全文获取类型
收费全文 | 348篇 |
免费 | 14篇 |
专业分类
化学 | 260篇 |
晶体学 | 6篇 |
力学 | 5篇 |
数学 | 5篇 |
物理学 | 86篇 |
出版年
2023年 | 2篇 |
2021年 | 3篇 |
2020年 | 4篇 |
2019年 | 7篇 |
2017年 | 5篇 |
2016年 | 2篇 |
2015年 | 11篇 |
2014年 | 8篇 |
2013年 | 9篇 |
2012年 | 25篇 |
2011年 | 30篇 |
2010年 | 6篇 |
2009年 | 8篇 |
2008年 | 20篇 |
2007年 | 18篇 |
2006年 | 13篇 |
2005年 | 25篇 |
2004年 | 16篇 |
2003年 | 20篇 |
2002年 | 29篇 |
2001年 | 13篇 |
2000年 | 7篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 7篇 |
1996年 | 3篇 |
1995年 | 5篇 |
1994年 | 7篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 4篇 |
1980年 | 1篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1975年 | 2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362条查询结果,搜索用时 15 毫秒
1.
Keigo Fugami Takashi Nishikata Masayuki Kameyama 《Journal of organometallic chemistry》2003,687(2):567-569
Palladium-catalyzed reaction between 1-alkenyltin trichlorides and norbornene resulted in stereoselective formation of 3-alkylidenepentacyclo[9.2.1.5,81.1,110.2,1004,9]pentadecane instead of an expected simple alkenylstannylation product. Generation of trichlorostannane and its decomposition product, tin(II) chloride, was confirmed by trapping it with methyl propiolate and norbornene and analysis of the reaction by 119Sn NMR, respectively. 相似文献
2.
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
3.
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
4.
Motozaki T Sawamura K Suzuki A Yoshida K Ueki T Ohara A Munakata R Takao K Tadano K 《Organic letters》2005,7(11):2265-2267
[reaction: see text]. We have completed the total synthesis of natural (+)-tubelactomicin A (1), a 16-membered macrolide antibiotic. This Letter presents a highly efficient synthesis of the upper-half segment (C14-C24) and the completion of the total synthesis featuring a high-yielding Stille coupling for the connection of the upper-half and lower-half segments and Mukaiyama macrolactonization for the construction of the entire structure of 1. 相似文献
5.
Nakamura T Ikemoto JY Fujitsuka M Araki Y Ito O Takimiya K Aso Y Otsubo T 《The journal of physical chemistry. B》2005,109(30):14365-14374
The dramatic changes of the lifetimes of the charge-separated (CS) states were confirmed in zinc porphyrin (ZnP)-oligothiophene (nT)-fullerene (C(60)) linked triads (ZnP-nT-C(60)) with the solvent polarity. After the selective excitation of the ZnP moiety of ZnP-nT-C(60), an energy transfer took place from the (1)ZnP moiety to the C(60) moiety, generating ZnP-nT-(1)C(60). In polar solvents, the CS process also took place directly via the (1)ZnP moiety, generating ZnP(*+)-nT-C(60)(*-), as well as the energy transfer to the C(60) moiety. After this energy transfer, an indirect CS process took place from the (1)C(60) moiety. In the less polar solvent anisole, the radical cation (hole) of ZnP(*+)-nT-C(60)(*-) shifted to the nT moiety; thus, the nT moiety behaves as a cation trapper, and the rates of the hole shift were evaluated to be in the order of 10(8) s(-1); then, the final CS states ZnP-nT(*+)-C(60)(*-) were lasting for 6-7 mus. In the medium polar solvent o-dichlorobenzene (o-DCB), ZnP-nT(*+)-C(60)(*-) and ZnP(*+)-nT-C(60)(*-) were present as an equilibrium, because both states have almost the same thermodynamic stability. This equilibrium resulted in quite long lifetimes of the CS states (450-910 mus) in o-DCB. In the more polar benzonitrile, the generation of ZnP-nT(*+)-C(60)(*-) was confirmed with apparent short lifetimes (0.6-0.8 mus), which can be explained by the fast hole shift to more stable ZnP(*+)-nT-C(60)(*-) followed by the faster charge recombination. It was revealed that the relation between the energy levels of two CS states, which strongly depend on the solvent polarity, causes dramatic changes of the lifetimes of the CS states in ZnP-nT-C(60); that is, the most appropriate solvents for the long-lived CS state are intermediately polar solvents such as o-DCB. Compared with our previous data for H(2)P-nT-C(60), in which H(2)P is free-base porphyrin, the lifetimes of the CS states of ZnP-nT-C(60) are approximately 30 times longer than those in o-DCB. 相似文献
6.
Stereoselective polymerization of racemic lactide (rac-LA) was examined using Al-achiral ligand complexes. By introduction of substituents in aromatic rings of Schiff base ligands, a higher selectivity was obtained without any chiral auxiliaries in the catalyst via a chain-end control mechanism. The T(m) values (T(m) 170-192 degrees C) were comparable to or higher than that of homochiral polymer, poly(L-LA) (T(m) 162 degrees C), and a thermally more stable polylactide than poly(L-LA) was prepared from rac-LA. 相似文献
7.
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
8.
9.
Laboratory- and rotating- frame spin-lattice relaxation times (T(1) and T(1rho)) of (1)H and (13)C in lyophilized poly(vinylpyrrolidone) (PVP) and methylcellulose (MC) are determined to examine feasibility of using T(1) and T(1rho) as a measure of molecular motions on large time scales related to the storage stability of lyophilized formulations. The T(1rho) of proton and carbon was found to reflect the mobility of PVP and MC backbones, indicating that it is useful as a measure of large-time-scale molecular motions. In contrast to the T(1rho), the T(1) of proton measured in the same temperature range reflected the mobility of PVP and MC side chains. The T(1) of proton may be useful as a measure of local molecular motions on a smaller-time-scale, although the measurement is interfered by moisture under some conditions. The temperature dependence of T(1) and T(1rho) indicated that methylene in the MC molecule had much higher mobility than that in the dextran molecule, also indicated that methylene in the PVP side chain had a higher mobility than that in the MC side chain. 相似文献
10.
Masahiko Okada Keigo Aoi Wataru Mizuno Shinji Ito 《Journal of polymer science. Part A, Polymer chemistry》1993,31(5):1135-1140
New polyesters 6a–6c consisting of 2,4-linked tetrahydrofuran rings were synthesized by bulk polycondensation of methyl trans- and cis-4-hydroxytetrahydrofuran-2-carboxylates ( 5a and 5b ) and a stereoisomeric mixture of methyl 4-hydroxy-5-methyltetrahydrofuran-2-carboxylate ( 5c ) at high temperature. These monomers were prepared from methyl glycolate or methyl lactate and diethyl maleate through a four-step reaction sequence. The polycondensation was carried out without solvent at different temperatures ranging from 150 to 220°C. Titanium isopropoxide was most effective among the catalysts examined, giving polyesters with number-average molecular weights up to 2 × 104. Polyester 6a consisting of trans-2,4-linked tetrahydrofuran rings was soluble in trifluoroacetic acid and a mixed solvent of chloroform and methanol (10/1, v/v). Polyester 6b composed of cis-2,4-linked tetrahydrofuran rings was soluble in dimethyl sulfoxide and dimethylformamide in addition to the two solvents for 6a . Polyester 6c with 5-methyl-substituted tetrahydrofuran rings was composed of a mixture of stereoisomeric units and thus was soluble in a variety of solvents including chloroform, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, and dimethylformamide. The glass transition temperatures of 6a, 6b , and 6c determined by DSC were 109, 88, and 66°C. These polyesters were found to be very slowly hydrolyzed in a neutral phosphate buffer solution at ambient temperature. © 1993 John Wiley & Sons, Inc. 相似文献