全文获取类型
收费全文 | 504篇 |
免费 | 20篇 |
专业分类
化学 | 478篇 |
晶体学 | 1篇 |
力学 | 2篇 |
数学 | 9篇 |
物理学 | 34篇 |
出版年
2023年 | 4篇 |
2022年 | 3篇 |
2021年 | 2篇 |
2020年 | 3篇 |
2019年 | 10篇 |
2018年 | 5篇 |
2016年 | 10篇 |
2015年 | 10篇 |
2014年 | 8篇 |
2013年 | 15篇 |
2012年 | 32篇 |
2011年 | 42篇 |
2010年 | 13篇 |
2009年 | 16篇 |
2008年 | 31篇 |
2007年 | 38篇 |
2006年 | 36篇 |
2005年 | 29篇 |
2004年 | 36篇 |
2003年 | 21篇 |
2002年 | 30篇 |
2001年 | 8篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 7篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 8篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 7篇 |
1983年 | 2篇 |
1982年 | 10篇 |
1981年 | 7篇 |
1980年 | 11篇 |
1979年 | 4篇 |
1978年 | 5篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1970年 | 1篇 |
1969年 | 2篇 |
1968年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有524条查询结果,搜索用时 0 毫秒
1.
Isao Tanikawa Nobuo Hirakawa Hiroko Hosono Hiroshi Nakamura 《Analytical sciences》2007,23(11):1267-1274
Hydro-membrane gas chromatography (HMGC) is achieved by the annular condensation of water in a capillary column at less than 70 degrees C. The annular membrane of water is formed as a result of the wettability of the stationary phase, which is induced at a water contact angle ranging from 75 degrees to 79 degrees, as derived from a solubility parameter (delta) range of 15.7 +/- 0.3 MPa(1/2) of the coated resin. The range of the liquid to gas volume ratio (beta) required to support the annular membrane should be kept between 0.00005 and 0.0003. In the case of a 0.25-mm i.d. column, the ratio can be set by the combination of a 0.1 to 0.2 microl min(-1) water supply rate and helium gas flow rate. Separation by HMGC develops not only a gas-solid partition but also a focusing effect on the water membrane. One feature of HMGC is that it gives a non-adsorption chromatogram based on the blocking effect of pre-adsorbed water; furthermore, despite the presence of a relatively large quantity of water, the electron impact ionization efficiency is kept the same as in the usual GC/MS condition. The detection limit with the injection of 1 microl of aquatic solution was estimated to be less than 0.1 ppb of low-molecular-weight fatty acids with s/n = 5 on a mass chromatogram at m/z 45. The HMGC/EI-MS system can be applied to the trace analysis of C1 to C3 volatile acids, volatile inorganic acids, and halogenated organic acids in water. 相似文献
2.
We study the limit theorem related to the interface of the three-dimensional Ising model. Dobrushin proved that the interface does not fluctuate and becomes rigid for sufficiently large. We define the random fieldX
L
(t, s), 0t, s1, on the interface, and prove that XL(t, s) converges to the Brownian sheet as L for sufficiently large, whereL denotes the size of the system. This result does not mean that the interface itself converges to the Brownian sheet. 相似文献
3.
8,2'-O-Cycloadenosine was protected at 3' and 5'-OHs with acetyl groups and cleaved using liq. H2S. Subsequent dethiolation and mesylation gave 2'-O-mesyl-3',5'-di-O-acetyl-arabinosyladenine (6). When 6 or its deacetylated parent compound (7) was heated with sodium azide in DMF, 3'-azido-3'-deoxyxylofuranosyladenine (9) was the only product. The cyclonucleoside was then protected with tetrahydropyranyl groups and subjected to a similar series of reactions as above to give 2'-O-mesyl-3',5'-di-O-tetrahydropyranylarabinosyladenine (14). The compound 14 was heated with sodium azide after which acidic deprotection afforded 2'-azido-2'-deoxyadenosine (16). Hydrogenation of 16 gave 2'-amino-2'-deoxyadenosine (18). 2'-Chloro-2'-deoxyadenosine (19) was also obtained by treatment of 14 with lithium chloride and subsequent deprotection. UV, IR and NMR spectral data of these compounds are described. 相似文献
4.
5.
Ohkoshi S Tokoro H Hozumi T Zhang Y Hashimoto K Mathonière C Bord I Rombaut G Verelst M Cartier dit Moulin C Villain F 《Journal of the American Chemical Society》2006,128(1):270-277
This article describes the studies of a photomagnetic cyanide-bridged Cu-Mo bimetallic assembly, Cu(II)(2)[Mo(IV)(CN)(8)].8H(2)O (Cu(II), S = (1)/(2); Mo(IV), S = 0) (1), which has an intervalence transfer (IT) band from Mo(IV)-CN-Cu(II) to Mo(V)-CN-Cu(I) around 480 nm. Wide-angle X-ray scattering and X-ray spectroscopic studies provide precise information about the 3D connectivity and the local environment of the transition metal ions. Irradiating with blue light causes solid 1 to exhibit a spontaneous magnetization (Curie temperature = 25 K). The thermal reversibility is carefully studied and shows the long-time stability of the photoinduced state up to 100 K. Photoreversibility is also observed; i.e., the magnetization is induced by irradiation with light below 520 nm, while the magnetization is reduced by irradiation with light above 520 nm. The UV-vis absorption spectrum after irradiation shows a decrease of the IT band and the appearance of the reverse-IT band in the region of 600-900 nm (lambda(max) = 710 nm). This UV-vis absorption spectrum is recovered to the original spectrum by irradiation with 658-, 785-, and 840-nm light. In this photomagnetic effect, the excitation of the IT band causes an electron transfer from Mo(IV) to Cu(II), producing a ferromagnetic mixed-valence isomer of Cu(I)Cu(II)[Mo(V)(CN)(8)].8H(2)O (Cu(I), S = 0; Cu(II), S = (1)/(2); Mo(V), S = (1)/(2)) (1'). 1' returns to 1 by irradiation of the reverse-IT band, which obeys the scheme for the potential energy surface in mixed-valence class II compounds. 相似文献
6.
Shirahata T Kibune M Yoshino H Imakubo T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(27):7619-7630
The unsymmetrical pi donor dimethyl(ethylenedioxy)tetraselenafulvalene (DMEDO-TSeF) has provided six new organic superconductors with a monovalent square-planar [Au(CN)(4)](-) ion and cyclic ethers as solvent of crystallization. The six new organic superconductors kappa-(DMEDO-TSeF)(2)[Au(CN)(4)](solv.) [solv.=1,3-dioxolane (DOL), 2,5-dihydrofuran (DHF), tetrahydropyran (THP), 1,3-dioxane (1,3-DOX), 3,4-dihydro-2H-pyran (DHP), or 1,4-dioxane (1,4-DOX)] are classified into two subphases kappa(L) and kappa' according to the differences in their space group symmetry. kappa(L)-(DMEDO-TSeF)(2)[Au(CN)(4)](solv.) (solv.=DOL, DHF, THP, 1,3-DOX or DHP) crystallizes in the orthorhombic space group Pnma, and T(c) of the kappa(L) phase varies by 1.7-5.3 K according to the size and shape of the solvent of crystallization. On the other hand, kappa'-(DMEDO-TSeF)(2)[Au(CN)(4)](solv.) (solv.=DOL or 1,4-DOX) crystallizes in the noncentrosymmetric monoclinic space group Cc. The kappa'-phase containing 1,4-DOX shows superconductivity at 4.2 K, but the kappa'-phase containing DOL does not show superconductivity down to 1.4 K. Systematic investigation of the six new organic superconductors, together with the two previously reported superconductors kappa(H)- and kappa(L)-(DMEDO-TSeF)(2)[Au(CN)(4)](THF), revealed that the T(c) of the present system is finely tunable by utilizing the effect of the solvent of crystallization. 相似文献
7.
Okamoto K Sakagami M Feng F Togame H Takemoto H Ichikawa S Matsuda A 《The Journal of organic chemistry》2012,77(3):1367-1377
Full details of the total synthesis of pacidamycin D (4) and its 3'-hydroxy analogue 32 are described. The chemically labile Z-oxyacyl enamide moiety is the most challenging chemical structure found in uridylpeptide natural products. Key elements of our approach to the synthesis of 4 include the efficient and stereocontrolled construction of the Z-oxyvinyl halides 6 and 7 and their copper-catalyzed cross-coupling with the tetrapeptide carboxamide 5, a thermally unstable compound containing a number of potentially reactive functional groups. This synthetic route also allowed us to easily prepare 3'-hydroxy analogue 32. The assemblage by cross-coupling of the Z-oxyvinyl halide 6 and the carboxamide 5 at a late stage of the synthesis provided ready access to a range of uridylpeptide antibiotics and their analogues, despite their inherent labile nature with potential epimerization, simply by altering the tetrapeptide moiety. 相似文献
8.
Microchip-based immunoassay system with branching multichannels for simultaneous determination of interferon-gamma 总被引:1,自引:0,他引:1
A bead-bed immunoassay system suitable for simultaneous assay of multiple samples was constructed on a microchip. The chip had branching multichannels and four reaction and detection regions; the constructed system could process four samples at a time with only one pump unit. Interferon gamma was assayed by a 3-step sandwich immunoassay with the system coupled to a thermal lens microscope as a detector. The biases of the signal intensities obtained from each channel were within 10%, and coefficients of variation were almost the same level as the single straight channel assay. The assay time for four samples was 50 min instead of 35 min for one sample in the single-channel assay; hence higher throughput was realized with the branching structure chip. 相似文献
9.
Suzuki T Arai K Goto H Hanano M Watanabe J Tomono K 《Chemical & pharmaceutical bulletin》2002,50(6):741-743
Nifedipine-containing calcium phosphate cement (CPC) was prepared, and nifedipine (NF) release from this preparation was evaluated by the shaking method (SK), Japanese Pharmacopoeia XIV (JPXIV) paddle method (PD), and JPXIV flow-through cell method (FT). The release of NF from the CPC preparation continued for 7 d or longer by all these methods. This suggests that the release of NF can be controlled by preparing NF-containing CPC. The release pattern of NF from CPC in these tests was found to follow the Higuchi equation. However, the Higuchi constant differed among the three dissolution tests, probably because the apparent tortuosity of capillary system (tau) varied. 相似文献
10.
Machida K Takehara E Kobayashi H Kikuchi M 《Chemical & pharmaceutical bulletin》2003,51(12):1417-1419
Two new iridoid glycosides, 7 beta,8 beta-epoxy-8 alpha-dihydrogeniposide (1) and 8-epiapodantheroside (2), were isolated, together with six known (3-8) and three artifact (9-11) iridoids, from the leaves of Gardenia jasminoides cv. fortuneana Hara. Their structures were established based on chemical and spectral data. 相似文献