全文获取类型
收费全文 | 2142篇 |
免费 | 92篇 |
国内免费 | 6篇 |
专业分类
化学 | 1659篇 |
晶体学 | 33篇 |
力学 | 11篇 |
数学 | 99篇 |
物理学 | 438篇 |
出版年
2023年 | 14篇 |
2021年 | 23篇 |
2020年 | 24篇 |
2019年 | 35篇 |
2018年 | 31篇 |
2017年 | 12篇 |
2016年 | 45篇 |
2015年 | 41篇 |
2014年 | 68篇 |
2013年 | 94篇 |
2012年 | 90篇 |
2011年 | 156篇 |
2010年 | 84篇 |
2009年 | 84篇 |
2008年 | 116篇 |
2007年 | 132篇 |
2006年 | 131篇 |
2005年 | 111篇 |
2004年 | 98篇 |
2003年 | 108篇 |
2002年 | 103篇 |
2001年 | 61篇 |
2000年 | 39篇 |
1999年 | 26篇 |
1998年 | 15篇 |
1997年 | 16篇 |
1996年 | 25篇 |
1995年 | 13篇 |
1994年 | 19篇 |
1993年 | 12篇 |
1992年 | 19篇 |
1991年 | 16篇 |
1990年 | 20篇 |
1989年 | 15篇 |
1988年 | 21篇 |
1987年 | 19篇 |
1986年 | 9篇 |
1985年 | 17篇 |
1984年 | 25篇 |
1983年 | 17篇 |
1982年 | 19篇 |
1981年 | 15篇 |
1980年 | 25篇 |
1979年 | 21篇 |
1978年 | 29篇 |
1977年 | 15篇 |
1976年 | 18篇 |
1975年 | 10篇 |
1974年 | 18篇 |
1973年 | 10篇 |
排序方式: 共有2240条查询结果,搜索用时 31 毫秒
61.
In order to develop tumor-localizing fluorescent diagnostic agents without phototoxicity, various heterodimers linked by some spacers between a chlorine derivative and its Mn or Cu complex were synthesized. The representative agent of them was named HAT-D01 and has a molecular formula of m -phthalyl-{[13,17-bispropanoic acid-3-ethenyl-8-formylethylidene-7-hydroxy-2,7,12,18-tetramethyl-porphyrinate]-manganese (III)}-[3'-ethenyl-8'-formylethylidene-7'-hydroxy-2',7', 12', 18'-tetramethyl-porphine-13', 17'-bispropanoyl aspartic acid]-bishydrazone. 相似文献
62.
Determination of cadmium in river water by sequential metal vapour elution analysis (column temperature; > 1500 K) with argon and hydrogen carrier gas and with atomic absorption spectrometric detection is described. The column is made of a molybdenum capillary tube (i.d. 1.22 mm) and the temperature is 1760 K. The cadmium vapor was separated from those of calcium, iron and sodium. The calibration graph was linear up to 15 μ/ml. Relative standard deviations of 0.8–4.3% were obtained in the range 1 to 15 μ/ml. Cadmium in spiked samples (river water) was determined. The results were in good agreement with the amount spiked. 相似文献
63.
Akiko Saito Mana Emoto Akira Tanaka Yuki Doi Kazuaki Shoji Yoshiyuki Mizushina Hiroshi Ikawa Hiromi Yoshida Nobuyasu Matsuura Noriyuki Nakajima 《Tetrahedron》2004,60(52):12043-12049
A simple method for the synthesis of procyanidin B3 substituted with a galloyl group at the 3 and 3″ position is described. Condensation of a benzylated catechin-3-O-gallate electrophile with a nucleophile, catechin and catechin-3-O-gallate, proceeded smoothly and stereoselectively to afford the corresponding dimer gallates, procyanidin B3-3-O-gallate and procyanidin B3-3,3″-di-O-gallate, in good yields. Further, their antioxidant activities on UV-induced lipid peroxide formation, DPPH radical scavenging activity and inhibitory activity of DNA polymerase were also investigated. Among three procyanidin B3 congeners (procyanidin B3, 3-O-gallate and 3,3″-di-O-gallate), the 3,3″-di-O-gallate derivative showed the strongest antioxidant and radical scavenging activity. Interestingly, the 3-O-gallate derivative was the strongest inhibitor of mammalian DNA polymerase with IC50 value of 0.26 μM, although it showed the weakest antioxidant and radical scavenging activity. It became apparent that the presence of a galloyl group at the C-3 position in the proanthocyanidin oligomer was very important for biological activity, however, the antioxidant activity of these compounds was not parallel to the DNA polymerase inhibitory activity. 相似文献
64.
Sato H Tashiro K Shinmori H Osuka A Murata Y Komatsu K Aida T 《Journal of the American Chemical Society》2005,127(38):13086-13087
Upon binding with C60 and diamines, such as 4,4'-bipyridine (bpy) and N,N,N',N'-tetramethylhexane-1,6-diamine (TMHDA), cyclic host 1 possessing two electronically coupled binding sites displays negative homotropic cooperativity and positive heterotropic cooperativity, and their ternary mixtures preferentially form inclusion complexes with hetero-guest pairs 1 supersetC60*bpy and 1 supersetC60*TMHDA under appropriate conditions. Spectroscopic titration profiles in toluene at 20 degrees C demonstrated that the association constants (Kassoc) of C60 with monodiamine complexes 1 supersetbpy (2.8 x 105 M-1) and 1 supersetTMHDA (1.5 x 105 M-1) are 8.5 and 4.5 times greater than that of C60 with guest-free 1 (3.3 x 104 M-1), respectively. On the other hand, mono-C60 complex 1 supersetC60 was 6.1 times more accessible than guest-free 1 toward TMHDA. Absorption spectroscopy in the absence of 1 indicated no direct interaction between C60 and diamines. 相似文献
65.
Optically pure P-chiral (dialkyl)arylphosphine-boranes having high structural diversity were prepared by two- or three-component coupling of fluorobenzenechromium complexes, P-chiral secondary phosphine-boranes, and other nucleophiles. The stereochemical integrity at the P-stereogenic center was completely retained during the SNAr process when the reaction was carried out in THF at low temperature. 相似文献
66.
Morishita H Ohashi S Oku T Nakajima Y Kojima S Ryufuku M Nakamura H Ohmiya Y 《Photochemistry and photobiology》2002,75(3):311-315
Two marine dinoflagellates, Lingulodinium polyedrum and Pyrocystis lunula, emit light in a reaction involving the enzymatic oxidation of its tetrapyrrole luciferin by molecular oxygen. The characteristic properties of P. lunula luciferase have not been clarified, whereas L. polyedrum luciferase, which has three active domains, has been characterized. A cloned partial cDNA of the P. lunula luciferase encodes an active fragment corresponding to part of domain 2 and all of domain 3 of L. polyedrum luciferase. The homology of the amino acid sequence between the two luciferases in domain 3 is about 84.3%. A recombinant His-tagged luciferase fragment containing domain 3 (Mr = 46 kDa) catalyzed the light-emitting oxidation of luciferin (lambdamax = 474 nm). This protein was purified by a single affinity-chromatography procedure. The pH-activity profile and the bioluminescence spectrum of the recombinant enzyme having a third domain are almost identical to those of an extract from P. lunula cultured in vitro. The recombinant enzyme is active at pH 8.0, although the recombinant enzyme derived from the second domain of L. polyedrum luciferase is inactive at pH 8.0. Substitution of Glu-201 by histidine in the third domain of P. lunula luciferase showed a decrease of activity above pH 7.0, suggesting that histidine residues could be responsible for pH-sensitivity in dinoflagellate luciferase. 相似文献
67.
Yoshizawa M Nagao M Umemoto K Biradha K Fujita M Sakamoto S Yamaguchi K 《Chemical communications (Cambridge, England)》2003,(15):1808-1809
Despite their structural similarity, triangular tetradentate ligands 2b and 2c experience different assembly pathways on complexation with (en)Pd(NO3)2 to give M8L4 tetrahedral (3) and open cone (4) structures, respectively, due to steric restriction by side chains at the corner or on the edge of the ligands. 相似文献
68.
Yasuo Kimura Takashi Hamasaki Hiromitsu Nakajima Akira Isogai 《Tetrahedron letters》1982,23(2):225-228
Aszonalenin () has been isolated from together with LL-S490β () and the structure of has been established by spectroscopic evidences and chemical transformation. 相似文献
69.
Improved synthesis of four stereoisomeric chiral 1,3-dimethyl-1,2,3,4-tetrahydroisoquinolines (1a, b, ent-1a, b) was achieved via the super acid-induced cyclization of chiral N-[1-methyl-2-(phenylsulfinyl)ethyl]-N-(1-phenylethyl)formamides (4a, b, ent-4a, b) using the Pummerer-type cyclization reaction as a key step. The cyclization leading to the isoquinoline ring proceeded in a quantitative manner when trifluoromethane sulfonic acid (TFSA) was used as the super acid, although Friedel-Crafts-type alkylation of 4-phenylsulfanyl TIQ derivatives (5) with benzene used as the solvent accompanied cyclization to yield the 4-phenyl-TIQs (7). The byproduct (7) was exclusively formed when a large excess amount of TFSA was used. 相似文献
70.
Takashi Nakajima T. N. Chang 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1996,36(1):41-46
We present a semi-empirical calculational procedure for thep 5 nl bound excited states of rare gas atoms based on the use of an LS-dependent orbital for an excitednl electron outside a frozen Hartree-Fockp 5 core. The spin-orbit interaction is accounted for approximately using a localized Hartree potential. The contribution from the long-range core polarization is estimated by using a parametrized potential. A model potential is also introduced to represent partially the short-range multi-electron interactions for thep 5 np levels. The energy levels are calculated by diagonalizing the Hamiltonian matrix following anLS →jl transformation. The calculated fine structure of the Nep 5 ns,p 5 np,p 5 nd, andp 5 nf ¦ (jl)KJ〉 levels are in close agreement with the observed level splittings. The transition probabilities are also in agreement with earlier theoretical and experimental results. 相似文献