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排序方式: 共有158条查询结果,搜索用时 15 毫秒
1.
Shusuke Sato Fumitaka Kudo Michel Rohmer Tadashi Eguchi 《Angewandte Chemie (International ed. in English)》2020,59(1):237-241
Adenosylhopane is a crucial intermediate in the biosynthesis of bacteriohopanepolyols, which are widespread prokaryotic membrane lipids. Herein, it is demonstrated that reconstituted HpnH, a putative radical S‐adenosyl‐l ‐methionine (SAM) enzyme, commonly encoded in the hopanoid biosynthetic gene cluster, converts diploptene into adenosylhopane in the presence of SAM, flavodoxin, flavodoxin reductase, and NADPH. NMR spectra of the enzymatic reaction product were identical to those of synthetic (22R)‐adenosylhopane, indicating that HpnH catalyzes stereoselective C?C formation between C29 of diploptene and C5′ of 5′‐deoxyadenosine. Further, the HpnH reaction in D2O‐containing buffer revealed that a D atom was incorporated at the C22 position of adenosylhopane. Based on these results, we propose a radical addition reaction mechanism catalyzed by HpnH for the formation of the C35 bacteriohopane skeleton. 相似文献
2.
Wenjuan Ji Xinjian Ji Qi Zhang Dhanaraju Mandalapu Zixin Deng Wei Ding Peng Sun Qi Zhang 《Angewandte Chemie (International ed. in English)》2020,59(23):8880-8884
Sulfur‐based homolytic substitution (SH reaction) plays an important role in synthetic chemistry, yet whether such a reaction could occur on the positively charged sulfonium compounds remains unknown. In the study of the anaerobic coproporphyrinogen III oxidase HemN, a radical S‐adenosyl‐l ‐methionine (SAM) enzyme involved in heme biosynthesis, we observed the production of di‐(5′‐deoxyadenosyl)methylsulfonium, which supports a deoxyadenosyl (dAdo) radical‐mediated SH reaction on the sulfonium center of SAM. The sulfonium‐based SH reactions were then investigated in detail by density functional theory calculations and model reactions, which showed that this type of reactions is thermodynamically favorable and kinetically competent. These findings represent the first report of sulfonium‐based SH reactions, which could be useful in synthetic chemistry. Our study also demonstrates the remarkable catalytic promiscuity of the radical SAM superfamily enzymes. 相似文献
3.
In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: AuxHySz clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of AuxHySz (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of AuxHySz clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M−S+H)Na+, (M+H)Na+, AuMNa+, (M2−S)Na+, and M2Na+ are determined, and also in cationized forms with K+. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM2 and Au2M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of AuxMw where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule. 相似文献
4.
The synthesis of a family of N-mustard analogs of S-adenosyl-l-methionine (SAM) containing azides and alkynes at the N6-position of the adenosine base has been accomplished from commercially available inosine. Further biochemical analysis of these analogs indicates successful modification of pUC19 plasmid DNA in an enzyme-dependent fashion with DNA methyltransferases M.TaqI and M.HhaI. 相似文献
5.
《Analytical letters》2012,45(18):3373-3382
Abstract This letter demonstrates a selective NH4 + detection using a synthesized thiazole benzo crownether ethylamine‐lipoic acid conjugate (1) monolayer. A self‐assembled monolayer (SAM) of 1 was formed on Au surface and well characterized by atomic‐force microscopy, Fourier transform infrared reflection absorption spectroscopy and cyclic voltammetry (CV). A good selectivity for NH4 + sensing was observed in a range of 1.0×10?1 to 1.0×10?6 M by surface plasmon resonance. 相似文献
6.
7.
Powdery mildew is one of the most serious diseases, which has a significant impact on the production of winter wheat. As an effective alternative to traditional sampling methods, remote sensing can be a useful tool in disease detection. This study examines the potential of a moderate resolution multispectral satellite image in disease monitoring at regional scale. At the suburban area around Beijing, a large size ground survey sample (n = 90) and the corresponding HJ-CCD image were acquired at the grain filling stage of winter wheat. A number of spectral features were found to be sensitive to powdery mildew through an independent t-test. Based on these spectral features, classification models were established using both spectral information divergence (SID) and spectral angle mapper (SAM), respectively. The results showed that the overall accuracies of disease identification and severity estimation were moderate. The estimation of normal and seriously infected samples yielded higher accuracies than slightly infected samples. The single phase HJ-CCD can only be used for locating the infected areas of powdery mildew, whereas is unable to discriminate the severity levels of disease. The presence of several stressors and disturbances other than disease is a possible reason of the unsatisfactory performance of disease monitoring models. Therefore, the integration of multi-phase onboard data and some relevant ancillary data is necessary to improve the accuracy and reliability of disease monitoring at regional scale. 相似文献
8.
Polina Angelova Kalina Kostova Karsten Hinrichs Dimiter Tsankov 《Central European Journal of Chemistry》2005,3(4):658-667
New 4-substituted benzyl esters of 16-mercaptohexadecanoic acid were prepared by developing a practicable synthetic procedure
and using readily available staring materials. The compounds synthesized have been characterized by NMR, MS, IR spectra and
elemental analysis. The mercapto derivatives are precursors for the formation of self-assembled monolayers on metal substrates.
Dedicated to Professor Dr. Manfred Hesse on the occasion of his 70
th
birthday 相似文献
9.
Kenji Hara Keiji Iwahashi Satoru Takakusagi Kohei Uosaki Masaya Sawamura 《Surface science》2007,601(22):5127-5132
Functionalization of self-assembled monolayer (SAM) of alkanethiolate with metal containing unit is one of the versatile methods to obtain functional surfaces such as heterogeneous catalysts. However, organic molecules that strongly bind to transition metals at SAM terminal are limited. Recently N-heterocyclic carbenes (NHCs) such as cyclic diaminocarbenes have emerged as strongly σ-donating ligands forming a robust bond with broad spectrum of transition metals. In the present study, for the purpose of establishment of a new robust basement for heterogeneous metal catalysts, a SAM of the alkanethiolate terminated with NHC-rhodium(I) complex moiety was prepared by utilizing a newly designed disulfide molecule bearing NHC-metal complex terminals. X-ray photoelectron spectroscopy (XPS) analysis and angle resolved XPS measurement revealed successful formation of the Rh-complex-terminated SAM on a gold substrate. Infrared reflection absorption spectroscopy (IRRAS) analysis suggested that the linker methylene chains connecting the rhodium complex moiety and the gold surface are in a loosely packed structure. This unique chemical species, NHC, would be a promising candidate as a basement for the construction of functional surface. 相似文献
10.