全文获取类型
收费全文 | 11057篇 |
免费 | 376篇 |
国内免费 | 48篇 |
专业分类
化学 | 7370篇 |
晶体学 | 70篇 |
力学 | 411篇 |
综合类 | 1篇 |
数学 | 1521篇 |
物理学 | 2108篇 |
出版年
2023年 | 72篇 |
2022年 | 172篇 |
2021年 | 351篇 |
2020年 | 240篇 |
2019年 | 233篇 |
2018年 | 212篇 |
2017年 | 203篇 |
2016年 | 428篇 |
2015年 | 349篇 |
2014年 | 387篇 |
2013年 | 702篇 |
2012年 | 770篇 |
2011年 | 827篇 |
2010年 | 584篇 |
2009年 | 541篇 |
2008年 | 718篇 |
2007年 | 656篇 |
2006年 | 542篇 |
2005年 | 485篇 |
2004年 | 416篇 |
2003年 | 367篇 |
2002年 | 298篇 |
2001年 | 199篇 |
2000年 | 177篇 |
1999年 | 130篇 |
1998年 | 110篇 |
1997年 | 83篇 |
1996年 | 111篇 |
1995年 | 84篇 |
1994年 | 74篇 |
1993年 | 84篇 |
1992年 | 76篇 |
1991年 | 64篇 |
1990年 | 53篇 |
1989年 | 49篇 |
1988年 | 42篇 |
1987年 | 40篇 |
1986年 | 36篇 |
1985年 | 63篇 |
1984年 | 54篇 |
1983年 | 35篇 |
1982年 | 38篇 |
1981年 | 34篇 |
1980年 | 44篇 |
1979年 | 27篇 |
1978年 | 36篇 |
1976年 | 27篇 |
1975年 | 29篇 |
1974年 | 19篇 |
1973年 | 22篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
121.
Aguado GP Moglioni AG García-Expósito E Branchadell V Ortuño RM 《The Journal of organic chemistry》2004,69(23):7971-7978
The hydrogenation reactions of several cyclobutyl enamides derived from (-)-alpha-pinene or (-)-verbenone have been investigated by using different catalysts. The chiralities of both the substrate and the catalyst as well as the Z/E stereochemistry of the double bond have been considered, and the observed diastereoselectivity has been rationalized. For enamides with the double bond separated from the cyclobutane by a methylene, the Wilkinson catalyst did not induce any diastereoselection, but excellent diastereoselectivity was observed when using Et-DuPHOS-Rh and ChiraPHOS-Rh. The configuration of the new stereogenic center was catalyst-dependent and can be rationalized according to the Halpern mechanism. For (Z)-enamides with the double bond directly linked to the cyclobutane ring, the chirality of the substrate governed the diastereoselection and the Halpern mechanism seemed not to be operative in the hydrogenation with ChiraPHOS, with the configuration of the new stereogenic center being determined by steric effects. On the contrary, the chirality of the catalyst was the factor determining the stereochemistry of the major products with alkyl-DuPHOS-Rh. Z/E stereochemistry influenced the stereodifferentiation, and a different behavior for each Z or E stereoisomer was found. For both (Z)- and (E)-enamides, some instances of match/mismatch between the chirality of the substrate and that of the catalyst were observed. As a result of all of these studies, a series of new cyclobutyl alpha-amino acids has been synthesized. These products are interesting to incorporate into conformationally constrained peptides. 相似文献
122.
ágnes Zsigmond Ramóna Madácsi Ferenc Notheisz Erzsébet Mernyák and Ferenc Joó 《Reaction Kinetics and Catalysis Letters》2006,87(2):297-304
Summary [RuCl2(PPh3)3], [{RuCl2(TPPMS)2}2] and their heterogenized analogs were applied in the selective hydrogenation of 17-keto- and α,β-unsaturated ketosteroids.
In basic conditions these complexes selectively hydrogenated the C=O bonds, similarly to the results obtained in the case
of α,β-unsaturated aldehydes. A new method was developed for the synthesis of an expensive steroid alcohol, which can be prepared
traditionally in a more complicated way. 相似文献
123.
H. A. Ergül S. Topcuo?lu E. Ölmez Ç. K?rbaşo?lu 《Journal of Radioanalytical and Nuclear Chemistry》2006,268(1):133-136
Summary Radionuclide (137Cs, 238U, 232Th and 40K) concentrations were determined in a sediment trap and bottom sediment samples collected from a station at the eastern Turkish
coast of the Black Sea. The specific activity of the 137Cs radionuclide in the settling particles ranged from 0.04±0.01 to 0.10±0.02 Bq. g-1dry weight. The calculated flux rate of the 137Cs was between 0.37 and 2.59 Bq. m-2. d-1in the sampling periods of 2002 and 2003. The 137Cs concentration in the bottom sediment profile were between 0.039±0.013-9.083±0.017 Bq. g-1dry weight in the same station. The vertical profile of the radionuclides suggests that they have little mobility during the
17 years after the Chernobyl accident. 相似文献
124.
The purpose of this study is to investigate the influence of nickel, which is an alloying element in commonly used metallic biomaterials, on the biomaterials mineralization process. An electrochemical method was developed to quantify this metal ion in osteoblast-like cell culture medium (OST) by performing adsorptive cathodic stripping voltammetry (CSV) with dimethylglyoxime (DMG) at a mercury film microelectrode (MFM). The optimized analytical conditions and the square-wave CSV parameters for the analysis are: DMG concentration: 5.00 × 10−4 mol L−1; ammonium chloride buffer: 0.10 mol L−1 (pH 9.2); frequency: 50 Hz, amplitude 20 mV; step: 2 mV; adsorption time: 10 s, deposition potential: −0.70 V and reduction potential: −1.20 V. The limit of detection was 7.70 × 10−9 mol L−1 for an adsorption time of 10 s. The results achieved by CSV using the MFM were compared to those obtained by atomic absorption spectrometry (AAS) to ensure the reliability of the electrochemical method. The mineralization process was evaluated by biochemical and histochemical assays. 相似文献
125.
A way of using gravity flow to induce a linear convection within a microfluidic system is presented. It is shown and mathematically supported that tilting a 1 cm long covered microchannel is enough to generate flow rates up to 1000 nL.min(-1), which represents a linear velocity of 2.4 mm.s(-1). This paper also presents a method to monitor the microfluidic events occurring in a covered microchannel when a difference of pressure is applied to force a solution to flow in said covered microchannel, thanks to electrodes inserted in the microfluidic device. Gravity-induced flow monitored electrochemically is applied to the performance of a parallel-microchannel enzyme-linked immunosorbent assay (ELISA) of the thyroid-stimulating hormone (TSH) with electrochemical detection. A simple method for generating and monitoring fluid flows is described, which can, for instance, be used for controlling parallel assays in microsystems. 相似文献
126.
127.
128.
Jo?o L M Santos Arnaud Clausse José L F C Lima M L M F S Saraiva António O S Rangel 《Analytical sciences》2005,21(4):461-464
A new flow methodology exploiting the multi-pumping approach was developed for the spectrophotometric determination of ambroxol hydrochloride in pharmaceutical preparations. The flow manifold was implemented by using, exclusively, multiple solenoid-actuated micro-pumps, which acted simultaneously as sample insertion, solutions propelling and reagents commutation units. Linear calibration plots were obtained over an ambroxol concentration ranging from 10 to 200 mg l(-1) (r.s.d. < 0.5%, n = 15) and a sampling rate of about 60 samples per hour (flow rate = 1.92 ml min(-1), sample volume = 80 microl). 相似文献
129.
Summary A method is reported for the determination of dibutyltin (DBT), diphenyltin (DPhT), tributyltin (TBT), and triphenyltin (TPhT)
species at the nanogram per litre concentration level in natural water samples. Analytes were isolated from samples by solid-phase
extraction and analysed both off-line and on-line by reversed-phase high-performance liquid chromatography with post-column
derivatization and fluorimetric detection. Several SPE cartridges and eluents were evaluated; C18 enrichment and elution with a mixture of methanol, acetic acid, and water was found most suitable. Preconcentration factors
up to 250 can be achieved when a 500-mL sample is processed. Detection limits, recovery rates, and the precision of the whole
process have been determined. The method has been applied to the determination of organotin species in spiked natural water
samples collected on the NW Mediterranean coast. Recovery rates range from 75 to 110% and detection limits are at the low
ng L−1 level (1–3 ng Sn L−1 for DPhT, DBT, and PhT and 40 ng Sn L−1 for TBT when 250 mL spiked sea water is processed.) 相似文献
130.
J. V. Kunzler W. Schreiner A. Bristoti D. E. BrandÃo 《Journal of Thermal Analysis and Calorimetry》1977,11(1):81-86
Saturation magnetization measurements as a function of temperature were performed on Cu2Mn(Al1–xSnx) Heusler alloys to study the existence of stable structures. The derivatograph was applied to study the thermal effects.
Work supported in part by Conselho Nacional de Desenvolvimento Cientifico e Tecnologico and Banco Nacional de Desenvolvimento Economico, Brasil. 相似文献
Zusammenfassung Sättigungsmagnetisierungsmessungen als Funktion der Temperatur sowie Derivatographie wurden an Heusler-Legierungen der Formel Cu2Mn(Al1–xSnx) zu Untersuchungen der Existenz einer stabilen Struktur vorgenommen.
Résumé Etude de l'existence d'une structure stable dans les alliages de Heusler Cu2Mn(Al1–xSnx), à l'aide d'un Derivatograph et par des mesures de magnétisation à saturation en fonction de la température.
XecnepaCu2Mn(Al1–xSnx), , , . .
Work supported in part by Conselho Nacional de Desenvolvimento Cientifico e Tecnologico and Banco Nacional de Desenvolvimento Economico, Brasil. 相似文献