全文获取类型
收费全文 | 21725篇 |
免费 | 808篇 |
国内免费 | 8篇 |
专业分类
化学 | 14332篇 |
晶体学 | 159篇 |
力学 | 365篇 |
数学 | 3707篇 |
物理学 | 3978篇 |
出版年
2023年 | 145篇 |
2022年 | 121篇 |
2021年 | 208篇 |
2020年 | 322篇 |
2019年 | 324篇 |
2018年 | 457篇 |
2017年 | 407篇 |
2016年 | 826篇 |
2015年 | 640篇 |
2014年 | 668篇 |
2013年 | 1438篇 |
2012年 | 1403篇 |
2011年 | 1386篇 |
2010年 | 825篇 |
2009年 | 755篇 |
2008年 | 1222篇 |
2007年 | 1261篇 |
2006年 | 1117篇 |
2005年 | 1041篇 |
2004年 | 941篇 |
2003年 | 722篇 |
2002年 | 633篇 |
2001年 | 489篇 |
2000年 | 445篇 |
1999年 | 326篇 |
1998年 | 223篇 |
1997年 | 213篇 |
1996年 | 284篇 |
1995年 | 200篇 |
1994年 | 227篇 |
1993年 | 189篇 |
1992年 | 186篇 |
1991年 | 175篇 |
1990年 | 170篇 |
1989年 | 149篇 |
1988年 | 140篇 |
1987年 | 133篇 |
1986年 | 132篇 |
1985年 | 193篇 |
1984年 | 195篇 |
1983年 | 123篇 |
1982年 | 128篇 |
1981年 | 140篇 |
1980年 | 137篇 |
1979年 | 94篇 |
1978年 | 95篇 |
1977年 | 102篇 |
1976年 | 82篇 |
1975年 | 86篇 |
1973年 | 71篇 |
排序方式: 共有10000条查询结果,搜索用时 62 毫秒
181.
The gaseous products of the thermal decomposition of formates have been investigated and compared with the products of formaldehyde and synthesis gas transformation under analogous conditions in the presence of the solids formed in the thermal decomposition of particular formates. It was found that formaldehyde transformation leads to organic compounds identical to those obtained in the thermal decomposition of the respective formates, while synthesis gas does not react under such conditions. This fact substantiates the hypothesis that formaldehyde is a precursor of the organic compounds identified in the thermal decomposition of formates. The nature of the organic componds obtained in the thermal decomposition of formates indicates that the formaldehyde formed in the initial stages is then transformed in the Cannizzaro or Tishchenko reactions.
Zusammenfassung Die gasförmigen Produkte der thermischen Zersetzung von Formiaten wurden untersucht und mit den Produkten verglichen, die bei der Umwandlung von Formaldehyd und Synthesegas unter analogen Bedingungen in Gegenwart von bei der thermischen Zersetzung von speziellen Formiaten gebildeten Feststoffen entstehen. Formaldehydumwandlungen führen zu organischen Verbindungen, die identisch mit denen sind, die bei der thermischen Zersetzung des betreffenden Formiats gebildet werden, während Synthesegas unter solchen Bedingungen nicht reagiert. Dies erhärtet die Hypothese, daß Formaldehyd eine Vorstufe der bei der thermischen Zersetzung von Formiaten identifizierten organischen Verbindungen ist. Die Natur der bei der thermischen Zersetzung von Formiaten auftretenden organischen Verbindungen weist darauf hin, daß das in den ersten Reaktionsschritten gebildete Formaldehyd nach der Cannizzaro-oder Tishchenko-Reaktion weiterreagiert.
, , . , i , . . , , . , , , .相似文献
182.
183.
F. F. C. Bazito S. I. Córdoba de Torresi R. M. Torresi 《Journal of Solid State Electrochemistry》2007,11(11):1471-1479
Poly(phenylene sulfide phenyleneamine), PPSA, is a copolymer of poly(aniline) and poly(phenylene sulfide), soluble in conventional
organic solvents as tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, and cyclohexanone. In this research, its electrochemical
behavior has been studied in acetonitrile in the presence of different electrolytes, where the loss of electroactivity was
observed after few cycles. In this paper, the charge compensation dynamics of PPSA is analyzed through electrochemical quartz
crystal microbalance experiments and electroacoustic impedance measurements. Raman spectroscopy data have shown that once
the oxidation of the sulfur atom occurs, a loss of electroactivity is observed, being not possible to recover the pristine
state of the polymer. Fourier transform infrared (FTIR) and X-ray diffraction (XRD) data obtained for the fully oxidized polymer
are consistent with the formation of a networked polymer due to the electrophilic attack of the positive sulfur atom on the
activated aromatic rings. Electrochemical quartz crystal microbalance results clearly show that the degree of irreversibility
fully depends on the chemical nature of the anions with a negligible participation of the cations of the electrolytic solution.
This work is in memoriam of Prof. Dr. Francisco C. Nart, dearest friend and colleague, whose scientific skills and enthusiasm
will always be remembered. 相似文献
184.
185.
Thermal degradation of copolymers of styrene and methyl-vinyl-silane by pyrolysis gas chromatography
Pyrolysis gas chromatographic investigations have been carried out on copolymers of styrene with trimethyl-vinyl-silane and of styrene with dimethyl-phenyl-vinyl-silane, in order to study the mechansims of thermal degradation and the copolymer structures. We have identified the pyrolysis products and measured their relative amounts. The experiments show that the controlling factor in the mechanism of the degradation is the nature of the side-group attached to the carbon atom at which chain scission occurs. If this side-group is phenyl, the main degradation process is depropagation; if it is if it is trimethyl-silyl or dimethyl-phenyl-silyl, intramolecular hydrogen abstraction followed by β scission becomes more important than depropagation. From the point of view of degradation mechanism, the nature of the side-group attached to the carbon atom from which the hydrogen is abstracted is of minor importance.We estimated the average copolymer block length from the amounts of products containing both comonomers as well as from the amounts of trimer composed of the same monomer. 相似文献
186.
Joan Albaigés Josep M. Bayona Pilar Fernandez Joan Grimalt Antoni Rosell Rafel Simó 《Mikrochimica acta》1991,104(1-6):13-27
An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon. 相似文献
187.
Pilar Alonso Isabel de Frutos Teresa Gutiérrez Antonio Doadrio López 《Transition Metal Chemistry》1987,12(2):133-136
Summary The synthesis and the dinuclear or mononuclear nature of several molybdenum(VI) and molybdenum(V) oxocomplexes derived from 1,3-diphenyl-1,3-propanedione (HLL) are described. These complexes were identified by i.r. and electronic spectra, magnetic susceptibility and analytical data, and are assigned the following formulae: [MoO2(LL)2], [Mo2O5(LL)2], [Mo2O4(LL)2], [MoOCl(LL)2], [MoCl2(LL)] and [MoO(OH)(LL)2)]. The low magnetic moments of the dinuclear complexes are due, in part, to intramolecular interactions. The i.r. data show that the dionate is bound by two oxygen atoms forming a chelate six-membered ring. 相似文献
188.
F. Garcias J. A. Alonso M. Barranco J. M. López A. Mañanes J. Németh 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1994,31(4):275-277
The competition experimentally observed between asymmetric fission and neutral monomer evaporation as dissociation channels of excited doubly charged sodium clusters has been investigated by means of an axially symmetric, fully selfconsistent Kohn-Sham method. Ellipsoidal equilibrium configurations for parent and daughter clusters have been considered using a deformed jellium model.This paper was originally submitted in connection with the 2nd. Int. Conference on Atomic and Nuclear Clusters held in Santorini from 28. June–2. July 1993 and is published here as a regular article after an independent refereeing procedure according to the standards of Z. Phys. D 相似文献
189.
Gábor Blaskó S.Fazal Hussain Alan J. Freyer Maurice Shamma 《Tetrahedron letters》1981,22(33):3127-3130
The dark yellow indenobenzazepine alkaloids lahorine () and lahoramine () have been found in Lam. (Fumariaceae). In a transformation with biogenetic implications, treatment of the spirobenzylisoquinolines dihydrofumariline () and dihydroparfumidine () with methanesulfonyl chloride and triethylamine in dry THF, followed by iodine oxidation, provided and , respectively. 相似文献
190.
Burguera JL Quintana IA Salager JL Burguera M Rondón C Carrero P Anton de Salager R Petit de Peña Y 《The Analyst》1999,124(4):593-599
An on-line time based injection system used in conjunction with cold vapor generation atomic absorption spectrometry and microwave-aided oxidation with potassium persulfate has been developed for the determination of the different mercury species in fish-eggs oil samples. A three-phase surfactant-oil-water emulsion produced an advantageous flow when a peristaltic pump was used to introduce the highly viscous sample into the system. The optimum proportion of the oil-water mixture ratio was 2:3 v/v with a Tween 20 surfactant concentration in the emulsion of 0.008% v/v. Inorganic mercury was determined after reduction with sodium borohydride while total mercury was determined after an oxidation step with persulfate prior to the reduction step to elemental mercury with the same reducing agent. The difference between total and inorganic mercury determined the organomercury content in samples. A linear calibration graph was obtained in the range 0.1-20 micrograms l-1 of Hg2+ by injecting 0.7 ml of samples. The detection limits based on 3 sigma of the blank signals were 0.11 and 0.12 microgram l-1 for total and inorganic mercury, respectively. The relative standard deviation of ten independent measurements were 2.8 and 2.2% for 10 micrograms l-1 and 8.8 and 9.0% for 0.1 microgram l-1 amounts of total and inorganic mercury, respectively. The recoveries of 0.3, 0.6 and 8 micrograms l-1 of inorganic and organic mercury added to fish-eggs oil samples ranged from 93.0 to 94.8% and from 100 to 106%, respectively. Good agreement with those values obtained for total mercury content in real samples by electrothermal atomic absorption spectrometry was also obtained, differences between mean values were < 7%. With the proposed procedure, 22 proteropterous catfish-eggs oil samples from the northwestern coast of Venezuela were measured; while the organic mercury lay in the range 2.0 and 3.3 micrograms l-1, inorganic mercury was not detected. 相似文献