全文获取类型
收费全文 | 2464篇 |
免费 | 90篇 |
国内免费 | 12篇 |
专业分类
化学 | 1824篇 |
晶体学 | 10篇 |
力学 | 38篇 |
数学 | 456篇 |
物理学 | 238篇 |
出版年
2023年 | 14篇 |
2022年 | 23篇 |
2021年 | 39篇 |
2020年 | 43篇 |
2019年 | 44篇 |
2018年 | 23篇 |
2017年 | 21篇 |
2016年 | 69篇 |
2015年 | 43篇 |
2014年 | 57篇 |
2013年 | 88篇 |
2012年 | 117篇 |
2011年 | 114篇 |
2010年 | 58篇 |
2009年 | 85篇 |
2008年 | 135篇 |
2007年 | 106篇 |
2006年 | 102篇 |
2005年 | 98篇 |
2004年 | 89篇 |
2003年 | 98篇 |
2002年 | 94篇 |
2001年 | 46篇 |
2000年 | 68篇 |
1999年 | 51篇 |
1998年 | 60篇 |
1997年 | 59篇 |
1996年 | 55篇 |
1995年 | 40篇 |
1994年 | 48篇 |
1993年 | 35篇 |
1992年 | 32篇 |
1991年 | 37篇 |
1990年 | 26篇 |
1989年 | 28篇 |
1988年 | 30篇 |
1987年 | 25篇 |
1986年 | 16篇 |
1985年 | 26篇 |
1984年 | 40篇 |
1983年 | 28篇 |
1982年 | 35篇 |
1981年 | 33篇 |
1980年 | 26篇 |
1979年 | 16篇 |
1978年 | 15篇 |
1977年 | 18篇 |
1976年 | 19篇 |
1975年 | 10篇 |
1973年 | 7篇 |
排序方式: 共有2566条查询结果,搜索用时 125 毫秒
41.
The reaction of styrene oxide, a potential carcinogen in humans, with DNA constituents has been used to develop an improved method for quantification of DNA adducts. To enable monitoring of DNA adducts caused by xenobiotics at physiological relevant levels, a robust, reliable and powerful method based on monitoring of phosphorus in nucleotides is described. An efficient enzymatic digestion step and a sample-preconcentration procedure are essential, and enable separation of alkylated nucleotides from the large excess of native nucleotides. The adducts are detected by means of the phosphorus signal measured at mass m/z=31 with an inductively-coupled-plasma mass spectrometer. Bis(4-nitrophenyl)phosphate (BNPP) serves as internal standard for quantification of the adducts. The absolute limit of detection, 45 fmol, corresponds to detection of three modified nucleotides among 107 native nucleotides (the calculation is based on use of 50 g calf thymus DNA). An adduct formation ratio at the DNA of 3.6 adducts per 1000 nucleotides was measured, which is 75% lower than for reaction with monomeric 2-deoxy-nucleotides. In addition, a substantial amount of phosphate adducts were detected, but in DNA the rate of phosphate formation was lower than with monomeric nucleotides. Most probably these adducts escaped unnoticed when 31P-post-labelling was employed. 相似文献
42.
The synthesis of 4-(1-haloalkyl)-2-azetidinones and 4-(2-haloalkyl)-2-azetidinones was investigated with use of the Staudinger reaction between in situ generated ketenes and alpha-haloimines or beta-haloimines. This new class of functionalized 2-azetidinones was further evaluated for its potential use as intermediates in the synthesis of highly functionalized compounds. The reaction of 4-(1-haloalkyl)-2-azetidinones and 4-(2-haloalkyl)-2-azetidinones with sodium methoxide in methanol yielded ring-opened products, i.e., methyl 2-alkoxy-4-(alkylamino)pentenoate and methyl 5-(alkylamino)pentenoate, respectively. Further attention was paid in detail to the reaction mechanism involved in this peculiar transformation. It was proven that these reactions proceeded via intermediate aziridines or azetidines. 相似文献
43.
Norbert de Kimpe Bart de Corte Roland Verhe Laurent de Buyck Niceas Schamp 《Tetrahedron letters》1984,25(10):1095-1098
The reaction of organometallic reagents, e.g. alkyllithiums, cuprates and alkylcoppers, with α-haloimines gave selectively a variety of synthetically useful reactions, including coupling to 1,4-diimines, homologation, and production of heterocycles. 相似文献
44.
Using photoacoustic laser spectroscopy, the noninvasive determination of blood constituents like hemoglobin and glucose is feasible. The aim of our investigations is the development of a sensor which is suitable for continuously noninvasive monitoring of blood glucose concentrations in diabetic patients. For this purpose a photoacoustic sensor head was developed and coupled via an optical fiber bundle to an array of 8 laser diodes emitting at various wavelengths in the near infrared region. Applying a special modulation scheme, the tiny changes of the absorption coefficient of whole blood caused by the variations of blood glucose concentrations could be measured. A resolution of 70 mg/dl was achieved, a value which is already close to the clinical requirements for a continuously working glucose sensor. 相似文献
45.
The first examples of sequential photocycloaddition-rearrangement reactions of naphthalene-tethered resorcinol ethers are described. Bichromophoric aromatic compounds with naphthalene and resorcinol ether moieties were irradiated in the presence/absence of a small amount of acid to give the corresponding cycloaddition-rearrangement products. From the determination of quantum yields, steady-state fluorescence spectral studies, and fluorescence lifetime measurements, the mechanism of this novel photoinduced multistep reaction was elucidated to involve the initial intramolecular exciplex formation, followed by the intramolecular [2 + 2] photocycloaddition between the two aromatic rings and the subsequent acid-catalyzed skeletal rearrangement of the resulting cyclobutane derivative leading to the final products. 相似文献
46.
Josef Edinger Heinz Falk Walter Jungwirth Norbert Müller Ulrich Zrunek 《Monatshefte für Chemie / Chemical Monthly》1984,115(8-9):1081-1099
From an investigation of the ICD of bilatrienes-abc and 2,3-dihydrobilatrienes-abc induced by mixtures of CCl4 with (+)-cis-Pinane, (–)-lactic and (+)-tartaric acid esters it is concluded that specific interactions between chromophore and the chiral reagents afford a partial resolution of the labile racemate of helices. Attaching chiral residues covalently to the chromophore induces very low resolution of the same kind in case of apolar ligands like a cholesteryl-residue. However, with polar ligands as in the case ofBoc-lysyl derivatives enantiomeric excesses up to 90% are achieved depending on the solvent used.
Herrn Prof. Dr.Karl Schlögl zu seinem 60. Geburtstag gewidmet. 相似文献
47.
48.
Helmut Marko Norbert Müller Heinz Falk 《Monatshefte für Chemie / Chemical Monthly》1989,120(2):163-168
Summary The intermolecular complex formation of bilirubin and biliverdin with two proteins (basic pancreatic trypsin inhibitor and lysozyme) were studied by optical and chiroptical methods. Evidence for specific intermolecular interactions of biliverdin with both proteins was found. Bilirubin forms a soluble complex only with lysozyme.
UV-VIS und CD-spektroskopische Untersuchungen intermolekularer Wechselwirkungen von Gallenpigmenten mit kleinen Proteinen
Zusammenfassung Die intermolekulare Komplexbildung von Bilirubin und Biliverdin mit zwei Proteinen (basischer pankreatischer Trypsininhibitor und Lysozym) wurden mittels optischer und chiroptischer Spektroskopie untersucht. Für Biliverdin konnten intermolekulare Wechselwirkungen mit beiden Proteinen nachgewiesen werden. Bilirubin bildet nur mit Lysozym einen löslichen Komplex.相似文献
49.
Rhodococcus equi A4, Rhodococcus erythropolis NCIMB 11540 and Rhodococcus sp. R312 were investigated towards their ability to produce β-amino amides and acids from β-amino nitriles. The microorganisms show comparable trends: five-membered alicyclic 2-amino nitriles were transformed significantly faster than the six-membered compounds and the products of trans-2-amino nitriles (amides and acids) were formed considerably faster than the cis-counterparts (amides). The trans-five membered nitriles gave the amides (1b, 5b) in excellent enantiomeric excess (94-99%), the biotransformation of trans-six membered substrates resulted in the formation of the acid (3c, 7c) in excellent ee (87-99%). The ee's of the cis-compounds were throughout lower. Fifteen new substances were synthesized and characterized in the course of this work. 相似文献
50.
Dieter Leibfritz Erhard Haupt Norbert Dubischar Heinrich Lachmann Raymond Oekonomopulos Günther Jung 《Tetrahedron》1982,38(14):2165-2181
The uncommon amino-acid 2-methylalanine (α-aminoisobutyric acid, Aib) was investigated by 13C-NMR. The chemical shifts of amino- or carboxy-protected derivatives of Aib and of protected oligopeptides are discussed with respect to neighbouring groups and amino acids. The pH-dependence of the 13C-NMR spectra of Aib, Aib-Ala, Ala-Aib, Aib-Ala-Aib and Aib-Ala-Aib-Ala-Aib was studied. Using these examples, a new and advantageous method is demonstrated for the first time for the evalutions of NMR titration curves, which uses so-called chemical shift diagrams (CS diagrams). 相似文献