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101.
Somisara DM Bühl M Lebl T Richardson NV Slawin AM Woollins JD Kilian P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(9):2666-2677
Syntheses and full characterisation data (including single crystal diffraction) of three 1,2‐diphosphonium dicationic species with the naphthalene‐1,8‐diyl (Nap) backbone are reported. The oxidation of Nap[P(NMe2)2]2 with P2I4 to its 1,2‐dication was achieved. meso‐ and rac‐forms of “all carbon” 1,2‐diphosphonium dications were obtained in good yields and purity by double alkylation of the parent diphosphine (1,2‐diphenyl‐1,2‐diphosphaacenaphthene) with methyl triflate or trimethyloxonium tetrafluoroborate. Each methylating reagent produces one of the rac‐ or meso‐forms of the dication diastereospecifically. Structural parameters of the new dications are discussed with respect to other phosphorus 1,2‐dications. DFT (B3LYP) computations revealed the significant role of the naphthalene backbone in stabilisation of the dicationic motif and helped to assess the energy cost of the steric clash of a variety of groups attached to the peri‐positions of naphthalene. The synthesis and single crystal X‐ray data of the extremely crowded Nap[P(?Se)(OiPr)2]2 are discussed, and are contrasted with the unsuccessful synthesis of Nap(PtBu2)2 from NapLi2 and ClPtBu2. 相似文献
102.
Petr tpni
ka Ivana Císaov Michal Hor
ek Karel Mach 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(10):1204-1205
The title compound, (η5‐cyclopentadienyl)[(1,2,3,4,5‐η)‐4‐ferrocenyl‐1,2,5,6‐tetrakis(trimethylsilyl)cyclohexa‐2,4‐dien‐1‐yl]titanium(II), [TiFe(C5H5)2(C23H42Si4)] or [Ti{η5‐C6H2{Fe(η5‐C5H4)(η5‐C5H5)}{Si(CH3)3}4}(η5‐C5H5)], possesses two directly linked metallocene units that subtend an angle of 52.9 (1)° (defined by the least‐squares planes of the directly connected π‐ligands) associated with the steric requirements of the bulky trimethylsilyl substituents. The cyclohexadienyl ligand adopts an envelope conformation; the perpendicular distance of its η5‐plane to the Ti atom is 1.512 (1) Å. 相似文献
103.
Dalibor Huska Vojtech Adam Petr Babula Libuse Trnkova Jaromir Hubalek Josef Zehnalek Ladislav Havel Rene Kizek 《Mikrochimica acta》2011,173(1-2):189-197
The expression of genes responsible for the biosynthesis of stress proteins corresponds to the exposition of an organism to abiotic and/or biotic stress. We utilize two types of paramagnetic particles for isolation of total mRNA from early somatic embryos of Norway Spruce (Picea abies /L./ Karst.) and maize plants (Zea mays L.) treated with cadmium(II) ions. The paramagnetic particles were evaluated for analysis of real samples, and poly-adenine was used as a model mRNA. Various approaches (from non-automatic to fully automatic) were tested in terms of handling the particles. Figa
Microfluidic robotic device coupled with electrochemical sensor field 相似文献
104.
Kotek J Lubal P Hermann P Císarová I Lukes I Godula T Svobodová I Táborský P Havel J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(1):233-248
In an aqueous solution at room temperature, 1,4,8,11-tetraazacyclotetradecane-1,8-bis(methylphosphonic acid) (H(4)L(1)) and Cu(I) (I) form a pentacoordinated (pc) complex, pc-[Cu(L(1))](2-), exhibiting conformation I of the cyclam ring. At high temperature, the complex isomerises to a hexacoordinated isomer, trans-O,O-[Cu(L(1))](2-), with a trans-III conformation of the cyclam ring. In pc-[Cu(L(1))](2-), four ring nitrogen atoms and one phosphonate oxygen atom are arranged around Cu(I) (I) in a structure that is half-way between a trigonal bipyramid and a tetragonal pyramid, with one phosphonic acid group uncoordinated. In the trans-O,O-[Cu(L(1))](2-) isomer, the nitrogen atoms form a plane and the phosphonic acid groups are in a mutually trans configuration. A structurally very similar ligand, 4-methyl-1,4,8,11-tetraazacyclotetradecane-1,8-bis(methylphosphonic acid) (H(4)L(2)), forms an analogous pentacoordinated complex, pc-[Cu(L(2))](2-), at room temperature. However, the complex does not isomerise to the octahedral complex analogous to trans-O,O-[Cu(L(1))](2-). Because of the high thermodynamic stability of pc-[Cu(L(1))](2-), (logbeta=25.40(4), 25 degrees C, I=0.1 mol dm(-3) KNO(3)) and the formation of protonated species, Cu(I) (I) is fully complexed in acidic solution (-log [H(+)] approximately 3). Acid-assisted decomplexation of both of the isomers of [Cu(H(2)L(1))] takes place only after protonation of both uncoordinated oxygen atoms of each phosphonate moiety and at least one nitrogen atom of the cycle. The exceptional kinetic inertness of both isomers is illustrated by their half-lives tau(1/2)=19.7 min for pc-[Cu(H(2)L(1))] and tau(1/2) about seven months for trans-O,O-[Cu(H(2)L(1))] for decomplexation in 5 M HClO(4) at 25 degrees C. The mechanism of formation of pc-[Cu(L(1))](2-) is similar to those observed for other macrocyclic complexes. 相似文献
105.
Dionigi C Calestani G Ferraroni T Ruani G Liotta LF Migliori A Nozar P Palles D 《Journal of colloid and interface science》2005,290(1):201-207
The importance of pure-phase titanium oxide materials as catalysts, sensors, and photonic band-gap materials has been growing steadily. Recently, more attention has been focused on nanostructured titanium oxide showing controlled and periodic porosity on a nanometric scale. The nanocrystal size control of porous nanostructured titanium oxide in an anatase form is a crucial step for the organic template method. Simple template removal by evaporation in an inert atmosphere is reported in this article and compared with the calcination technique usually reported in the literature. The proposed method allows the formation of a double-porous (macro and meso) anatase phase. We demonstrate that it highly preserves the macropore order into a titanium oxide material and induces narrowly dispersed mesopores by controlling the nano-crystal size that is kept around 6 nm. For the proposed method, polystyrene beads are particularly suitable as templates, being evaporated in the temperature range of anatase existence. The final high surface area makes the materials appealing for applications as photocatalysts or sensors. 相似文献
106.
Stará IG Alexandrová Z Teplý F Sehnal P Starý I Saman D Budesínský M Cvacka J 《Organic letters》2005,7(13):2547-2550
[reaction: see text] A new approach to nonracemic [7]helicene-like molecules has been developed. Stereoselective Co(I)-mediated [2 + 2 + 2] cycloisomerization of aromatic triynes containing an asymmetric carbon atom produces [7]helicene-like scaffolds in diastereomeric ratios up to 100:0. This central-to-helical chirality transfer can be controlled by the absolute configuration at the asymmetric center and by the presence of carbon substituents. 相似文献
107.
Viacheslav I. Tsirelnikov Boris V. Lokshin Prof. Dr. Petr Melnikov Valter A. Nascimento 《无机化学与普通化学杂志》2012,638(14):2335-2339
The dependence of the gallium trichloride saturated and unsaturated vapor pressures on temperature was studied by the static method using a quartz membrane zero‐manometer and taking into account the volume of its working chamber and substance mass. Conclusions about the presence of a distinguishable amount of trimeric molecules along with dimeric and momomeric molecules in the vapor were drawn on the basis of the obtained data. The following rough thermodynamic characteristics of a gaseous trimer of gallium trichloride were calculated: ΔfH° (Ga3Cl9, gas, 298 K) = –1466 kJ · mol–1. S°(Ga3Cl9, gas, 298 K) = 654 J · mol–1 · K–1. These data were used to elucidate the composition of the gaseous phase at a total pressure of 1 atm in the temperature range of 400–750 K. The suggested existence of trimeric molecules was not contradicted by vibrational spectroscopic analysis of gallium trichloride saturated vapor. 相似文献
108.
The electrodeless discharge lamp: a prospective tool for photochemistry: Part 3. The microwave photochemistry reactor 总被引:1,自引:0,他引:1
Petr Kln Milan Hjek Vladimír Církva 《Journal of photochemistry and photobiology. A, Chemistry》2001,140(3):1077-189
A simple and original microwave photochemical reactor is described in detail. It consists of an electrodeless discharge lamp placed into the reaction vessel in a modified domestic microwave oven. The microwave field generates ultraviolet radiation by the lamp at the same time when it interacts with the reaction mixture. The construction, experimental set-ups, applications, and safety precautions are discussed. 相似文献
109.
Iron Dicarbonyl Complexes Featuring Bipyridine‐Based PNN Pincer Ligands with Short Interpyridine CC Bond Lengths: Innocent or Non‐Innocent Ligand? 下载免费PDF全文
110.
A Bis(pyridine N‐oxide) Analogue of DOTA: Relaxometric Properties of the GdIII Complex and Efficient Sensitization of Visible and NIR‐Emitting Lanthanide(III) Cations Including PrIII and HoIII 下载免费PDF全文
Henrique F. Carvalho Dr. João M. C. Teixeira Carlos T. B. Paula Prof. Petr Hermann Dr. Carlos Platas‐Iglesias Prof. Stephane Petoud Prof. Éva Tóth Prof. Carlos F. G. C. Geraldes 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14834-14845
We report the synthesis of a cyclen‐based ligand (4,10‐bis[(1‐oxidopyridin‐2‐yl)methyl]‐1,4,7,10‐tetraazacyclododecane‐1,7‐diacetic acid= L1 ) containing two acetate and two 2‐methylpyridine N‐oxide arms anchored on the nitrogen atoms of the cyclen platform, which has been designed for stable complexation of lanthanide(III) ions in aqueous solution. Relaxometric studies suggest that the thermodynamic stability and kinetic inertness of the GdIII complex may be sufficient for biological applications. A detailed structural study of the complexes by 1H NMR spectroscopy and DFT calculations indicates that they adopt an anti‐Δ(λλλλ) conformation in aqueous solution, that is, an anti‐square antiprismatic (anti‐SAP) isomeric form, as demonstrated by analysis of the 1H NMR paramagnetic shifts induced by YbIII. The water‐exchange rate of the GdIII complex is ${k{{298\hfill \atop {\rm ex}\hfill}}}$ =6.7×106 s?1, about a quarter of that for the mono‐oxidopyridine analogue, but still about 50 % higher than the ${k{{298\hfill \atop {\rm ex}\hfill}}}$ of GdDOTA (DOTA=1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid). The 2‐methylpyridine N‐oxide chromophores can be used to sensitize a wide range of LnIII ions emitting in both the visible (EuIII and TbIII) and NIR (PrIII, NdIII, HoIII, YbIII) spectral regions. The emission quantum yield determined for the YbIII complex (${Q{{{\rm L}\hfill \atop {\rm Yb}\hfill}}}$ =7.3(1)×10?3) is among the highest ever reported for complexes of this metal ion in aqueous solution. The sensitization ability of the ligand, together with the spectroscopic and relaxometric properties of its complexes, constitute a useful step forward on the way to efficient dual probes for optical imaging (OI) and MRI. 相似文献