全文获取类型
收费全文 | 171314篇 |
免费 | 1552篇 |
国内免费 | 507篇 |
专业分类
化学 | 88249篇 |
晶体学 | 3039篇 |
力学 | 7154篇 |
综合类 | 3篇 |
数学 | 19514篇 |
物理学 | 55414篇 |
出版年
2020年 | 1398篇 |
2019年 | 1552篇 |
2018年 | 1980篇 |
2017年 | 2065篇 |
2016年 | 3184篇 |
2015年 | 1889篇 |
2014年 | 3112篇 |
2013年 | 7659篇 |
2012年 | 5747篇 |
2011年 | 6877篇 |
2010年 | 5021篇 |
2009年 | 5002篇 |
2008年 | 6533篇 |
2007年 | 6428篇 |
2006年 | 6076篇 |
2005年 | 5502篇 |
2004年 | 5091篇 |
2003年 | 4592篇 |
2002年 | 4450篇 |
2001年 | 5218篇 |
2000年 | 3861篇 |
1999年 | 2967篇 |
1998年 | 2481篇 |
1997年 | 2385篇 |
1996年 | 2237篇 |
1995年 | 2113篇 |
1994年 | 2091篇 |
1993年 | 2000篇 |
1992年 | 2304篇 |
1991年 | 2244篇 |
1990年 | 2193篇 |
1989年 | 2121篇 |
1988年 | 2119篇 |
1987年 | 2122篇 |
1986年 | 2019篇 |
1985年 | 2629篇 |
1984年 | 2683篇 |
1983年 | 2381篇 |
1982年 | 2492篇 |
1981年 | 2307篇 |
1980年 | 2284篇 |
1979年 | 2426篇 |
1978年 | 2462篇 |
1977年 | 2388篇 |
1976年 | 2436篇 |
1975年 | 2360篇 |
1974年 | 2327篇 |
1973年 | 2504篇 |
1972年 | 1623篇 |
1971年 | 1337篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
771.
772.
Summary A gas Chromatographic determination of traces of alkali metal O,O-diethyl phosphorodithioates is described. The salts were converted into a volatile derivative by alkylation with diazomethane. The product was identified by gas chromatography-mass spectrometry. With aqueous samples a linear relationship of peak height to amount of salt was obtained in the range 0.04–1 ng and for urine samples a calibration curve was constructed. The detection limit (signal to noise ratio 4/1) was 40 pg of salt. The procedure was successfully used for monitoring phosalone absorption by occupationally exposed persons.
Presented at the Fourth International Congress of Pesticide Chemistry (IUPAC), Zürich, July 24–28, 1978. 相似文献
Zusammenfassung Eine gaschromatographische Bestimmung von Spuren Alkalisalz des Diäthyldithiophosphorsäureesters wurde beschrieben. Die Salze wurden durch Alkylieren mit Diazomethan in ein flüchtiges Derivat übergeführt. Dessen Identifizierung erfolgte mittels eines gaschromatographisch-massenspektrometrischen Systems. In Wasserproben wurde ein lineares Verhältnis der Peakhöhen und der Salzmenge festgestellt und für Urinproben wurde eine Eichkurve ermittelt. Die Nachweisgrenze (Signal zu Rausch 41) wurde bei 40 pg Salz festgestellt. Die Methode wurde für die Kontrolle der Absorption von Phosalon bei beruflich exponierten Personen erfolgreich angewendet.
Presented at the Fourth International Congress of Pesticide Chemistry (IUPAC), Zürich, July 24–28, 1978. 相似文献
773.
The infrared and Raman spectra of gaseous and solid (CH3)3 GeNCO and solid (CH3)3GeNCS have been recorded over the frequency range 20–4000 cm?1 . The Raman spectra of the liquids have also been recorded. Assignments of the normal modes have been made on the bases of band types, Raman depolarization values, and characteristic frequencies. Spectral data indicate that (CH3)3 GeNCO is non-linear in all phases and that (CH3)3GeNCS has a linear or quasi-linear heavy atom skeleton in the fluid phases. 相似文献
774.
D. T. Clark B. J. Cromarty A. Dilks 《Journal of polymer science. Part A, Polymer chemistry》1978,16(12):3173-3184
Nonempirical LCAO MO SCF computations (in the ΔSCF formalism) have been carried out of binding energies and relaxation energies for an extensive series of oxygen-containing organic systems encompassing most of the common functionalities. The molecules for which experimental data are available for comparison demonstrate the adequacy of the treatment for describing the relative binding energies for both the Cls and Ols core levels. A sound basis is therefore provided for the discussion of relative core binding energies (Cls and Ols) for functionalities for which experimental data are not available, that is, hydroperoxides, peroxides, peroxyacids, and peroxyesters, a knowledge of which is essential for investigations of the surface oxidation of polymers by means of ESCA. Cls shifts are discussed in terms of primary and secondary substituent effects of oxygen, which greatly simplify the analysis of complex unresolved spectra, whereas for the Ols levels a similar but less straightforward situation exists. The relaxation energies associated with both Cls and Ols core ionization follow a dependence on the binding energy for a given structural type. 相似文献
775.
V. A. Denisenko V. L. Novikov A. V. Kamernitskii G. B. Elyakov 《Russian Chemical Bulletin》1977,26(6):1317-1319
Conclusions The combined use of the1H and13C NMR spectra makes it possible to unequivocally assign 1-methyl-4-octalin-l,2-dicarboxylic acids and their derivatives to the proper steric series.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1429–1431, June, 1977. 相似文献
776.
Doz. Dr. P. Bukovec B. Orel J. Šiftar 《Monatshefte für Chemie / Chemical Monthly》1974,105(6):1299-1305
The IR- and Raman Spectra of several compounds of the stoichiometryM 2 I M IIIF5H2O and their deuterated analogs have been interpreted on the basis of their crystal structures. The compounds studied were divided into two classes regarding the bonding of water molecules. The main spectroscopic difference between the two classes was found in the region of H2O vibrations in good agreement with theoretical predictions. The metal—fluorine and metal—oxygene vibrations gave no direct information concerning the two types of water. 相似文献
777.
The acidolytic cleavage of a series of new N-aralkyloxycarbonyl protecting groups has been found to proceed as a first-order reaction, the rate of cleavage being dependent on the stability of the corresponding aralkyl carbonium ions. Some of the groups are cleaved at much the same rate as the N-trityl residue and up to 60000 times faster than the t-butyloxycarbonyl (Boc) group. The rate is also strongly influenced by the acidity of the reaction media. The relative rates at which aralkyloxycarbonyl and Boc groups are split off can be largely controlled by appropriate selection of the reaction conditions. The implications of these findings for peptide syntheses are discussed and the use of the 2-(p-diphenyl)-isopropyloxycarbonyl residue as an especially suitable N-protecting group is proposed. 相似文献
778.
G. V. Nizova G. V. Losenkova G. B. Shul''pin 《Reaction Kinetics and Catalysis Letters》1991,45(1):27-34
A new system CrCl3–C6H5CH2N(C2H5)3Cl–CH3CN for photooxygenation of alkanes is suggested. Unlike metal chlorides and oxocomplexes, it oxidizes alkanes to produce ketones and small amounts of alcohol. Adding of benzene, methylene chloride or ethanol to the cyclohexane solution rises the oxygenation rate and changes the ketone/alcohol ratio. With small amounts of hydroquinone the formation rate of cyclohexanone (but not of cyclohexanol) sharply decreases. Kinetic isotope effect in the oxidation of C6H12 and C6D12 is 1 for cyclohexanol and 2.9 for cyclohexanone. Cyclohexanol formation is assumed to follow a mechanism that does not involve free radicals. Free radicals can participate in the route toward ketone.
CrCl3–C6H5CH2N(C2H5)3Cl–CH3CN . , . , /. ( ) . C6H12 C6D12 1 2,9 . , , . , .相似文献
779.
B. Boutevin G. Falgayrettes Y. Hervaud Y. Piétrasanta 《European Polymer Journal》1984,20(11):1067-1072
Recovered polyethylene is used with polyethylene waxes as a new binder for mineral granules. This binder is characterized and optimized mainly on a rheological basis. Its fluid index (I.F.), molecular distribution and crystallinity are especially studied. Its rheograms and tensile properties are compared with those of industrial polyethylene (I.F. = 250). The dimensional shrinkages of such binders during cooling from 190° to ambient temperature are measured. 相似文献
780.
K. A. Volkova A. N. Nikol'skaya E. P. Levanova A. N. Volkov B. A. Trofimov 《Chemistry of Heterocyclic Compounds》1979,15(12):1296-1298
Alkylthio-substituted dienic 1,3-dioxolan-2-ones and bis(4,4-diorganyl-5-methyli-dene-1,3-dioxolan-2-ones) were obtained in high yields by the reaction of 2-methyl-6-alkylthio-5-hexen-3-yn-2-ols and tertiary diacetylenic glycols with carbon dioxide under pressure in the presence of catalytic amounts of triethylamine and monovalent copper salts.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1617–1619, December, 1979.Original article submitted January 24, 1979. 相似文献