全文获取类型
收费全文 | 457篇 |
免费 | 23篇 |
国内免费 | 4篇 |
专业分类
化学 | 378篇 |
力学 | 11篇 |
数学 | 55篇 |
物理学 | 40篇 |
出版年
2023年 | 6篇 |
2022年 | 4篇 |
2021年 | 6篇 |
2020年 | 9篇 |
2019年 | 12篇 |
2018年 | 5篇 |
2017年 | 10篇 |
2016年 | 9篇 |
2015年 | 8篇 |
2014年 | 21篇 |
2013年 | 19篇 |
2012年 | 24篇 |
2011年 | 32篇 |
2010年 | 16篇 |
2009年 | 22篇 |
2008年 | 34篇 |
2007年 | 29篇 |
2006年 | 30篇 |
2005年 | 33篇 |
2004年 | 13篇 |
2003年 | 28篇 |
2002年 | 22篇 |
2001年 | 5篇 |
2000年 | 7篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 9篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 4篇 |
1989年 | 3篇 |
1982年 | 1篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1960年 | 1篇 |
1959年 | 1篇 |
1898年 | 3篇 |
1881年 | 1篇 |
排序方式: 共有484条查询结果,搜索用时 171 毫秒
361.
The ion chromatography of chloro complexes of Au(III), Ir(IV), Ir(III), Os(IV), Pd(II), Pt(IV), Rh(III) and Ru(III) was investigated using anion-exchange and ion-interaction techniques involving silica-based phases. Chloride was either absent or at a very low level and the pH was high enough to enable steel-fabricated liquid chromatography equipment to be used. With anion exchange, Ir(IV), Ir(III), Os(IV) and Pt(IV) gave good stable chromatography and all produced linear calibration plots, except Ir(IV) owing to instability of the sample solution. The detection limits were Ir(III) 5, Os(IV) 10 and Pt(IV) 2 ng ml?1. The ion-interaction technique was not so successful, only Au(III) and Pd(II) giving stable chromatography. The calibration plots were slightly curved, although acceptable, and the detection limits were 10 and 30 ng ml?1 for Au (III) and Pd(II), respectively. 相似文献
362.
We have gained some insight into the role of conformational effects on the regioselectivity of the macrocyclic intramolecular nitrile oxide cycloaddition observed in our (+)-brefeldin A synthesis. During the course of this regiochemical study, we have developed two novel stereoselective and regioselective schemes for total synthesis of (+)-brefeldin A (i.e. intramolecular nitrile oxide cycloaddition-isomerization and intermolecular nitrile oxide cycloaddition-ring closing metathesis strategies). 相似文献
363.
Milton M. Takeguchi Lynn B. Simpson David K. Smith Leroy R. Morse W. Scott Ramsey Ralph A. Messing Phil J. Martin Bhav P. Sharma 《Applied biochemistry and biotechnology》1981,6(4):273-282
The feasibility of using columnar reactors containing immobilized microorganisms for the rapid estimation of BOD was demonstrated
in this study. Dilutions of three types of industrial effluents were tested by the BOD5 test and by this experimental system. A high degree of correlation (r = 0.98) was observed between results of the two tests. The mean standard error of estimation of the experimental system was
11%. 相似文献
364.
365.
366.
The chromatographic behaviour of selected transition and heavy metal ions, the lanthanides, uranium and aluminium, on a neutral polystyrene-divinylbenzene (PS-DVB) stationary phase (7 microm Hamilton PRP-1) dynamically modified with 4-chlorodipicolinic acid, was investigated to evaluate retention characteristics. Complicated retention factor against pH plots were found for these metals demonstrating changes in retention order. It was concluded that complexation between the metal ions and the ligand adsorbed on the resin was strongly influenced by the decrease in dynamic loading with increase in pH, coinciding with changes in the metal-to-ligand ratio in the mobile phase. Possible reversed-phase interactions between metal-chlorodipicolinic acid complexes and the hydrophobic PS-DVB stationary phase also could not be ruled out. An eluent of 0.25 mM chlorodipicolinic acid, I M potassium nitrate at pH 2.2 was suitable for the separation of seven transition and heavy metal ions in under 20 min on a 250 x 4.6 mm column (with 50-mm guard column), determined in a certified water sample with good accuracy (R2 > or = 0.994) and reproducibility (RSD 1-4.2%). Pb(II), Cd(II) and Cu(II) were additionally analysed in <10 min in a more complicated certified rice flour matrix, using the same eluent but adjusted to pH 1.5, again with good accuracy (R2 > or = 0.998) and reproducibility (RSD 0.48-1.38%). 相似文献
367.
This full account presents the background on, discovery of, and extensive insight that has been gained into the oxidative intermolecular coupling of two different carbonyl species. Optimization of this process has culminated in reliable and scalable protocols for the union of amides, imides, ketones, and oxindoles using soluble copper(II) or iron(III) salts as oxidants. Extensive mechanistic studies point to a metal-chelated single-electron-transfer process in the case of copper(II), while iron(III)-based couplings appear to proceed through a non-templated heterodimerization. This work presents the most in-depth findings on the mechanism of oxidative enolate coupling to date. The scope of oxidative enolate heterocoupling is extensive (40 examples) and has been shown to be efficient even on a large scale (gram-scale or greater). Finally, the method has been applied to the total synthesis of the unsymmetrical lignan lactone (-)-bursehernin and a medicinally important 2,3-disubstituted succinate derivative. 相似文献
368.
Won Kon Kim Hyang-Ran Hwang Do Hyung Kim Phil Young Lee Yu Jung In Hye-Young Ryu Sung Goo Park Kwang-Hee Bae Sang Chul Lee 《Experimental & molecular medicine》2008,40(6):677-685
Atopic dermatitis (AD) is an inflammatory skin disorder that is both uncomfortable and distressing to patients, and its prevalence has been steadily increasing. It is obvious that the identification of efficient markers of AD in plasma would offer the possibility of effective diagnosis, prevention, and treatment strategies. In this study, a proteomic approach was used to analyze plasma glycoproteins from both children with AD and healthy child donors. Several protein spots showing significant quantitative changes in the AD patients were identified. Through sequential studies, it was confirmed that CD5L and ApoE were significantly up-regulated or down-regulated, respectively, in the plasma from AD patients compared with that from healthy donors. In addition, we suggest that the up-regulated CD5L in AD patients causes eosinophilia by inhibiting apoptosis or promoting the proliferation of eosinophils either in combination with or without IL-5. The glycoproteomic data in this study provides clues to understanding the mechanism of atopic alterations in plasma and suggests AD-related proteins can be used as candidate markers for AD. 相似文献
369.
Phil M. Oger I. Daniel A. SimionoviciA. Picard 《Spectrochimica Acta Part B: Atomic Spectroscopy》2008
X-ray spectroscopies are very powerful tools to determine the chemistry of complex dilute solutes in abiotic and biotic systems. We have assayed their suitability to monitor the chemistry of complex solutions in a live biotic system. The impact of the probe on cells was quantified for 4 different cellular organisms differing in their resistance level to environmental stresses. We show that none of the organisms tested can survive the radiation doses needed for the acquisition of meaningful spectroscopic data. Therefore, on one hand, X-ray spectroscopy cannot be applied to the monitoring of single cells, and cellular damages have to be taken into account in the interpretation of the evolution of such systems. On the other hand, due to the limited extension of X-ray induced cellular damages in the culture volume, it is possible to probe a population of live cells provided that the culture to beam probe ratio is large enough to minimize the impact of mortality on the evolution of the biological system. Our results suggest that it could be possible to probe the volume in the close vicinity of a cell without affecting its activity. Using this setup we could monitor the reduction of selenite by the X-ray sensitive bacterium, Agrobacterium tumefaciens strain C58, for 24 h. This method has a great potential to monitor the respiration of various metals, such as iron, manganese and arsenic, in situ under relevant environmental conditions by live microorganisms. 相似文献
370.
The neutral zirconium(IV) bis(thiophosphinic amidate) complex was demonstrated to be an effective precatalyst for 5-exo-, 6-exo-, and 7-exo-dig intramolecular hydroamination of aminoalkynes, producing the cyclic imines in excellent yields (92-98%). 相似文献