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1.
Differential-scanning-calorimetry, freeze-fracture electron microscopy, and31P-NMR spectroscopy were used to study the lyotropic and thermotropic properties of the system dihexadecylphosphatidylcholine/dihexadecylphosphatidic acid/water/ NaOH in dispersion with excess water at pH=14. The phase diagram showed that both phospholipids are demixed nearly completely in the gel phase. The coexistence of theP and theB -phase in the mixtures was pointed out in the freeze-fracture electron micrographs by the ripple structure (P -phase) and by the lamellar structure (B -phase).  相似文献   

2.
Starting from (+) (2R) methyl 5-ethyl-2,2-spirobiindane-5-carboxylate of known enantiomeric purity 79 optically active, configurationally correlated 5,5,6-trisubstituted 2,2-spirobiindanes (2–7) were prepared for the purpose of testing a shortened polynomal Ansatz for chirality functions. Their optical rotations and1H-nmr spectra are reported.In this context several 6-substituted 5-ethylindanes (1) were prepared as model compounds for synthetic transformations.
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3.
Eigenvectors of vibrating polyethylene chains with (200) and (110) folds have been calculated by solving the phonon-scattering problem exactly with the method of Green's function. The results are applied to analyze the resonance modes of the (200) fold (ggtgg: 1353, 1356, 1374 cm–1) and the (110) fold (approximately ggggtg: 820, 1288, 1342, 1348, 1372, 1374 cm–1) in terms of the characteristic vibrations of smaller subunits of the (200) fold (gg, gtg) and the (110) fold (ggggtg, gggg, gtg) which can be identified spectroscopcally.Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday  相似文献   

4.
Data published by La Mantia et al. [1] on dielectric dispersion and loss in polyethylene/nylon 6 blends are analyzed in terms of dielectric mixture formulae. It is shown that an ohmic interfacial polarization process can not be responsible for the unexpected increase of and values observed in these blends at high temperatures. The observed phenomena are tentatively attributed to space charge processes at the electrodes or to other defects dipole mechanisms.  相似文献   

5.
The capacitance and the dielectric loss tangents of CaCO3 filled polyethylene composites were studied. Composite samples, prepared by polymerizing ethylene on the surfaces of fillers, pre-treated by polymerization catalysts, were compared to normal mechanical mixtures. Dielectric dispersion,, and loss, , proved to be sensitive to heating or vacuum treatment. Investigation of samples under conditions of different relative humidities showed that the dielectric dispersion is due to adsorbed water. Both and increased with decreasing frequency and the ratio of loss and dispersion was nearly constant. Dielectric data measured at different relative humidities could be represented by a single Cole-Cole plot. Samples soaked in water for different periods yielded qualitatively similar but quantitatively different Cole-Cole plots. Composite samples showed higher losses at similar humidities.Possible interpretations in terms of a molecular relaxation model, an interfacial relaxation model, including a charged double layer mechanism, percolation theory and the universal response theory were examined, but none was able to fully explain the observed phenomena.  相似文献   

6.
The electrostatic interaction pressure of charged surface layers is considered qualitatively and quantitatively. In the case of mutual penetration of the surface layers in addition to Maxwell stress and osmotic resp. hydrostatic pressure an isotropic stress on the fixed charges carrying molecules of the surface layers has to be taken into account. The derivation of the pressure-distance equations is given starting from both thermodynamic/electrostatic and hydrostatic/electrostatic principles. A possible biological significance of the additional stress is discussed emphasizing its role in modifying the structure of surface layer molecules.List of symbols e 0 elementary charge - k Boltzmann constant - n i concentration of theith ionic species in the bulk solution - P hydrostatic pressure - P hydrostatic pressure in the bulk volume (× ) - P h integration constant, independent on ×:P h =P(h) - T absolute temperature - Z i electrovalence of theith ionic species - thickness of the surface layer - , 0 relative and absolute permittivities - II(×) osmotic pressure at position × - II osmotic pressure in the bulk solution (× ) - osmotic pressure in the symmetry plane of interacting identical surface layers (electric field strength equals zero) - integration constant, independent on ×: - e h electrostatic component of the disjoining pressure e h = e (h) - (×) mobile charge density profile (cations and anions of the electrolyte) - (×) fixed charge density profile - t(x) total charge density profile ( t = +) - 1(x) fixed charge density profile of one of the two surface layers ( 1(×) 0 for 0×) - (×) electric potential profile  相似文献   

7.
The structure-property relationships derived here permit the prediction of both the zero-shear viscosity 0, as well as the shear rate dependent viscosity . Using this molecular modeling it is now possible to predict over the whole concentration range, independently of the molecular weight, polymer concentration and imposed shear rate. However, the widely accepted concept: dilute — concentrated, is insufficient. Moreover it is necessary to take five distinct states of solution into account if the viscous behavior of polymeric liquids is to be described satisfactorily. For non-homogeneous, semi-dilute (moderately concentrated) solutions the slope in the linear region of the flow curve (= must be standardized against the overlap parameterc · []. As with the 0-M-c-relationship, a-M -c- relationship can now be formulated for the complete range of concentration and molecular weight. Furthermore, it is possible to predict the onset of shear induced degradation of polymeric liquids subjected to a laminar velocity field on the basis of molecular modeling. These theoretically obtained results lead to the previously made ad hoc conclusion (Kulicke, Porter [32]) that, experimentally, it is not possible to detect the second Newtonian region.Roman and Italian symbols a exponent of the Mark-Houwink relationship - b exponent of the third term of the 0-M -c relationship - c concentration /g · cm–3 - E number of entanglements per molecule - F(r) connector tension - f function - G i A shear modulus; A indicates that it /Pa has been evaluated by a transient shear flow experiment; i is the shear rate to whichG A refers to - G storage modulus /Pa - G p plateau modulus /Pa - H() relaxation spectrum /Pa - h shift factor (0/r) - K H Huggins constant - K b third constant of the 0-M -c relationship - K constant of the Mark-Houwink relationship - M molecular weight /g · mol–1 - M e molecular weight between two /g · mol–1 entanglement couplings - N number of segments per molecule - n slope in the power-law region of the flow curve - p p-th mode of the relaxation time spectrum - R gas constant /8.314 J·K–1·mol–1 - r direction vector - T temperature /K Greek symbols ß reduced shear rate - shear rate /s–1 - shear viscosity /Pa·s - s solvent viscosity /Pa·s - sp specific viscosity - 0 zero-shear viscosity /Pa·s - apparent viscosity at shear rate - reduced viscosity - viscosity of polymeric liquid in /Pa·s the second Newtonian region - [] intrinsic viscosity/cm3·g–1 - screening length/m - /g·cm –3 density - relaxation time/s - 0 experimentally derived relaxation time/s - angular frequency of oscillation Indices conc concentrated - corr slope corrected - cr critical - deg degradation - e entanglement - exp experimental - mod moderately concentrated/semi-dilute - n number average - p polymer - R Rouse - rep reptation - s solvent - sp specific - theo theoretical - weight average - relaxation time - o experimental or steady state - * critical - ** transition moderately conc. — conc. - + transition dilute — moderately cone. Paper presented at the 2nd bilateral U.S.-West German Polymer Symposium, Yountville, the 7th–11th September 1987.  相似文献   

8.
Glaser  Robert  Geresh  Shimona  Luria  Shlomo  Drouin  Marc  Michel  André 《Structural chemistry》1994,5(4):277-282
Hydrogenation ofZ-(–)-(1R, 3R, 4S)-menthyl 2-formamido-4,4,4-trifluoro-2-butenoate catalyzed by Pd/C was performed at atmospheric pressure to yield a mixture of (2R, 1R, 3R, 4S)- and (2S, 1R, 3R, 4S)-menthyl 2-formamido-4,4,4-trifluorobutanoate diastereomers in a 5545 ratio, respectively. Repeated fractional crystallization from ethyl acetate and vapor diffusion of petroleum ether afforded (+)–(2S, 1R, 3R, 4S)-menthyl 2-formamido-4,4,4-trifluorobutanoate as clear colorless, crystalline prisms which were subjected to single-crystal X-ray diffraction analysis. The crystals belong to the orthorhombic system P212121, and at 213 K:a=5.054(1),b= 10.000(2),c=32.707(1) Å,V=1652.9(4) Å3,Z=4,R(F)=0.040, andR w (F)=0.037. The finding of the (2S)-configuration for the formamido-acid portion of the (+)-ester enabled the configurational assignment of the asymmetric hydrogenation products ofZ-methyl 2-formamido-4, 4,4-trifluoro-2-butenoate catalyzed by chiral diphosphine/rhodium(I) complexes.  相似文献   

9.
Bond strengths in RO-OOR, ROO-OH, and ROO-OOR (R, R = H, Me, Et, and Bu) molecules, calculated by the semiempirical quantum-chemical methods, were used to determine the enthalpies of formation of polyoxides RO x R (x = 3, 4) and related radicals and the bond strengths (D/kcal mol–1) in these molecules:D(ROOO-OR) = 33.2±0.9,D(ROOO-OH) = 37.5±0.7,D(R-O x R) = 76.0±1.2,D(H-000) = 58.6,D(R-000) = 42.8±0.8. A new value of Benson's polyoxide thermochemical increment, f H°[O-(O)2] = 11.1±1.0 kcal mol–1, was suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2190–2193, September, 1996.  相似文献   

10.
The decomposition of various symmetric and unsymmetric azo-initiators (1,1-dichloro-1,1-diphenyl-1,1-azoethane, 2,2-dichloro-2,2-azopropane, 1,1-dichloro-1,1-azocyclohexane, 2,2-diacetoxy-2,2-azopropane, 1,1-diacetoxy-1,1-diphenyl-1,1-azoethane, 1,1-diacetoxy-1,1-azocyclohexane, 2,2-dipropionoxy-2,2-azopropane, 2,2-dicapronoxy-2,2-azopropane, 4,4-dimethyl-1,4-azobutyrolactone, azoisobutyronitrile, 2-t-butylazo-2-cyanobutan, 2-t-bytylazo-1-cyanocyclohexan) in solution was studied in dependence of temperature. Volumetry and differential-scanning-calorimetry (DSC) were used to determine decomposition rates; first order kinetics was found in all cases.
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11.
The effect of representing dielectric properties in terms of the complex polarizability c = – i is examined. Loss curves ( and tan ) are shifted towards higher frequencies, revealing the existence of new relaxations and allowing the clarifications of ones already known. We have calculated the shift ratios (at maximum or tan )/ (at maximum or tan ) from the more conventional empirical equations representing the dielectric behavior. Some examples are given.  相似文献   

12.
Summary 2-O-Ethyluracil and 2-O-ethylthymine were silylated with 1,1,1,3,3,3-hexamethyldisilazane and condensed in the presence ofTMS triflate with 2,3-dideoxy-3-fluoro-D-erythro-pentofuranoside, 3-azido-2,3-dideoxy-D-erythro-pentofuranoside, and 2,3-dideoxy-3-phthalimido--D-erythro-pentofuranose derivatives to give the corresponding 2-O-ethyl nucleosides. Deprotection with saturated methanolic ammonia afforded the 2,3-dideoxy-3-fluoro-2-O-ethyluridines, whereas 3-azido-2,3-dideoxy-3-O-ethyluridine was obtained by deprotection with tetrabutylammonium fluoride in tetrahydrofuran. 3-Amino-2,3-dideoxy-3-O-ethyluridine could be obtained only by treatment of the corresponding 3-azido nucleoside with triphenylphosphine in pyridine. 3-Deoxy-2-O-ethyl-3-fluorothymidine (6b) showed moderate activity against HIV-1.
Synthese von 2-O-Ethyl-Analogen von 3-Azido- und 3-Fluor-23-dideoxyuridinen und Bestimmung ihrer biologischen Aktivität gegenüber HIV
Zusammenfassung 2-O-Ethyluracil und 2-O-Ethylthymin wurden mit 1,1,1,3,3,3-Hexamethyldisilazan silyliert und in Gegenwart vonTMS-triflat mit 2,3-Dideoxy-3-fluoro-D-erythro-pentofuranosid, 3-Azido-2,3-dideoxy-D-erythro-pentofuranosid und 2,3-Dideoxy-3-phthalimido--D-erythro-pentofuranosederivaten zu den entsprechenden 2-O-Ethyl-Nucleosiden umgesetzt. Entfernung der Schutzgruppe mit gesättigter methanolischer Ammoniaklösung lieferte 2,3-Dideoxy-3-fluor-2-O-ethyluridin; 3-Azido-2,3-dideoxy-3-O-ethyl-uridin wurde durch Entschützung mit Tetrabutylammoniumfluorid in Tetrahydrofuran erhalten. 3-Amino-2,3-dideoxy-3-O-ethyl-uridin konnte nur durch Behandeln des entsprechenden 3-Azido-Nucleosids mit Triphenylphosphin in Pyridin hergestellt werden. 3-Deoxy-2-O-ethyl-3-fluor-thymidin (6b) zeigt geringe Aktivität gegenüber HIV-1.
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13.
Summary All optically active title compounds were obtained from the 4,4-diacetyl-spiro compound2; (+)- and (–)-2 were accessible by chromatography on triacetyl cellulose in ethanol. The enantiomeric purities were established from chromatographic data. The chirality (–)-(2R) was deduced for all new compounds on the basis of the CD spectra of (–)-2 and (–)-2,2-spirobi-(5,6,7,8-tetrahydrobenzo[f]indane). From the molar rotations of these 4,4-disubstituted 2,2-spirobiindanes (empirical) ligand parameters were determined (using the so-called shortened approach). Generally, the values of in these compounds are higher than those of the analogous tetrahydrobenzoindane derivatives.
Herrn Prof. Dr.F. Sauter mit besten Wünschen zum 65. Geburtstag gewidmet  相似文献   

14.
Summary In an attempt to develop potential inhibitors ofUDP-glucuronosyltransferase, some 5-O-amino acid derivatives of uridine were synthesized. N-protectedL-amino acids were coupled at the 5-O-position of 2,3-O-isopropylideneuridine by esterification employing the method of symmetrical anhydrides in presence of 4-dimethylaminopyridine, 5-O-(N-benzyloxycarbonyl-O-tert.butyl-L-threonl)-23-O-isopropylideneuridine (1), 5-O-(N-tert.butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylideneuridine and (2), 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (3), and 5-O-(N-tert.butyloxycarbonyl-L-valyl)-2,3-O-isopropylideneuridine (4) were obtained in good yield after column chromatography on silica gel. The treatment of2 withTFA/CH2Cl2 (6:1) at room temperature for 30 min led to a selective removal of theBoc group without deblocking of the 2,3-O-isopropylidene group of uridine. Treatment of2 withTFA/H2O (5:1) at room temperature for 1 h, however, released bothBoc and 2,3-isopropylidene groups. TheZ group of1 was deprotected by catalytic hydrogenolysis over 10% Pd/C/ammonium formate.
Synthese von 5-O-Aminosäurederivaten des Uridins als potentielle Inhibitoren derUDP-Glukuronosyl-Transferase
Zusammenfassung In einem Versuch, potentielle Inhibitoren derUDP-Glukuronosyl-Transferase zu entwickeln, wurden einige 5-O-Aminosäurederivate des Uridins synthetisiert. N-GeschützteL-Aminosäuren wurden durch Veresterung mit der 5-O-Position des 2,3-isopropylidenuridins gekuppelt (Methode der symmetrischen Anhydride in der Gegenwart von 5-Dimethylaminopyridin). Solcherweise wurden 5-O-(N-Benzyloxycarbonyl-O-tert.butyl-L-threonly)-2,3-O-isopropylidenuridin (1), 5-O-(N-tert.Butyloxycarbonyl-O-benzyl-L-seryl)-2,3-O-isopropylidenuridin (2), 5-O-(N-tert.Butyloxycarbonyl-L-leucyl)-2,3-O-isopropylidenuridin (3) und 5-O-(N-tert.Butyloxycarbonyl-L-valyl)-2,3-O-isopropylidenuridine (4) nach Säulenchromatographie (Kieselgel) in guter Ausbeute hergestellt. Die Behandlung von2 mitTFA/CH2Cl2 (6:1) bei Zimmertemperatur (30 min) führte zu einer selektiven Abspaltung derBoc-Gruppe ohne Deblockierung der 2,3-O-Isopropylidengruppe des Uridins. Eine Behandlung von2 mitTFA/H2O (5:1) bei Zimmertemperatur für 1 Stunde führte hingegen zur Abspaltung sowohl derBoc als auch der 2,3-O-Isopropylidengruppe. DieZ-Gruppe von1 wurde durch katalytische Hydrogenolyse auf 10% Pd/C/Ammoniumformiat abgespalten.
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15.
Two-dimensional magic-angle-spinning (2D-MAS) NMR has been used to measure the orientation parameter, P2, of the diphenylene propane unit in bisphenol-A polycarbonate oriented by stretching to various extension ratios,, atT=295K andT= 403 K.P 2 is proportional to the birefringencen, with a maximum birefringencen 0= 0.189. There is some evidence that the order parameterP 2 of the DPP units with respect to the chain axis deviates from unity.n 0 is therefore expected to be different from the birefringence,n 0 , of perfectly aligned chains of polycarbonate. The experimental results obtained forP 2() are compared to those predicted by the aggregate model.  相似文献   

16.
A new series of organometallic ionic chelates of the type [Cp 2Zr(sal)]+ [ROCS2/RRNCS2], where Hsal = salicylaldehyde;R =Me, Et, i-Pr ori-Bu andR =R =Me, Et, i-Pr;R =Me,R = benzyl orR =Et,R =m-tolyl, have been synthesized in aqueous medium by the reaction of [Cp 2Zr(sal)]+Cl andROCS 2 K+/RRNCS 2 Na+. These compounds have been characterized by chemical analyses, electrical conductance, electronic, IR and1H-NMR spectral studies. These studies indicate that the complexes are 1:1 electrolytes and the salicylaldehyde ligand is chelating in all these complexes. Therefore, a tetrahedral coordination about the zirconium atom is proposed.
Salicylaldehydo-Chelate von Bis(cyclopentadienyl)-zirkonium(IV)
Zusammenfassung Eine neue Gruppe von organometallischen ionischen Chelaten vom Typ [Cp 2Zr(sal)]+ [ROCS2/RRNCS2] (mit Hsal = Salicyladehyd;R =Me, Et, i-Pr oderi-Bu undR =R =Me, Et, i-Pr;R =Me,R = Benzyl oderR =Et,R =m-Tolyl) wurde in wäßrigem Medium mittels der Reaktion von [Cp 2Zr(sal)]+Cl mitROCS 2 K+/RRNCS 2 Na+ hergestellt. Die erhaltenen Verbindungen wurden mittels chemischer Analyse, elektrischer Leitfähigkeit und der IR- sowie1H-NMR-Spektren charakterisiert. Diese Untersuchungen zeigen, daß die Komplexe 1:1-Elektrolyte sind, wobei der Salicylaldehyd-Ligand in allen Fällen an der Chelatbildung beteiligt ist. Es wird daher für das Zirkoniumatom eine tetrahedrale Koordination vorgeschlagen.
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17.
In 4-nitro-4-aminodiphenyl (NAD) layers the photocapacitance (PhC) transients were investigated. PhC spectral distribution as well as the temperature dependences of time constants (under/on/or after/off/illumination) have been measured. The photocapacitance spectral distribution possesses maxima at 350, 500, and 750 nm. It was shown that on (T) is of exponential form while off (T) is more complicated. The values of thermal activation energies (0.65±0.05) eV of both time constants coincide. The mechanism of photocapacitance process has been disclosed in NAD layers.  相似文献   

18.
The results of X-ray diffraction patterns of homologous thallium soaps TlC n (n-8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 20 and 22) in dependence on the temperature showed that the structures of the phases below the temperature range of the liquid-crystalline neat phase (so called phase C1, phase C2, phase I, phase II) are crystalline-like, not liquid-crystalline.As function of the chain length of the fatty acid group, we found the following phase sequences to be a function of temperature: TlC8: phase Ineat phase: TlC9–Tl14: phase C2phase IIphase Ineat phase; TlC15, TlC16: phase C1phase IIphase Ineat phase; TlC17–TlC22: phase C1phase IIneat phase.From the X-ray patterns of the thallium soaps were calculated the lattice parameters and the unit cells of these homologues at various temperatures. The comparison between the lattice parameters of the homologues showed, surprisingly, that these parameters were independent of chain length and temperature. This X-ray data are the basis for the following development of structure models of the phase C1, phase C2, phase I, and phase II, including the neat phase (see Part 2).  相似文献   

19.
The Dinitrone 2,2-diphenyl-3,3-bi-3H-indole-1,1-dioxide acts as a demethylating and dehydrogenating agent. The mechanism of interaction of the dinitrone with donors and acceptors does not involve intermediate charge-transfer complexes probably due to a self association between dinitrone molecules (as supported by X-ray determinations). The crystal structure of the dinitrone was obtained by direct methods;a=9.967 (2),b=19.817 (3),c=10.875 (2) Å, =111.2 (2)°, space group P21/n. The finalR andR w were 0.089 and 0.063 for all measured reflexes.
2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid: Molekulare Wechselwirkungen und Kristallstruktur
Zusammenfassung Das Dinitron 2,2-Diphenyl-3,3-bi-3H-indol-1,1-dioxid wirkt als Demethylierungs- und Oxydationsmittel. Die Wechselwirkung des Dinitrons mit Elektronen-Acceptoren und Elektronen-Donatoren geht wegen der Selbstassoziation zwischen den Dinitron-Molekülen ohne die dazwischenliegende Bildung eines Charge-Transfer-Komplexes vor sich; das wird auch von Röntgenstrukturuntersuchungen gestützt. Die Kristallstruktur wurde mit direkten Methoden ermittelt:a=9.967 (2),b=19.817 (3),c=10.875 (2) Å; =111.2 (2)°. P21/n. Die endgültigen WerteR undR w waren 0.089 und 0.063 für alle gemessenen Reflexe.
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20.
Several series of porous, biodegradable PU/PLLA foams were used for meniscus reconstruction in dogs. PLLA-fiber reinforced PU/PLLA composites, PU/PLLA, and PU foams were implanted in severe meniscus lesions. The healing process was initiated as a result of blood vessels and other cells ingrowth into these porous materials. To accomplish good ingrowth of fibrocartilaginous tissue, the materials should have interconnected macropores of 200–300n with a high total pore volume. PLLA fibers were used to reinforce the materials, but seem to retard the degradation process and the ingrowth of fibrocartilaginous tissue.  相似文献   

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