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211.
A MORPHOLOGICAL STUDY OF POLY(DIVINYLBENZENE-co-ACRYLIC ACID) IN CROSSLINKING PRECIPITATION POLYMERIZATION 总被引:1,自引:0,他引:1
Feng Bai Xin-lin Yang Wen-qiang Huang 《高分子科学》2006,(2):163-171
Divinylbenzene-80 (DVB-80) and polar monomer acrylic acid (AA) having hydrogen bonding at a total monomer loading of 5 vol% were precipitated-copolymerized in a variety of organic solvents with 2,2'-azobis(isobutyronitrile) (AIBN) as initiator. The experiments were investigated from a two-dimensional matrix, i.e., the actual crosslinking degree of DVB varying from 0 to 80% and the solvent composition varying from 0 to 100% of toluene mixture with acetonitrile, when the mixture of acetonitrile and toluene was used as the reaction solvent. Under various reaction conditions, six distinct morphologies including soluble polymers, swellable microgels, coagulum, irregular microparticles, and nano-/micrometer microspheres were formed and the structures of these polymer architectures were described. A morphological map was utilized to discuss the effects of both crosslinking degree of DVB and composition of solvent on the transitions between morphology domains. The results demonstrated that the microspheres are formed by an internal contraction due to the marginal solvency of the continuous phase and the crosslinking of the polymer network through the covalent bonding from DVB as well as the interchain hydrogen-bonding between the carboxylic acid units. 相似文献
212.
Laura Masgrau Àngels González-Lafont José M. Lluch 《Theoretical chemistry accounts》2002,108(1):38-40
Variational transition state theory including tunneling corrections (as implemented in Polyrate 8.7) and using multilevel
energy calculations at the MCCM-CCSD(T)-1sc level for the CH4 + OH reaction and at the MCCM-CCSD(T)-2m level for the CD4 + OH process, reproduces very well the experimental rate constants. However, no single methodology was found that reproduces
equally well the experimental rate constants for both title reactions.
Received: 24 March 2002 / Accepted: 11 April 2002 / Published online: 4 July 2002 相似文献
213.
Summary Frequency distributions of energy deposition in microscopic tissue volumes determined by means of a ?Rossi type? proportional
counter for 31, 12 and 8 MeV proton beams and, dose response curves for mortality and chromosome aberrations in cultured human
cells exposed to the same beams are analysed with a view to determining suitable parameters to specify radiation quality.
The behaviour of quantities LET,Z
*2/β2 and the microdosimetric parameter
as a function of energy are compared with the corresponding behaviour of the most significant radiobiological parameters
as mean lethal dose per targetD
0, mean inactivation dose
, intensity of chromosome aberrations, and dicentrics. It is shown that
is the most suitable physical parameter to characterize the relative effectiveness of protons in the (8÷31) MeV range.
Work partially supported by grant No. 8000165896 for the Finalized Project ?Tumor Growth Control?. 相似文献
214.
The scaled-particle theory has been applied to the calculation of the thermodynamic changes associated with the formation of a cavity in several isotopic varieties of liquid water and methanol. From these results, the thermodynamic functions for the transfer of a cavity (or a hard-sphere solute) have been computed for the following solvent pairs: H2OD2O, H2OH2
18O, H2
18OD2
18O, D2OD2
18O, CH3OHCH3OD. For the last two of these solvents, density measurements required for the calculations were carried out as a function of temperature. The calculated deuterium solvent isotope effect on the heats and entropies of hard-sphere solutes in water is much greater than the18O isotope effect; the former also exhibits a more pronounced temperature dependence. The transfer functions computed for hard-sphere solutes are compared to experimental data on the transfer of various solutes from H2O to D2O and from CH3OH to CH3OD. In most of the cases examined, the cavity effect accounts for a large part of the transfer quantities measured for rare gases, hydrocarbons, and solutes containing a significant hydrocarbon substituent. 相似文献
215.
Wurche F Sicking W Sustmann R Klärner FG Rüchardt C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(11):2707-2721
The effect of pressure on the oxidation of hydroarenes 3-9 with 2,3-dichloro-5,6-dicyano-1,4-quinone (DDQ; 1 a) or o-chloranil (10), leading to the corresponding arenes, has been investigated. The activation volumes were determined from the pressure dependence of the rate constants of these reactions monitored by on-line UV/Vis spectroscopic measurements in an optical high-pressure cell (up to 3500 bar). The finding that they are highly negative and only moderately dependent on the solvent polarity (DeltaV( not equal ) = -13 to -25 in MTBE and -15 to -29 cm(3) mol(-1) in MeCN/AcOEt, 1:1) rules out the formation of ionic species in the rate-determining step and is good evidence for a hydrogen atom transfer mechanism leading to a pair of radicals in the rate-determining step, as was also suggested by kinetic measurements, studies of kinetic isotope effects, and spin-trapping experiments. The strong pressure dependence of the kinetic deuterium isotope effect for the reaction of 9,10-dihydroanthracene 5/5-9,9,10,10-D(4) with DDQ (1 a) can be attributed to a tunneling component in the hydrogen transfer. In the case of formal 1,3-dienes and enes possessing two vicinal C--H bonds, which have to be cleaved during the dehydrogenation, a pericyclic hydrogen transfer has to considered as one mechanistic alternative. The comparison of the kinetic deuterium isotope effects determined for the oxidation of tetralin 9/9-1,1,4,4-D(4)/9-2,2,3,3-D(4)/9-D(12) either with DDQ (1 a) or with thymoquinone 1 c indicates that the reaction with DDQ (1 a) proceeds in a stepwise manner through hydrogen atom transfer, analogously to the oxidations of 1,4-dihydroarenes, whereas the reaction with thymoquinone 1 c is concerted, following the course of a pericyclic hydrogen transfer. The difference in the mechanistic courses of these two reactions may be explained by the effect of the CN and Cl substituents in 1 a, which stabilize a radical intermediate better than the alkyl groups in 1 c. The mechanistic conclusions are substantiated by DFT calculations. 相似文献
216.
A. L. Stroyuk A. I. Kryukov S. Ya. Kuchmii V. D. Pokhodenko 《Theoretical and Experimental Chemistry》2005,41(2):67-91
The appearance of quantum size effects in ultradisperse semiconductors, their quantitative analysis, and their effect on the absorption of light and on the photophysical (vibrational relaxation of photogenerated “hot” charge carriers, band-band and “defect” luminescence) and certain primary photochemical processes (the accumulation of excess negative charge by the semiconductor nanoparticles, interphase electron transfer, etc.) are discussed.__________Translated from Teoreticheskaya i Eksperimental’naya Khimiya, Vol. 41, No. 2, pp. 67–87, March–April, 2005. 相似文献
217.
A simple detection method to observe the uniplanar orientation behavior of native cellulose microfibrils to the cell wall surface by using Fourier transform infrared (FTIR) spectroscopy in the transmission mode is reported. Four bands at 1372, 1355, 1337, and 1317 cm−1 (the latter two have been mentioned previously by Liang and Marchessault (1960, J. Polym. Sci. 43: 85–100)) were found to be sensitive to such orientation: the two middle bands at 1355 and 1337 cm−1 increase remarkably when the 0.60–61 nm lattice planes lie parallel to the cell wall surfaces. The reverse was true when the 0.53–54 nm lattice planes oriented preferentially. Polarization of the two bands at 1372 and 1355 cm−1 was parallel, while that of the other two bands at lower wavenumbers, i.e., at 1337 and 1317 cm−1, was perpendicular to the molecular axis of cellulose. These bands were assigned to OH-related motion, probably to in-plane OH bending, as reported by Maréchal and Chanzy (2000, J. Mol. Spectrosc. 523: 183–196). 相似文献
218.
Changes in the hybrid state of atomic orbitals of nitrogen and p-character of LEP, which occur under the effect of saturated hydrocarbon radicals and polar substituents in aliphatic amines, differ substantially. Therefore, the effect of the both substituents on the basicity constants of amines cannot be described by the single formal type of interaction. The anomalous changes in the basicity in the series of primary, secondary, and tertiary alkylamines, which are discussed in the literature, and the correlations pK
BH+ = f(*) and G
B = f(*) are, in fact, imaginary, because the alkyl radicals at the N atom do not manifest the electron-donor properties. 相似文献
219.
Esko Taskinen 《Structural chemistry》1998,9(6):411-418
The spatial structures of a number of mono- and disubstituted 1,1-dimethoxycyclohexanes (cyclohexanone dimethyl acetals) were studied by 13C NMR spectroscopy. In the monosubstituted acetals, substituents (Me, Et, i-Pr, and MeO) on C-2 are axially oriented, contrary to their normal, equatorial orientation on C-3 and C-4. Besides the spectroscopic study, the relative thermodynamic stabilities of the cis-trans isomers of a few 2,X-dialkyl (X = 3, 4, 5, or 6) derivatives of the parent cyclohexanone dimethyl acetal were determined by acid-catalyzed chemical equilibration in MeOH solution. In the most stable isomeric form, the 2-substituent is axial and the other equatorial. In the less stable isomer, both substituents are equatorial, excluding the cis-2,6-dimethyl derivative, where the 13C NMR shift data point to a predominance of the diaxial form. In general, the enthalpy difference between the isomeric forms is ca. 9 kJ mol–1, while the entropy term favors the less stable isomer by 4 to 16 J K–1 mol–1. In the 2,6-dimethyl derivatives, however, the trans form is favored by only 0.8 kJ mol–1 in G
m
at 298.15 K. The main findings of the experimental work are in good agreement with ab initio calculations. 相似文献
220.
X. Li Y. Zhao X. Jing F. Liu F. Hao 《International journal of quantum chemistry》2006,106(5):1086-1092
The equilibrium geometries, vibrational frequencies, and dissociation energies of rare gas iodine clusters Rg2I?(Rg = Ar, Kr, Xe) were calculated at the Hartree–Fock (HF), second‐order Møller–Plesset (MP2), the coupled cluster method with single and double excitation and a noniterative correction for triple excitations method [CCSD(T)] levels. The title species have bent C2v structure of about 60° angle. The electron correlation effects and relativistic effects on the geometry and stability were investigated at CCSD(T) level. Both effects stabilize title species. The calculated electron affinities are in good agreement with the experimental results available. The effect of high angular momentum functions (g and h) was studied. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献