全文获取类型
收费全文 | 1603篇 |
免费 | 323篇 |
国内免费 | 414篇 |
专业分类
化学 | 1487篇 |
晶体学 | 12篇 |
力学 | 53篇 |
综合类 | 18篇 |
数学 | 177篇 |
物理学 | 593篇 |
出版年
2024年 | 2篇 |
2023年 | 19篇 |
2022年 | 42篇 |
2021年 | 50篇 |
2020年 | 60篇 |
2019年 | 52篇 |
2018年 | 54篇 |
2017年 | 49篇 |
2016年 | 67篇 |
2015年 | 81篇 |
2014年 | 101篇 |
2013年 | 117篇 |
2012年 | 122篇 |
2011年 | 151篇 |
2010年 | 132篇 |
2009年 | 109篇 |
2008年 | 124篇 |
2007年 | 103篇 |
2006年 | 117篇 |
2005年 | 96篇 |
2004年 | 80篇 |
2003年 | 76篇 |
2002年 | 105篇 |
2001年 | 104篇 |
2000年 | 66篇 |
1999年 | 54篇 |
1998年 | 41篇 |
1997年 | 16篇 |
1996年 | 9篇 |
1995年 | 15篇 |
1994年 | 13篇 |
1993年 | 16篇 |
1992年 | 10篇 |
1991年 | 18篇 |
1990年 | 6篇 |
1989年 | 2篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1982年 | 2篇 |
1974年 | 2篇 |
1973年 | 4篇 |
1969年 | 4篇 |
1968年 | 7篇 |
1967年 | 3篇 |
1966年 | 5篇 |
1962年 | 2篇 |
1903年 | 2篇 |
排序方式: 共有2340条查询结果,搜索用时 15 毫秒
1.
Zhi‐Yong Huang Jin‐Can Shen Zhi‐Xia Zhuang Xiao‐Ru Wang Frank S. C. Lee 《应用有机金属化学》2004,18(6):255-261
Cinnabar, as one of the most widely used mineral drugs in traditional Chinese medicines, has been proven to have prominent curative effects in clinical use for more than 2000 years. But the safety and toxicity of the drug has been under constant debate in clinic usage. Metallothionein (MT) contains about 30% of cysteine in the molecule, and plays an important detoxification role against heavy metals. In this study, it was used as a biomarker to assess mercurial accumulation in rats fed orally with cinnabar. After feeding rats with cinnabar by gastric gavage at different dosages and at different times, the distribution of heavy metals (including mercury, copper and zinc) and MT was investigated among rat tissues, including liver, kidney, heart, brain, testis and blood. Metals and MT determinations were carried out using inductively coupled plasma mass spectrometry (ICP‐MS) and a modified mercury saturation assay technique respectively. The results indicated that mercury was easily accumulated in the tissues of rats exposed to cinnabar, especially in kidney. For example: at a feeding dosage of 5 g kg?1 (bw) for 4 weeks, the mercury concentrations in kidney were 13, 8.7, 21.6 and 26 times those in liver, testis, brain and heart respectively; and at 2.5 g kg?1 (bw) for 2 weeks, the mercury concentrations in kidney were 21, 2.1, 3 and 21 times those in liver, testis, brain and heart respectively. In addition, mercury in kidney and liver of all cinnabar groups was significantly higher than that of the control group (P < 0.01). A high positive correlation observed between MT concentrations and mercury levels in both liver and kidney (R2 = 0.9299, P < 0.02 for liver; R2 = 0.9923, P < 0.0008 for kidney) indicated that MT could be used as a biomarker for mercury in tissues. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
2.
Yan Zhao Xingbin Yang Ru Jiang Xiaoli Sun Wenmin Liu Shengyong Zhang 《Analytical sciences》2006,22(5):747-751
The investigation on capillary electrophoretic enantioseparation of six synthetic compounds containing vicinal diol groups has been undertaken to acquire the optimum conditions using native beta-cyclodextrin (beta-CD) as chiral selector and borate as a background electrolyte. The separation was carried out in an uncoated capillary (58.5 cm x 75 microm i.d., effective length 48.5 cm) and the effects of several important factors were investigated in detail. The results showed that beta-CD as a chiral selector exhibited good enantioselectivity and that the enantioseparation was greatly influenced by the structure of the diols, the borate concentration and the buffer pH. The optimum performance was obtained for the chiral vicinal diols under the conditions of 200 mM borate buffer of pH 9.8 containing 1.7% beta-CD at an applied voltage of 15 kV and a capillary temperature of 20 degrees C. Under the conditions, four diols were baseline separated with fast analysis time and the good theoretical plate numbers (above 10 x 10(4)) and favorable migration-time reproducibilities (RSDs below 3.0%) were obtained. The separation results were satisfactory. 相似文献
3.
Zusammenfassung Die Reaktion von 1-Nitroso-2-naphthol mit 1-und 2-Naphthol sowie die Reaktion von 2-Nitroso-1-naphthol mit 2-Naphthol in Äthanol und in Äther bei Anwesenheit von HNO3 gibt 5H-Dibenzo[a,j]phenoxazon-(5) (I), 5H-Dibenzo[a,j]phenoxazon-(5)-14-oxid (II), 5H-Dibenzo[a,h]phenoxazon-(5) (III) sowie 5H-Dibenzo[a,h]phenoxazon-(5)-14-oxid (IV). Es wurde ein Reaktionsmechanismus vorgeschlagen und die Konstitution der hergestellten Verbindungen spektrophotometrisch und potentiometrisch bestimmt.
Mit 4 Abbildungen 相似文献
The reaction of 1-nitroso-2-naphthol with 2-and 2-naphthol and the reaction of 2-nitroso-1-naphthol with 2-naphthol in ethanol or ether in the presence of nitric acid have been studied. The main reaction products isolated were the dibenzophenoxazones I–IV. The reaction mechanism for their formation is proposed.
Mit 4 Abbildungen 相似文献
4.
Seong J Rohrbacher A Li ZR Janda KC Tao FM Spiegelman F Halberstadt N 《The Journal of chemical physics》2004,120(16):7456-7463
The potential energy surface of He2Ne+ has been reinvestigated using a combination of ab initio and diatomics-in-molecule (DIM) calculations. In contrast to the reports of two recent studies the ion is found to have an asymmetric linear He-Ne-He structure, with no barrier to formation from the separated atoms on the ground-state surface. The He-Ne+ bond lengths at the potential minimum are 1.51 and 1.81 A, and the total bonding energy is 0.717 eV. Comparing the He2Ne+ energy to that of HeNe+, the bonding energy for the second helium atom is 0.06 eV, about 10% of that of the first He atom. The saddle point between the two equivalent minima is a symmetric structure, 0.0074 eV above the potential minimum. A symmetric geometry becomes the overall potential minimum if the 2s hole on the Ne is excluded from the reference states of a multireference configuration interaction calculation. A DIM potential was created for the HenNe+ family of ions. The DIM potential is consistent with the asymmetric He2Ne+ ion serving as a core; it predicts a slightly more asymmetric geometry than the ab initio results. Additional helium atoms form five-membered rings around the bonds of the core ion to fill the first shell and then add to the ends of the cluster. The asymmetric core ion and the highly compact structure help to account for the lack of apparent shell structure in the mass spectrometry of HenNe+ clusters. Finally, we recommend that the value De=0.63+/-0.04 eV be adopted for the ground state of HeNe+. 相似文献
5.
Zusammenfassung In dieser Arbeit wurden Schlußfolgerungen über den simultanen Verlauf der beiden Reduktionsphasen von Resazurin überprüft.Weiters wurden Bedingungen für die quantitative titanometrische Bestimmung von Resazurin und seiner Derivate ermittelt.
Mit 4 Abbildungen 相似文献
The conclusions about the simultaneous course of reduction of Resazurin to Resorufin and Resorufin to Dihidroresorufin were verified in this work.The conditions for the quantitative titanometric determination of Resazurin and its derivatives were found.
Mit 4 Abbildungen 相似文献
6.
Zusammenfassung Die Reaktion von 2-Nitroso-1-naphthol mit Resorcin bzw. Orcin in Äther bei Anwesenheit von HNO3 liefert Benzo[c]phenoxazon-(9) (I), Benzo[c]phenoxazon-(9)-12-oxid (II), Methyl-benzo[c]phenoxazon-(9) (III) sowie 11-Methyl-benzo[c]phenoxazon-(9)-12-oxid (IV). Die Struktur der isolierten Substanzen wurde durch Reduktion mittels TiCl3 sowie durch die UV- und IR-Spektren gestützt.
Mit 1 Abbildung 相似文献
The reaction of 2-nitroso-1-naphthol with resorcinol and orcinol in ether solution in the presence of nitric acid has been studied. From the reaction mixture the benzophenoxazones I–IV have been isolated. Structures were assigned on the grounds of UV and IR spectra and partly by using TiCl3 as a reducing agent.
Mit 1 Abbildung 相似文献
7.
Gholam H. Hakimelahi Min-Jen Shiao Jih Ru Hwu Hady Davari 《Helvetica chimica acta》1992,75(6):1840-1847
Syntheses of the cis-configurated isopenam 9 (Scheme 1), isocephem 14 (Scheme 2), and isocephem 19 (Scheme 3) are described. The key step in the preparation of 14 and 19 involved a Pummerer-type rearrangement of the corresponding sulfoxides 12 and 18 . These β-lactams were found to possess biological activity against several pathogenic microorganisms in vitro. The electronic activation of the lactam moiety of 19 remarkably enhanced its biological activity. A retinoic moiety was attached to 19 via an amino linker. The resultant retinamido-β-lactam 21 showed significant cytostatic activity in tracheal organ cultures obtained from vitamin-A-deficient hamsters. 相似文献
8.
Zusammenfassung 1,3-Dimethyl-4,5-diaminouracil (DAL) hat sich als sehr empfindliches Reagens zum selektiven Nachweis von Co2+-Ionen im stark alkalischen Medium einer Phosphatpufferlösung (pH=11,20) erwiesen. Es wurden vier Additionsverbindungen von DAL mit den Zentralatomen Cd(II), Pd(II), Ni(II) und Co(II) im Verhältnis Me DAL=1 2 hergestellt. Spektrophotometrische Untersuchungen weisen darauf hin, daß bei pH 6 bis 7 eine Komplexverbindung im Verhältnis CoDAL=12 gebildet wird.
Summary 1,3-dimethyl-4,5-diaminouracil (DAL) has been found to be a very sensitive reagent for the selective detection of Co2+ ions in strong alkaline medium of a phosphate buffer solution (pH=11.20). Four addition compounds of DAL with the central atoms Cd(II), Pd(II), Ni(II) and Co(II) with the ratio MeDal=12 have been prepared. Spectrophotometric studies indicate that at pH=6–7, complex compound is produced with the ratio CoDAL=12.相似文献
9.
Solid-phase spectrophotometric microdetermination of iron with ascorbic acid and ferrozine 总被引:1,自引:0,他引:1
M. L. Fernández-de Córdova A. Ruíz-Medina A. Molina-Díaz 《Analytical and bioanalytical chemistry》1997,357(1):44-49
A very sensitive and selective method for the determination of trace amounts of iron has been developed, based on the reduction
of Fe(III) to Fe(II) by ascorbic acid, followed by chromogenic chelation of Fe(II) with ferrozine. The complex Fe(II)-ferrozine
is easily sorbed on a dextran-type anion-exchange gel packed in a 1 mm cell, and the absorbance of the gel is measured directly
at 569 and 800 nm. The extended linear range of the determination is 0.5–10 ng ml-1 of iron (apparent molar absorptivity=4.4×107 l mol-1 cm-1) and the precision (RSD) 1.3% for a concentration of 5 ng ml-1 of iron (n=10). The detection limit for a sample volume of 1000 ml, using 0.040 g of anion-exchanger, corresponds to 0.12 ng ml-1. The method has been successfully applied to the determination of iron in natural and waste waters, wine, soil extract and
previously digested vegetal tissues, drugs and human hair.
Received: 20 November 1995/Revised: 23 January 1996/Accepted: 26 January 1996 相似文献
10.