全文获取类型
收费全文 | 8608篇 |
免费 | 272篇 |
国内免费 | 35篇 |
专业分类
化学 | 6834篇 |
晶体学 | 106篇 |
力学 | 110篇 |
数学 | 939篇 |
物理学 | 926篇 |
出版年
2023年 | 96篇 |
2022年 | 416篇 |
2021年 | 443篇 |
2020年 | 250篇 |
2019年 | 253篇 |
2018年 | 215篇 |
2017年 | 184篇 |
2016年 | 334篇 |
2015年 | 239篇 |
2014年 | 333篇 |
2013年 | 517篇 |
2012年 | 552篇 |
2011年 | 617篇 |
2010年 | 421篇 |
2009年 | 339篇 |
2008年 | 503篇 |
2007年 | 473篇 |
2006年 | 442篇 |
2005年 | 340篇 |
2004年 | 306篇 |
2003年 | 220篇 |
2002年 | 198篇 |
2001年 | 110篇 |
2000年 | 77篇 |
1999年 | 55篇 |
1998年 | 67篇 |
1997年 | 56篇 |
1996年 | 75篇 |
1995年 | 49篇 |
1994年 | 52篇 |
1993年 | 45篇 |
1992年 | 36篇 |
1991年 | 38篇 |
1990年 | 33篇 |
1989年 | 40篇 |
1988年 | 27篇 |
1987年 | 29篇 |
1986年 | 34篇 |
1985年 | 49篇 |
1984年 | 28篇 |
1983年 | 21篇 |
1982年 | 31篇 |
1981年 | 21篇 |
1980年 | 24篇 |
1979年 | 20篇 |
1977年 | 14篇 |
1976年 | 17篇 |
1974年 | 13篇 |
1970年 | 12篇 |
1968年 | 12篇 |
排序方式: 共有8915条查询结果,搜索用时 0 毫秒
41.
Anna M. Maj Albert Demonceau Alfred F. Noels 《Journal of organometallic chemistry》2007,692(14):3048-3056
A range of new imidazolium and imidazolinium chlorides bearing biphenyl units on their nitrogen atoms was synthesized. They differed by the electron-withdrawing or -donating nature and the steric bulk of the substituents on their aromatic rings. These various N-heterocyclic carbene (NHC) precursors were combined with the [RuCl2(p-cymene)]2 dimer and potassium tert-butoxide to generate the corresponding ruthenium-arene complexes [RuCl2(p-cymene)(NHC)] in situ. The catalytic activity of these species was investigated in the photoinduced ring-opening metathesis polymerization (ROMP) of cyclooctene. The results obtained confirmed the necessity of blocking the ortho-positions of the phenyl rings in the vicinity of the metal center in order to attain high catalytic efficiencies. They also showed that changing the steric and electronic properties of the substituents on the remote phenyl rings of the biphenyl units had no significant influence on the outcome of the polymerization. 相似文献
42.
F. I. Zubkov V. P. Zaitsev A. A. Orlova A. S. Peregudov N. M. Mikhailova A. V. Varlamov 《Russian Journal of Organic Chemistry》2007,43(8):1202-1208
Dimethyl acetylenedicarboxylate reacts with 4-substituted and 3,4-fused 2-furyl-1,2,3,4-tetrahydroquinoline derivatives at the furan fragment according to the [4 + 2]-cycloaddition pattern. The reaction is not stereoselective, and it yields two diastereoisomeric 7-oxabicyclo[2.2.1]hepta-2,5-dienes whose structure was determined by X-ray analysis and NMR spectroscopy. 相似文献
43.
Gibasiewicz K Szrajner A Ihalainen JA Germano M Dekker JP van Grondelle R 《The journal of physical chemistry. B》2005,109(44):21180-21186
Almost all photosystem I (PSI) complexes from oxygenic photosynthetic organisms contain chlorophylls that absorb at longer wavelength than that of the primary electron donor P700. We demonstrate here that the low-energy pool of chlorophylls in the PSI-LHCI complex from the green alga Chlamydomonas reinhardtii, containing five to six pigments, is significantly blue-shifted (A(max) at 700 nm at 4 K) compared to that in the PSI core preparations from several species of cyanobacteria and in PSI-LHCI particles from higher plants. This makes them almost isoenergetic with the primary donor. However, they keep the other characteristic features of "red" chlorophylls: clear spectral separation from the bulk chlorophylls, big Stokes shift revealing pronounced electron-phonon coupling, and large homogeneous and inhomogeneous broadening of approximately 170 and approximately 310 cm(-1), respectively. 相似文献
44.
T. Yu. Orlova Yu. S. Nekrasov P. V. Petrovskii M. G. Ezernitskaya T. V. Magdesieva S. V. Milovanov K. P. Butin 《Russian Chemical Bulletin》1998,47(9):1785-1788
The behavior of binuclear “ladder” type complexes FpL, where Fp=Cp(CO)2Fe, L=p-MeC6H4Cr(CO)3 (4), CH2C6H5Cr(CO)3 (5), andp-FpC6H4Cr(CO)3 (6), under conditions of metallation was studied. Unlike compounds5 and6, the σ-bound ligand L in compound4 migrates from the iron atom to the cyclopentadienyl ring to give complexes Me(CO)2FeC5H4−C6H4(p-Me)Cr(CO)3. The electrochemical reduction potentials of the complexes4–6 and the rearrangement products were measured. The migration activity of L is determined by the ease of reductive cleavage
of the Fe−L bond and the susceptibility of the system to undergo intramolecular electron transfer from the Cp ligand to the
aromatic ring.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1832–1835, September, 1998. 相似文献
45.
Many abiotic and biotic factors can influence the partitioning equilibrium of heavy metals, thus influencing metal impact on aquatic environments. Unicellular algal species release soluble organic substances able to complex metals. In our laboratory a Cr-tolerant strain was selected and isolated from a wild type strain of Scenedesmus acutus. The exudates released by the two strains counteracted the growth inhibition caused by Cr(VI) and the exudates of the Cr-tolerant strain were more effective. On the contrary, the exudates did not reduce chromium toxicity to the cladoceran Daphnia magna. The reduction of chromium effect on algae seems the consequence of an algae-specific interaction among Cr(VI), exudates and algal cells. Chromium uptake resulted to be energy-dependent since bioaccumulation rate in subdued light condition was lower than at high light intensity. The effect of Cr(VI) on algae changed depending on metabolism of the cells and in particular it seemed to be related to the bioaccumulation rate. Tolerance in the selected strain could not be ascribed to a lower uptake of chromium. The difference in sensitivity to chromium between the two strains was exploited to evaluate if tolerance acquired by algae could have consequences for Daphnia. After treatment with Cr(VI), the two strains of S. acutus were used as food source for D. magna. The results indicate that chromium is accumulated by algae in a form not available for daphnids and that Cr tolerance acquired by the algae can be of some advantage to the consumer organism. 相似文献
46.
Gallium metal is effective in mediating the allylation of various carbonyl compounds and imines under solvent-free conditions, with the application of sonic energy, affording the corresponding homoallylic alcohols and amines. The imines themselves were also prepared under solventless conditions in high yield, thereby establishing a two-step solvent-free synthesis of homoallylic amines. In comparison, indium metal produced a mixture of the desired homoallylic secondary amine and the bis-allylated species via an iminium ion intermediate. 相似文献
47.
Giampiero Bartocci Anna Spalletti Ugo Mazzucato 《Research on Chemical Intermediates》1995,21(7):735-747
A fluorimetric and photochemical study of cis-9-styrylanthracene as a function of temperature has been carried out in different solvents with the aim of answering some open questions about the behavior of its first excited singlet state, S1. In non-polar solvents, a parallel photoreactive pathway, leading to a cyclization adduct, was found to compete with fluorescence and isomerization already at 200 K, its contribution increasing markedly with temperature. The cis » trans photoisomerization occurs prevalently by a triplet mechanism, a detectable contribution of diabatic and adiabatic isomerization in S1 being operative in these solvents from room temperature upwards. In polar solvents, the main deactivation pathway competitive with fluorescence is isomerization to trans, which occurs prevalently through a mixed singlet mechanism with a major diabatic and a minor adiabatic components. 相似文献
48.
V. P. Tashchi T. I. Rukasov Yu. G. Orlova Yu. A. Putsykin Yu. A. Baskakov 《Chemistry of Heterocyclic Compounds》1982,18(6):566-568
2-(-Oximinoethyl)-2-methylthiirane was obtained by the reaction of 3,4-dibromo-3-methyl-2-butanone oxime with sodium sulfide. At the same time, the O-carbamoyl derivative of the ,-dibromo oxime was converted to the corresponding substituted ,-unsaturated oxime under the same conditions. Thiirane oxime, like its O-carbamoyl derivative, underwent the desulfuration that is characteristic for thirranes under the influence of tributylphosphine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 751–753, June, 1982. 相似文献
49.
50.
Aviñó A Cubero E González C Eritja R Orozco M 《Journal of the American Chemical Society》2003,125(51):16127-16138
The structural, dynamical, and recognition properties of antiparallel DNA triplexes formed by the antiparallel d(G#G.C), d(A#A.T), and d(T#A.T) motifs (the pound sign and dot mean reverse-Hoogsteen and Watson-Crick hydrogen bonds, respectively) are studied by means of "state of the art" molecular dynamics simulations. Once the characteristics of the helix are defined, molecular dynamics and thermodynamic integration calculations are used to determine the expected stabilization of the antiparallel triplex caused by the introduction of 8-aminopurines. Finally, oligonucleotides containing 8-aminopurine derivatives are synthesized and tested experimentally using several approaches in a variety of systems. A very large stabilization of the triplex is found experimentally, as predicted by simulations. These results open the possibility for the use of oligonucleotides carrying 8-aminopurines to bind single-stranded nucleic acids by formation of antiparallel triplexes. 相似文献