全文获取类型
收费全文 | 5103篇 |
免费 | 184篇 |
国内免费 | 20篇 |
专业分类
化学 | 3582篇 |
晶体学 | 66篇 |
力学 | 68篇 |
数学 | 495篇 |
物理学 | 1096篇 |
出版年
2023年 | 50篇 |
2022年 | 86篇 |
2021年 | 134篇 |
2020年 | 121篇 |
2019年 | 135篇 |
2018年 | 98篇 |
2017年 | 108篇 |
2016年 | 194篇 |
2015年 | 142篇 |
2014年 | 151篇 |
2013年 | 309篇 |
2012年 | 331篇 |
2011年 | 429篇 |
2010年 | 259篇 |
2009年 | 243篇 |
2008年 | 344篇 |
2007年 | 320篇 |
2006年 | 275篇 |
2005年 | 259篇 |
2004年 | 245篇 |
2003年 | 182篇 |
2002年 | 138篇 |
2001年 | 94篇 |
2000年 | 77篇 |
1999年 | 52篇 |
1998年 | 38篇 |
1997年 | 35篇 |
1996年 | 50篇 |
1995年 | 34篇 |
1994年 | 25篇 |
1993年 | 30篇 |
1992年 | 43篇 |
1991年 | 22篇 |
1990年 | 14篇 |
1989年 | 22篇 |
1988年 | 10篇 |
1987年 | 15篇 |
1986年 | 13篇 |
1985年 | 21篇 |
1984年 | 16篇 |
1983年 | 10篇 |
1982年 | 11篇 |
1981年 | 13篇 |
1980年 | 12篇 |
1979年 | 7篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1976年 | 10篇 |
1975年 | 12篇 |
1974年 | 7篇 |
排序方式: 共有5307条查询结果,搜索用时 15 毫秒
81.
Qi ZM Matsuda N Santos J Yoshida T Takatsu A Kato K 《Journal of colloid and interface science》2004,271(1):249-253
Broadband, time-resolved optical waveguide (OWG) spectroscopy has been used for in situ, real-time investigation into the self-assembly of metal nanoparticle monolayers. The OWG spectroscopy makes it possible to use the transverse electric (TE) and transverse magnetic (TM) modes to measure surface plasmon absorption of immobilized metal nanoparticles in two directions, parallel and normal to the waveguide surface. Therefore, this technique can provide direction-dependent information on the metal nanoparticles at the interface. In this paper, a 50-microm-thick glass plate was used as a slab waveguide and the kinetics of Au nanoparticle adsorption on a hemoglobin-functionalized glass substrate was examined in the early stage of self-assembly. The findings show that with the TE mode the surface plasmon resonance (SPR) behavior for immobilized Au nanoparticles is different from that with the TM mode. 相似文献
82.
Moreno M. M. Torres Santos R. H. A. Gambardella M. T. P. Camargo A. J. da Silva A. B. F. Trsic M. 《Structural chemistry》1998,9(5):365-373
The crystal and molecular structures of the following molecules have been determined: 1-acetyl-indoline, 1-acetyl-5-nitro-indoline, l-acetyl-5-nitro-7-bromo-indoline, 1-acetyl-5-bromo-7-nitroindoline, and l-acetyl-5-bromo-7-nitro-indol. Molecular orbital calculations are performed for these compounds and two related species. 相似文献
83.
A phytochemical investigation in plantlets of the Brazilian medicinal tree Virola surinamensis resulted in the isolation and structural determination of four new compounds: 3-hydroxy-4-methyl-2-(11'-piperonyl-n-undecyl)-butenolide; 3-hydroxy-4-methyl-2-(7'-piperonyl-n-heptyl)-butanolide; 9'-(3,4-methylenedioxy-phenyl)-nonanoic acid and 13'-(3,4-methylene-dioxyphenyl)-tridecanoic acid. Thirteen compounds previously isolated from seeds and adult plants were also reported. 相似文献
84.
In this paper we consider the essential electronic excited states in parallel chains of semiconducting polymers that are currently being explored for photovoltaic and light-emitting diode applications. In particular, we focus upon various type II donor-acceptor heterojunctions and explore the relation between the exciton binding energy to the band offset in determining the device characteristic of a particular type II heterojunction material. As a general rule, when the exciton binding energy is greater than the band offset at the heterojunction, the exciton will remain the lowest-energy excited state and the junction will make an efficient light-emitting diode. On the other hand, if the offset is greater than the exciton binding energy, either the electron or hole can be transferred from one chain to the other. Here we use a two-band exciton to predict the vibronic absorption and emission spectra of model polymer heterojunctions. Our results underscore the role of vibrational relaxation and suggest that intersystem crossings may play some part in the formation of charge-transfer states following photoexcitation in certain cases. 相似文献
85.
Gutiérrez MC Sleegers A Simpson HD Alphand V Furstoss R 《Organic & biomolecular chemistry》2003,1(20):3500-3506
The first fluorogenic assay allowing for detection of microbial enzymes able to perform Baeyer-Villiger oxidation is described. This is based on the use of 4-oxopentyl umbelliferyl ether 1 as a fluorogenic substrate. When Baeyer-Villigerases active against this test ketone are present in the selected whole cells, 1 is transformed into 3-hydroxypropyl umbelliferyl ether 3, which, in a subsequent step, releases the fluorescent product umbelliferone. Different microorganisms, known to be endowed with Baeyer-Villigerase activity, were assayed. 相似文献
86.
Koumi P Green HE Hartley S Jordan D Lahec S Livett RJ Tsang KW Ward DM 《Electrophoresis》2004,25(14):2227-2241
The demand for high-throughput DNA profiling has increased with the introduction of national DNA databases and has led to the development of automated methods of short tandem repeat (STR) profile production; however, a potential bottleneck still exists at the gel electrophoresis stage. Capillary electrophoresis sequencers capable of processing 96 samples with considerably reduced manual intervention are now available. In this paper, we compare the ABI Prism 377 slab-gel sequencer currently used by the Forensic Science Service with three leading capillary array electrophoresis instruments: the ABI Prism 3700, the Amersham MegaBACE 1000 and the 16-capillary ABI Prism 3100. We describe the experiments used to evaluate and validate these platforms for forensic use with the STR multiplex Ampf/STR SGMplus [1, 2], along with comparative data from the ABI Prism 377 sequencer. 相似文献
87.
Vera R. L. Constantino Luiz F. C. de Oliveira Paulo S. Santos Henrique E. Toma 《Transition Metal Chemistry》1994,19(1):103-107
Summary The synthesis, spectra and electrochemistry of [Ru(bipy)2-(picOH)]+ and -picO-[Ru(bipy)2]2
2+ (bipy = 2,2-bipyridine and picOH = 3-hydroxypicolinate ion) are described. The spectroscopic properties in the visible region are dominated by the intense Ru bipy chargetransfer transitions. In the binuclear complex, the two [Ru(bipy)2L]2+ moieties are nonequivalent, exhibiting E
1/2 = 0.69 and 1.20 V versus s.h.e. The partially oxidized species exhibits a weak intervalence transfer band at 1085 nm, and is consistent with a Robin-Day class II mixed valence complex. 相似文献
88.
Luciana B.O. dos Santos 《Analytica chimica acta》2005,528(1):21-27
This paper describes the development of a sequential injection analysis method to automate the determination of atrazine by square wave voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. To perform these tasks, an 800 μL monosegment is formed, composed by 400 μL of sample and 400 μL of buffer/standard solution. To obtain an efficient homogenization, the sample solution is divided in five zones intercalated by four zones of the Britton-Robinson buffer (pH 2.0) in presence of appropriate concentration of NaNO3 and varying atrazine standard concentrations. This mixture zone is isolated from the carrier solution by two 100 μL air bubbles. After homogenization in an auxiliary reaction coil the mixture zone is injected toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode, at a flow rate of 50 μL s−1. After a suitable delay time, the potential is scanned from −0.5 to −1.2 V versus Ag/AgCl using a frequency of 300 Hz and pulse height of 25 mV. The linear dynamic range is observed for atrazine concentrations between 1.16 × 10−7 and 2.32 × 10−6 mol L−1, obeying the linear equation ip = (−6.91 ± 0.07) × 108[atrazine] + (4 ± 8), with r2 = 0.9996, for which the slope is given in nA L mol−1. The detection and quantification limits of the method are 2.1 × 10−8 and 7.0 × 10−8 mol L−1, respectively. The sampling frequency is 37 h−1, when the standard addition protocol is followed. This frequency can be increased to 42 h−1 if the protocol to obtain in-line calibration curve is used for quantification. The method was applied for determination of atrazine in spiked river water samples and its accuracy was evaluated by comparison with the batch standard addition approach, which revealed that there is no evidence of statistically significant differences between the two methods. 相似文献
89.
Thompson H Wasse JC Skipper NT Hayama S Bowron DT Soper AK 《Journal of the American Chemical Society》2003,125(9):2572-2581
The technique of hydrogen/deuterium isotopic substitution has been used to extract detailed information concerning the solvent structure in pure ammonia and metallic lithium-ammonia solutions. In pure ammonia we find evidence for approximately 2.0 hydrogen bonds around each central nitrogen atom, with an average N-H distance of 2.4 A. On addition of alkali metal, we observe directly significant disruption of this hydrogen bonding. At 8 mol % metal there remains only around 0.7 hydrogen bond per nitrogen atom. This value decreases to 0.0 for the saturated solution of 21 mol % metal, as all ammonia molecules have then become incorporated into the tetrahedral first solvation spheres of the lithium cations. In conjunction with a classical three-dimensional computer modeling technique, we are now able to identify a well-defined second cationic solvation shell. In this secondary shell the nitrogen atoms tend to reside above the faces and edges of the primary tetrahedral shell. Furthermore, the computer-generated models reveal that on addition of alkali metal the solvent molecules form voids of approximate radius 2.5-3.0 A. Our data therefore provide new insight into the structure of the polaronic cavities and tunnels, which have been theoretically predicted for lithium-ammonia solutions. 相似文献
90.
Abstract— The quantum yields for the photohydration of dimethyluracil were determined for concentrations in the range 5 × 10--1--1 × 10--3M by use of 240–280 nm irradiation. The average quantum yield (0.0139 f 0.0005) was independent of both concentration and irradiation wavelength. 相似文献