全文获取类型
收费全文 | 2796篇 |
免费 | 87篇 |
国内免费 | 11篇 |
专业分类
化学 | 2122篇 |
晶体学 | 28篇 |
力学 | 40篇 |
数学 | 151篇 |
物理学 | 553篇 |
出版年
2022年 | 31篇 |
2021年 | 21篇 |
2020年 | 38篇 |
2019年 | 47篇 |
2018年 | 31篇 |
2017年 | 19篇 |
2016年 | 47篇 |
2015年 | 33篇 |
2014年 | 50篇 |
2013年 | 113篇 |
2012年 | 119篇 |
2011年 | 166篇 |
2010年 | 73篇 |
2009年 | 87篇 |
2008年 | 146篇 |
2007年 | 150篇 |
2006年 | 157篇 |
2005年 | 144篇 |
2004年 | 117篇 |
2003年 | 95篇 |
2002年 | 83篇 |
2001年 | 66篇 |
2000年 | 52篇 |
1999年 | 47篇 |
1998年 | 32篇 |
1997年 | 34篇 |
1996年 | 48篇 |
1995年 | 37篇 |
1994年 | 25篇 |
1993年 | 35篇 |
1992年 | 46篇 |
1991年 | 29篇 |
1990年 | 32篇 |
1989年 | 35篇 |
1988年 | 41篇 |
1987年 | 34篇 |
1986年 | 29篇 |
1985年 | 63篇 |
1984年 | 37篇 |
1983年 | 30篇 |
1982年 | 33篇 |
1981年 | 32篇 |
1980年 | 29篇 |
1979年 | 41篇 |
1978年 | 33篇 |
1977年 | 28篇 |
1976年 | 22篇 |
1975年 | 24篇 |
1974年 | 27篇 |
1973年 | 25篇 |
排序方式: 共有2894条查询结果,搜索用时 312 毫秒
91.
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
92.
93.
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
94.
Significant improvement in enantioselectivity and catalyst activity was achieved for the catalytic enantioselective Strecker reaction. Using a catalyst (1-2.5 mol %) prepared from Gd(OiPr)3 and d-glucose derived ligand 1, and in the presence of 2,6-dimethylphenol as an additive, high enantioselectivity was obtained from a wide range of ketoimines, including heteroaromatic and cyclic ketoimines. The new method was applied to an efficient catalytic asymmetric synthesis of sorbinil, a therapeutic agent for diabetic complications. 相似文献
95.
OH and HO(2) radicals, atmospheric detergents, and the reservoir thereof, play central roles in tropospheric chemistry. In spite of their importance, we had no choice but to trust their concentrations predicted by modeling studies based on known chemical processes. However, recent direct measurements of these radicals have enabled us to test and revise our knowledge of the processes by comparing the predicted and observed values of the radical concentrations. We developed a laser-induced fluorescence (LIF) instrument and successfully observed OH and HO(2) at three remote islands of Japan (Oki Island, Okinawa Island, and Rishiri Island). At Okinawa Island, the observed daytime level of HO(2) agreed closely with the model estimates, suggesting that the photochemistry at Okinawa is well described by the current chemistry mechanism. At Rishiri Island, in contrast, the observed daytime level of HO(2) was consistently much lower than the calculated values. We proposed that iodine chemistry, usually not incorporated into the mechanism, is at least partly responsible for the discrepancy in the results. At night, HO(2) was detected at levels greater than 1 pptv at all three islands, suggesting the presence of processes in the dark that produce radicals. We showed that ozone reactions with unsaturated hydrocarbons, including monoterpenes, could significantly contribute to radical production. 相似文献
96.
A new-type of sol-gel/organic hybrid composite material using gelatin or chitosan with tetramethoxysilane was developed for the bovine serum albumin (BSA)-encapsulated monolithic column for capillary electrochromatography (CEC). The composite monolith was used to immobilize BSA in a fused-silica capillary. The addition of gelatin and chitosan to the alkoxysilane enabled the enantioseparation of Trp. A very small amount of these polymers were effective for the enantioseparation. Especially, the monolithic column prepared from chitosan with tetramethoxysilane showed a high enantioselectivity for Trp enantiomers and the value (alpha' = t2/t1, t1: fast eluted enantiomer, t2: second eluted enantiomer) reached 1.15 on CEC mode. Furthermore, the composite materials exhibited a higher stability compared to the silica sol-gel column. These results showed that the sol-gel/organic hybrid composite was useful as a monolithic matrix for the BSA-encapsulated column for CEC. 相似文献
97.
Shinichi Yamabe Shigeki Kato Hiroshi Fujimoto Kenichi Fukui 《Theoretical chemistry accounts》1973,30(4):327-337
An ab initia molecular orbital calculation was done as to a reacting system, NH3+HF=NH4F, with the inclusion of the solvent effect as the origin of dipolar field. The reactants were assumed to stay in dimers, (NH3)2 and (HF)2, in advance to the reaction, and the respective partners of two reactants were regarded as point dipoles. The system was stabilized to some extent by two dipoles adopted. A study of configuration analysis on this system was made with and without the dipoles. Their effect was found to be favorable for proceeding of the reaction. 相似文献
98.
A highly sensitive assay for tyrosine hydroxylase (TH) activity by high-performance liquid chromatography (HPLC) with amperometric detection was devised based on the rapid isolation of enzymatically formed DOPA by a double-column procedure, the columns fitted together sequentially (the top column of Amberlite CG-50 and the bottom column of aluminium oxide). DOPA was adsorbed on the second aluminium oxide column, then eluted with 0.5 M hydrochloric acid, and assayed by HPLC with amperometric detection. D-Tyrosine was used for the control. alpha-Methyldopa was added to the incubation mixture as an internal standard after incubation. This assay was more sensitive than radioassays and 5 pmol of DOPA formed enzymatically could be measured in the presence of saturating concentrations of tyrosine and 6-methyltetrahydropterin. The TH activity in 2 mg of human putamen could be easily measured, and this method was found to be particularly suitable for the assay of TH activity in a small number of nuclei from animal and human brain. 相似文献
99.
Partial degradation and biological activities of an antitumor polysaccharide from rice bran. 总被引:8,自引:0,他引:8
Y Tanigami S Kusumoto S Nagao S Kokeguchi K Kato S Kotani T Shiba 《Chemical & pharmaceutical bulletin》1991,39(7):1782-1787
A rice bran polysaccharide designated RON was subjected either to partial hydrolysis with formic acid or to partial degradation by ultrasonic irradiation. A significant change in the molecular size was also observed during simple chromatography of RON on a strongly acidic ion exchange resin, although the apparent molecular weight of RON had been assumed to be more than 1 x 10(6) daltons (Da). This fact indicates that RON exists as molecular aggregates, presumably mediated by metal cations. Degradation products with average molecular weights above ca. 1 x 10(4) Da which were obtained by any of the three methods still retained the following activities of RON: in vivo antitumor activity against Meth-A fibrosarcoma in mice by oral administration, and in vitro macrophage stimulatory effects to induce tumoricidal activity and interleukin 1 production. This molecular size was proven to be the minimum requisite for these activities because smaller fragments were scarcely active. The aggregation was characteristic of RON but not essential for its antitumor activity because definite, though slightly reduced, activity was exhibited even by the smaller fragments obtained after the ion exchange resin treatment. 相似文献
100.
A series of complexes, [M(bpy)(SAr)2] (M = platinum(II) or palladium(II), bpy = 2,2'-bipyridine, SAr = 2- or 4-(acylamino)benzenethiolate, or 2-(alkylcarbamoyl)benzenethiolate), were synthesized and characterized on the basis of 1H NMR, IR, and electrochemical properties. The structures of [Pt(bpy)(S-2-Ph3CCONHC6H4)2] (1) and [Pt(bpy)(S-2-t-BuNHCOC6H4)2] (3) were determined by X-ray analysis. The complexes have intramolecular NH...S hydrogen bonds between the amide NH group and the sulfur atom. A weak NH...S hydrogen bond in these complexes and [Pd(bpy)(S-2-Ph3CCONHC6H4)2] (4) is detected from the 1H NMR spectra and the IR spectra in chloroform and in the solid state. [Pt(bpy)(S-2-Ph3CCONHC6H4)2] (1) exhibits a remarkably high-energy-shifted lowest-energy band in UV-visible spectra and has a positively shifted oxidation potential. The blue-shift of 42 nm and the positive shift of +0.24 V, as compared to those of [Pt(bpy)(SC6H5)2), are due to the effect of the NH...S hydrogen bond. 相似文献