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21.
Deo P Deo N Somasundaran P Jockusch S Turro NJ 《The journal of physical chemistry. B》2005,109(44):20714-20718
Structural changes of pyrene-labeled and unlabeled poly(maleic acid/octyl vinyl ether) (PMAOVE) and poly(maleic acid/methyl vinyl ether) (PMAMVE) with changes in pH have been investigated in this study. The changes in the photophysical properties of pyrene are interpreted to investigate uncoiling or swelling of the polymeric chains with pH. The vibrational fine structure of the pyrene fluorescence (I(3)/I(1)) and the ratio between excimer and monomer fluorescence (I(e)/I(m)) of both pyrene-labeled and unlabeled PMAMVE and PMAOVE suggest that, at pH 4, the polymers are in the coiled form and PMAOVE forms hydrophobic nanodomains. An increase in pH ionizes a number of COOH groups on both PMAMVE and PMAOVE, which leads to the stretching or swelling of the polymers. 相似文献
22.
Kristin fischer Stefan Spange Steffen Fischer Cornelia Bellmann Jörg Adams 《Cellulose (London, England)》2002,9(1):31-40
The surface polarity of native celluloses has been investigated by the following solvatochromic dyes: dicyano-bis (1,10)-phenanthroline iron (II) Fe(phen)2 (CN)2 (1), bis(4-N,N-dimethylamino)-benzophenone (2), and cou-marine 153 (3). Linear Solvation Energy (LSE) relationships and the UV/Vis data have been used to characterize the surface polarity of different native cellulose batches in terms of the empirical Kamlet–Taft polarity parameters (hydrogen bond acidity), (hydrogen bond basicity), and * (dipolarity/polarizability). , , *and calculated Reichardt's E T (30) values are reported for various native and regenerated cellulose samples with different degrees of crystallinity. The degree of crystallinity of the cellulose samples has been determined by X-ray. The microcrystalline environment of cellulose can be exactly parameterized in terms of the , and *values. It shows a fairly strong acidity and a low dipolarity/polarizability. For the amorphous sections smaller and larger * values are observed. The correspondence of the empirical polarity parameters determined has been discussed in relation to results from pyrene fluorescence and zetapotential measurements. 相似文献
23.
Reactions of π-Organonickel Complexes with Tertiary Phosphanes In a hexane solution Ni(C5H5)2 reacts with PBu3 or Ph2PBu forming the nickel(O) complexes Ni(PBu3)4 or Ni(Ph2PBu)4 (A). Under the same conditions only one cyclopentadienyl ligand is substituted by PhPBu2 and the nickel(I) compound (C5H5)Ni (PhPBu2)2 (B) is obtained. Products of the reactions between B and α,α′-dipyridyl, hydrogen chlorid in ether, or Ni(PhPBu2),Cl2 are Ni(dipy)2, [PhPHBu2]2[NiCl4], or (C5H5) Ni(PhPBu2)2Cl. By the reaction with HgCl2 a cyclopentadienyl compound of an unknown structur is formed. The compound Ni(PhPBu2)4 which is analogous to A is synthesized by the reduction of bis(acety1acetonato)-nickel with Et2AlOEt in the presence of PhPBu2 or by the reaction of bis (cyclooctadiene-1,5)-nickel with PhPBu2. 相似文献
24.
Steffen Wolf Benedikt Sohmen Bjrn Hellenkamp Johann Thurn Gerhard Stock Thorsten Hugel 《Chemical science》2021,12(9):3350
We report on a study that combines advanced fluorescence methods with molecular dynamics (MD) simulations to cover timescales from nanoseconds to milliseconds for a large protein. This allows us to delineate how ATP hydrolysis in a protein causes allosteric changes at a distant protein binding site, using the chaperone Hsp90 as test system. The allosteric process occurs via hierarchical dynamics involving timescales from nano- to milliseconds and length scales from Ångstroms to several nanometers. We find that hydrolysis of one ATP is coupled to a conformational change of Arg380, which in turn passes structural information via the large M-domain α-helix to the whole protein. The resulting structural asymmetry in Hsp90 leads to the collapse of a central folding substrate binding site, causing the formation of a novel collapsed state (closed state B) that we characterise structurally. We presume that similar hierarchical mechanisms are fundamental for information transfer induced by ATP hydrolysis through many other proteins.We report on a study that combines advanced fluorescence methods with molecular dynamics simulations to cover timescales from nanoseconds to milliseconds for a large protein, the chaperone Hsp90. 相似文献
25.
26.
Downey Rodney G.; Lempp Steffen; Shore Richard A. 《Journal London Mathematical Society》1996,54(3):417-439
We show that there is a degree a REA in and low over 0' suchthat no minimal degree below 0' jumps to a degree above a. Wealso show that every nonlow recursively enumerable degree boundsa nonlow minimal degree. 相似文献
27.
W. Uhlig 《无机化学与普通化学杂志》1992,618(12):144-147
Synthesis of Siloxanes on the Basis of Silyltriflates The reaction of silyltriflates with silanols leads to the formation of siloxanes. This method is of importance if the synthesis of silyltriflates is more simply and selectively than the preparation of the corresponding chlorosilanes. This is observed in the case of functional substituted silyltriflates or triflate derivatives of oligosilanes. The synthetic potential of these compounds for the preparation of siloxanes is shown on selected examples. 相似文献
28.
Iris Reimann Steffen Mergemeier Ingo Ebner Fritz Scholz 《Fresenius' Journal of Analytical Chemistry》1995,353(2):206-210
A determination of ethanol is described, which is based on a purging system in conjunction with a photoionization detector. With that system a fast and reliable determination of ethanol in aqueous solutions is possible. The system has been used for the analysis of wine. The 3-detection limit has been 0.005% ethanol, the relative standard deviation 4.8 to 6.0% and the time constant of the entire analytical system 20 s. The photoionization detector has been also applied to the analysis of artificial and genuine human breath. A comparison with gas-chromatography and non-dispersive IR-detection has been proven the reliability of results. 相似文献
29.
Hofmann C Boll R Heitmann B Hauser G Dürr C Frerich A Weitnauer G Glaser SJ Bechthold A 《Chemistry & biology》2005,12(10):1137-1143
The oligosaccharide antibiotic avilamycin A is composed of a polyketide-derived dichloroisoeverninic acid moiety attached to a heptasaccharide chain consisting of six hexoses and one unusual pentose moiety. We describe the generation of mutant strains of the avilamycin producer defective in different sugar biosynthetic genes. Inactivation of two genes (aviD and aviE2) resulted in the breakdown of the avilamycin biosynthesis. In contrast, avilamycin production was not influenced in an aviP mutant. Inactivation of aviGT4 resulted in a mutant that accumulated a novel avilamycin derivative lacking the terminal eurekanate residue. Finally, AviE2 was expressed in Escherichia coli and the gene product was characterized biochemically. AviE2 was shown to convert UDP-D-glucuronic acid to UDP-D-xylose, indicating that the pentose residue of avilamycin A is derived from D-glucose and not from D-ribose. Here we report a UDP-D-glucuronic acid decarboxylase in actinomycetes. 相似文献
30.
Ingo Hartenbach Falk Lissner Tanja Nikelski Steffen F. Meier Helge Müller‐Bunz Thomas Schleid 《无机化学与普通化学杂志》2005,631(12):2377-2382
About Lanthanide Oxotantalates with the Formula MTaO4 (M = La – Nd, Sm – Lu) Besides being a by‐product of solid state syntheses in tantalum ampoules the lanthanide(III) oxotantalates of the formula MTaO4 can be easily prepared by sintering lanthanide sesquioxide M2O3 and tantalum(V) oxide Ta2O5 with sodium chloride as flux. Under these conditions two structure types emerge depending upon the M3+ cationic radius. For M = La – Pr the MTaO4‐type tantalates crystallize in the space group P21/c with lattice constants of a = 762(±1), b = 553(±4), c = 777(±4) pm, β = 101(±1)° and four formula units per unit cell. With M = Nd, Sm – Lu, the monoclinic cell dimensions (space group P2/c) shrink to the lattice constants like a = 516(±9), b = 551(±9), c = 534(±9) pm, β = 96.5(±0.3)° and there are only two formula units present. Both structures show a coordination sphere of eight oxygen atoms for the lanthanide trications shaped as distorted square antiprism for the structure with the larger lanthanides (in the following referred to as A‐type) and as trigonal dodecahedron for the structure with the smaller ones (called as B‐type in the following). The coordination environment about the Ta5+ cations can be described as a slightly distorted octahedron (CN = 6) for the A‐type structure of MTaO4 and a heavily distorted one (CN = 6) for the B‐type. The difference between the two types results from the interconnection of these [TaO6]7? octahedra. Whereas they are connected via four vertices to form corrugated layers according to parallel the bc‐plane in the A‐type, the octahedra of the B‐type MTaO4 structure share edges to built up zig‐zag chains along the c axis. 相似文献