全文获取类型
收费全文 | 927篇 |
免费 | 43篇 |
国内免费 | 7篇 |
专业分类
化学 | 607篇 |
晶体学 | 3篇 |
力学 | 35篇 |
数学 | 197篇 |
物理学 | 135篇 |
出版年
2023年 | 8篇 |
2022年 | 8篇 |
2021年 | 19篇 |
2020年 | 29篇 |
2019年 | 22篇 |
2018年 | 11篇 |
2017年 | 11篇 |
2016年 | 29篇 |
2015年 | 32篇 |
2014年 | 28篇 |
2013年 | 50篇 |
2012年 | 53篇 |
2011年 | 80篇 |
2010年 | 33篇 |
2009年 | 44篇 |
2008年 | 66篇 |
2007年 | 63篇 |
2006年 | 49篇 |
2005年 | 44篇 |
2004年 | 53篇 |
2003年 | 40篇 |
2002年 | 39篇 |
2001年 | 11篇 |
2000年 | 16篇 |
1999年 | 10篇 |
1998年 | 3篇 |
1997年 | 9篇 |
1996年 | 15篇 |
1995年 | 13篇 |
1994年 | 20篇 |
1993年 | 9篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1988年 | 2篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 7篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1976年 | 4篇 |
1974年 | 2篇 |
1971年 | 2篇 |
1970年 | 1篇 |
1969年 | 3篇 |
1968年 | 1篇 |
1937年 | 1篇 |
排序方式: 共有977条查询结果,搜索用时 15 毫秒
141.
Tsikouris O Bartl T Tousek J Lougiakis N Tite T Marakos P Pouli N Mikros E Marek R 《Magnetic resonance in chemistry : MRC》2008,46(7):643-649
Substituted pyrazolopyridines are potent inhibitors of phosphodiesterases and cyclin-dependent kinases. In this study, NMR was used to investigate the potential N1-H and N2-H tautomerism of 5-substituted pyrazolo[3,4-c]pyridine derivatives. Six compounds were fully characterized by using (1)H, (13)C, and (15)N chemical shifts and indirect (1)H--(13)C and (1)H--(15)N coupling constants. The (1)H NMR spectra were measured over a broad range of temperatures. All of the compounds were shown to exist predominantly in the N1-H tautomeric form. Complementary quantum-chemical calculations of the chemical shieldings and indirect spin-spin couplings support the structural conclusions drawn. 相似文献
142.
Antonio C Larson T Gilday A Graham I Bergström E Thomas-Oates J 《Rapid communications in mass spectrometry : RCM》2008,22(9):1399-1407
This work describes the development and application of an on-line liquid chromatography/mass spectrometry (LC/MS) method using hydrophilic interaction chromatography (HILIC) coupled to negative ion mode electrospray ionisation ion trap mass spectrometry (ESI-MS) for the analysis of highly polar carbohydrate-related metabolites commonly found in plants, ranging from reducing and non-reducing sugars and sugar alcohols to sugar phosphates. Using this method, separation and detection of a mixture of eight authentic standard compounds containing glucose (Glc), sucrose (Suc), raffinose, verbascose, mannitol, maltitol, glucose-6-phosphate (Glc6P) and trehalose-6-phosphate (Tre6P) were achieved in less than 15 min. The method is rapid, robust, selective, and sensitive, with limits of detection (LODs) ranging from 0.2 microM obtained for neutral sugars, to 1.0 microM obtained for sugar alcohols, and 2.0 microM obtained for negatively charged sugar phosphates. We have studied the negative ion collision-induced dissociation (CID) fragmentation behaviour of the non-reducing raffinose family oligosaccharides (RFOs) raffinose, stachyose, and verbascose. Mainly Bi and Ci glycosidic and Ai cross-ring structurally informative cleavages are observed. We have applied this HILIC/ESI-MS method for the analysis of Arabidopsis thaliana wild-type Columbia-0 (Col-0) and its starchless phosphoglucomutase mutant (pgm1) leaf extracts. The method was used to quantify Glc, Suc, raffinose, and Glc6P in A. thaliana extracts. Data obtained using this HILIC/ESI-MS method were compared with those obtained using a comparable porous graphitic carbon-based LC/ESI-MS method. 相似文献
143.
Hopley C Bristow T Lubben A Simpson A Bull E Klagkou K Herniman J Langley J 《Rapid communications in mass spectrometry : RCM》2008,22(12):1779-1786
Product ion spectra produced by collision-induced dissociation (CID) in tandem mass spectrometry experiments can differ markedly between instruments. There have been a number of attempts to standardise the production of product ion spectra; however, a consensus on the most appropriate approach to the reproducible production of spectra has yet to be reached. We have previously reported the comparison of product ion spectra on a number of different types of instruments - a triple quadrupole, two ion traps and a Fourier transform ion cyclotron resonance mass spectrometer (Bristow AWT, Webb KS, Lubben AT, Halket JM. Rapid Commun. Mass Spectrom. 2004; 18: 1). The study showed that a high degree of reproducibility was achievable. The goal of this study was to improve the comparability and reproducibility of CID product ion mass spectra produced in different laboratories and using different instruments. This was carried out experimentally by defining a spectral calibration point on each mass spectrometer for product ion formation. The long-term goal is the development of a universal (instrument independent) product ion mass spectral library for the identification of unknowns.The spectra of 48 compounds have been recorded on eleven mass spectrometers: six ion traps, two triple quadrupoles, a hybrid triple quadrupole, and two quadrupole time-of-flight instruments. Initially, 4371 spectral comparisons were carried out using the data from eleven instruments and the degree of reproducibility was evaluated. A blind trial has also been carried out to assess the reproducibility of spectra obtained during LC/MS/MS.The results suggest a degree of reproducibility across all instrument types using the tuning point technique. The reproducibility of the product ion spectra is increased when comparing the tandem in time type instruments and the tandem in space instruments as two separate groups. This may allow the production of a more limited, yet useful, screening library for LC/MS/MS identification using instruments of the same type from different manufacturers. 相似文献
144.
Neverov AA Liu CT Bunn SE Edwards D White CJ Melnychuk SA Brown RS 《Journal of the American Chemical Society》2008,130(20):6639-6649
The di-Zn(II) complex of 1,3-bis[ N1, N1'-(1,5,9-triazacyclododecyl)]propane with an associated methoxide ( 3:Zn(II) 2: (-)OCH 3) was prepared and its catalysis of the methanolysis of a series of fourteen methyl aryl phosphate diesters ( 6) was studied at s (s)pH 9.8 in methanol at 25.0 +/- 0.1 degrees C. Plots of k obs vs [ 3:Zn(II) 2: (-)OCH 3] free for all members of 6 show saturation behavior from which K(M) and kcat (max) were determined. The second order rate constants for the catalyzed reactions (kcat (max)/K(M)) for each substrate are larger than the corresponding methoxide catalyzed reaction (k 2 (-OMe)) by 1.4 x 10(8) to 3 x 10 (9)-fold. The values of k cat (max) for all members of 6 are between 4 x 10(11) and 3 x 10(13) times larger than the solution reaction at s (s)pH 9.8, with the largest accelerations being given for substrates where the departing aryloxy unit contains ortho-NO 2 or C(O)OCH 3 groups. Based on the linear Br?nsted plots of k cat (max) vs s (s)pKa of the phenol, beta lg values of -0.57 and -0.34 are determined respectively for the catalyzed methanolysis of "regular" substrates that do not contain the ortho-NO 2 or C(O)OCH 3 groups, and those substrates that do. The data are consistent with a two step mechanism for the catalyzed reaction with rate limiting formation of a catalyst-coordinated phosphorane intermediate, followed by fast loss of the aryloxy leaving group. A detailed energetics calculation indicates that the catalyst binds the transition state comprising [CH 3O (-): 6], giving a hypothetical [ 3:Zn(II) 2:CH 3O (-): 6] complex, by -21.4 to -24.5 kcal/mol, with the strongest binding being for those substrates having the ortho-NO 2 or C(O)OCH 3 groups. 相似文献
145.
Manganese silicalite-2 was synthesized at high pH using the molecular cluster Mn 12O 12(O 2CCH 3) 16 as a Mn source. The silicalite-2 (ZSM-11) materials were synthesized using 3,5-dimethyl- N, N-diethylpiperdinium hydroxide as a structure-directing agent to produce phase-pure ZSM-11 materials. No precipitation of manganese hydroxide was observed, and synthesis resulted in the incorporation of up to 2.5 mol % Mn into the silicalite-2 with direct substitution into the framework verified by the linear relationship between the unit cell volume and loading. The Mn is reduced to Mn (II) during hydrothermal synthesis and incorporated into the silicalite-2 framework during calcination at 500 degrees C. Further calcination at 750 degrees C does not affect the crystallinity but oxidizes essentially all of the Mn (II) to Mn (III) in the framework. The large difference in oxidation temperatures between the II and III oxidation states provides a means of producing relatively pure manganese(II) and manganese(III) silicalite-2 materials for applications such as catalysis. 相似文献
146.
Palladium-catalyzed Negishi cross-coupling involving primary and secondary alkyls, even in the presence of beta-H, can be achieved at ambient temperature using chelating ligands containing a phosphine and an electron-deficient olefin. The superior effects of the ligands were shown not only in the desired cross-coupling product yields but also in the fast reaction at mild conditions. This reaction has been also scaled up to 50 g in 0.005 mol % catalyst (20,000 TONs) at room temperature. 相似文献
147.
148.
"Microfluidic drifting"--implementing three-dimensional hydrodynamic focusing with a single-layer planar microfluidic device 总被引:2,自引:0,他引:2
We introduce a novel fluid manipulation technique named "microfluidic drifting" to enable three-dimensional (3D) hydrodynamic focusing with a simple single-layer planar microfluidic device. 相似文献
149.
[reaction: see text] beta-C-galacto-Pyranosides with CHF and CF2 substitutes for the glycosidic oxygen were prepared through a four-step sequence starting from a central 1-thio-1,2-O-isopropylidene acetal alcohol and different alpha-fluoro- and alpha,alpha-difluoro acids. The key step in the synthesis is the oxocarbenium cyclization of an intermediate enol ether-thioacetal to a C1-substituted glycal. 相似文献
150.