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81.
New Investigations about Oxo Uranates: On α-Li6UO6. With a Remark about β-Li6UO6 The crystal structure of transparent, bright yellow single crystals of α-Li6UO6 has been determined. [a = 838.07(5), c = 738.34(7) pm; dpyk = 4.02, dx = 4.17 g · cm?3; space group R3 ; Z = 3; R = 3.17%, Rw = 3.06%; 408 symmetry independent I0(hkl); AgKα fourcircle diffractometer Philips PW 1100]. The structure is dominated by a threedimensional framwork of “hollow spaces”, built up by 12 O2? (and 12 Li+). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed. 相似文献
82.
To the Knowledge of the NaCl Family of Structure: The Crystal Structure of NaMnO2 Ochre coloured single crystals of NaMnO2 show a monoclinic [a = 5.662 Å, b = 2.860 Å, c = 5.799 Å, β = 113.1°] variant [C–C2/m; Na in 2(d), Mn in 2(a), O in 4(i), R = 11.2% (MoKα)] of the α-NaFeO2-type of structure. The Jahn-Teller-distortion within the {MnO6}-Group ist remarkable with Mn ? O = 1.93 (4×), 2.40 (2 ×) Å. NaMnO2 posesses temperature indepent paramagnetism: +Mol =+3450 · 10?6 cgs. The Madelung Part of Lattice Energy is calculated and discussed. 相似文献
83.
Inkjet printing represents a highly promising polymer deposition method, which is used for, for example, the fabrication of multicolor polyLED displays and polymer-based electronics parts. The challenge is to print well-defined polymer structures from dilute solution. We have eliminated the formation of ring stains by printing nonvolatile acetophenone-based inks on a perfluorinated substrate using different polymers. (De)pinning of the contact line of the printed droplet, as related to the choice of solvent, is identified as the key factor that determines the shape of the deposit, whereas the choice of polymer is of minor importance. Adding 10 wt % or more of acetophenone to a volatile solvent (ethyl acetate)-based polymer solution changes the shape of the deposit from ring-like to dot-like, which may be due to the establishment of a solvent composition gradient. Arrays of closely spaced dots have also been printed. The size of the dots is considerably smaller than the nozzle diameter. This may prove a potential strategy for the inkjet printing of submicrometer structures. 相似文献
84.
A new multiple-layer matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) sample-spotting technique is described. This fast and easy technique was evaluated with poly(ethylene glycol) (PEG) standards and optimized conditions for these synthetic polymers were obtained. PEGs up to 35 kDa were detectable with this approach and single monomer resolution was observed up to 20 kDa. The spotting was performed using a multiple-layer approach, which offers the capability of complex sample preparation without the requirement of premixing the different matrix, analyte and doping salt solutions. The technique reduces the time required for sample preparation and offers high flexibility with respect to sample composition and solvents utilized for the crystallization of the compounds. The technique is thus perfectly suited for applications in combinatorial material research. 相似文献
85.
Immo Weber Frank W. Heinemann Panagiotis Bakatselos Ulrich Zenneck 《Helvetica chimica acta》2007,90(4):834-845
A pressure‐controlled procedure for the SN1 reaction of rac‐1‐[(dimethylamino)methyl]‐2‐(tributylstannyl)ferrocene ( 1 ) to rac‐1‐(phthalimidomethyl)‐2‐(tributylstannyl)ferrocene ( 2 ) was developed. Pd0‐Catalyzed Stille coupling of 2 with iodobenzene afforded rac‐1‐phenyl‐2‐(N‐phthalimidomethyl)ferrocene ( 5 ) in 74% yield; after trace enrichment by crystallization of the combined mother liquors, one single crystal of each, 5 , catalysis intermediate trans‐iodo(σ‐phenyl)bis(triphenylarsino)palladium(II) ( 7 ), trans‐diiodobis(triphenylarsino)palladium(II) ( 8 ), and rac‐2,2′‐bis(phthalimidomethyl)‐1,1′‐biferrocene ( 9 ) could be isolated by crystal sorting under a microscope and characterized by X‐ray crystal structure analysis. Furthermore, 5 was deprotected to amine ( 11 ), which does even survive the Birch reduction to rac‐1‐(aminomethyl)‐2‐(cyclohexa‐2,5‐dienyl)ferrocene ( 12 ). 相似文献
86.
The interactions of [Pt(en)Cl(ACRAMTU-S)](NO3)2 (PT-ACRAMTU, en = ethane-1,2-diamine, ACRAMTU = 1-[2-(acridin-9-ylamino)ethyl]-1,3-dimethylthiourea) with adenine in DNA have been studied using a combination of analytical and high-resolution structural methods. For the first time, a cytotoxic platinum(II) complex has been demonstrated to form adducts in the minor groove of DNA through platination of the adenine-N3 endocyclic nitrogen. An acidic depurination assay was developed that allowed the controlled and selective (pH 2, 60 degrees C, 12 h) release of platinum-modified adenine from drug-treated nucleic acid samples. From the digested mixtures, three adducts were isolated by semipreparative reverse phase high-performance liquid chromatography and studied by electrospray ionization mass spectrometry (in-line LC-MS), variable-pH 1H NMR spectroscopy, and, where applicable, X-ray crystallography. The three species were identified as the N7 (A-I), N3 (A-II), and N1 (A-III) linkage isomers of [Pt(en)(ACRAMTU-S)(adenine)]3+ (A). Incubations carried out with the single- and double-stranded model sequences, d(TA)5 and d(TA)15, as well as native DNA indicate that the adduct profiles (A-I:A-II:A-IIIratios) are sensitive to the nature of the nucleic acid template. A-II was found to be a double-strand specific adduct. The crystal structure of this adduct has been determined, providing ultimate evidence for the N3 connectivity of platinum. A-II crystallizes in the triclinic space group P in the form of centrosymmetric dimers, {[Pt(en)(ACRAMTU-S)(adenine-N3)]2}6+. The cations are stabilized by a combination of adenine-adenine base pairing (N6...N1 2.945(5) A) and mutual acridine-adenine base stacking. Tandem mass spectra and 1H chemical shift anomalies indicate that this type of self-association is not merely a crystal packing effect but persists in solution. The monofunctional platination of adenine at its N7, N3, and N1 positions in a significant fraction of adducts breaks a longstanding paradigm in platinum-DNA chemistry, the requirement for nucleophilic attack of guanine-N7 as the principal step in cross-link formation. The biological consequences and potential therapeutic applications of the unique base and groove recognition of PT-ACRAMTU are discussed. 相似文献
87.
Heterogeneous structure of silk fibers from Bombyx mori resolved by 13C solid-state NMR spectroscopy
Asakura T Yao J Yamane T Umemura K Ulrich AS 《Journal of the American Chemical Society》2002,124(30):8794-8795
The molecular conformation of silk fibrion is characterized by solid-state 13C NMR before spinning (silk I structure) and after spinning (silk II structure). We compare native silk fibers with the quasi-crystalline Cp-fraction and a synthetic model peptide (Ala-Gly)15, both of which can be converted either into silk I by dialysis from 9 M LiBr or into silk II by treatment with formic acid. Our results demonstrate that silk II fibers are intrinsically heterogeneous, consisting of beta-sheets, distorted beta-turns, and distorted beta-sheets. This higher-order heterogeneity is revealed by the 13C-NMR Cbeta-peak of Ala, indicating that the Ala side chains are stacked partially in parallel and partially face-to-face, at a ratio of 1:2. 相似文献
88.
Henri Ulrich F. A. Stuber G. M. Peters A. A. R. Sayigh 《Journal of polymer science. Part A, Polymer chemistry》1976,14(3):565-571
Several light-sensitive arenesulfonylazido polycarboxylic acids were synthesized by a one-step reaction of a polymeric anhydride with a light-sensitive monofunctional alcohol, or by the reverse reaction, i.e., reaction of a polymeric alcohol with a light-sensitive monofunctional anhydride. The polycarboxylic acids are soluble in polar organic solvents and in aqueous base. Neutralization of part of the carboxyl groups gives rise to the formation of water-soluble polymers. Coreaction of poly(maleic anhydride-co-methyl vinyl ether) with 2-hydroxyethyl 4-sulfonylazidocarbanilate and 2-hydroxyethyl trans-2,5-dimethoxystilbene-4′-carbamate produces a light-sensitive polycarboxylic acid with “built-in” sensitizer. 相似文献
89.
[reaction: see text]. The alpha-deprotonation of alkynyl carbamates 3 with the chiral base (-)-sparteine (4)/n-butyllithium, transmetalation with ClTi(O(i)()Pr)3, and subsequent substitution with an aldehyde results in the formation of enantioenriched 4-hydroxyallenyl carbamates 11. Stereoselection is determined by dynamic resolution of the lithium/(-)-sparteine complexes by selective crystallization. 相似文献
90.
New five-coordinate Pt(IV) complexes [{(o-R2-p-R'-C6H2)NC(R' ')}2CH]PtMe3 (R, R', R' ' = alkyl or H) are reported. The complex with R = Me, R' = tBu, R' ' = Me generates unsaturated Pt(II) species capable of alkane C-H bond activation and stoichiometric dehydrogenation. 相似文献