全文获取类型
收费全文 | 47947篇 |
免费 | 4820篇 |
国内免费 | 6733篇 |
专业分类
化学 | 35924篇 |
晶体学 | 530篇 |
力学 | 2015篇 |
综合类 | 355篇 |
数学 | 6214篇 |
物理学 | 14462篇 |
出版年
2024年 | 45篇 |
2023年 | 424篇 |
2022年 | 520篇 |
2021年 | 1085篇 |
2020年 | 1058篇 |
2019年 | 1136篇 |
2018年 | 970篇 |
2017年 | 878篇 |
2016年 | 1665篇 |
2015年 | 1634篇 |
2014年 | 1831篇 |
2013年 | 3081篇 |
2012年 | 3426篇 |
2011年 | 4702篇 |
2010年 | 3038篇 |
2009年 | 3056篇 |
2008年 | 2986篇 |
2007年 | 2822篇 |
2006年 | 2561篇 |
2005年 | 2568篇 |
2004年 | 3417篇 |
2003年 | 2490篇 |
2002年 | 2430篇 |
2001年 | 1760篇 |
2000年 | 1194篇 |
1999年 | 1005篇 |
1998年 | 839篇 |
1997年 | 705篇 |
1996年 | 619篇 |
1995年 | 564篇 |
1994年 | 438篇 |
1993年 | 782篇 |
1992年 | 792篇 |
1991年 | 520篇 |
1990年 | 512篇 |
1989年 | 463篇 |
1988年 | 196篇 |
1987年 | 132篇 |
1986年 | 140篇 |
1985年 | 163篇 |
1984年 | 134篇 |
1983年 | 99篇 |
1982年 | 79篇 |
1981年 | 76篇 |
1980年 | 62篇 |
1979年 | 41篇 |
1978年 | 41篇 |
1977年 | 48篇 |
1976年 | 36篇 |
1974年 | 33篇 |
排序方式: 共有10000条查询结果,搜索用时 171 毫秒
991.
Alvaro M Formentín P García H Palomares E Sabater MJ 《The Journal of organic chemistry》2002,67(15):5184-5189
Three N-alkylpyridinium photosensitizers having chiral alkyl groups have been prepared by reacting 2,4,6-triphenylpyrylium tetrafluoroborate ion with (1R,2S)-(-)-norephedrine, (S)-(+)-2-(aminomethyl)pyrrolidine, and (R)-(-)-1-cyclohexylethylamine. Laser flash photolysis allows detection of the corresponding triplet excited states that are quenched by hydrogen atom donors and electron donors. Asymmetric quenching of the chiral triplet excited state was observed using enantiomerically pure 1,2-diamino cyclohexane as quencher. Low enantiomeric excess values (up to 7%) were measured for the photochemical cyclization of 5-methyl-4-hexenoic acid to its corresponding gamma-lactone using these chiral N-alkylpyridinium as photosensitizers. 相似文献
992.
In order to study the influence of the side-chain orientation on the peptide backbone conformation we have synthesised the model dipeptides t-BuCO-l-Pro-(1S,2R)-c6Phe-NHMe and t-BuCO-l-Pro-(1R,2S)-c6Phe-NHMe, incorporating each enantiomer of the trans cyclohexane analogue of phenylalanine (trans-1-amino-2-phenylcyclohexanecarboxylic acid). The orientation of the aromatic side-chain determines the β-turn type accommodated by these peptides to the point that the (1S,2R)-c6Phe derivative retains the type I β-turn in the crystalline state, in contrast to the behaviour exhibited by the natural counterpart t-BuCO-l-Pro-l-Phe-NHMe. 相似文献
993.
The 4f-5d transition rates for rare-earth ions in crystals can be calculated with an effective transition operator acting between model 4f(N) and 4f(N-1)5d states calculated with effective Hamiltonian, such as semiempirical crystal Hamiltonian. The difference of the effective transition operator from the original transition operator is the corrections due to mixing in transition initial and final states of excited configurations from both the center ion and the ligand ions. These corrections are calculated using many-body perturbation theory. For free ions, there are important one-body and two-body corrections. The one-body correction is proportional to the original electric dipole operator with magnitude of approximately 40% of the uncorrected electric dipole moment. Its effect is equivalent to scaling down the radial integral (5d/r/4f) to about 60% of the uncorrected HF value. The two-body correction has magnitude of approximately 25% relative to the uncorrected electric dipole moment. For ions in crystals, there is an additional one-body correction due to ligand polarization, whose magnitude is shown to be about 10% of the uncorrected electric dipole moment. 相似文献
994.
995.
Hong SJ Ryu JY Lee JY Kim C Kim SJ Kim Y 《Dalton transactions (Cambridge, England : 2003)》2004,(17):2697-2701
The structures of new polymeric compounds containing Cu(II) ions and btp (2,6-bis(N'-1,2,4-triazolyl)pyridine) ligands have been determined. The btp ligands bridge Cu(II) ions to form double zigzag chains, [Cu(ClO4)2(btp)2] 3 with perchlorate anions, and form single zigzag chains, [Cu(btp)(H2O)4](SO4).2H2O 4 with sulfate anions. The polymeric compound 3 was found to effectively catalyze the epoxide ring-opening reaction with methanol, while polymeric compound 4 was almost inactive with epoxides under the same conditions. The polymeric compound 3 showed an efficient catalytic activity and regioselective reactivity in the ring opening of epoxides and allowed reuse without a significant loss of activity through three runs with epoxides. 相似文献
996.
Reaction conditions and structure of the starting enamines (cyclic or open-chain) determine greatly the final products of the title reactions. Whereas in benzene and acetonitrile, DMAD and 1 give a mixture of the diastereoisomeric dienamines 5, in methanol they afford pirrolizine 3. Enaminofuranones 2 and 10 furnish the corresponding “Michael adducts” 7a,b,c and 11a,b,c but fail to yield pirrolizines. It has been demonstrated that above b and c adducts differ exclusively on the arrangement of groups around a chiral axis. 相似文献
997.
Aránzazu Espina Enrique Jaimez Sergei A. Khainakov Camino Trobajo José R. García Julio Rodríguez 《Journal of inclusion phenomena and macrocyclic chemistry》1998,30(4):333-352
The intercalation of some amines (aniline, benzylamine, cyclohexylamine,piperidine, pyridine, pyrazine and piperazine) into -titaniumphosphate, Ti(HPO4)2×H2O,has been investigated by the batch method and/or by exposing the host to thevapour of the amines. The changes in the interlayer distance of the solidduring the intercalation process was followed by X-ray powder diffraction.The new intercalates were characterised by chemical and thermal analysis.Materials with a monolaminar and/or bilaminar arrangement of amine moleculesin the phosphate interlayer region are obtained depending on the nature ofthe amine. Due to steric hindrance, saturated phases are not obtained forall amines studied. The thermal decomposition of the intercalates (nitrogenatmosphere), takes place in three stages: dehydration, removal of amines andcondensation of the hydrogenphosphate to pyrophosphate groups. 相似文献
998.
999.
CeO2及Pt/CeO2催化剂上H2、O2的作用特性 总被引:12,自引:1,他引:12
采用TPD、TPR、FT-IR和TPEC等方法研究了CeO_2及Pt/CeO_2上H_2、O_2作用特性。结果表明, Pt促进CeO_2还原, 并形成高活动性氢物种。Pt的存在使吸H_2和放氢温度下阵达300 ℃。部分还原的CeO_2常温下吸附氧形成分子离子氧物种(O_2~-, O_2~(2-)), Pt的存在改变氧化铈催化剂在常温下氧吸附物种的形态, 以解离态存在。氧化铈上吸附的氧物种在升温时可部分脱附, 高于170 ℃时则转化为晶格氧。 相似文献
1000.
A simple continuous flow generation of volatile bromine is described for the determination of low concentrations of the elements by atmospheric-pressure argon microwave induced plasma (MIP) surfatron. Bromine is continuously generated by mixing the bromide with sulphuric acid and hypochlorite solutions. The bromine vapor is separated from the aqueous phase by a gas-liquid separator and is desiccated by passing it through concentrated sulphuric acid. The detection limit attained was 2 microg/l. and the precision was +/-0.7% (at the 80 microg/l. level). The proposed determination is very selective if oxidizing/reducing agents are absent. The procedure has been tested for bromide determination in two drug preparations. Good agreement between the experimental results and the certified values has been obtained. 相似文献