in three dimensional colour pictures. 相似文献
164.
165.
In this paper three Banach spacesA
0(),A
andA
1() of functions holomorphic in the unit ballB of
n
are defined. We exhibit bounded projections fromC
0(B) ontoA
0(), fromL
1(B) ontoA
1(), and fromL(B) ontoA(). Using these projections, we show thatA
0()* A
1() andA
1()* A().Supported in part by the National Natural Science Foundation of China. 相似文献
166.
167.
Mössbauer measurements in a-(Fe0.765Mn0.235)78Sn2Si6B14 have been performed with57Fe and119Sn. Both hyperfine fields show a kink near 70 K, indicating a freezing of the transverse spins. The ratio of the two hyperfine fields contains information about the correlation of the transverse spins. The ratioB
hf(Sn)/B
hf(Fe) stays constant aboveT
xy
and rises belowT
xy
. This indicates an alignment of the transverse spins on a local scale, as was also found inAuFe and a-FeZr. 相似文献
168.
The reaction of tungstate ions with the gamma-10-tungstosilicate in mixed water-ethanol (v/v) yields the corresponding isomer of the 12-tungstosilicate isolated as its tetrabutylammonium salt. It was characterized by means of (183)W NMR, infrared, Raman, and UV spectroscopies and was identified with the isomer resulting from the Keggin structure (alpha-isomer) by rotation of two tritungstic groups by pi/3. Cyclic voltammetry shows that the reducibility increases in the sequence alpha-beta-gamma as the number of rotated tritungstic groups. Whereas the gamma-12-tungstosilicate anion is unstable in pure aqueous solution whatever the pH value, it is stable in mixed aqueous-organic or pure organic solvents, even at boiling temperatures. In contrast, the two- and four-electron-reduced blue species are stable in aqueous media but not the one-electron-reduced blue. Study of the (183)W NMR spectrum of the two-electron-reduced species showed that the two spin-paired electrons are delocalized on all the W atoms on the NMR time scale but have a larger residency time on one group of four atoms. 相似文献
169.
170.
本文考察了磺胺二甲嘧啶在多种底液中的极谱伏安行为,发现其在BritonRobinson(BR)缓冲溶液(pH2.2)中产生一个良好的还原峰,峰电位为-0.85V(vs.SCE),峰电流与磺胺二甲嘧啶浓度在1×10-73×10-4mol/L范围内呈良好的线性关系,检出限为9×10-8mol/L,大多数金属离子和无机阴离子不干扰测定,可望用于定量测定用多种电化学方法研究了该还原峰电流的性质,结果表明,它是具有吸附性质的不可逆还原峰 相似文献