全文获取类型
收费全文 | 2714篇 |
免费 | 67篇 |
国内免费 | 12篇 |
专业分类
化学 | 2167篇 |
晶体学 | 38篇 |
力学 | 37篇 |
数学 | 104篇 |
物理学 | 447篇 |
出版年
2023年 | 15篇 |
2022年 | 23篇 |
2021年 | 24篇 |
2020年 | 32篇 |
2019年 | 38篇 |
2018年 | 23篇 |
2016年 | 52篇 |
2015年 | 42篇 |
2014年 | 53篇 |
2013年 | 156篇 |
2012年 | 126篇 |
2011年 | 136篇 |
2010年 | 103篇 |
2009年 | 101篇 |
2008年 | 145篇 |
2007年 | 132篇 |
2006年 | 143篇 |
2005年 | 136篇 |
2004年 | 118篇 |
2003年 | 108篇 |
2002年 | 157篇 |
2001年 | 59篇 |
2000年 | 48篇 |
1999年 | 45篇 |
1998年 | 31篇 |
1997年 | 32篇 |
1996年 | 41篇 |
1995年 | 30篇 |
1994年 | 28篇 |
1993年 | 32篇 |
1992年 | 35篇 |
1991年 | 29篇 |
1990年 | 21篇 |
1989年 | 20篇 |
1988年 | 17篇 |
1987年 | 22篇 |
1986年 | 20篇 |
1985年 | 53篇 |
1984年 | 33篇 |
1983年 | 22篇 |
1982年 | 39篇 |
1981年 | 25篇 |
1980年 | 31篇 |
1979年 | 30篇 |
1978年 | 29篇 |
1977年 | 24篇 |
1976年 | 26篇 |
1975年 | 23篇 |
1974年 | 14篇 |
1973年 | 19篇 |
排序方式: 共有2793条查询结果,搜索用时 15 毫秒
71.
Ishiguro R Yokoyama Y Maeda H Shimamura A Kameyama K Hiramatsu K 《Journal of colloid and interface science》2005,290(1):91-101
Infrared spectra of hen egg white lysozyme and bovine serum albumin (BSA) adsorbed on a solid poly tris(trimethylsiloxy)silylstyrene (pTSS) surface in D2O solution were measured using attenuated total reflection (ATR) Fourier transform infrared spectroscopy. From the area and shape of the amide I' band of each spectrum, the adsorption amount and the secondary structure were determined simultaneously, as a function of adsorption time. We could show that the average conformation for all the adsorbed lysozyme molecules was solely determined by the adsorption time, and independent of the bulk concentration, while the adsorption amount increased with the bulk concentration as well as the adsorption time. These results suggest that lysozyme molecules form discrete assemblies on the surface, and that the surface assemblies grow over several hours to have a definite architecture independent of the adsorption amount. As for BSA, the extent of the conformational change was solely determined by the adsorption amount, regardless of the bulk concentration and the adsorption time. These differences in the adsorption properties of lysozyme and BSA may reflect differences in their conformational stabilities. 相似文献
72.
(Ss)-3-(p-Tolylsufinyl)-2-furaldimine was synthesized, and condensation of the chiral furaldimine with lithium ester enolates has been examined. The product distribution of the reaction is dependent upon reaction conditions and on the kind of the substituent placed on the esters. Disubstituted ester enolate resulted in the exclusive formation of (4R)-beta-lactam, while unsubstituted, tert-butyl ester enolate preferentially gave (3R)-beta-amino ester. With the monosubstituted ester enolates, the condensation afforded (4R)-beta-lactams and/or (3R)-beta-amino esters as major products. This method has been applied to an efficient route to chiral furyl beta-lactams. 相似文献
73.
Yoshio Masuda 《Thermochimica Acta》1980,39(3):235-241
The thermal dehydration reactions of two kinds of copper(II) formate dihydrate, which differ in origin and preparation history, have been investigated by means of TG, DTA and DSC. The kinetics of isothermal dehydration were studied by weight loss, and the difference in kinetic behavior between these two samples was related to the difference in origin and preparation history. On the whole, the dehydration mechanisms of these two samples were found to be phase boundary controlled contracting interface reactions. 相似文献
74.
Yoshio Masuda 《Thermochimica Acta》1983,60(2):203-210
The thermal dehydration of some rare earth metal formate dihydrates were studied by means of thermogravimetry, differential thermal analysis and differential scanning calorimetry.The dehydration took place successively as a one step reaction for all of the formate dihydrates examined. The reaction order of dehydration was found to be for all of the salts examined, which indicated that the rate of dehydration was controlled by a chemical process at a phase boundary.The values of the activation energy, frequency factor and the enthalpy change of dehydration for all of the dihydrates were 108–142 kJ mole?1, 1016–1017 min?1 and 109–147 kJ mole?1, respectively.Both the temperature at which the dehydration occurred and the enthalpy change increased as the reciprocal of the radius of the metallic ion increased. 相似文献
75.
Miki Murata Hiyoruki Yamasaki Tsukasa Ueta Masayuki Nagata Masanori Ishikura Shinji Watanabe Yuzuru Masuda 《Tetrahedron》2007,63(19):4087-4094
The general and efficient silylation of aryl halides has been developed utilizing triethoxysilane and a rhodium catalyst. The substrate scope is broad and includes ortho-, meta-, and para-substituted electron-rich and -deficient aryl iodides. In addition, the silylation of aryl bromides and fluoroalkanesulfonates proceeded in the presence of tetra-n-butylammonium iodide. 相似文献
76.
Michiya Itoh Kenji Murata Kunihiro Tokumura Koichi Shudo Naoki Miyata Toshihiko Okamoto 《Tetrahedron》1979,35(9):1059-1063
Photorearrangement reactions of K-region arene oxides, 9,10-epoxy-9,10-dihydrophenanthrene (1a), 3-acetyl-9,10-epoxy-9,10-dihydrophenanthrene (1b), and 3,4-epoxy-3,4-dihydropyrene (1c) in dichloroethane (DCE) solution were investigated by steady irradiation and nanosecond transient spectroscopy. Photorearrangements producing substituted oxepins, 2 occur via the singlet excited state of these compounds, while the phenolic products, 9-hydroxyphenanthrene (3a), 3-acetyl-9-hydroxyphenanthrene (3b), and 4-hydroxypyrene (3c) are formed via the triplet state. Phenol 3 formation from the triplet 1 sensitized by the triplet 3 (i.e. product sensitization) is proposed for the photorearrangement reactions of 1a and 1c, and this process is the only way phenol (3a) is formed because of the negligible intersystem crossing probability of 1a. No product sensitization occurs in the photorearrangement reaction of 1b. 相似文献
77.
An efficient synthesis of cyclodextrins (CDs) by using the intramolecular glycosylation is demonstrated. alpha-CD, an alpha(1-->4)linked hexaglucoside, was prepared via a block condensation of three maltose units. A modified key maltose intermediate as a precursor to both glycosyl donor and acceptor components was prepared in 6 steps starting from maltose. All the glycosylation for chain elongation and cyclization of saccharides was carried out after tethering the donor to the acceptor by the phthaloyl bridge to give the desired saccharides in good yields with complete alpha-selectivity. delta-CD composed of 9 glucose units was synthesized by the same manner from three maltotriose units. 相似文献
78.
Four new iridoid glycosides, named L-phenylalaninosecologanin (1), 7-O-(4-beta-D-glucopyranosyloxy-3-methoxybenzoyl)secologanolic acid (2), 6'-O-(7alpha-hydroxyswerosyloxy)loganin (3) and (Z)-aldosecologanin (5), were isolated, together with a known one, newly named (E)-aldosecologanin (4), from the stems and leaves of Lonicera japonica. Their structures were established on the basis of chemical and spectral data. 相似文献
79.
Takatsugu Masuda Cara L. Nygren Kunimitsu Uchinokura 《Journal of solid state chemistry》2003,176(1):175-179
The structure of Cu2Fe2Ge4O13, previously thought to be CuFeGe2O6, has been determined from single-crystal X-ray diffraction data to be monoclinic, P21/m, a=12.1050(6), b=8.5073(4), c=4.8736(2) Å, β=96.145(1)°, Z=2, with R1=0.0231 and wR2=0.0605. The unique structure has an oligomer of four germanate tetrahedra, cross-linked laterally by square-planar copper ions, joined end-to-end by a zigzag chain of edge-sharing iron oxide octahedra. Running along the a-direction the metal oxide chain consists of alternating Cu-Cu and Fe-Fe dimers. A hypothetical series of homologous structures (Cun−2Fe2GenO3n+1 with n=3,4,…,∞) with different length germanate oligomers is proposed, where as n increases, the infinite chain of the CuGeO3 is approached. In this context, Cu2Fe2Ge4O13 is viewed as being built from blocks of CuGeO3 and the Fe oxide chains. This material has significance to the study of low-dimensional mixed-spin systems. 相似文献
80.
Belik AA Azuma M Matsuo A Whangbo MH Koo HJ Kikuchi J Kaji T Okubo S Ohta H Kindo K Takano M 《Inorganic chemistry》2005,44(19):6632-6640
SrCu2(PO4)2 was prepared by the solid-state method at 1153 K. Its structure was solved by direct methods in the space group Pccn (No. 56) with Z = 8 from synchrotron X-ray powder diffraction data measured at room temperature. Structure parameters were then refined by the Rietveld method to obtain the lattice parameters, a = 7.94217(8) A, b = 15.36918(14) A, and c = 10.37036(10) A. SrCu2(PO4)2 presents a new structure type and is built up from Sr2O16 and Cu1Cu2O8 units with Cu1...Cu2 = 3.256 A. The magnetic properties of SrCu2(PO4)2 were investigated by magnetic susceptibility, magnetization up to 65 T, Cu nuclear quadrupole resonance (NQR), electron-spin resonance, and specific heat measurements. With spin-dimer analysis, it was shown that the two strongest spin-exchange interactions between Cu sites result from the Cu1-O...O-Cu2 and Cu2-O...O-Cu2 super-superexchange paths with Cu1...Cu2 = 5.861 A and Cu2...Cu2 = 5.251 A, and the superexchange associated with the structural dimer Cu1Cu2O8 is negligible. The magnetic susceptibility data were analyzed in terms of a linear four-spin cluster model, Cu1-Cu2-Cu2-Cu1 with -2J(1)/kB = 82.4 K for Cu1-Cu2 and -2J(2)/k(B) = 59 K for Cu2-Cu2. A spin gap deduced from this model (Delta/kB = 63 K) is in agreement with that obtained from the Cu NQR data (Delta/kB = 65 K). A one-half magnetization plateau was observed between approximately 50 and 63 T at 1.3 K. Specific heat data show that SrCu2(PO4)2 does not undergo a long-range magnetic ordering down to 0.45 K. SrCu2(PO4)2 melts incongruently at 1189 K. We also report its vibrational properties studied with Raman spectroscopy. 相似文献