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31.
The performance of a recently developed method to generate representative atomistic models of amorphous polymers has been investigated. This method, which is denoted SuSi, can be defined as a random generator of energy minima. The effects produced by different parameters used to define the size of the system and the characteristics of the generation algorithm have been examined. Calculations have been performed on poly(L,D-lactic) acid (rho = 1.25 g/cm3) and nylon 6 (rho = 1.084 g/cm(3)), which are important commercial polymers. 相似文献
32.
Leung KC Aricó F Cantrill SJ Stoddart JF 《Journal of the American Chemical Society》2005,127(16):5808-5810
The versatility and efficiency of dynamic covalent chemistry (DCC) has been exploited in the convergent synthesis of mechanically interlocked dendrimers that are based upon the mutual recognition expressed between secondary dialkylammonium ions and crown ether-like macrocycles. Reversible imine bond formation is employed to clip two acyclic fragments, one of them a diformylpyridine unit bearing a dendritic side chain, and the other a complementary dianiline in the shape of the di(o-aminophenyl)ether of tetraethylene glycol, around each arm of a tritopic trisammonium ion core, thereby affording a branched [4]rotaxane. This template-directed strategy has been demonstrated to work in very high yields (>90%) with successive generations (G0-G2) of a modified Fréchet-type dendritic wedge attached to the 4-position of the diformylpyridine unit. Reduction of these dynamic dendritic systems is achieved upon treatment with borane.THF and results in kinetically stable compounds. The inherent modularity of the overall process should allow for the rapid and straightforward access to many other analogous mechanically interlocked systems in which either the branched core or the dendritic periphery can be modified to suit the needs of any given application of these molecules. Indeed, the dynamic nature of the initial thermodynamically mediated assembly could be utilized in order to amplify particular products from a potential library as a result of a selective recognition process. 相似文献
33.
González-Núñez ME Mello R Royo J Asensio G Monzó I Tomás F López JG Ortiz FL 《The Journal of organic chemistry》2005,70(9):3450-3457
[reaction: see text] Data on the apparent dipole moment of thianthrene-5-oxide (1) and (1)H NMR spectra in different solvents support the conformational mobility of 1, which flaps between two limit boat conformations with the sulfinyl group in pseudoequatorial and pseudoaxial positions, respectively. The conformational equilibrium of 1 occurs too fast for the (1)H NMR (500 MHz) time-scale even at -130 degrees C, and the equilibrium constant has not been determined. The apparent dipole moments of 1 in n-hexane and 1,4-dioxane and the (1)H NMR spectra of 1 and the model compounds cis- and trans-thianthrene-5,10-dioxides (2) and thianthrene (5) in different solvents and at various temperatures confirm that the relative position of the conformational equilibrium of 1 is solvent-dependent, and more polar solvents favor the conformation with the sulfoxide group in the pseudoaxial position (1(')(ax)). Variable-temperature (1)H NMR spectra have established the interconversion barrier of trans-2 and confirmed that the conformational equilibrium of cis-2 is strongly displaced toward the conformation with both sulfinyl groups in the pseudoequatorial position. The (1)H NMR data support the transannular interaction of the functional groups in 1 and trans-2. 相似文献
34.
A novel method is reported for screening for point mutations in genomic DNA: free-zone capillary electrophoresis in very acidic buffers. This method exploits the charge difference among the four different bases (C, T, A, G) in a pH window between 2.5 and 3.5, where the four titration curves fan out. The method is applied to the detection of the beta-39 missense mutation in the beta-globin gene in thalassemias. A 60-mer fragment straddling the mutation site has been amplified. In an isoelectric buffer (iminodiacetic acid) of pH 3.3, partial resolution between the wild type and mutated strands is obtained. In a pH 3.0 phosphate buffer, baseline resolution is achieved between the two strands in a heterozygous individual. Due to the short size of the amplified fragment, this method can only be applied to routine screening for known mutations because resolution was lost in a fragment 100 bases long. 相似文献
35.
A systematic study of the fluorescence of complexes of some flavone derivatives with organotin compounds in hexane and in an aqueous micellar medium on Triton X-100 is reported. Some relationships between fluorescence intensity and the structure of the fluorogenic reagent or that of the organotin compound can be deduced, and the most suitable reagent for each organotin species can be chosen on the basis of sensitivity and selectivity. Results point out that flavone derivatives are appropriate post-column derivatization reagents for organotin compounds in liquid chromatography. 相似文献
36.
Prof. Dr. Hans Nowotny Josef Tomiska László Erdélyi Adolf Neckel 《Monatshefte für Chemie / Chemical Monthly》1977,108(1):7-19
By means of vapor pressure measurements using theTorker method (Torsion-Knudsen Effusion Recoil) as well as theKnudsen tanspiration technique in connection with a mass spectrometer, the heats of formation of the following compounds were found to be –6.5±0.7 kcal/g atom (Mn0.366Si0.634), –7.8±0.6 kcal/g atom (Mn0.50Si0.50), –7.3±0.6 kcal/g atom (Mn0.625Si0.375), and –6.6±0.6 kcal/g atom (Mn0.75Si0.25).
Mit 7 Abbildungen 相似文献
Mit 7 Abbildungen 相似文献
37.
Szabó KJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(21):5268-5275
The synthetic scope of the allyl-palladium chemistry can be extended to involve electrophilic reagents. The greatest challenge in these reactions is the catalytic generation of an allyl-palladium intermediate incorporating a nucleophilic allyl moiety. A vast majority of the published reactions that involve palladium-catalyzed allylation of electrophiles proceed via bis(allyl)palladium intermediates. The eta(1)-moiety of the bis(allyl)palladium intermediates reacts with electrophiles, including aldehydes, imines, or Michael acceptors. Recently, catalytic electrophilic allylations via mono-allylpalladium complexes were also presented by employment of so-called "pincer complex" catalysts. 相似文献
38.
A new palladium-dipyridylmethylamine complex is an excellent catalyst for C-C bond-forming processes such as the Heck, Suzuki, and Sonogashira reactions in organic and aqueous solvents under homogeneous conditions. [reaction: see text] 相似文献
39.
The excess volumes of mixing for methanol and ethanol with secondary amines (diethylamine, di-n-propylamine and di-n-butylamine) have been measured over the whole composition range at 293.15 and 323.15 K. The excess volumes have been fitted to an equation of the type $$V^E /cm^3 mol^{--1} = x \left( {1 - x} \right) \sum\limits_{n = 0}^3 { A_n \left( {1 - 2x} \right)^n } $$ The different temperature dependences of the mixtures were explained by means of the association theory. 相似文献
40.
Bayó N Jiménez JC Rivas L Nicolás E Albericio F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(5):1096-1103
An optimized solid-phase strategy for the preparation of the cyclic lipononadepsipeptide [N-Mst(L-Ser1), D-Ser4, L-Thr6, L-Asp8, L-Thr9]syringotoxin is reported. The strategy is based on the use of a mild orthogonal protection scheme and the incorporation of the nonproteinogenic amino acid (Z)-Dhb into the peptide chain as the dipeptide Fmoc-Thr(tBu)-(Z)-Dhb-OH. The didehydrodipeptide was synthesized by a water-soluble carbodiimide-induced beta-elimination of a protected dipeptide containing a residue of Thr with its free hydroxy side chain unprotected. 相似文献