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151.
Pter Bagi Konstantin Karaghiosoff Mtys Czugler Dra Hessz Mihly Kllay Mikls Kubinyi Tibor Szilvsi Pter Pongrcz Lszl Kollr Istvn Timri Katalin E. Kvr Lszl Drahos Elemr Fogassy Gyrgy Keglevich 《Heteroatom Chemistry》2016,27(2):91-101
An efficient resolution method was elaborated for the preparation of (+)‐4‐chloro‐5‐methyl‐1‐phenyl‐1,2,3,6‐tetrahydrophosphinine oxide using the acidic Ca2+ salt of (–)‐O,O‐di‐p‐toluoyl‐(2R,3R)‐tartaric acid. Crystal structure of the diastereomeric complex was evaluated by single crystal X‐ray analysis. Beside this, the absolute P‐configuration was also determined by a circular dichroism (CD) spectroscopic study including theoretical calculations. The tetrahydrophosphinine oxide was then converted to the corresponding platinum complex whose stereostructure was investigated by high‐level quantum chemical calculations. The Pt complex was tested as a catalyst in the hydroformylation of styrene. 相似文献
152.
Ardanova LI Get'man EI Loboda SN Prisedsky VV Tkachenko TV Marchenko VI Antonovich VP Chivireva NA Chebishev KA Lyashenko AS 《Inorganic chemistry》2010,49(22):10687-10693
Polycrystalline hydroxyapatites Ca(10-x)REE(x)(PO(4))(6)(OH)(2-x)O(x) were synthesized and studied by X-ray powder diffraction, infrared absorption, diffuse-reflectance spectroscopy, and thermogravimetry. The solubility limits x(max) of rare earth elements (REE) in Ca hydroxyapatites decreases with an increasing REE atomic number from x(max) = 2.00 for La, Pr, and Nd to x(max) = 0.20 for Yb at 1100 °C. Refinements of X-ray diffraction patterns by the Rietveld method show that REE atoms substitute for Ca preferentially at the Ca(2) sites of the apatite structure. The substitution decreases the Ca(2)-O(4) atomic distances in the calcium coordination polyhedra and increases the Ca(2)-O(1,2,3) distances. This observation shows that interatomic distances depend not only on radii of the ions involved in the substitution but also on their charges. 相似文献
153.
Vidma KV Bogdanchikov GA Baklanov AV Chestakov DA Parker DH 《The Journal of chemical physics》2010,133(19):194306
Van der Waals binding energies for the X-O(2) complexes (X=Xe, CH(3)I, C(3)H(6), C(6)H(12)) are determined by analysis of experimental velocity map imaging data for O((3)P(2)) atoms arising from UV-photodissociation of the complex [A. V. Baklanov et al., J. Chem. Phys. 126, 124316 (2007)]. Several dissociation pathways have been observed, we focus on the channel corresponding to prompt dissociation of X-O(2) into X+2O((3)P) fragments, which is present for complexes of O(2) with all partners X. Our method is based on analysis of the kinetic energy of all three photofragments, where the O atom kinetic energy was directly measured in the experiment and the kinetic energy of the X partner was calculated using momentum conservation, along with the measured angular anisotropy for O atom recoil. We exploit the fact that the clusters are all T-shaped or nearly T-shaped, which we also confirm by ab initio calculations, along with knowledge of the transition dipole governing radiative absorption by the complex. The effect of partitioning the kinetic energy between translation along the X-O(2) and O-O coordinates on the angular anisotropy of the O atom recoil direction is discussed. Van der Waals binding energies of 110±20 cm(-1), 280±20 cm(-1), 135±30 cm(-1), and 585±20 cm(-1) are determined for Xe-O(2), CH(3)I-O(2), C(3)H(6)-O(2), and C(6)H(12)-O(2) clusters, respectively. 相似文献
154.
155.
Anisimova TB Bokach NA Luzyanin KV Haukka M Kukushkin VY 《Dalton transactions (Cambridge, England : 2003)》2010,39(44):10790-10798
The reaction between K[PtCl(3)(Me(2)SO)] or prepared in this work cis- and trans-[PtCl(2)(NCNR(2))(Me(2)SO)] (R(2) = Me(2), 1; C(4)H(8)O, 2; C(5)H(10) 3) with an excess of NCNR(2) in water gives the cationic bischelate [Pt{κ(2)-N,N'-NH=C(NMe(2))OC(NMe(2))=NH}(2)](2+) (4(2+)) and the monochelates [PtCl{κ(2)-N,O-NH=C(NR(2))NC(NR(2))=O}(Me(2)SO)] (R(2) = C(4)H(8)O, 5; C(5)H(10), 6). Complex 4(2+) was released from the reaction mixture as 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2) or it was precipitated as 4·[A](2) (A = pic, 4·[pic](2); PF(6), 4·[PF(6)](2); BPh(4), 4·[BPh(4)](2)·(NH(2)CONMe(2))) by addition of picric acid, NaPF(6), or NaBPh(4), respectively, to the filtrate obtained after separation of 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2). In 2, the dialkylcyanamide ligand undergoes bond cleavage giving the known trans-[PtCl(2){N(H)C(4)H(8)O}(Me(2)SO)] (trans-7). All complexes were characterized by elemental analyses (C, H, N), high resolution ESI-MS, IR, (1)H and (13)C{(1)H} NMR spectroscopic techniques, including 2D NMR correlation experiments ((1)H,(1)H-COSY, (1)H,(13)C-HMQC/(1)H,(13)C HSQC, (1)H,(13)C-HMBC, and (1)H,(1)H-NOESY). The structures of cis-1, cis-3, 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2), 4·[BPh(4)](2)·(NH(2)CONMe(2)) and 5 were determined by a single-crystal X-ray diffraction. 相似文献
156.
Zhongchen Wu Konstantin Chingin Huanwen Chen Liang Zhu Bin Jia Renato Zenobi 《Analytical and bioanalytical chemistry》2010,397(4):1549-1556
The development of analytical techniques suitable for sensitive, high-throughput, and nondestructive food analysis has been
of increasing interest in recent years. In this study, mass-spectral fingerprints of various cheese products were rapidly
recorded in the mass range of m/z 50–300 Da without any sample pretreatment, using neutral desorption extractive electrospray ionization mass spectrometry
(ND-EESI-MS) in negative ion mode. The results demonstrate that both volatile and nonvolatile analytes on greasy cheese surfaces
can be directly sampled by a neutral desorption gas beam. The influence of the neutral desorption gas flow on the analyte
signal was systematically investigated. Under optimized experimental conditions, reproducible results were obtained using
ND-EESI-MS. Principal component analysis was applied to differentiate a total of 49 individual cheese samples (four different
types), which were purchased from three different supermarkets. All samples were successfully classified according to their
types; but distributors and sensory properties were not distinguishable from the spectra data. The principal components 2,
3, and 4 scores showed an excellent capacity of distinguishing types of cheese. Molecular markers of interest can be identified
using tandem mass spectrometry and matching the data with those from reference compounds. The experimental data show that
ND-EESI-MS is able to sensitively and directly detect analytes on greasy surfaces without chemical contamination, providing
a convenient method for high-throughput food analysis with a high degree of safety. 相似文献
157.
Konstantin E. Komolov Mònica Aguilà Darwin Toledo Joan Manyosa Pere Garriga Karl-Wilhelm Koch 《Analytical and bioanalytical chemistry》2010,397(7):2967-2976
Surface plasmon resonance spectroscopy allows the study of protein interaction dynamics in real-time. Application of this
technique to G-protein coupled receptors, the largest family of receptors involved in signal transduction, has been complicated
by their low level of expression and the critical dependence of their native conformation on the hydrophobic transmembrane
lipid environment. Here, we investigate and compare three different strategies to immobilize rhodopsin, a prototypical G-protein
coupled receptor on a sensor chip surface using antibodies and a lectin for receptor capturing. By further probing of different
experimental conditions (pH, detergent type) we identified the optimal factors to maintain rhodopsin in a functional conformation
and extended this approach to recombinant rhodopsin that was heterologously expressed in COS cells. Functional operation of
rhodopsin on the sensor chip surface was proven by its activation and subsequent light-stimulated G-protein coupling. The
influence of these experimental parameters on the association and dissociation kinetics of G-protein receptor coupling was
determined. Thereby, we found that the kinetics of Gt interaction were not changed by the strategy of immobilization or the type of detergent. Regeneration of opsin directly on
a chip allowed recycling of the immobilized native and recombinant receptor. Thus, the approach provides an experimental framework
for choosing the most suitable conditions for the solubilization, immobilization, and for functional tests of rhodopsin on
a biosensor surface. 相似文献
158.
Liang Zhu Zhong Hu Gerardo Gamez Wai Siang Law HuanWen Chen ShuiPing Yang Konstantin Chingin Roman M. Balabin Rui Wang TingTing Zhang Renato Zenobi 《Analytical and bioanalytical chemistry》2010,398(1):405-413
By gently bubbling nitrogen gas through beer, an effervescent beverage, both volatile and non-volatile compounds can be simultaneously sampled in the form of aerosol. This allows for fast (within seconds) fingerprinting by extractive electrospray ionization mass spectrometry (EESI-MS) in both negative and positive ion mode, without the need for any sample pre-treatment such as degassing and dilution. Trace analytes such as volatile esters (e.g., ethyl acetate and isoamyl acetate), free fatty acids (e.g., caproic acid, caprylic acid, and capric acid), semi/non-volatile organic/inorganic acids (e.g., lactic acid), and various amino acids, commonly present in beer at the low parts per million or at sub-ppm levels, were detected and identified based on tandem MS data. Furthermore, the appearance of solvent cluster ions in the mass spectra gives insight into the sampling and ionization mechanisms: aerosol droplets containing semi/non-volatile substances are thought to be generated via bubble bursting at the surface of the liquid; these neutral aerosol droplets then collide with the charged primary electrospray ionization droplets, followed by analyte extraction, desolvation, ionization, and MS detection. With principal component analysis, several beer samples were successfully differentiated. Therefore, the present study successfully extends the applicability of EESI-MS to the direct analysis of complex liquid samples with high gas content. Figure
By gently bubbling nitrogen gas through beer, both volatile and non-volatile compounds can be simultaneously sampled in the form of aerosol for further analysis, allowing fast chemically fingerprinting using extractive electrospray ionization mass spectrometry (EESI-MS). 相似文献
159.
Maria A. Peshkova Natalia V. Timofeeva Sergei M. Korneev Konstantin N. Mikhelson 《Electroanalysis》2010,22(19):2147-2156
A novel way of synthesis is developed for the Ba2+ selective neutral Ionophore 2a : 2,2′‐[1,2‐phenylenebis(oxyethane‐2,1‐diyloxy)]bis(N‐benzyl‐N‐phenylacetamide) and its methyl ( 2b ), buthyl ( 2c ), and hexyl ( 2d ) derivatives. Ba2+ selective electrodes based on Ionophores 2a – d are compared with those with commonly used Ionophore 1 : N,N,N′,N′‐tetracyclohexyl‐oxybis(o‐phenyleneoxy) diacetamide. It is shown that Ionophores 2a – d , particularly 2b , are superior for measurements of Ba2+ in the presence of Ca2+, and in acidic solutions. Segmented sandwich membrane studies suggest formation of complexes IL22+ for Ba2+, Ca2+ and Mg2+ ions with Ionophore 2b , while H+ ions apparently form complexes H2L2+. The values of the complex formation constants are consistent with the selectivity coefficients. 相似文献
160.
Ganna A. Senchyk Andrey B. Lysenko Eduard B. Rusanov Alexander N. Chernega Konstantin V. Domasevitch 《Acta Crystallographica. Section C, Structural Chemistry》2010,66(7):m180-m183
In the structures of the CdII pseudohalide coordination polymer poly[[diaquabis[μ2‐3,3′‐bis(1,2,4‐triazol‐4‐yl)‐1,1′‐biadamantane‐κ2N1:N1′]cadmium(II)] dithiocyanate dihydrate], {[Cd(C24H32N6)2(H2O)2](NCS)2·2H2O}n, (I), and the isomorphous selenocyanate analogue, {[Cd(C24H32N6)2(H2O)2](NCSe)2·2H2O}n, (II), the CdII cations occupy inversion centres and have octahedral CdN4O2 environments, completed by four N atoms of the organic ligands [Cd—N = 2.316 (2) and 2.361 (2) Å for (I), and 2.313 (3) and 2.372 (3) Å for (II)] and two trans‐coordinated aqua ligands [Cd—O = 2.3189 (15) Å for (I) and 2.323 (2) Å for (II)]. In each compound, the ligand displays a bidentate N1:N1′‐bridging mode, connecting the metal centres at a distance of 14.66 Å into two‐dimensional nets of (4,4)‐topology, while the uncoordinated thio(seleno)cyanate anions reside inside the net cavities. Hydrogen bonding between the water molecules, anions and 1,2,4‐triazole N atoms supports the tight packing, with an interlayer distance of 6.09 Å. 相似文献