全文获取类型
收费全文 | 442篇 |
免费 | 15篇 |
专业分类
化学 | 376篇 |
晶体学 | 1篇 |
力学 | 5篇 |
数学 | 12篇 |
物理学 | 63篇 |
出版年
2023年 | 3篇 |
2021年 | 6篇 |
2020年 | 2篇 |
2019年 | 11篇 |
2018年 | 5篇 |
2016年 | 11篇 |
2015年 | 5篇 |
2014年 | 11篇 |
2013年 | 19篇 |
2012年 | 17篇 |
2011年 | 37篇 |
2010年 | 25篇 |
2009年 | 19篇 |
2008年 | 42篇 |
2007年 | 30篇 |
2006年 | 24篇 |
2005年 | 28篇 |
2004年 | 17篇 |
2003年 | 19篇 |
2002年 | 26篇 |
2001年 | 4篇 |
2000年 | 8篇 |
1999年 | 5篇 |
1996年 | 5篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 6篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 6篇 |
1974年 | 5篇 |
1973年 | 9篇 |
1970年 | 2篇 |
1969年 | 2篇 |
1968年 | 1篇 |
1967年 | 1篇 |
排序方式: 共有457条查询结果,搜索用时 0 毫秒
91.
Horikiri H Hirano N Tanaka Y Oishi J Hatakeyama H Kawamura K Nagase H 《Chemical & pharmaceutical bulletin》2004,52(6):664-669
Syntheses of 10-oxo, 10alpha-hydroxy, and 10beta-hydroxy derivatives of a potent kappa-opioid receptor selective agonist, TRK-820, are described. These derivatives were supposed to be potential degradation products in formulation of TRK-820 as a result of autoxidation. 10-Oxo-TRK-820 11 was derived from 10-oxo-4,5-epoxymorphinan 14 in 10 steps in 32% overall yield. Reduction of the 10-oxo group in 4,5-epoxymorphinan with NaBH(4) gave 10beta-hydroxy-4,5-epoxymorphinan, exclusively. A stepwise inversion method of the 10beta-hydroxy group to produce 10alpha-hydroxy-4,5-epoxymorphinan was established. By HPLC analyses, 10alpha-hydroxy-TRK-820 12 was confirmed to be one of the degradation products in developing formulation of TRK-820. 相似文献
92.
Validation of real-time PCR analyses for line-specific quantitation of genetically modified maize and soybean using new reference molecules 总被引:12,自引:0,他引:12
Shindo Y Kuribara H Matsuoka T Futo S Sawada C Shono J Akiyama H Goda Y Toyoda M Hino A 《Journal of AOAC International》2002,85(5):1119-1126
Novel analytical methods based on real-time quantitative polymerase chain reactions by use of new reference molecules were validated in interlaboratory studies for the quantitation of genetically modified (GM) maize and soy. More than 13 laboratories from Japan, Korea, and the United States participated in the studies. The interlaboratory studies included 2 separate stages: (1) measurement tests of coefficient values, the ratio of recombinant DNA (r-DNA) sequence, and endogenous DNA sequence in the seeds of GM maize and GM soy; and (2) blind tests with 6 pairs of maize and soy samples, including different levels of GM maize or GM soy. Test results showed that the methods are applicable to the specific quantitation of the 5 lines of GM maize and one line of GM soy. After statistical treatment to remove outliers, the repeatability and reproducibility of these methods at a level of 5.0% were <13.7 and 15.9%, respectively. The quantitation limits of the methods were 0.50% for Bt11, T25, and MON810, and 0.10% for GA21, Event176, and Roundup Ready soy. The results of blind tests showed that the numerical information obtained from these methods will contribute to practical analyses for labeling systems of GM crops. 相似文献
93.
Imamura K Tada Y Tanaka H Sakiyama T Nakanishi K 《Journal of colloid and interface science》2002,250(2):409-414
We have developed here for the first time a novel method to generate hydroxyl radicals, *OH, by applying slightly negative electric potentials (-0.2--0.8 V vs Ag/AgCl) to the surface of a metal (or metal oxide) that is in contact with hydrogen peroxide solution containing a supporting electrolyte. Namely, *OH radicals were generated at the surface by the electrolysis of hydrogen peroxide according to the equation, H2O2+e- --> *OH+OH-. This method was used to clean a stainless steel fouled with a model protein, beta-lactoglobulin. The *OHs generated at the surface were effective in removing beta-lactoglobulin that had been irreversibly adsorbed, by several minutes of treatment at room temperature (22+/-2 degrees C). The removal rates measured for various concentrations of H2O2 and supporting electrolyte and different potentials were determined exclusively by the electric current. 相似文献
94.
Partition efficiency of the high-pitch locular multilayer coil was evaluated in countercurrent chromatographic (CCC) separation of proteins with an aqueous-aqueous polymer phase system using the small-scale cross-axis coil planet centrifuge (X-axis CPC) fabricated in our laboratory. The separation column was specially made by high-pitch (ca 5 cm) winding of 1.0 mm I.D., 2.0 mm O.D. locular tubing compressed at 2 cm intervals with a total capacity of 29.5 mL. The protein separation was performed using a set of stable proteins including cytochrome C, myoglobin, and lysozyme with the 12.5% (w/w) polyethylene glycol (PEG) 1000 and 12.5% (w/w) dibasic potassium phosphate system (pH 9.2) under 1000 rpm of column revolution. This high-pitch locular tubing yielded substantially increased stationary phase retention than the normal locular tubing for both lower and upper mobile phases. In order to demonstrate the capability of the high-pitch locular tubing, the purification of collagenase from the crude commercial sample was carried out using an aqueous-aqueous polymer phase system. Using the 16.0% (w/w) PEG 1000 - 6.3% (w/w) dibasic potassium phosphate - 6.3% (w/w) monobasic potassium phosphate system (pH 6.6), collagenase I, II, V and X derived from Clostridium hystolyticum were separated from other proteins and colored small molecular weight compounds present in the crude commercial sample, while collagenase N-2 and S-1 from Streptomyces parvulus subsp. citrinus were eluted with impurities at the solvent front with the upper phase. The collagenase from C. hystolyticum retained its enzymatic activity in the purified fractions. The overall results demonstrated that the high-pitch locular multilayer coil is effectively used for the CCC purification of bioactive compounds without loss of their enzymatic activities. 相似文献
95.
Matsunaga Y Takechi K Akasaka T Ramesh AR James PV Thomas KG Kamat PV 《The journal of physical chemistry. B》2008,112(46):14539-14547
An oligophenyleneethynylene (OPE), 1,4-bis(phenyleneethynyl)-2,5-bis(hexyloxy)benzene (2), is coupled with pyrene to extend the conjugation and allow its use as a light-harvesting molecule [Py-OPE (1)]. The absorption and emission maxima of 1 are red-shifted compared to those of 2. Similar differences in the singlet and triplet excited-state properties are evident. The fluorescence yield of 2 in toluene is 0.53, which is slightly less than the value for the parent OPE (2) of 0.66. The excited singlet and triplet of 1 as characterized from transient absorption spectroscopy exhibit lifetimes of 1.07 ns and 4.0 micros, respectively, in toluene. When 1 was cast as a film on a glass electrode (OTE) and excited with a 387-nm laser pulse, we observed the formation of excitons that decayed within a few picoseconds. When 1 was cast as a film on a SnO2-modified conducting glass electrode (OTE/SnO2), a small fraction of excitons dissociated to produce a long-lived charge-separated state. The role of the SnO2 interface in promoting charge separation was inferred from the photoelectrochemical measurements. Under visible light excitation, the OTE/SnO2 electrode was capable of generating photocurrent (approximately 0.25 mA/cm2) with an incident photon conversion efficiency (IPCE) of approximately 6%. 相似文献
96.
Endo H Hayashi Y Kitani Y Ren H Hayashi T Nagashima Y 《Analytical and bioanalytical chemistry》2008,391(4):1255-1261
l-Lysine (l-Lys) in living bodies is critical for metabolism; therefore, determination of its levels in food is important. Most enzymatic
methods for l-Lys analysis are performed using l-lysine oxidase (LyOx), but commercially manufactured LyOx is generally not highly selective for l-Lys among amino acids. We previously isolated LyOx as an antibacterial protein secreted from the skin of the rockfish Sebastes schlegeli. In the present study, we developed an optical enzyme sensor system for rapid and continuous determination of l-Lys using this LyOx. The system comprised an immobilized LyOx membrane, an optical oxygen probe, a flow system, and a personal
computer. The amount of l-Lys was detected as a decrease in the oxygen concentration due to the LyOx reaction. The specificity of the sensor was examined
against various amino acids. The sensor response was specific for l-Lys. Good reproducibility was obtained in 58 assays. The response of the sensor using commercially prepared LyOx was unstable
compared with the response using LyOx isolated in our laboratory. Our sensor system could be used for 5 weeks without our
having to change the enzyme membrane. The calibration curve for a standard l-Lys solution was linear from 0.1 to 3.0 mmol L−1. One assay could be completed within 2 min. The sensor was applied to determine the l-Lys content in food samples such as bonito cooking water and scallop hepatopancreas. The values obtained using the sensor
and conventional high-performance liquid chromatography methods were well correlated. 相似文献
97.
Ferrocene, a double-decker organometallic compound that generates angular motion, can be used as a unique rotary module for molecular machines. By interlocking a ferrocene-based rotary module with a photochromic unit, we have developed novel molecular machines that operate via power-conversion mechanisms. This design strategy, which mimics real machines in our daily life, allows for remote control of molecular events. 相似文献
98.
Yuji TanakaTakeshi Yamada Yasuko InOsamu Muraoka Tetsuya KajimotoReiko Tanaka 《Tetrahedron》2011,67(4):782-792
A new gedunin, three new mexicanolides and three new phragmalin-type limonoids named Andirolides A (1), B (2), C (3), D (4), E (5), F (6), and G (7) were isolated from oil of the flower of Carapa guianensis Aublet (Meliaceae). Their absolute stereostructures were determined by 2D NMR and CD spectra, and single-crystal X-ray analysis, and all compounds were confirmed to have the C-17βH configuration. Considering the similarity in CD spectra between Andirolide G (7) and the xyloccensins reported by Wu, we concluded that the structures of xyloccensins should be revised so as to have the absolute configuration of 17R. 相似文献
99.
100.
Susanne Baldermann Peter Fleischmann Mareike Bolten Naoharu Watanabe Peter Winterhalter Yoichiro Ito 《Journal of chromatography. A》2009,1216(19):4263-4267
Centrifugal precipitation chromatography was developed approximately 10 years ago. In contrast to other counter-current chromatographic techniques, the centrifugal precipitation chromatography system is operated with two mutually miscible solutions separated by a cut-off membrane. Centrifugal precipitation chromatography was firstly introduced for the separation of proteins using an ammonium sulfate gradient. In this study we describe a novel approach using solvent-based protein precipitation for the isolation of active plant enzymes from tea leaves (Camellia sinensis) by centrifugal precipitation chromatography. We developed a gradient based on acetone and Tris-buffer, because the biological activity of carotenases in tea leaves cannot be preserved in the presence of ammonium sulfate. Parameters such as the critical solvent concentration, flow rate, buffer concentration, and sample load were determined and/or optimized. Subsequently, the newly developed separation protocol was successfully used for the isolation of active carotenoid cleavage enzymes from tea leaves. The isolated enzymes showed high enzymatic activities and purities and could be directly used for enzymatic assays and structure elucidation. 相似文献