全文获取类型
收费全文 | 3160篇 |
免费 | 71篇 |
国内免费 | 21篇 |
专业分类
化学 | 2324篇 |
晶体学 | 26篇 |
力学 | 29篇 |
综合类 | 1篇 |
数学 | 290篇 |
物理学 | 582篇 |
出版年
2021年 | 20篇 |
2020年 | 26篇 |
2019年 | 32篇 |
2018年 | 22篇 |
2017年 | 18篇 |
2016年 | 30篇 |
2015年 | 55篇 |
2014年 | 64篇 |
2013年 | 167篇 |
2012年 | 129篇 |
2011年 | 173篇 |
2010年 | 92篇 |
2009年 | 82篇 |
2008年 | 169篇 |
2007年 | 188篇 |
2006年 | 171篇 |
2005年 | 165篇 |
2004年 | 163篇 |
2003年 | 161篇 |
2002年 | 159篇 |
2001年 | 72篇 |
2000年 | 68篇 |
1999年 | 47篇 |
1998年 | 34篇 |
1997年 | 28篇 |
1996年 | 38篇 |
1995年 | 20篇 |
1994年 | 33篇 |
1993年 | 35篇 |
1992年 | 36篇 |
1991年 | 34篇 |
1990年 | 34篇 |
1989年 | 21篇 |
1988年 | 33篇 |
1987年 | 38篇 |
1986年 | 29篇 |
1985年 | 51篇 |
1984年 | 44篇 |
1983年 | 29篇 |
1982年 | 35篇 |
1981年 | 28篇 |
1980年 | 38篇 |
1979年 | 41篇 |
1978年 | 31篇 |
1977年 | 24篇 |
1976年 | 25篇 |
1975年 | 30篇 |
1974年 | 45篇 |
1973年 | 28篇 |
1972年 | 18篇 |
排序方式: 共有3252条查询结果,搜索用时 31 毫秒
61.
A continuous-flow hydride generator is modified and miniaturized for the determination of picogram amounts of arsenic by atomic absorption spectrometry. A 300-μl sample is dropped into a teflon cup and pumped into an alkaline sodium tetrahydroborate stream, which is acidified in a reaction coil. The evolved hydride is swept with argon through a phase separator into an electrically-heated quartz absorption cell and the absorbance is recorded. To eliminate differences in sensitivity between arsenic(III) and arsenic(V) without prereduction by potassium iodide, it is important that arsenic(V) be mixed with tetrahydroborate prior to mixing with hydrochloric acid. The method has a detection limit of 0.08 ng As ml?1 (24 pg) and the calibrations is linear up to 50 ng As ml?1. The relative standard deviation for 10 replicate measurements is 5.4% for 0.5 ng As ml?1. The addition of potassium iodide and hydroxylamine is confirmed to be effective in minimizing some interferences. The sampling rate is 90 h?1. Results for NBS biological and steel reference materials demonstrate applicability of the technique. 相似文献
62.
Masaaki Tomura Md. Akhtaruzzaman Kazuharu Suzuki Yoshiro Yamashita 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):o373-o375
In the crystal structures of the title compounds, C6H2I2N2S, (I), and C12H4I2N4S2, (II), respectively, a large number of short inter‐heteroatom contacts, such as S?N, I?I and N?I, are observed. In (II), which is non‐centrosymmetric, two halves of the molecule are related by a crystallographic twofold axis. 相似文献
63.
Ye S Zhou W Abe M Nishida T Cui L Uosaki K Osawa M Sasaki Y 《Journal of the American Chemical Society》2004,126(24):7434-7435
A highly selective ligand exchange reaction is realized in the self-assembled monolayer (SAM) of a triruthenium cluster on a gold electrode surface under precise electrochemical potential control. CO as well as NO molecules, which are known to play key roles in many chemical, biological, and environmental systems, can be efficiently introduced into the SAM by electrochemically tuning the electronic state of the Ru site. These unique surface reactions are more convenient and efficient than conventional ligand exchange reactions in solution and could be used for the elucidation of the electron-transfer mechanism in a biological system as well as in the development of molecular sensors and devices. 相似文献
64.
Efficient routes to hitherto unknown 1d-2,5-di-azido-di-deoxy-allo-inositol, 1d-2,5-di-amino-di-deoxy-allo-inositol, 1l-1-azido-1-deoxy-chiro-inositol and 1l-1-amino-1-deoxy-chiro-inositol were developed by using cheaply available myo-inositol as the starting material. Preliminary investigations on the enzyme inhibitory properties were done. The methodology reported is amenable to gram scale synthesis and thus can find application in natural product synthesis. 相似文献
65.
Masaaki Suzuki Yoshihumi Sato Hiroshi Akatsuka 《Plasma Chemistry and Plasma Processing》1996,16(3):399-415
The objective of the present work is to investigate the behavior of hydrogen in an atmospheric-pressure free-burning argon are when a small amount of hydrogen is added into the arc. A two-dimensional model calculation is carried out under the assumption that the ionization reaction of argon is in equilibrium and the reactions among hydrogen molecules, atoms, ions, and electrons are not necessarily in equilibrium. This calculation gives the following conclusion. The hydrogen mass fraction of 0.001 is too small to affect the flow and temperature fields markedly, and the concentration ratios among the hydrogen species are in equilibrium in the greater part of the arc region except for same parts with a steep temperature gradient. The hydrogen mass Junction, however, is not uniform in the me and, especially in the high-temperature region near the cathodes, over three dynes mass fraction of the hydrogen accumulates and flows downstream to cause a high flux of hydrogen atom toward the anode. This phenomena can be explained by the large difference between the diffusivity of hydrogen atom and that of hydrogen ion in argon ion. 相似文献
66.
Kazuhiro Watanabe Noboru Akino Tetsuo Aoyagi Noboru Ebisawa Yukio Fujiwara Atsusi Honda Takashi Inoue Takao Itoh Mikito Kawai Minoru Kazawa Junichi Koizumi Masaaki Kuriyama Kenji Miyamoto Naoki Miyamoto Kazuhiko Mogaki Yoshihiro Ohara Tokumichi Ohga Yoshikazu Okumura Hiroshi Oohara Katsumi Ohshima Fujio Satoh Kazuhiko Shimizu Syunji Takahashi Hirotsugu Usami Katsutomi Usui Masahiro Yamamoto Takeshi Yamazaki 《Radiation Physics and Chemistry》1997,49(6):631-639
A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D− ion beam. In the preliminary experiment using one ion source, a D− ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D− beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/ID− < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H− ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator. 相似文献
67.
Paul H. Chen William F. Kuhn Fritz Will Robert M. Ikeda 《Journal of mass spectrometry : JMS》1970,3(2):199-209
The mass spectra of three bicyclic γ-lactones have been studied, and the fragmentation pathways have been proposed with the aid of accurate mass measurements and metastable transitions. An unusually low [M ? CH3] ion and the presence of an abundant [M ? C5H9] ion in the mass spectrum of dihydroactinidiolide were interpreted as a possible rearrangement involving a methyl migration. The eliminations of methyl radical, carbon monoxide and ketene are important processes in many cases. 相似文献
68.
Yoshihisa Kurasawa Tomoyoshi Hosaka Yuko Matsumoto Aiko Ishikura Kazue Ikeda Atsushi Takada Ho Sik Kim Yoshihisa Okamoto 《Journal of heterocyclic chemistry》1994,31(6):1697-1700
The reaction of 7-chlorotetrazolo[1,5-α]quinoxaline 5-oxide 6a with acetic anhydride gave 7-chloro-5-(7-chlorotetrazolo[1,5-α]quinoxalin-4-yl)-4,5-dihydro-4-oxotetrazolo[1,5-α]quinoxaline 7a , while the reaction of 7-chloro-1,2,4-triazolo[4,3-α]quinoxaline 5-oxide 6b with acetic anhydride afforded 7-chloro-5-(7-chloro-1,2,4-triazolo[4,3-α]quinoxalin-4-yl)-4,5-dihydro-4-oxo-1,2,4-triazolo[4,3-α]quinoxaline 7b and 7-chloro-4,5-dihydro-4-oxo-1,2,4-triazolo[4,3-α]quinoxaline 8b . The reaction of compound 6a or 6b with acetic anhydride/acetic acid provided 7-chloro-4,5-dihydro-4-oxo-tetrazolo[1,5-α]quinoxaline 8a or compound 8b , respectively. 相似文献
69.
Photoirradiation at >300 nm of aqueous suspensions of several natural crystal specimens and synthesized crystallites of mercury(II) sulfide (HgS) induced deaminocyclization of optically active or racemic lysine into pipecolinic acid (PCA) under deaerated conditions. This is the first example, to the best of our knowledge, of photoinduced chemical reactions of natural biological compounds over natural minerals. It was found that the natural HgS crystals had activity higher than those of synthesized ones but lower than those of other sulfides of transition metals, e.g., CdS and ZnS, belonging to the same II-IV chalcogenides. In almost all of the photoreactions, decompostion of HgS occurred to liberate hydrogen sulfide (H(2)S) and Hg(2+), and the latter seemed to have undergone in-situ reductive deposition on HgS as Hg(0) after a certain induction period (24-70 h) during the photoirradiation, as indicated by the darkened color of the suspensions. The formation of PCA, presumably through combination of oxidation of lysine and reduction of an intermediate, cyclic Schiff base, could also be seen after a certain induction time of the Hg(0) formation. This was supported by the fact that the addition of small amount of Hg(2+) (0.5 wt % of HgS) increased the PCA yield by almost 2-fold. We also tried to elucidate certain aspects of the plausible stereochemical reactions in relation to the chiral crystal structure of HgS. Although, in some experiments, slight enantiomeric excess of the product PCA was observed, the excess was below or equal to the experimental error and no other supporting analytical data could not be obtained; we cannot conclude the enantiomeric photoproduction of PCA by the natural chiral HgS specimen. 相似文献
70.
Ishikawa T Shimizu K Ishii H Ikeda S Saito S 《The Journal of organic chemistry》2001,66(11):3834-3847
To explore a novel concept for controlling diastereoselectivity, systematic studies on the sense and degree of diastereotopic groups and face selections in intramolecular [3 + 2] (nitrile oxide and nitrone) and [2 + 2 + 1] (Pauson-Khand) cycloadditions have been conducted. Optically pure methyl (S)-3,4-O-isopropylidene-3,4-dihydroxybutanoate (5) and methyl (S)-2,3-O-isopropylidene-2,3-dihydroxypropanoate (6) were converted to substrate aldehydes (1-4) that bear geminal allyl groups and four types of controllers with the intention of imparting a stereochemical bias to the allylic groups and their faces. The controllers involve 1,2-bis(tert-butyldimethylsiloxy), 1,3-bis(tert-butyldimethylsiloxy), 1,2-acetonide, and 1,3-acetonide groups, which are referred to as 1,2-(TBDMSO)(2), 1,3-(TBDMSO)(2), 1,3-dioxolane, and 1,3-dioxane, respectively. Twelve runs of cycloaddition reactions as combinations between the three types of reactions and the four types of substrates were performed to provide bicyclo[4.3.0] or -[3.3.0] adducts of synthetic importance in which isoxazolidine, isoxazoline, or cyclopentenone segments were fused. For every case, high levels of diastereoselectivity have been achieved: >99% (in eight cases), 82%, and 76% for the discrimination of diastereotopic groups and 68-->99% for the discrimination of diastereotopic faces. On the basis of the absolute structures of the cycloadducts, plausible stereochemical models are proposed. 相似文献