全文获取类型
收费全文 | 1398篇 |
免费 | 43篇 |
国内免费 | 1篇 |
专业分类
化学 | 839篇 |
晶体学 | 12篇 |
力学 | 43篇 |
数学 | 103篇 |
物理学 | 445篇 |
出版年
2022年 | 11篇 |
2021年 | 16篇 |
2020年 | 18篇 |
2019年 | 21篇 |
2018年 | 10篇 |
2016年 | 19篇 |
2015年 | 23篇 |
2014年 | 28篇 |
2013年 | 63篇 |
2012年 | 61篇 |
2011年 | 70篇 |
2010年 | 48篇 |
2009年 | 33篇 |
2008年 | 75篇 |
2007年 | 80篇 |
2006年 | 78篇 |
2005年 | 61篇 |
2004年 | 61篇 |
2003年 | 48篇 |
2002年 | 37篇 |
2001年 | 30篇 |
2000年 | 25篇 |
1999年 | 12篇 |
1998年 | 8篇 |
1997年 | 20篇 |
1996年 | 11篇 |
1995年 | 23篇 |
1994年 | 32篇 |
1993年 | 36篇 |
1992年 | 17篇 |
1991年 | 13篇 |
1990年 | 22篇 |
1989年 | 18篇 |
1988年 | 14篇 |
1987年 | 11篇 |
1986年 | 12篇 |
1985年 | 13篇 |
1984年 | 22篇 |
1983年 | 14篇 |
1982年 | 21篇 |
1981年 | 17篇 |
1980年 | 12篇 |
1979年 | 12篇 |
1978年 | 22篇 |
1977年 | 14篇 |
1976年 | 25篇 |
1975年 | 14篇 |
1974年 | 19篇 |
1973年 | 11篇 |
1972年 | 10篇 |
排序方式: 共有1442条查询结果,搜索用时 15 毫秒
1.
2.
[3,3]-Sigmatropic rearrangements of allyl tetronates and allyl tetramates to give 3-allyltetronic or -tetramic acids, respectively, proceed within 20-60 min under microwave irradiation (300 W, 130-190 °C). Consecutive (homo)sigmatropic [1,5] H-shifts such as oxa-ene reactions are promoted less effectively, which allows the isolation of Claisen intermediates of sigmatropic domino sequences, in contrast to conventional heating. 相似文献
3.
Isabel Cristina S. F. Jardim Kenneth E. Collins Carol H. Collins 《Microchemical Journal》2004,77(2):191-198
Polysiloxanes immobilized onto the surfaces of porous silica particles have proven to be good stationary phases for the separation of multiresidues of pesticides and their metabolic/degradation products by reversed-phase high-performance liquid chromatography (RP-HPLC). Similar materials have proven effective for pre-concentration and clean-up procedures using solid phase extraction. The present paper describes the preparation and some applications of several of these packing materials. 相似文献
4.
Summary Six commercial hydrogen standards containing helium, oxygen, nitrogen, methane and carbon dioxide at trace levels were analyzed
by gas chromatography, for periods up to 105 days. The concentrations, in the range of 0–120 μmol mol−1, were stable (with the exception of oxygen) but often significantly different from the certified values provided by the suppliers,
especially for helium, oxygen and nitrogen. Concurrently, some experiments were carried out to verify the stability of gas
mixtures based on hydrogen stored in cylinders submitted to different chemical and physical treatments. The causes that led
to the deviations observed, as well as the decreases in oxygen, are discussed.
Presented at the 21st ISC held in Stuttgart, Germany, 15th–20th September, 1996. 相似文献
5.
6.
7.
Copolymerization of vinyl acetate with allyl carbonates that contain isopropyl groups yields highly branched poly(vinyl acetates). 相似文献
8.
Yan B Collins N Wheatley J Irving M Leopold K Chan C Shornikov A Fang L Lee A Stock M Zhao J 《Journal of combinatorial chemistry》2004,6(2):255-261
We have developed a high-throughput purification system to purify combinatorial libraries at a 50-100-mg scale with a throughput of 250 samples/instrument/day. We applied an accelerated retention window method to shorten the purification time and targeted one fraction per injection to simplify data tracking, lower QC workload, and simplify the postpurification processing. First, we determined the accurate retention time and peak height for all compounds using an eight-channel parallel LC/UV/MS system, and calculated the specific preparative HPLC conditions for individual compounds. The preparative HPLC conditions include the compound-specific gradient segment for individual compounds with a fixed gradient slope and the compound-specific UV or ELSD threshold for triggering a fraction collection device. A unique solvent composition or solvent strength was programmed for each compound in the preparative HPLC in order to elute all compounds at the same target time. Considering the possible deviation of the predicted retention time, a 1-min window around the target time was set to collect peaks above a threshold based on UV or ELSD detection. Dual column preparative instruments were used to maximize throughput. We have purified more than 500 000 druglike compounds using this system in the past 3 years. We report various components of this high-throughput purification system and some of our purification results. 相似文献
9.
Daniel E. Lynch Gillian E. Spicer Ian Mcclenaghan 《Journal of heterocyclic chemistry》2005,42(7):1363-1368
Three α‐phenylmalonamides have been prepared by the selective nucleophilic cleavage of 5,7‐dimethyl‐2‐phenyl‐1‐oxo‐1H‐pyrazolo[1,2‐a]pyrazol‐4‐ylium‐3‐olate in solventless microwave syntheses. The three weak nucleophiles employed were aniline, p‐chloroaniline and m‐toluidine. The α‐phenylmalonamides of these three aniline derivatives could not be prepared using the previously reported solvent syntheses via 3‐oxopyrazolo[1,2‐a]pyrazol‐8‐ylium‐1‐olates. All products were characterised using, infrared spectroscopy, 1H nmr and electrospray mass spectrometry. The single crystal X‐ray structures of the starting pyrazolo‐[1,2‐a]pyrazole and α‐phenylmalon‐m‐toluidide are also reported. 相似文献
10.
A highly sensitive and selective liquid chromatography-mass spectrometry (LC-MS) method has been developed for the determination of epirubicin in serum and cell specimens using daunorubicin as an internal standard. Using atmospheric pressure chemical ionisation (APCI), the epirubicin metabolites were readily distinguishable by their fragmentation pattern in the mass spectrometer. Selected reaction monitoring (SRM) mode was employed for quantitation of epirubicin and the metabolites. Following extraction, chromatography was performed on a C18 column with a mobile phase consisting of water-acetonitrile-formic acid, pH 3.2, with a flow rate of 200 μl/min. The limit of detection (LOD) and the limit of quantitation (LOQ) of this method in serum were determined to be 1.0 and 2.5 ng/ml, respectively. Linearity of the method was verified over the concentration range of 2.5-2000 ng/ml, with a high correlation coefficient (R2 ≥ 0.998). For the extraction procedure, an aliquot of 500 μl serum, spiked with internal standard, was extracted using a chloroform-2-isopropanol (2:1, v/v) mixture. The method has been applied to the analysis of epirubicin in cancer cell samples and the identification of known and unknown metabolites in clinical trial patient serum samples. 相似文献