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991.
Dmitrii P. Krut’ko Maxim V. Borzov Mikhail Yu. Antipin 《Journal of organometallic chemistry》2004,689(3):595-604
A novel half-sandwich Zr(IV) complex [η5:η1-N-C5(CH3)4CH2CH2N(CH3)2]ZrCl3 (6) together with zirconocene dichlorides [η5-C5(CH3)4CH2CH2N(CH3)2][η5-C5(CH3)5]ZrCl2 (4) and [η5-C5(CH3)4CH2CH2N(CH3)2]2ZrCl2 (5) have been prepared. Complex 6 has been isolated and characterized in three different forms, namely, as an adduct with THF 6a, an adduct with tetrahydrothiophene 6b, and a solvent-free form 6c. Molecular structures of complexes 4, 6b, and 6c have been established by X-ray diffraction analysis. Complex 6c has been shown to be a monomeric solvent-free half sandwich Zr(IV) complex. The dynamic behavior of complex 6a in a non-solvating medium (an equilibrium between 6a and 6c along with a degenerate interconversion of the Zr-Ccp-CH2-CH2-N(CH3)2-(Zr) pseudo-five-member metallacycle) have been studied by the variable-temperature 1H and 13C{1H} NMR spectroscopy. The activation parameters for the degenerate five-member cycle interconversion have been elucidated. 相似文献
992.
聚氨酯弹性体相分离程度的研究 总被引:3,自引:0,他引:3
热塑型聚氨酯弹性体(TPUE)的动态力学性能和热性能研究已有许多报导,但多集中于弹性体的链结构及其组成等方面,本文则侧重于研究聚醚氨酯(ET)和聚酯氨酯的相分离过程及其程度,考察硬段含量(W_h)和软段分子量(M_(n·3)等因素对微相结构的影响。 相似文献
993.
A dynamic ultrasound-assisted extraction step is proposed for the quantitative extraction of Cd and Pb from plant leaves prior to determination by electrothermal atomic absorption spectrometry (ETAAS). Beech leaves (a certified reference material—CRM 100—where the target analytes were not certified) were used for optimizing the extraction step by a multivariate approach. The samples (0.25 g) were subjected to dynamic ultrasound-assisted extraction with dilute nitric acid as extractant. The method was validated with a certified reference material BCR-062 (olive leaves) where both Cd and Pb are certified. The good agreement between the certified values and those found using the proposed method demonstrates its usefulness. The repeatability was 2.0 and 0.9% and the within-laboratory reproducibility was 7.1 and 2.8% for Cd and Pb, respectively. The precision of the method, together with its efficiency, rapidity, low cost and environmental acceptability makes it a good alternative for the determination of trace metals from plant material. 相似文献
994.
E. Porteus 《Journal of Optimization Theory and Applications》1982,36(3):419-432
The study of infinite-horizon nonstationary dynamic programs using the operator approach is continued. The point of view here differs slightly from that taken by others, in that Denardo's local income function is not used as a starting point. Infinite-horizon values are defined as limits of finite-horizon values, as the horizons get long. Two important conditions of an earlier paper are weakened, yet the optimality equations, the optimality criterion, and the existence of optimal structured strategies are still obtained. 相似文献
995.
Krisztina A. Vincze-Minya Alois Schausberger 《Monatshefte für Chemie / Chemical Monthly》2006,137(7):911-918
Summary. Melts of polyethylene-propylene-rubber (EPR, blends of linear polyethylene, linear polypropylene, and PE-PP copolymer) show phase separation. The influence of the phase morphology on the viscoelastic behaviour is studied with the
aid of the dynamical moduli. The measured moduli of the fraction of the linear homopolymer of an EPR agree with the moduli
calculated from the molar mass distribution of this fraction. In contrast, the copolymer fraction shows a strong rubber-like
behaviour (represented by a characteristic relaxation time spectrum). Mixtures of 80 wt% linear PP and of EPRs with low copolymer content are not rubber-like liquids. In addition, the moduli from them can be calculated from
the moduli of the components with the aid of Palierne’s emulsion model. This clearly reveals that the linear PP forms the matrix in this case. Mixtures of 80 wt% linear PP and of EPRs with high copolymer content show rubber-like behaviour and Palierne’s emulsion model is not applicable on them. Obviously, the copolymer fraction forms a physical network. 相似文献
996.
The viscoelastic behavior of multiwall carbon nanotube (MWCNT) reinforced polyamide 66 (PA 66) was evaluated to investigate the effect of CNT content and loading frequency on dynamic moduli (i.e. storage modulus E′ and loss modulus E″) and damping factor tan. PA 66/CNT disk samples with five different CNT contents ranging from 3 wt % to 15 wt % were manufactured by injection molding. Testing was performed over the frequency range of 0.1–100 Hz at room temperature. Dynamic mechanical analysis results show that the mechanical properties are highly functions of tested frequency and the improvement on loss and storage modulus of nanocomposites with the addition of CNT is highly dependent on tested frequencies. The variability in loss modulus is significantly higher than the variability in the storage modulus indicating the correlation of loss modulus with uncertainties present in nanocomposite microstructure while storage modulus is essentially independent of microstructure for a given reinforcement content. 相似文献
997.
Dynamic light scattering (DLS) measurements were carried out on aqueous solutions of low-methoxyl pectin at different temperatures and polymer concentration. Low temperature and increased polymer concentration promote the formation of multichain aggregates. The time correlation data obtained from the DLS experiments revealed, for all polymer solutions, the existence of two relaxation modes, one single exponential at short times followed by a stretched exponential at longer times. In the semidilute regime, a temperature reduction induced enhanced chain associations in the solutions with high values of the slow relaxation time and a strong wave vector dependence of the slow mode. These features could be rationalized in the framework of the coupling model of Ngai. At low temperatures (10 °C), gelation occurs in the semidilute regime and a transparent gel is formed. In this state, the profile of the correlation function changes and nonergodic signs are observed. The conjecture is that the association complexes and the gel network are stabilized through intermolecular hydrogen bonds, which are broken-up at higher temperatures. The hydrogen-bonded structures are formed in a process where the polymer chains have been “zipped” together in a cooperative manner. 相似文献
998.
Antje Potthast Thomas Rosenau Richard Buchner Thomas Röder Gerald Ebner Hartmut Bruglachner Herbert Sixta Paul Kosma 《Cellulose (London, England)》2002,9(1):41-53
The water content in the binary systemN,N-dimethylacetamide/lithium chloride (DMAc/LiCl), acommon cellulose solvent, has been proven to be a crucial parameter. A quickdetermination of water content in DMAc based on the solvatochromism of aUV-active betain probe dye has been developed and validated. An analogousmethod, based on the solvatochromic fluorescence shift ofZelinskij's dye, which strongly depends on thesolventpolarity, was established for water determination in DMAc containing LiCl.Precise physicochemical data of the system DMAc/LiCl, such as density,viscosity, and conductivity, have been obtained. The limiting solubility forLiCl in absolute DMAc is 8.46 wt%. As shown by lightscattering experiments, water in DMAc/LiCl induces aggregation upon standingforlonger periods of time, which is even more prominent for diluted solutions andthose having a poor state of dissolution. 相似文献
999.
Erich Kleinpeter Michael Gäbler Werner Schroth 《Monatshefte für Chemie / Chemical Monthly》1988,119(2):233-246
The temperature-variable1H and13C NMR spectra of a series heteroanalogous mono- and dibenzo-1,5-cyclooctadiene derivatives have been obtained, and the present dynamic process discussed in terms of the preferred conformations of the eight-membered ring and the occuring ring interconversional process as well. The boat conformation, which is at – 120 °C still the average of the apparent twist boat conformations, has been identified by dynamic NMR spectroscopy, interconverting via a boat inversional mode. The free energies of activation,
, for the latter process have been determined and discussed according to structural variations, the concentration of the samples, present heteroatoms, and solvent influences, respectively. A few chemical shift aspects of more general interest are mentioned.
Intramolekulare Beweglichkeit heteroanaloger Benzo-und Dibenzo-1,5-cyclooctadiene
Zusammenfassung Die1H- und13C-NMR-Spektren einer Reihe heteroanaloger Benzo- und Dibenzo-1,5-cyclooctadiene werden berichtet und der bei Temperaturvariation meßbare dynamische Prozeß hinsichtlich Vorzugskonformationen des 8-Ringes bzw. der Art des vorliegenden Ringinversionsprozesses diskutiert. Die Bootkonformation (bei – 120 °C noch ein schnelles Gleichgewicht der entsprechenden Twist-Boot-Konformationen) wird mittels dynamischer NMR-Spektroskopie nachgewiesen und die 8-Ringinversion über einen Bootinversionscyclus realisierend identifiziert. Hierfür meßbare freie Aktivierungsenthalpien, , werden bezüglich struktureller Einflüsse, der Probenkonzentration, vorhandener Heteroatome und des Lösungsmittels diskutiert. Einige Effekte auf die chemischen Verschiebungen von mehr allgemeinem Charakter werden berichtet.相似文献
1000.
The five new silanes C5Me3RSiMenCl3 − n (n = 3, R = i-Pr (5); n = 2, R = i-Pr (6); n = 2, R = s-Bu (7); n = 2, R = cyclohexyl (8); and n = 3, R = t-Bu (9)) were synthesized by reaction of 1-alkyl-2,3,4-trimethylcyclopentadienyl lithium salts with appropriate chlorosilane and characterized by NMR, MS, and IR spectra. At elevated temperatures (250-360 K), all the silanes undergo a non-degenerate sigmatropic silyl rearrangement, which generates non-equivalent structures a and b. The presence of minor structure c was observed in compounds 5 and 7 only. The Diels-Alder cycloaddition of 5 with strong dienophiles tetracyanoethylene (TCNE), and dimethylacetylenedicarboxylate (DMAD) provides compounds 10 and 11, which confirmed isomers a and b, respectively. The free energy of activation of b → a isomerization for compounds 5-8 evaluated from variable temperature NMR spectra show only marginal influence of group R on the 1,2-silyl shift rate. Moreover, in compounds 5 and 7, the process b → a was found significantly faster than b → c process in the above-mentioned temperature range. 相似文献