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51.
We report the use of a novel pulsed ESR technique for distance measurement, based on the detection of double quantum coherence (DQC), which yields high quality dipolar spectra, to significantly extend the range of measurable distances in proteins using nitroxide spin-labels. Eight T4 lysozyme (T4L) mutants, doubly labeled with methanethiosulfonate spin-label (MTSSL), have been studied using DQC-ESR at 9 and 17 GHz. The distances span the range from 20 A for the 65/76 mutant to 47 A for the 61/135 mutant. The high quality of the dipolar spectra also allows the determination of the distance distributions, the width of which can be used to set upper and lower bounds in future computational strategy. It is also demonstrated that the shape of these distributions can reveal the presence of multiple conformations of the spin-label, an issue of critical relevance to the structural interpretation of the distances. The distances and distributions found in this study are readily rationalized in terms of the known crystal structure, the characteristic conformers of the nitroxide side chains, and molecular modeling. This study sets the stage for the use of DQC-ESR for determining the tertiary structure of large proteins with just a small number of long-distance constraints. 相似文献
52.
Regio‐ and Enantio‐selective Chemo‐enzymatic C−H‐Lactonization of Decanoic Acid to (S)‐δ‐Decalactone
Jack Manning Michele Tavanti Joanne L. Porter Nico Kress Sam P. DeVisser Nicholas J. Turner Sabine L. Flitsch 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(17):5724-5727
The conversion of saturated fatty acids to high value chiral hydroxy‐acids and lactones poses a number of synthetic challenges: the activation of unreactive C?H bonds and the need for regio‐ and stereoselectivity. Here the first example of a wild‐type cytochrome P450 monooxygenase (CYP116B46 from Tepidiphilus thermophilus) capable of enantio‐ and regioselective C5 hydroxylation of decanoic acid 1 to (S)‐5‐hydroxydecanoic acid 2 is reported. Subsequent lactonization yields (S)‐δ‐decalactone 3 , a high value fragrance compound, with greater than 90 % ee. Docking studies provide a rationale for the high regio‐ and enantioselectivity of the reaction. 相似文献
53.
Richard C. Brewster Jack T. Suitor Adam W. Bennett Stephen Wallace 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(36):12539-12544
Microorganisms can be programmed to perform chemical synthesis via metabolic engineering. However, despite an increasing interest in the use of de novo metabolic pathways and designer whole‐cells for small molecule synthesis, the inherent synthetic capabilities of native microorganisms remain underexplored. Herein, we report the use of unmodified E. coli BL21(DE3) cells for the reduction of keto‐acrylic compounds and apply this whole‐cell biotransformation to the synthesis of aminolevulinic acid from a lignin‐derived feedstock. The reduction reaction is rapid, chemo‐, and enantioselective, occurs under mild conditions (37 °C, aqueous media), and requires no toxic transition metals or external reductants. This study demonstrates the remarkable promiscuity of central metabolism in bacterial cells and how these processes can be leveraged for synthetic chemistry without the need for genetic manipulation. 相似文献
54.
Takashi Kashiwagi Eric Grulke Jenny Hilding Richard Harris Walid Awad Jack Douglas 《Macromolecular rapid communications》2002,23(13):761-765
Nanocomposites based on poly(propylene) and multi‐wall carbon nanotubes (up to 2 vol.‐%) were melt blended, yielding a good dispersion of nanotubes without using any organic treatment or additional additives. Carbon nanotubes are found to significantly enhance the thermal stability of poly(propylene) in nitrogen at high temperatures. Specifically, the nanotube additive greatly reduced the heat release rate of poly(propylene). They are found to be at least as effective a flame‐retardant as clay/poly(propylene) nanocomposites. 相似文献
55.
TNA, or threose nucleic acid, is capable of Watson-Crick base pairing with DNA, RNA, and TNA; coupled with its chemical simplicity, this suggests that TNA is a possible progenitor of RNA. As an initial step toward developing the molecular tools necessary to investigate the functional capabilities of TNA by in vitro selection, we have screened a variety of DNA polymerases for activity on a TNA template. We report that despite having a repeating unit that is one atom shorter than that of DNA, several polymerases showed surprisingly good ability to copy limited stretches of TNA. 相似文献
56.
The aim of the present work was to improve the discriminatory potential, and hence the probative value, of Y-STR-based testing by extending the set of Y chromosome STR loci available for forensic casework. In accordance with the requirements of a Y chromosome multiplex analytical system developed specifically for forensic casework use, we have sought to maximize the number of loci able to be co-amplified, ensure appropriate assay sensitivity (1–2 ng of input genomic DNA), balance inter-locus signals and minimize confounding female DNA artifacts. Two Y chromosome STR systems, multiplex I (MPI) and multiplex II (MPII), have been developed which permit the robust co-amplification of 18 Y-STRs. The loci include DYS19, DYS385(a) and (b), DYS388, DYS389I and II, DYS390, DYS391, DYS392, DYS393, DYS425, DYS434, DYS437, DYS438, DYS439, Y-GATA-C4, Y-GATA-A7.1 (DYS460) and Y-GATA-H4. The two multiplex systems are robust over a wide range of primer, magnesium, and DNA polymerase concentrations and perform well under a variety of cycling conditions. Complete male haplotypes can be obtained with as little as 100–250 pg of template DNA. Although a limited number of female DNA artifacts are observed in mixed stains in which the male DNA comprises 1/100 of the total, the male profile is easily discernible. Slightly modified versions of MPI and MPII demonstrate a significant reduction in female artifacts. Thus, it may not be necessary to employ a differential extraction strategy to obtain a male haplotype (or haplotypes in the case of multiple male donors) in cases of sexual assault. The potential utility of MPI and MPII for forensic casework is exemplified by their ability to dissect out the male haplotype in post-coital vaginal swabs and to determine the number of male donors in mixed semen stains.This study has emphasized the need for novel Y-STR multiplexes developed for forensic use to undergo a series of validation exercises that go beyond simply optimizing the PCR reaction conditions. Specifically, stringent performance checks on their efficacy need to be carried out using casework-type specimens in order to determine potential confounding effects from female DNA. 相似文献
57.
58.
Mary M. Gilbert Jack J. Donn Martha Peirce Kenneth R. Sundberg Klaus Ruedenberg 《Journal of computational chemistry》1985,6(3):209-215
A method of graphically exhibiting detailed information about a three-dimensional electron distribution function f(x,y,z) is described. Contour lines f = constant are drawn on a set of equidistant parallel planes that intersect the distribution, and a perspective view of all contours on all planes is displayed. Representative examples are given. 相似文献
59.
Annegret K. Hall Jack M. Harrowfield Brian W. Skelton Allan H. White 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(4):407-411
The sodium salt of a complex anion formed between gadolinium(III) and three variously deprotonated chelidamic acid (4‐hydroxypyridine‐2,6‐dicarboxylic acid) ligand moieties, assigned as Na5[Gd(C7H2NO5)2(C7H3NO5)]·16H2O, i.e. pentasodium (4‐hydroxypyridine‐2,6‐dicarboxylate)bis(4‐oxidopyridine‐2,6‐dicarboxylate)gadolinium(III) hexadecahydrate, forms as colourless monoclinic crystals upon vapour diffusion of ethanol into its aqueous solution. The ligand moieties, assigned as two trianionic and one dianionic chelidamate species, are all tridentate in the complex anion of tricapped trigonal prismatic donor‐atom geometry. The geometry of the ligands and that of the primary coordination sphere is very similar to that of the analogous anionic tris(ligand)–rare earth complexes of the pyridine‐2,6‐dicarboxylate (dipicolinate) dianion. 相似文献
60.
Angelo J. Amoroso Brian F. G. Johnson Jack Lewis Chi-Keung Li Catherine A. Morewood Paul R. Raithby Maria D. Vargas Wing-Tak Wong 《Journal of Cluster Science》1995,6(1):163-173
Reduction of the heptaosmium cluster [Os7(CO)21] With [Et4N][NH4) gives the cluster dianion [Os7(CO)20]2–,1, in high yield. The reaction of the dianion with [AuPR
3Cl] (R=Et or Ph) in the presence of TlPF6 forms [Os7((CO)20(AuPR
3)2] [R=Et (2a);R = Ph(2b)] in 80% yield, while the corresponding reaction with (Os(C6H6)(CH3CN)3]2+ gives [Os8(CO)20 (
6-C6H6)] (3) in reasonable yield (ca. 30%). The dianion,1, and the clusters2 and3 have been fully characterized by bout spectroscopic and crystallographic methods. The crystal structure of the [Ph4P]+ salt of1 shows that the metals in the anion adopt a capped octahedral geometry, with all twenty carbonyl ligands in terminal sites. The metal core geometry in2a is best described as a tricapped octahedron, and is based on the structure of the dianion1 with two adjacent octahedral faces capped by the Au atoms of the two AuPEt3 groups. In a similar fashion, the geometry of3 is related to that of1 with the addition of an Os(C6H6) unit capped to a triangular face, to give a bicapped octahedral framework. 相似文献