全文获取类型
收费全文 | 4504篇 |
免费 | 626篇 |
国内免费 | 172篇 |
专业分类
化学 | 4403篇 |
晶体学 | 3篇 |
力学 | 24篇 |
综合类 | 23篇 |
数学 | 609篇 |
物理学 | 240篇 |
出版年
2024年 | 2篇 |
2023年 | 52篇 |
2022年 | 136篇 |
2021年 | 202篇 |
2020年 | 214篇 |
2019年 | 155篇 |
2018年 | 170篇 |
2017年 | 134篇 |
2016年 | 220篇 |
2015年 | 241篇 |
2014年 | 281篇 |
2013年 | 400篇 |
2012年 | 245篇 |
2011年 | 313篇 |
2010年 | 237篇 |
2009年 | 282篇 |
2008年 | 257篇 |
2007年 | 269篇 |
2006年 | 230篇 |
2005年 | 208篇 |
2004年 | 164篇 |
2003年 | 154篇 |
2002年 | 201篇 |
2001年 | 59篇 |
2000年 | 69篇 |
1999年 | 62篇 |
1998年 | 55篇 |
1997年 | 43篇 |
1996年 | 38篇 |
1995年 | 29篇 |
1994年 | 31篇 |
1993年 | 23篇 |
1992年 | 10篇 |
1991年 | 12篇 |
1990年 | 8篇 |
1989年 | 7篇 |
1988年 | 9篇 |
1987年 | 12篇 |
1986年 | 5篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 7篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1976年 | 2篇 |
1973年 | 2篇 |
1969年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有5302条查询结果,搜索用时 17 毫秒
91.
T. Raju K. Kulangiappar M. Anbu Kulandainathan A. Muthukumaran 《Tetrahedron letters》2005,46(41):7047-7050
Electrochemical bromination of toluene and substituted toluenes by two-phase electrolysis yields the corresponding α-brominated products. The reaction has been carried out in a single compartment cell with platinum electrodes at 0 °C in chloroform using an aqueous sodium bromide solution (60%) containing a catalytic amount of HBr. Two-phase electrolysis results in high yields (60-95%) of monobromo compounds with very high regioselectivity (>95%). 相似文献
92.
Natural products have been synthesized for billions of years in animals, plants, and microorganisms. As a rule they occur enantiomerically pure. Their chiral character corroborates their use in metabolism or as biologically active agents. Natural products may be insufficient in quality or quantity. They have recently begun to become accessible, either unchanged or modified, by biological synthesis; here, too, they are obtained enantiomerically pure. In the last twenty years chemical synthesis has become a major concern of organic chemists. Their target compounds are primarily enantiomerically pure natural products or biologically active variants thereof. 相似文献
93.
Quantum chemical calculations at mPW1PW91 level, with full geometry optimization, using the 6-31g(d) basis set, and GIAO (gauge including atomic orbitals) 13C NMR chemical shifts using the 6-31g(d,p) basis set, are here utilized as a support to define the configurational features of the natural product passifloricin A, whose previously proposed relative configuration has been recently shown, by synthetic studies, to be incorrect. This study suggests that the relative stereostructure for passifloricin A corresponds to the δ-lactone of the (5R,7R,9S,11R)-tetrahydroxyhexacos-2-enoic acid. 相似文献
94.
Francisco Sarabia 《Tetrahedron letters》2003,44(41):7671-7675
A synthetic approach to the [15]-membered stevastelins, a novel class of immunosuppressant agents, is reported based on a macrolactamization route to the 2,3-epoxy derivative 6. The synthesis of this compound was achieved via a stereoselective epoxidation of the allylic alcohol 13, followed by a coupling reaction with a variety of peptide derivatives to give the epoxy peptides 7-10. After an extensive study of cyclizations with these precursors, the best result was achieved with the macrolactamization of 8 in the presence of DEPC, to obtain the epoxy cyclic depsipeptide 6 in 42% yield. From this product, an epoxy analogue of stevastelin B, compound 27, was prepared. Finally, the synthesis of the natural product was attempted through the opening of the oxirane ring contained in 6 and 26, with a variety of methyl cuprate reagents, but without success. 相似文献
95.
C. C. Camarasu 《Chromatographia》2002,56(1):S131-S135
Summary A sensitive headspace SPME method for the extraction of residual solvents from pharmaceutical products has been developed
and optimized. It was found that minimizing sample and headspace volume has a beneficial effect on extraction efficiency.
At the same time the method reproducibility was seriously affected by reducing sample and headspace volume. The added air
volume was not found to have any significant influence on method sensitivity. The method showed reproducibilities of less
than 10% and detection limits as low as 1 ppb for benzene and dichloromethane. The headspace SPME method is around 1000 times
more sensitive than static headspace. The optimized parameters were headspace volume 1.5 mL, sample volume 10 μL, and extraction
time 30 min. The method was successfully applied to the identification of unknown residual solvents in three different proprietary
active drug substances and was successfully applied to the confirmation of the presence of benzene in a proprietary drug substance.
Presented at Balaton Symposium '01 on High-Performance Separation Methods, Siófok, Hungary, September 2–4, 2001 相似文献
96.
The introduction of quality standards for vegetable oil methyl esters is gaining in importance due to their increased use as diesel fuel substitutes and as technical products. Free and esterified sterols, the main constituents of the unsaponifiable matter in vegetable oils, are recovered in vegetable oil methyl esters and may influence the technical properties of vegetable oil methyl ester products. A rapid gas chromatographic method for the qualitative and quantitative determination of free and esterified sterols in vegetable oil methyl esters has therefore been developed. The concentration of the free sterols as well as their qualitative and quantitative composition and the concentration of the sterol esters have been determined in rape seed oil methyl ester samples by GC–FID. Prior to analysis, the free sterols were silylated with N,O-bis(trimethylsilyl)trifluoroacetamide with 1% of trimethylchlorosilane; betulinol was used as an internal standard. Calibration was performed by analysis of standard solutions containing β-sitosterol, cholesteryl stearate, and betulinol. The reproducibility of the quantitative results has been evaluated by repeated injections of the same test solution and by repeated complete analysis of the same sample. 相似文献
97.
F. Gugumus 《Polymer Degradation and Stability》2006,91(6):1346-1355
Most products formed on polyethylene oxidation result from hydroperoxide decomposition. The product yields can be calculated for various mechanisms of hydroperoxide decomposition. This work concerns the reaction of a hydroperoxide with an alcohol group thought to be dominant in the advanced stages of polyethylene processing in the high temperature range (170-200 °C). Besides hydrogen abstraction by caged alkoxy radicals already envisaged previously, the possibility of β-scission is taken into account. This additional reaction introduces significant complexity into the reaction schemes. This is especially so because additional caged radical pairs must be included into the schemes and the calculations. It becomes possible to calculate the yields of aldehyde and vinyl groups that do not result from hydroperoxide decomposition in the absence of β-scission. The yields of the main oxidation products such as alcohols and ketones are not much affected by taking into account β-scission. The yield of aldehydes is important in the whole temperature range and increases considerably if the temperature is raised from 170 to 200 °C. It becomes more important than the ketone yield. The vinyl groups are formed in amounts corresponding roughly to 10-15% of the trans-vinylene groups in the temperature range of 170-200 °C. 相似文献
98.
Drahl C Cravatt BF Sorensen EJ 《Angewandte Chemie (International ed. in English)》2005,44(36):5788-5809
Researchers in the post-genome era are confronted with the daunting task of assigning structure and function to tens of thousands of encoded proteins. To realize this goal, new technologies are emerging for the analysis of protein function on a global scale, such as activity-based protein profiling (ABPP), which aims to develop active site-directed chemical probes for enzyme analysis in whole proteomes. For the pursuit of such chemical proteomic technologies, it is helpful to derive inspiration from protein-reactive natural products. Natural products use a remarkably diverse set of mechanisms to covalently modify enzymes from distinct mechanistic classes, thus providing a wellspring of chemical concepts that can be exploited for the design of active-site-directed proteomic probes. Herein, we highlight several examples of protein-reactive natural products and illustrate how their mechanisms of action have influenced and continue to shape the progression of chemical proteomic technologies like ABPP. 相似文献
99.
This paper presents a simple, rapid and reproducible method of analysis of salbutamol in pharmaceutical products, utilizing batch injection analysis (BIA) associated with amperometric detection. A study of salbutamol oxidation demonstrated a strong dependence between electrode fouling and pH. All determinations were done utilizing a glassy carbon electrode in presence of 3.0 mol l−1 NaOH. A large linear dynamic range from 8×10−7 to 2×10−4 mol l−1 was obtained by using an injected volume of 100 μl with a detection limit of 2.5×10−7 mol l−1. R.S.D. of 0.92% for 50 successive injections of 4×10−6 mol l−1 of salbutamol and a sample throughput of 60 samples per hour were achieved. The method was applied for salbutamol quantification in syrups. 相似文献
100.
Shaofeng Zhang Yong-Seung Shin Richard Mayer Franco Basile 《Journal of Analytical and Applied Pyrolysis》2007,80(2):353-359
An on-probe pyrolyzer has been constructed and interfaced with desorption electrospray ionization (DESI) mass spectrometry (MS) for the rapid analysis of non-volatile pyrolysis products. The detection and analysis of non-volatile pyrolysis products of peptides, proteins and the synthetic polymer poly(ethylene glycol) were demonstrated with this instrument. The on-probe pyrolyzer can be operated off-line or on-line with the DESI source and was interfaced with a tandem MS (MS/MS) instrument, which allowed for structure characterization of the non-volatile pyrolytic products. Advantages of this system are its simplicity and speed of analysis since the pyrolysis is performed in situ on the DESI source probe and hence, it avoids extraction steps and/or the use of matrices (e.g., as in MALDI–MS analyses). 相似文献