排序方式: 共有16条查询结果,搜索用时 15 毫秒
1.
2.
3.
4.
Cho J Jeon S Wilson SA Liu LV Kang EA Braymer JJ Lim MH Hedman B Hodgson KO Valentine JS Solomon EI Nam W 《Nature》2011,478(7370):502-505
Oxygen-containing mononuclear iron species--iron(III)-peroxo, iron(III)-hydroperoxo and iron(IV)-oxo--are key intermediates in the catalytic activation of dioxygen by iron-containing metalloenzymes. It has been difficult to generate synthetic analogues of these three active iron-oxygen species in identical host complexes, which is necessary to elucidate changes to the structure of the iron centre during catalysis and the factors that control their chemical reactivities with substrates. Here we report the high-resolution crystal structure of a mononuclear non-haem side-on iron(III)-peroxo complex, [Fe(III)(TMC)(OO)](+). We also report a series of chemical reactions in which this iron(III)-peroxo complex is cleanly converted to the iron(III)-hydroperoxo complex, [Fe(III)(TMC)(OOH)](2+), via a short-lived intermediate on protonation. This iron(III)-hydroperoxo complex then cleanly converts to the ferryl complex, [Fe(IV)(TMC)(O)](2+), via homolytic O-O bond cleavage of the iron(III)-hydroperoxo species. All three of these iron species--the three most biologically relevant iron-oxygen intermediates--have been spectroscopically characterized; we note that they have been obtained using a simple macrocyclic ligand. We have performed relative reactivity studies on these three iron species which reveal that the iron(III)-hydroperoxo complex is the most reactive of the three in the deformylation of aldehydes and that it has a similar reactivity to the iron(IV)-oxo complex in C-H bond activation of alkylaromatics. These reactivity results demonstrate that iron(III)-hydroperoxo species are viable oxidants in both nucleophilic and electrophilic reactions by iron-containing enzymes. 相似文献
5.
Z Ma S W Morris V Valentine M Li J A Herbrick X Cui D Bouman Y Li P K Mehta D Nizetic Y Kaneko G C Chan L C Chan J Squire S W Scherer J K Hitzler 《Nature genetics》2001,28(3):220-221
t(1;22) is the principal translocation of acute megakaryoblastic leukemias. Here we show this chromosomal rearrangement to result in the fusion of two novel genes, RNA-binding motif protein-15 (RBM15), an RNA recognition motif-encoding gene with homology to Drosophila spen, and Megakaryoblastic Leukemia-1 (MKL1), a gene encoding an SAP (SAF-A/B, Acinus and PIAS) DNA-binding domain. 相似文献
6.
Desnues C Rodriguez-Brito B Rayhawk S Kelley S Tran T Haynes M Liu H Furlan M Wegley L Chau B Ruan Y Hall D Angly FE Edwards RA Li L Thurber RV Reid RP Siefert J Souza V Valentine DL Swan BK Breitbart M Rohwer F 《Nature》2008,452(7185):340-343
Viruses, and more particularly phages (viruses that infect bacteria), represent one of the most abundant living entities in aquatic and terrestrial environments. The biogeography of phages has only recently been investigated and so far reveals a cosmopolitan distribution of phage genetic material (or genotypes). Here we address this cosmopolitan distribution through the analysis of phage communities in modern microbialites, the living representatives of one of the most ancient life forms on Earth. On the basis of a comparative metagenomic analysis of viral communities associated with marine (Highborne Cay, Bahamas) and freshwater (Pozas Azules II and Rio Mesquites, Mexico) microbialites, we show that some phage genotypes are geographically restricted. The high percentage of unknown sequences recovered from the three metagenomes (>97%), the low percentage similarities with sequences from other environmental viral (n = 42) and microbial (n = 36) metagenomes, and the absence of viral genotypes shared among microbialites indicate that viruses are genetically unique in these environments. Identifiable sequences in the Highborne Cay metagenome were dominated by single-stranded DNA microphages that were not detected in any other samples examined, including sea water, fresh water, sediment, terrestrial, extreme, metazoan-associated and marine microbial mats. Finally, a marine signature was present in the phage community of the Pozas Azules II microbialites, even though this environment has not been in contact with the ocean for tens of millions of years. Taken together, these results prove that viruses in modern microbialites display biogeographical variability and suggest that they may be derived from an ancient community. 相似文献
7.
Valentine J Zhang S Zentgraf T Ulin-Avila E Genov DA Bartal G Zhang X 《Nature》2008,455(7211):376-379
Metamaterials are artificially engineered structures that have properties, such as a negative refractive index, not attainable with naturally occurring materials. Negative-index metamaterials (NIMs) were first demonstrated for microwave frequencies, but it has been challenging to design NIMs for optical frequencies and they have so far been limited to optically thin samples because of significant fabrication challenges and strong energy dissipation in metals. Such thin structures are analogous to a monolayer of atoms, making it difficult to assign bulk properties such as the index of refraction. Negative refraction of surface plasmons was recently demonstrated but was confined to a two-dimensional waveguide. Three-dimensional (3D) optical metamaterials have come into focus recently, including the realization of negative refraction by using layered semiconductor metamaterials and a 3D magnetic metamaterial in the infrared frequencies; however, neither of these had a negative index of refraction. Here we report a 3D optical metamaterial having negative refractive index with a very high figure of merit of 3.5 (that is, low loss). This metamaterial is made of cascaded 'fishnet' structures, with a negative index existing over a broad spectral range. Moreover, it can readily be probed from free space, making it functional for optical devices. We construct a prism made of this optical NIM to demonstrate negative refractive index at optical frequencies, resulting unambiguously from the negative phase evolution of the wave propagating inside the metamaterial. Bulk optical metamaterials open up prospects for studies of 3D optical effects and applications associated with NIMs and zero-index materials such as reversed Doppler effect, superlenses, optical tunnelling devices, compact resonators and highly directional sources. 相似文献
8.
The homologue of the Duchenne locus is defective in X-linked muscular dystrophy of dogs 总被引:20,自引:0,他引:20
B J Cooper N J Winand H Stedman B A Valentine E P Hoffman L M Kunkel M O Scott K H Fischbeck J N Kornegay R J Avery 《Nature》1988,334(6178):154-156
9.
Crystallization of an adenovirus protein (the hexon) 总被引:4,自引:0,他引:4
10.
Molecular recognition by proteins is fundamental to almost every biological process, particularly the protein associations underlying cellular signal transduction. Understanding the basis for protein-protein interactions requires the full characterization of the thermodynamics of their association. Historically it has been virtually impossible to experimentally estimate changes in protein conformational entropy, a potentially important component of the free energy of protein association. However, nuclear magnetic resonance spectroscopy has emerged as a powerful tool for characterizing the dynamics of proteins. Here we employ changes in conformational dynamics as a proxy for corresponding changes in conformational entropy. We find that the change in internal dynamics of the protein calmodulin varies significantly on binding a variety of target domains. Surprisingly, the apparent change in the corresponding conformational entropy is linearly related to the change in the overall binding entropy. This indicates that changes in protein conformational entropy can contribute significantly to the free energy of protein-ligand association. 相似文献