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131.
Crystal Structures of KNdTe4, RbPrTe4, and RbNdTe4 — Investigations concerning the Thermal Stability of KNdTe4 as well as some Remarks concerning Additional Representatives of the Composition ALnTe4 (A = K, Rb, Cs and Ln = Rare Earth Metal) Of the compounds ALnQ4 (A = Na, K, Rb, Cs; Ln = Lanthanoid; Q = S, Se and Te) the crystal structures of the three new tellurides KNdTe4, RbPrTe4 and RbNdTe4 were determined by X‐ray single‐crystal structure analysis and of the three additional new ones KCeTe4, KPrTe4 and CsNdTe4 by X‐ray powder diffraction experiments. All six new compounds are isotypic with KCeSe4. Characteristic for the crystal structure of the compounds mentioned above are layers built from (Q2)2— dumbbells in form of 4.32.4.3 nets with embedded cations A+ and Ln3+ between them, which are coordinated eightfold in form of square‐shaped antiprisms by Q ions. The distances Te‐Te within the dumbbells were found to be 277.8(2) pm for all investigated tellurides. By combination of X‐ray diffraction and DTA measurements it was shown that the compound KNdTe4 is metastable at ambient temperature with a limited existence range between the temperatures 260 and 498 °C. 相似文献
132.
Depecker G Patino N Di Giorgio C Terreux R Cabrol-Bass D Bailly C Aubertin AM Condom R 《Organic & biomolecular chemistry》2004,2(1):74-79
A cyclic molecule including a hexameric PNA sequence has been designed and synthesized in order to target the TAR RNA loop of HIV-1 through the formation of a "kissing complex". For comparison, its linear analogue has also been investigated. The synthesis of the cyclic and linear PNA has been accomplished following a liquid-phase strategy using mixed PNA and fully N-protected (aminoethylglycinamide) fragments. The interactions of this cyclic PNA and its linear analogue with TAR RNA have been studied and the results indicate clearly that no interaction occurs between the cyclic antisense PNA and TAR RNA, whereas a tenuous interaction has been detected with its linear PNA analogue. 相似文献
133.
Christophe Vande Velde Evi Bultinck Karla Tersago Christian Van Alsenoy Frank Blockhuys 《International journal of quantum chemistry》2007,107(3):670-679
Unhindered ortho‐dimethoxy‐substituted phenyl rings often display a coplanar conformation. A theoretical study of a series of methoxybenzenes consisting of methoxybenzene (anisole), the three dimethoxybenzenes, and 1,2,4,5‐tetramethoxybenzene, at the DFT/B3LYP/6‐311++G** level of theory, allows us to identify the factors influencing the conformational preference and attribute the coplanarity of such methoxy groups to mesomeric effects. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
134.
QI Qu Edward Tucker Sherril D. Christian 《Journal of inclusion phenomena and macrocyclic chemistry》2002,43(3-4):213-222
A series of sulfoalkyl ether -cyclodextrin derivatives, including sulfoethyl, sulfopropyl and sulfobutyl ethyl -cyclodextrins, have been synthesized and characterized. Each sulfoalkyl ether -cyclodextrin is a mixture of various degrees of substitution and different positional isotherms. Elemental analysis, 1H NMR, MS, and Differential Scanning Calorimetry analysis were used to determine the average degree of substitution for each -cyclodextrin derivative. The average degrees of substitution are 3.4, 1.6 and 2.5 for sulfoethyl, sulfopropyl and sulfobutyl ether -cyclodextrin, respectively. The water solubility of these derivatives is substantially higher than that of -cyclodextrin. 1H NMR indicates thatsulfoethyl ether -cyclodextrin may have major substitution on the secondaryhydroxyl group while the major substitution in sulfopropyl and sulfobutyl ether-cyclodextrin could be on the primary hydroxyl group. MS spectra showthat no more than one substitution occurred on a single glucose unit. 相似文献
135.
Torsten Meyer Thomas Hellweg Stefan Spange Stephanie Hesse Christian Jger Cornelia Bellmann 《Journal of polymer science. Part A, Polymer chemistry》2002,40(18):3144-3152
Polyvinylamine hydrogels with silica particles encapsulated (PVAm/silica) were produced by a two‐step synthesis. In the first step, polyvinylformamide/silica (PVFA/silica) hybrids were synthesized from vinylformamide (VFA) and 1,3‐divinylimidazolidin‐2‐one (1,3‐bisvinylethyleneurea, BVU), as the crosslinker, by radical copolymerization in silica/water suspensions using different compositions of VFA/BVU. The target product PVAm/silica was obtained by acidic hydrolysis of the PVFA/silica hydrogels in a second step. The chemical structures of both hydrogels, PVFA/silica and PVAm/silica, respectively, were revealed by solid‐state 13C(1H) cross‐polarity/magic‐angle spinning NMR spectroscopy. Both hydrogels swelled significantly in water. The swelling capacity of the two systems was characterized by the correlation length ξ (or hydrodynamic blob size) of the network meshes with small‐angle neutron scattering experiments. ξ is significantly larger for PVAm/silica than for PVFA/silica, which corresponds to the observed higher swelling capacity of this polyelectrolyte material. Furthermore, the swelling behavior of the hybrid hydrogels was quantitatively described in terms of free swell capacity, centrifuge‐retention capacity, adsorption against pressure, and free swell rate as compared with values of the corresponding copolymer hydrogels. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3144–3152, 2002 相似文献
136.
Daniel Obrecht Christian Lehmann Ruth Ruffieux Peter Schnholzer Klaus Müller 《Helvetica chimica acta》1995,78(6):1567-1587
A series of novel open-chain and cyclic conformationally constrained (R)- and (S)-α,α-disubstituted tyrosine analogues 1a–e were synthesized in good yields and high optical purities (Schemes 1 and 2). The absolute configurations of these tyrosine analogues were unambiguously determined based on the X-ray structures of the precursor diastereoisomeric peptides of type 4 and 5 . Four of these structures are described (Figs. 1–4), showing β-turn type-I geometries for dipeptides 4a, 5b , and 4c and an extended conformation for peptide 5c (Table 3). The conversion of the free amino acids 1a–c into suitably protected building blocks 11a–d and 15d,e for peptide synthesis is discussed (Schemes 3 and 4). 相似文献
137.
Pressure-dependent luminescence spectra of trans-dioxo complexes of rhenium(V) with ancillary ethylenediamine ligands exhibit resolved vibronic structure in the O=Re=O symmetric stretching mode at room temperature. The intensity distribution within the vibronic progression changes with pressure, leading to band shapes that are also pressure-dependent. These spectroscopic features arise from coupled electronic states and depend on the energy differences between ground and excited states, which vary by 2500 cm(-1) for the three complexes with ethylenediamine, tetramethylethylenediamine, and tetraethylethylenediamine ancillary ligands. We describe the pressure-dependent vibronic structure and band shapes with anharmonic adiabatic potential energy surfaces for the ground states of all complexes. The calculated spectra reveal the pressure dependence of the energies of electronic origins, luminescence band maximums, offsets between ground- and emitting-state potential minimums, and vibrational frequencies. The largest pressure effects are observed where the coupled electronic states are close in energy. 相似文献
138.
We recently reported on the synthesis and pairing properties of the DNA analogue bicyclo[3.2.1]amide DNA (bca-DNA). In this analogue the nucleobases are attached via a linear, 4-bond amide-linker to a structurally preorganized sugar-phosphate backbone unit. To define the importance of the degree of structural rigidity of the bca-backbone unit on the pairing properties, we designed the structurally simpler cyclopentane amide DNA (cpa-DNA), in which the bicyclo[3.2.1]-scaffold was reduced to a cyclopentane unit while the base-linker was left unchanged. Here we present a synthetic route to the enantiomerically pure cpa-DNA monomers and the corresponding phosphoramidites containing the bases A and T, starting from a known, achiral precursor in 9 and 12 steps, respectively. Fully modified oligodeoxynucleotides were synthesized by standard solid-phase oligonucleotide chemistry, and their base-pairing properties with complementary oligonucleotides of the DNA-, RNA-, bca-DNA-, and cpa-DNA-backbones were assessed by UV melting curves and CD-spectroscopic methods. We found that cpa-oligoadenylates form duplexes with complementary DNA that are less stable by -2.7 degrees C/mod. compared to DNA. The corresponding cpa-oligothymidylates do not participate in complementary base-pairing with any of the investigated backbone systems except with its own (homo-duplex). As its congener bca-DNA, cpa-DNA seems to prefer left-handed helical duplex structures with DNA or with itself as indicated by the CD spectra. 相似文献
139.
Optical pH determination has the fundamental disadvantage of measuring a signal that depends on the ionic strength of the sample. The problem originates from the complex relationship between the proton activity and the concentration of the pH-sensitive dye. The effect of ionic strength on the signal depends on the charge of the indicator and its environment, e.g. the immobilisation matrix. We present novel lipophilic fluorescein esters carrying one negative charge. They are embedded in an uncharged, highly proton-permeable hydrogel to give optical pH sensors that show a negligible cross-sensitivity towards ionic strength. The fluorescent dyes differ in their substituents. This variation of substituents results in dissociation constants between 5.5 and 8.5. The indicators were made lipophilic by esterification of the carboxy group with a C(18) alkyl chain. Since their spectral properties are quite similar, two indicators may be used in one sensor. This results in an optical pH sensor with a dynamic range that extends from pH 4.5 to 8. 相似文献
140.
Nikhil M. Kriplani David P. Nackashi Christian J. Amsinck Neil H. Di Spigna Michael B. Steer Paul D. Franzon Ramon L. Rick Gemma C. Solomon Jeffrey R. Reimers 《Chemical physics》2006
Two efficient, physically based models for the real-time simulation of molecular device characteristics of single molecules are developed. These models assume that through-molecule tunnelling creates a steady-state Lorentzian distribution of excess electron density on the molecule and provides for smooth transitions for the electronic degrees of freedom between the tunnelling, molecular-excitation, and charge-hopping transport regimes. They are implemented in the fREEDA™ transient circuit simulator to allow for the full integration of nanoscopic molecular devices in standard packages that simulate entire devices including CMOS circuitry. Methods are presented to estimate the parameters used in the models via either direct experimental measurement or density-functional calculations. The models require 6–8 orders of magnitude less computer time than do full a priori simulations of the properties of molecular components. Consequently, molecular components can be efficiently implemented in circuit simulators. The molecular-component models are tested by comparison with experimental results reported for 1,4-benzenedithiol. 相似文献