全文获取类型
收费全文 | 3330篇 |
免费 | 112篇 |
国内免费 | 8篇 |
专业分类
化学 | 2236篇 |
晶体学 | 49篇 |
力学 | 123篇 |
数学 | 343篇 |
物理学 | 699篇 |
出版年
2023年 | 24篇 |
2022年 | 64篇 |
2021年 | 73篇 |
2020年 | 72篇 |
2019年 | 60篇 |
2018年 | 59篇 |
2017年 | 56篇 |
2016年 | 119篇 |
2015年 | 93篇 |
2014年 | 135篇 |
2013年 | 204篇 |
2012年 | 289篇 |
2011年 | 272篇 |
2010年 | 181篇 |
2009年 | 149篇 |
2008年 | 220篇 |
2007年 | 213篇 |
2006年 | 194篇 |
2005年 | 144篇 |
2004年 | 137篇 |
2003年 | 107篇 |
2002年 | 110篇 |
2001年 | 57篇 |
2000年 | 56篇 |
1999年 | 24篇 |
1998年 | 19篇 |
1997年 | 14篇 |
1996年 | 17篇 |
1995年 | 13篇 |
1994年 | 15篇 |
1993年 | 21篇 |
1992年 | 12篇 |
1991年 | 15篇 |
1990年 | 18篇 |
1989年 | 19篇 |
1988年 | 12篇 |
1987年 | 14篇 |
1986年 | 10篇 |
1985年 | 7篇 |
1984年 | 11篇 |
1983年 | 7篇 |
1982年 | 7篇 |
1981年 | 8篇 |
1980年 | 16篇 |
1979年 | 12篇 |
1978年 | 16篇 |
1977年 | 10篇 |
1976年 | 9篇 |
1974年 | 6篇 |
1973年 | 6篇 |
排序方式: 共有3450条查询结果,搜索用时 15 毫秒
91.
A bicyclo[3.1.0]hexane, with one cyclopropane carbon flanked by a ketone and an ester or an aldehyde, undergoes methanolysis with cleavage of one of the two activated cyclopropane bonds, depending on the reaction conditions. Acidic conditions yield primarily or exclusively a 4-methoxycyclohexane, while basic conditions yield a 3-methoxymethylcyclopentanone. 相似文献
92.
Yu Na Lim Soo Kyung Chae Woongbin Yim Ji‐Yong Park Woojin Yoon Hoseop Yun Eunha Kim Seung Uk Son Hye‐Young Jang 《应用有机金属化学》2019,33(3)
The reaction of [(domppp) Pd (OAc)2] [domppp = 1,3‐bis (di‐o‐methoxyphenylphosphino)propane] and imidazolium‐functionalized carboxylic acids containing various anions (Br?, PF6?, SbF6? and BF4?) resulted in the formation of nano‐sized Pd (II) aggregates under template‐free conditions. The rate of formation of aggregates can be modulated by changing the anion, affecting the rate of polymerization of CO and olefins without fouling. Herein, we describe the analysis of Pd (II) catalysts by dynamic light scattering, atomic force microscopy, X‐ray photoelectron spectroscopy and X‐ray crystallography, and co‐ and terpolymerization results including the catalytic activity, and bulk density and molecular weight of polymers. 相似文献
93.
Kang KR Kim JS Chung SI Park MH Kim YW Lim D Lee SY 《Experimental & molecular medicine》2002,34(6):489-495
Deoxyhypusine synthase catalyzes the first step in the posttranslational synthesis of an unusual amino acid, hypusine, in the eukaryotic translation initiation factor 5A (eIF-5A) precursor protein. We earlier observed that yeast recombinant deoxyhypusine synthase was phosphorylated by protein kinase C (PKC) in vitro (Kang and Chung, 1999) and the phosphorylation rate was synergistically increased to a 3.5-fold following treatment with phosphatidylserine (P.Ser)/diacylglycerol (DAG)/ Ca(2+), suggesting a possible involvement of PKC. We have extended study on the phosphorylation of deoxyhypusine synthase in vivo in different cell lines in order to define its role on the regulation of eIF5A in the cell. Deoxyhypusine synthase was found to be phosphorylated by endogenous kinases in CHO, NIH3T3, and chicken embryonic cells. The highest degree of phosphorylation was found in CHO cells. Moreover, phosphorylation of deoxyhypusine synthase in intact CHO cells was revealed and the expression of phosphorylated deoxyhypusine synthase was significantly diminished by diacyl ethylene glycol (DAEG), a PKC inhibitor, and enhanced by phorbol 12-myristate 13-acetate (PMA) or Ca(2+)/DAG. Endogenous PKC in CHO cell and cell lysate was able to phosphorylate deoxyhypusine synthase and this modification is enhanced by PMA or Ca(2+) plus DAG. Close association of PKC with deoxyhypusine synthase in the CHO cells was evident in the immune coprecipitation and was PMA-, and Ca(2+)/phospholipid dependent. These results suggest that phosphorylation of deoxyhypusine synthase was PKC-dependent cellular event and open a path for possible regulation in the interaction with eIF5A precursor for hypusine synthesis. 相似文献
94.
Novel silicon-based alternating copolymers: synthesis,photophysical properties,and tunable EL colors
Hwan Kyu Kim Kyung Lim Paik Nam Seob Baek Youngil Lee Katsumi Yoshino 《Macromolecular Symposia》2003,192(1):135-150
We synthesized novel silicon-based alternating copolymers for tunable electroluminescent (EL) colors by Heck synthetic method. Their thermal, photophysical and electroluminescent properties were studied. Most of them exhibited a blue-green EL color at the operating voltage of lower than 12 V. Unusually, we observed the white EL color from a EL device based on SiPhPVK. From photophysical studies and the time-resolved PL spectroscopies, it might be attributed to the formation of stabilized excited state in SiPhPVK. Furthermore, in order to reduce the operating voltage of their LED with increasing the electron affinity of the main chain in silicon-based alternating copolymers, we synthesized the silicon-based copolymers containing electron transporting oxadiazole units in main chain. We also studied their photophysical and electroluminescent properties. 相似文献
95.
Teik-Cheng Lim 《Journal of mathematical chemistry》2003,33(3-4):279-285
The van der Waals forces for non-bonded interaction can be expressed either by the Exponential-6 or by the Lennard-Jones(m-n) potential functions, whereby m > n. Hitherto a relationship exists between the Exponential-6 and the Lennard-Jones(12-6) potential functions, with a scaling factor = 13.772 at or near the equilibrium and = 12.0 for long range interaction. This paper attempts to develop relationships between Exponential-6 and a more generalized Lennard-Jones(m-n). Analysis reveals that the relationship exists only when n = 6 and that two sets of scaling factors (as functions of index m) applies for the relationship between Exponential-6 and the Lennard-Jones(m-6), whereby m > 6. 相似文献
96.
First-second shell interactions in metal binding sites in proteins: a PDB survey and DFT/CDM calculations 总被引:1,自引:0,他引:1
The role of the second shell in the process of metal binding and selectivity in metalloproteins has been elucidated by combining Protein Data Bank (PDB) surveys of Mg, Mn, Ca, and Zn binding sites with density functional theory/continuum dielectric methods (DFT/CDM). Peptide backbone groups were found to be the most common second-shell ligand in Mg, Mn, Ca, and Zn binding sites, followed (in decreasing order) by Asp/Glu, Lys/Arg, Asn/Gln, and Ser/Thr side chains. Aromatic oxygen- or nitrogen-containing side chains (Tyr, His, and Trp) and sulfur-containing side chains (Cys and Met) are seldom found in the second coordination layer. The backbone and Asn/Gln side chain are ubiquitous in the metal second coordination layer as their carbonyl oxygen and amide hydrogen can act as a hydrogen-bond acceptor and donor, respectively, and can therefore partner practically every first-shell ligand. The second most common outer-shell ligand, Asp/Glu, predominantly hydrogen bonds to a metal-bound water or Zn-bound histidine and polarizes the H-O or H-N bond. In certain cases, a second-shell Asp/Glu could affect the protonation state of the metal ligand. It could also energetically stabilize a positively charged metal complex more than a neutral ligand such as the backbone and Asn/Gln side chain. As for the first shell, the second shell is predicted to contribute to the metal selectivity of the binding site by discriminating between metal cations of different ionic radii and coordination geometries. The first-shell-second-shell interaction energies decay rapidly with increasing solvent exposure of the metal binding site. They are less favorable but are of the same order of magnitude as compared to the respective metal-first-shell interaction energies. Altogether, the results indicate that the structure and properties of the second shell are dictated by those of the first layer. The outer shell is apparently designed to stabilize/protect the inner-shell and complement/enhance its properties. 相似文献
97.
Kuan-Hon Lim 《Tetrahedron letters》2006,47(29):5037-5039
A new pentacyclic indole alkaloid of the pericine-type, valparicine, representing the first member of this sub-group, was obtained from a Malayan Kopsia species and the structure was established by spectroscopic analysis. A partial synthesis of valparicine and apparicine from pericine was carried out via the Potier-Polonovski reaction and the biogenetic implications are discussed. 相似文献
98.
Teik-Cheng Lim 《Journal of mathematical chemistry》2002,32(3):249-256
Molecular mechanics softwares adopt various set of force field functions. In some cases, reliable data from one set of force field parameters cannot be used in a software that adopts another set of force field. Using mathematical approach, exact relationships between parameters from three bond-bending force fields, namely the (i) harmonic cosine angle, (ii) polynomial series, and (iii) Fourier series, are herein developed. Parameters from these three potential functions are further related to the approximate form, the harmonic angle function, which is valid for small change in chemical bond angle. 相似文献
99.
100.
Todd P. Dinoia Shawn E. Conway Jong Sung Lim Mark A. McHugh 《Journal of Polymer Science.Polymer Physics》2000,38(21):2832-2840
The cloud‐point behaviors of poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride‐co‐22 mol % hexafluoropropylene) (VDF–HFP22) are reported at temperatures up to 250 °C and pressures up to 3000 bar in supercritical CO2, CHF3, CH2F2, CHClF2, CClF3, CH3CHF2, CH2FCF3, CHF2CF3, and CH3CClF2. The molecular weight of PVDF has a smaller effect on the cloud point than the solvent quality. Cloud‐point pressures for both fluoropolymers decrease as the solvent polarizability, polar moment per molar volume, and density increases. However, it is extremely difficult to dissolve either fluoropolymer in CClF3, which has a large polarizability and a small dipole moment. CO2 is an effective solvent because it complexes with the C F dipole at low temperatures where energetic interactions fix the phase behavior. In addition, polymer architecture has a strong impact on the cloud‐point pressure. VDF–HFP22 has lower cloud‐point pressures than PVDF in all solvents because it has a larger free volume that promotes facile interactions between the solvent and the polymer segments. Cloud‐point data are also reported for amorphous poly(tetrafluoroethylene‐co‐x mol % 2,2‐bistrifluoromethyl‐4,5‐difluoro‐1,3‐dioxole) (TFE–PDDx ; x = 65 and 85) in CO2. These data provide an interesting comparison to the PVDF–CO2 and VDF–HFP22–CO2 systems because TFE–PDD65 and TFE–PDD87 have very high glass‐transition temperatures of 160 and 240 °C, respectively. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2832–2840, 2000 相似文献