全文获取类型
收费全文 | 188篇 |
免费 | 8篇 |
专业分类
化学 | 130篇 |
晶体学 | 1篇 |
力学 | 2篇 |
物理学 | 63篇 |
出版年
2023年 | 1篇 |
2020年 | 1篇 |
2019年 | 2篇 |
2018年 | 1篇 |
2017年 | 1篇 |
2016年 | 1篇 |
2015年 | 4篇 |
2014年 | 4篇 |
2013年 | 3篇 |
2012年 | 4篇 |
2011年 | 16篇 |
2010年 | 1篇 |
2009年 | 2篇 |
2008年 | 6篇 |
2007年 | 9篇 |
2006年 | 8篇 |
2005年 | 14篇 |
2004年 | 9篇 |
2003年 | 17篇 |
2002年 | 26篇 |
2001年 | 13篇 |
2000年 | 5篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1995年 | 1篇 |
1994年 | 5篇 |
1993年 | 1篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 4篇 |
1979年 | 3篇 |
1975年 | 1篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1970年 | 4篇 |
1969年 | 2篇 |
1968年 | 3篇 |
排序方式: 共有196条查询结果,搜索用时 0 毫秒
1.
Factors affecting the storage stability of lyophilized cationic liposomes were investigated using liposomes prepared with various excipients and by different freezing rates, either quick freezing (freezing by immersion into liquid nitrogen) or slow freezing (cooling to -50 degrees C at a rate of -10 degrees C/h). Increases in the particle size of cationic liposomes observed during freeze-drying were inhibited by the addition of sucrose, trehalose and sucrose-dextran mixtures (1 : 1 and 2 : 1 by weight). The storage instability of the formulations, as indicated by changes in particle size, was affected by their glass transition temperature (T(g)). Addition of high-T(g) excipients resulted in smaller increases in the particle size, indicating improvement of storage stability. The storage stability of cationic liposome formulations was also affected by freezing rate. Formulations prepared by slow freezing exhibited better stability. Longer shear relaxation times were observed for formulations prepared by slow freezing compared with those prepared by quick freezing. This indicates that formulations prepared by slow freezing have a lower matrix mobility, which may result in better storage stability. T(g) or (1)H-NMR relaxation measurements could not detect differences in matrix mobility between formulations prepared by different freezing rates. Shear relaxation measurements seem to be a useful method for evaluating the storage stability of cationic liposome formulations. 相似文献
2.
The purpose of this study is to examine whether molecular dynamics (MD) simulations using a commercially available software for personal computers can estimate the glass transition temperature (Tg) of amorphous systems containing pharmaceutically-relevant excipients. MD simulations were carried out with an amorphous matrix model constructed from isomaltoheptaose, and the Tg estimated from the calculated density versus temperature profile was compared with the Tg measured by differential scanning calorimetry (DSC) for freeze-dried isomalto-oligomer having an average molecular weight close to that of isomaltoheptaose. The Tg values determined by DSC were lower by 10 to 20 K than those extrapolated from the Tg values estimated by MD simulation. Fragility parameter was estimated to be 56 and 51 from MD simulation and from DSC measurement, respectively. Thus, the results suggest that MD simulation can provide approximate estimates for the Tg and fragility parameter of amorphous formulations. However, a reduction of the cooling rate, achievable by sufficiently elongating the simulation duration, is necessary for more accurate estimation. 相似文献
3.
Oseki Y Fujitsuka M Hara M Cai X Ie Y Aso Y Majima T 《The journal of physical chemistry. B》2005,109(21):10695-10698
Photophysical properties of oligo(2,3-thienyleneethynylene)s (nTE, n denotes the number of thiophene rings, n = 2, 3) in benzene were investigated using steady-state, time-resolved fluorescence, and transient absorption spectroscopies. For 2TE, generation of the radiative S2 and nonradiative S1 states was confirmed. Upon excitation, the S2 state was initially generated and deactivated to the S1 state within 10 ps. The S1 state exhibited the transient absorption band at 470 nm, of which the lifetime was estimated to be 5.3 ns. In the case of 3TE, on the other hand, it was revealed that the radiative S1 state with a transient absorption peak at 650 nm was generated upon excitation. The T1 states of nTE were generated from the S1 states. The quantum yields were estimated to be 0.52 and 0.54 for 2TE and 3TE, respectively. Extremely fast reactions in the higher triplet excited state were indicated for both 2TE and 3TE. 相似文献
4.
5.
The effects of excipients on the protein stability during lyophilization as well as the storage stability of lyophilized bilirubin oxidase (BO) and beta-galactosidase (GA) formulations were studied using four polymer excipients: dextran, polyvinylalcohol (PVA), poly(acrylic acid) (PAA), and alpha, beta-poly(N-hydroxyethyl)-L-aspartamide (PHEA). Denaturation of BO and GA during lyophilization largely depended on the excipient used. Dextran appeared to cause severe damage to proteins, whereas PHEA protected proteins effectively from denaturation. Storage stability of BO and GA formulations also depended on the excipients, such that the formulations containing dextran and PAA were relatively unstable. Storage stability was improved by absorption of a small amount of water for all the formulations studied. Absorption of a larger amount of water, however, decreased the storage stability of the formulations containing PVA, PAA or PHEA. In contrast, the storage stability of formulations containing dextran did not decrease noticeably with increasing water. This may be because formulations containing dextran have a higher glass transition temperature than formulations containing PVA, PAA or PHEA when a large amount of water is absorbed. 相似文献
6.
A stereochemical scheme of propagation was proposed for polymerizations of vinyl and related monomers by Friedel-Crafts catalysts. For the cationic propagation proceeding via the simple carbonium ion pair, the following two factors were considered to be of primary importance in determining the steric course of propagation: (1) the conformation of the last two units of the propagating polymer segment and the direction of approach of the incoming monomer; (2) the tightness of the growing ion pair. Thus, the front-side (less hindered site) attack to the carbonium ion gives rise to a syndiotactic placement and the back-side attack an isotactic placement. The present model can satisfactorily explain the effects of substituents, catalysts, polymerization media, and polymerization temperature on the steric structure of polymers in cationic polymerization of vinyl ethers. Extension of the scheme to polymerization of the β-substituted vinyl ethers in nonpolar solvents predicts formation of the diisotactic structures consistent with the experimental result. The influences of the polymerization condition on the steric structure of polymer were studied for cationic polymerizations of α-methylstyrene at low temperatures. Highly syndiotactic polymers were obtained for homogeneous reactions in toluene-rich media. The isotactic unit increased by increasing the content of methylcyclohexane in the solvent mixture. The effect of catalysts, though insignificant in toluene-rich media, was clearly noted in methylcyclohexane-rich media, less active catalysts (e.g., SnCl4) yielding higher amounts of the isotactic unit than more active catalysts (e.g., AlCl3). These results can be readily accommodated in the present model. 相似文献
7.
The 7,8-bis(benzyloxy)bicyclo[2.2.2]octa-2,5-diene derivatives have been synthesized via Diels-Alder reaction of optically active 5,6-bis(benzyloxy)cyclohexa-1,3-diene and dienophiles. The corresponding tricarbonyliron complexes have also been synthesized in enantiomerically pure form. 相似文献
8.
Oike T Kurata T Takimiya K Otsubo T Aso Y Zhang H Araki Y Ito O 《Journal of the American Chemical Society》2005,127(44):15372-15373
The porphyrin-sexithiophene-fullerene triad 2, where the two central thiophene units of the sexithiophene spacer are bridged with a crown-ether-like polyether chain, undergoes efficient intramolecular electron transfer from the photoexcited porphyrin moiety to the fullerene through the sexithiophene. However, complexation with a sodium cation in the crown ether ring causes complete suppression of electron transfer as a result of a drastic conformational change of the sexithiophene backbone. Furthermore, decomplexation resumes the photoinduced electron transfer. This on/off switching phenomenon indicates that the polyether-bridged sexithiophene can function as a complexation-gated molecular wire. 相似文献
9.
Yoshio Aso Shoji Nishiguchi Tetsuya Jigami Tetsuo Otsubo Fumio Ogura 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):417-418
Several well-defined 3,4-thienylene-ethynylene oligomers with different chain lengths have been synthesized and characterized. X-Ray crystallographic analyses proved their unique, totally helical conformations. 相似文献
10.
Benzenetellurinyl trifluoromethanesulfonate in conjunction with acetonitrile readily effected amidotellurinylation reactions with alkynes. Most of the addition reactions proceeded in a trans fashion to form the (E)-β-acetamidovinyl phenyl telluroxides. Subsequently, it was found that the prevailing Markovnikov adducts from terminal alkynes immediately isomerized to (Z)-isomers which were isolated as the corresponding vinyltellurides. On the other hand, the adducts derived from internal alkynes thermally underwent a spontaneous intramolecular cyclization to be transformed eventually into oxazoles. 相似文献