全文获取类型
收费全文 | 7902篇 |
免费 | 202篇 |
国内免费 | 38篇 |
专业分类
化学 | 6116篇 |
晶体学 | 115篇 |
力学 | 121篇 |
数学 | 412篇 |
物理学 | 1378篇 |
出版年
2023年 | 35篇 |
2022年 | 62篇 |
2021年 | 76篇 |
2020年 | 90篇 |
2019年 | 122篇 |
2018年 | 71篇 |
2017年 | 56篇 |
2016年 | 146篇 |
2015年 | 146篇 |
2014年 | 175篇 |
2013年 | 392篇 |
2012年 | 411篇 |
2011年 | 486篇 |
2010年 | 268篇 |
2009年 | 302篇 |
2008年 | 488篇 |
2007年 | 505篇 |
2006年 | 546篇 |
2005年 | 477篇 |
2004年 | 450篇 |
2003年 | 367篇 |
2002年 | 364篇 |
2001年 | 164篇 |
2000年 | 130篇 |
1999年 | 96篇 |
1998年 | 94篇 |
1997年 | 88篇 |
1996年 | 98篇 |
1995年 | 87篇 |
1994年 | 63篇 |
1993年 | 73篇 |
1992年 | 91篇 |
1991年 | 63篇 |
1990年 | 46篇 |
1989年 | 43篇 |
1988年 | 52篇 |
1987年 | 61篇 |
1986年 | 75篇 |
1985年 | 86篇 |
1984年 | 83篇 |
1983年 | 42篇 |
1982年 | 70篇 |
1981年 | 70篇 |
1980年 | 61篇 |
1979年 | 66篇 |
1978年 | 51篇 |
1977年 | 43篇 |
1976年 | 43篇 |
1974年 | 35篇 |
1973年 | 31篇 |
排序方式: 共有8142条查询结果,搜索用时 15 毫秒
1.
2.
Several investigations on the extraction of dioxins from soil and fly ash with supercritical fluid have been reported; however, few of them describe the influence of components on the extraction. We extracted dioxins from eight samples with different values of organic carbon content and surface area with supercritical CO(2) at a temperature of 463 K, a pressure of 40 MPa, and using 10% toluene as an entrainer. We researched the influence of the characteristics of soil and fly ash on supercritical CO(2) extraction of dioxins. The results revealed that the extraction efficiencies of PCDD/DFs and PCBs were high for all soil samples, while that of fly ash samples decreased with the increase in organic carbon content and surface area. The extraction efficiencies of dioxins from four standard samples, activated carbon, humic acid, alumina, and florisil, were also examined. The results revealed that the extraction efficiencies were strongly influenced by activated carbon like components present in the samples. 相似文献
3.
4.
Shuichi Oi Mitsutoshi MoroHiroe Fukuhara Takanori KawanishiYoshio Inoue 《Tetrahedron》2003,59(24):4351-4361
The addition of arylstannanes to the carbon-heteroatom double bond in the presence of a catalytic amount of a cationic rhodium complex ([Rh(cod)(MeCN)2]BF4) was examined. The reactions of aldehydes, α-dicarbonyl compounds, and N-substituted aldimines with the arylstannanes gave corresponding alcohols, α-hydroxy carbonyl compounds, and amines, respectively. An arylrhodium complex generated by the transmetalation with the arylstannane was probably the active catalytic species. 相似文献
5.
Katsunari Inoue Kazuaki Kato Norimitsu Tohnai Mikiji Miyata 《Journal of polymer science. Part A, Polymer chemistry》2004,42(18):4648-4655
We studied simulations by computer graphics to estimate the steric mechanism of the asymmetric polymerization of prochiral diene monomers in channels of inclusion compounds of steroidal bile acids, such as deoxycholic acid (DCA) and cholic acid. We applied a hierarchization method to interpret the crystal structures of bile acids, clarifying that the chiral host molecules associated to form characteristic 21-helical assemblies with uneven surfaces. A detailed analysis of the uneven channels in a close-packing state indicated that there were many possible arrangements of the monomers in the channels. The plausible arrangements in the channel could explain a previous study, which showed that the polymerization in the DCA channel yielded chiral polymers with a predominant configuration from prochiral diene monomers, such as 2-methyl-trans-1,3-pentadiene. On the basis of such simulation studies of the arrangements of guest monomers in the channel, we examined a plausible steric mechanism for asymmetric inclusion polymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4648–4655, 2004 相似文献
6.
Yusong Wu Toshihiro Seo Shiro Maeda Takashi Sasaki Satoshi Irie Kensuke Sakurai 《Journal of Polymer Science.Polymer Physics》2004,42(22):4107-4115
Two benzoyl substituted chitosan derivatives, 3,6‐O‐dibenzoylchitosan (DBC) and 2‐N‐3,6‐O‐tribenzoylchitosan (TBC), were prepared, and their optical activities in organic solvent were investigated by circular dichroism (CD). For TBC, two splitting bands (a negative one at 288 nm and a positive one at 274 nm) corresponding to the 1Lb transition of the benzoyl group were observed in chloroform and dichloromethane, while only a negative CD band was recorded in N, N‐dimethylformamide (DMF). These results indicated that the transition moments of benzoyl groups were orderly arranged along the helical polymer chain when TBC was dissolved in a solvent with low polarity, but the same ordered structure did not appear in a polar solvent of DMF. For DBC, only negative CD signals corresponding to the 1Lb transition of the benzoyl group were observed, regardless of the solvent property, which indicated that the chromophores were not arranged in an ordered fashion with appropriate geometry to interact with one another to induce bi‐signate CD signals. Adding methanol or DMF to the solution of TBC/chloroform resulted in a progressive decrease of the intensity of the positive split band at 274 nm. The intensity of the positive band was weakened upon heating a solution of TBC/chloroform from 20 to 60 °C. The results suggested that the ordered arrangement of the chromophores in the TBC system was dependent on solvent and sensitive to temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4107–4115, 2004 相似文献
7.
The effect of α‐cyclodextrin (α‐CD) on the crystallization behavior of poly(3‐hydroxybutyrate) (PHB) was investigated with polarized optical microscopy, differential scanning calorimetry, and wide‐angle X‐ray diffraction. We found that the addition of α‐CD can greatly accelerate the crystallization of PHB and that α‐CD has a potential not only to enhance the nucleation but also to accelerate the crystallization of PHB. Compared to a conventional nucleation agent, such as talc, α‐CD is a natural product and has many advantages because it is environmentally friendly and safe to humans. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3461–3469, 2004 相似文献
8.
Mineo Hashizume Hiroaki Inoue Kiyofumi Katagiri Atsushi Ikeda Jun-Ichi Kikuchi 《Journal of Sol-Gel Science and Technology》2004,31(1-3):99-102
Morphological characterization of the organic-inorganic vesicular nanohybrids, Cerasomes, was performed in aqueous media from two aspects. Firstly, a novel Cerasome-forming lipid having two triethoxysilyl groups in the head moiety was synthesized and the physical property of the Cerasome was investigated. While the morphological stability of the Cerasomes, as evaluated from the vesicular collapse behavior against a micelle-forming nonionic surfactant, Triton-X 100, was extremely higher than that of the conventional phospholipid liposome, the stabilities were comparable to each other for the Cerasomes derived from the dual- and single-head lipids. On the other hand, the surface property of the Cerasome formed with the dual-head lipid more closely resembled the colloidal silica particles rather than that derived from the single-head lipid, as suggested by zeta-potential measurements. Secondly, the effect of the media pH on the morphological stability of the Cerasome formed with the single-head lipid was evaluated and appeared as a time difference in obtaining the morphological stability of the Cerasome. These morphological characteristics of the Cerasomes could be mainly owing to the development of the siloxane network on the vesicular surface. 相似文献
9.
The electrode reaction of decamethylferrocene (DMFc) dissolved in a thin layer of a room-temperature molten salt (RTMS), 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (C8mimC1C1N) or 1-octyl-3-methylimidazolium bis(pentafluoroethylsulfonyl)imide (C8mimC2C2N), on a self-assembled monolayer-modified gold electrode is coupled with the ion transfer across the interface between the RTMS and the outer aqueous solution (W) to give a voltammogram whose shape resembles a voltammogram of a simple one-electron transfer process. The electroneutrality of the RTMS layer during the oxidation of DMFc to decamethylferricenium ion is maintained by the concomitant dissolution of C8mim+ ion from the RTMS phase to the W phase, and the reduction of decamethylferricenium ion to DMFc is accompanied by the transfer of either C1C1N- or C2C2N- from RTMS to W. The midpoint potential of the voltammogram varies with the concentration of the salt in the aqueous phase, C8mimCl or LiCnCnN (n = 1 or 2), in a Nernstian manner, showing that the phase-boundary potential between the RTMS and the W is controlled by the partition of these ions. Although the phase-boundary potential across the RTMS / W interface is Nernstian with respect to the ions common to both phases at the equilibrium, the polarization at the RTMS / W interface under current flow distorts the shape of the voltammograms, resulting in a wider peak separation in the voltammogram. 相似文献
10.
Takashi Yoshitake Ryuji Iizuka Kaoru Fujino Osamu Inoue Kenji Yamagata Hitoshi Nohta Masatoshi Yamaguchi 《Analytical sciences》2004,20(12):1687-1690
An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification. 相似文献