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11.
Zusammenfassung Durch spektrophotometrische Messungen in Dimethylformamid (DMF) werden die Koordinationsformen [CuCl]+ und [CuCl3]– sowie [NiCl]+, [NiCl3]– und [NiCl4]2– nachgewiesen. Bei Nickel(II)-chlorid und Kupfer(II)-chlorid wird Autokomplexbildung diskutiert. Die Solvate [Cu(DMF)4] (ClO4)2 und [Ni(DMF)6] (ClO4)2 werden isoliert.Im Zuge der Untersuchungen über Chlorokomplexe von Ionen der Übergangsmetalle1, 2 in nichtwäßrigen Lösungsmitteln wurden die Spektren der Lösungen von Kupfer(II)- und Nikkel(II)-perchlorat inDMF in Gegenwart verschiedener Mengen Tetraäthylammoniumchlorid aufgenommen.Mit 5 Abbildungen 相似文献
12.
Briggs CR Allen MJ O'Hagan D Tozer DJ Slawin AM Goeta AE Howard JA 《Organic & biomolecular chemistry》2004,2(5):732-740
The energies of the gauche and anti conformers of 2-fluoroethylamine, 2-fluoroethanol and their protonated analogues are calculated using density functional theory. Unlike the non protonated systems, the protonated systems show a strong gauche effect where the C-F and the C-(+)NH(3) or C-F and C-(+)OH(2) bonds are gauche rather than anti to each other. Single crystal X-ray diffraction studies of 2-fluoroethylammonium compounds identify the same conformational preference. 相似文献
13.
Summary A high molecular weight sodium hyaluronate isolated from rooster combs was degraded by ultrasonication. High-performance size exclusion chromatography allowed rapid and accurate determination of molecular weight parameters (Mz, Mw, Mn) and distributions. The time dependence of hyaluronan ultrasonication to the molecular characteristics of the polymer was investigated. A non-random nature of the degradation process was demonstrated and the reciprocal Mn value was found to be linearly proportional to the time of ultrasonication. 相似文献
14.
Substituent effects on the rate constants for the photo-Claisen rearrangement of allyl aryl ethers 总被引:1,自引:0,他引:1
The photochemistry of 11 substituted allyl 4-X- and 3-X-aryl ethers 3 (ArOCH2-CH=CH2) has been examined in both methanol and cyclohexane as solvents. The ethers react by the photo-Claisen rearrangement to give allyl substituted phenols as the major primary photoproducts, as expected from the well-established radical pair mechanism. The excited singlet state properties (absorption spectra, fluorescence spectra, fluorescence quantum yields, and singlet lifetimes) were compared with a parallel set of unreactive 4-X- and 3-X-anisoles 4. The excited-state properties of three substituted 4-X-aryl 4-(1-butenyl) ethers 14 (ArOCH2CH2-CH=CH2) were also examined. The model compounds 4 and the reactive allyl ethers 3 have essentially identical rate constants for the excited-state processes with the exception of, the rate constant for homolytic cleavage from S(1) of the allyl ethers to give the radical pair. The difference between the fluorescence quantum yields and/or singlet lifetimes for 3 and 4 were used to obtain values of for all of the allyl ethers. These values exhibit a large substituent effect, spanning almost 2 orders of magnitude with electron-donating groups (CH3O, CH3) accelerating the reaction and electron-withdrawing ones (CN, CF3) slowing it down. The parallel range of rate constants observed in both methanol and cyclohexane indicates that ion pairs are not important intermediates in these rearrangements. Quantum yields of reaction (Phi(r)) for several of the more reactive ethers demonstrate that neither these values nor rate constants of reaction derived from them are reliable measures of the actual excited-state process. In fact, the values are significantly lower than the ones, indicating that the radical pairs undergo recombination to generate starting material. Finally, the rate constants were found to parallel a trend for the change in bond dissociation energy (deltaBDE) for the O-C (allyl) bond of the allyl ethers, indicating that other possible substituent effects are of minor importance. 相似文献
15.
Alexandra M. Antonio Kyle J. Korman Glenn P. A. Yap Eric D. Bloch 《Chemical science》2020,11(46):12540
Diverse strategies for the preparation of mixed-metal three-dimensional porous solids abound, although many of them lend themselves only moderate levels of tunability. Herein, we report the design and synthesis of surface functionalized permanently microporous coordination cages and their use in the isolation of mixed metal solids. Judicious alkoxide-based ligand functionalization was utilized to tune the solubility of starting copper(ii)-based cages and their resulting compatibility with the mixed-cage approach described here. We further prepared a family of isostructural molybdenum(ii) cages for a subset of the ligands. The preparation of mixed-metal cage solids proceeds under facile conditions where solutions of parent cages are mixed and product phases isolated. A suite of spectroscopic and characterization tools confirm the starting cages are intact in the amorphous product. Finally, we show that utilization of precise ligand functional groups can be used to prepare mixed cage solids that can be easily and cleanly separated into their constituent components through simple solvent washing or solvent extraction techniques.Surface-functionalized porous coordination cages can be used to create homogeneous mixed-cage alloys with high levels of tunability and processability. 相似文献
16.
Dr. Alexandra R. McNeill Dr. Rodrigo Martinez-Gazoni Prof. Roger J. Reeves Prof. Martin W. Allen Prof. Alison J. Downard 《Chemphyschem》2021,22(13):1344-1351
ZnO is a strong candidate for transparent electronic devices due to its wide band gap and earth-abundance, yet its practical use is limited by its surface metallicity arising from a surface electron accumulation layer (SEAL). The SEAL forms by hydroxylation of the surface under normal atmospheric conditions, and is present at all crystal faces of ZnO, although with differing hydroxyl structures. Multilayer aryl films grafted from aryldiazonium salts have previously been shown to decrease the downward bending at O-polar ZnO thin films, with Zn−O−C bonds anchoring the aryl films to the substrate. Herein we show that the Zn-polar (0001), O-polar (000 ), and non-polar m-plane (10 0) faces of ZnO single crystals, can also be successfully electrografted with nitrophenyl (NP) films. In all cases, X-ray photoelectron spectroscopy (XPS) measurements reveal that the downward surface band bending decreases after modification. XPS provides strong evidence for Zn−O−C bonding at each face. Electrochemical reduction of NP films on O-polar ZnO single crystals converts the film to a mainly aminophenyl layer, although with negligible further change in band bending. This contrasts with the large upward shifts in band bending caused by X-ray induced reduction. 相似文献
17.
Dr. Alexey S. Kiryutin Mikhail S. Panov Dr. Alexandra V. Yurkovskaya Prof. Dr. Konstantin L. Ivanov Prof. Dr. Geoffrey Bodenhausen 《Chemphyschem》2019,20(5):766-772
A study of long-lived spin order in chlorothiophene carboxylates at both high and low magnetic fields is presented. Careful sample preparation (removal of dissolved oxygen in solution, chelating of paramagnetic impurities, reduction of convection) allows one to obtain very long-lived singlet order of the two coupled protons in chlorothiophene derivatives, having lifetimes of about 130 s in D2O and 240 s in deuterated methanol, which are much longer than the T1-relaxation times (18 and 30 s, respectively, at a field =9.4 T). In protonated solvents the relaxation times become shorter, but the lifetime is still substantially longer than . In addition, long-lived coherences are shown to have lifetimes as long as 30 s. Thiophene derivatives can be used as molecular tags to study slow transport, slow dynamics and slow chemical processes, as has been shown in recent years. 相似文献
18.
Dula Amarasiriwardena Steven F. Durrant Alexandra Lásztity Antoaneta Kvska Mark D. Argentine Ramon M. Barnes 《Microchemical Journal》1997,56(3):352-372
Semiquantitative analysis with accuracy of ±30 to 50% is a valuable tool for rapid screening of samples prior to quantitative determination of trace metals. In this study semiquantitative analysis software available with commercial inductively coupled plasma–mass spectrometry (ICP-MS) instrumentation is applied for rapid multielemental analysis, and the accuracy and precision of this semiquantitative analysis approach is evaluated with biological certified reference materials. Samples were prepared by high-pressure, high-temperature nitric acid vapor-phase digestion. For most elements the measured semiquantitative results are in the range of the certified values. With appropriate analyte solution dilution, the measured concentrations of the major elements (e.g., Ca) also agree with certified values. The accuracy is within ±10% for 28 element determinations that include 16 individual elements (Ag, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Rb, Sb, Sr, Tl, and Zn) and ±20% for 54 element determinations that include three more elements (Mg, V, and U) in eight certified reference materials including water. The method precision is 11 ± 11% (relative standard deviation,n= 65). 相似文献
19.
Hans‐Jürgen Holdt Holger Müller Alexandra Kelling Hans‐Joachim Drexler Thomas Müller Thomas Schwarze Uwe Schilde Ines Starke 《无机化学与普通化学杂志》2006,632(1):114-122
Mercury(II) Chloride and Iodide Complexes of Dithia‐ and Tetrathiacrown Ethers The complexes [(HgCl2)2((ch)230S4O6)] ( 1 ), [HgCl2(mn21S2O5)] ( 2 ), [HgCl2(ch18S2O4)] ( 3 ) and [HgI(meb12S2O2)]2[Hg2I6] ( 4 ) have been synthesized, characterized and their crystal structures were determined. In [(HgCl2)2((ch)230S4O6)] two HgCl2 units are discretely bonded within the ligand cavity of the 30‐membered dichinoxaline‐tetrathia‐30‐crown‐10 ((ch)230S4O6) forming a binuclear complex. HgCl2 forms 1 : 1 “in‐cavity” complexes with the 21‐membered maleonitrile‐dithia‐21‐crown‐7 (mn21S2O5) ligand and the 18‐membered chinoxaline‐dithia‐18‐crown‐6 (ch18S2O4) ligand, respectively. The 12‐membered 4‐methyl‐benzo‐dithia‐12‐crown‐4 (meb12S2O2) ligand gave with two equivalents HgI2 the compound [HgI(meb12S2O2)]2[Hg2I6]. In the cation [HgI(meb12S2O2)]+ meb12S2O2 forms with the cation HgI+ a half‐sandwich complex. 相似文献
20.
Single cell analytics for proteomic analysis is considered a key method in the framework of systems nanobiology which allows a novel proteomics without being subjected to ensemble-averaging, cell-cycle, or cell-population effects. We are currently developing a single cell analytical method for protein fingerprinting combining a structured microfluidic device with latest optical laser technology for single cell manipulation (trapping and steering), free-solution electrophoretical protein separation, and (label-free) protein detection. In this paper we report on first results of this novel analytical device focusing on three main issues. First, single biological cells were trapped, injected, steered, and deposited by means of optical tweezers in a poly(dimethylsiloxane) microfluidic device and consecutively lysed with SDS at a predefined position. Second, separation and detection of fluorescent dyes, amino acids, and proteins were achieved with LIF detection in the visible (VIS) (488 nm) as well as in the deep UV (266 nm) spectral range for label-free, native protein detection. Minute concentrations of 100 fM injected fluorescein could be detected in the VIS and a first protein separation and label-free detection could be achieved in the UV spectral range. Third, first analytical experiments with single Sf9 insect cells (Spodoptera frugiperda) in a tailored microfluidic device exhibiting distinct electropherograms of a green fluorescent protein-construct proved the validity of the concept. Thus, the presented microfluidic concept allows novel and fascinating single cell experiments for systems nanobiology in the future. 相似文献