全文获取类型
收费全文 | 1309篇 |
免费 | 29篇 |
国内免费 | 2篇 |
专业分类
化学 | 1042篇 |
晶体学 | 12篇 |
力学 | 17篇 |
数学 | 35篇 |
物理学 | 234篇 |
出版年
2021年 | 9篇 |
2020年 | 12篇 |
2019年 | 16篇 |
2018年 | 6篇 |
2016年 | 18篇 |
2015年 | 19篇 |
2014年 | 25篇 |
2013年 | 52篇 |
2012年 | 56篇 |
2011年 | 81篇 |
2010年 | 37篇 |
2009年 | 38篇 |
2008年 | 82篇 |
2007年 | 60篇 |
2006年 | 68篇 |
2005年 | 67篇 |
2004年 | 60篇 |
2003年 | 46篇 |
2002年 | 57篇 |
2001年 | 36篇 |
2000年 | 19篇 |
1999年 | 13篇 |
1998年 | 12篇 |
1997年 | 9篇 |
1996年 | 15篇 |
1995年 | 6篇 |
1994年 | 12篇 |
1993年 | 21篇 |
1992年 | 16篇 |
1991年 | 23篇 |
1990年 | 13篇 |
1989年 | 13篇 |
1988年 | 20篇 |
1987年 | 30篇 |
1986年 | 15篇 |
1985年 | 27篇 |
1984年 | 20篇 |
1983年 | 12篇 |
1982年 | 27篇 |
1981年 | 25篇 |
1980年 | 20篇 |
1979年 | 16篇 |
1978年 | 10篇 |
1977年 | 17篇 |
1976年 | 6篇 |
1975年 | 9篇 |
1974年 | 12篇 |
1973年 | 8篇 |
1968年 | 7篇 |
1967年 | 6篇 |
排序方式: 共有1340条查询结果,搜索用时 15 毫秒
111.
Mitsuhiro Wada Chieko Morinaka Toshihiko Ikenaga Naotaka Kuroda Kenichiro Nakashima 《Analytical sciences》2002,18(6):631-634
An HPLC method with fluorescence detection for the determination of nitric oxide (NO) in cultivated plant cells (Agave pacifica, Agavaceae) was developed. NO was derivatized in situ with 2,3-diaminonaphthalene (DAN) as a labeling reagent and converted to 1(H)-naphthotriazole. The maximum peak height of the derivative was observed by incubation for 3 h at 25 degrees C with 0.2 mM DAN. Excess reagent in cells was removed by washing 3 times with 5 ml of water. The calibration curve for authentic standard of DAN-NO spiked to cultivated plant cells showed a good linearity (r = 0.995) in the range of 5.0 to 50 pmol/g cell. The detection limit at a signal-to-noise ratio of 3 was 3.4 pmol/g cells. The proposed method was successfully applied to the monitoring of NO concentration with cell growth. The effect of thermal treatment on the concentration of NO in plant cells was also examined. The concentration of NO in cells treated at 5 degrees C for 1 h was significantly higher than that treated at 25 degrees C and 35 degrees C for 1 h (n = 3, p < 0.05). 相似文献
112.
P. K. Kuroda 《Journal of Radioanalytical and Nuclear Chemistry》1990,142(1):101-112
The origin of the concept of a large-scale nuclear chain reaction occurring in nature can be traced back to the ideas expressed byAston in 1922 and byJoliot in 1935. Geochemical investigations on hot springs, which have been carried out at the University of Tokyo since the 1930s, played a key role in the early development of the theory of natural reactor. Results obtained from the studies, which have been carried out in various countries since the 1972 discovery of the Oklo phenomenon, reveal the fact that the natural reactors at Oklo may have indeed operated in a manner quite similar to the geysers or intermittent hot springs. A careful examination of the isotopic compositions of the so-called anomalous xenon from the Oklo reactor suggests that the natural reactors were operating at temperatures between the boiling point of iodine (183°C) and the melting point of tellurium (452°C), periodically being turned on and off. 相似文献
113.
-Ni(H2O)6 · SO4 and its selenate derivative exhibit chirality only in the solid-state. We have observed, for the first time, a sign inversion of CD (circular dichroism) in the 3A2g → 3T1g(P) Ni(II) d–d transition at near liquid nitrogen temperatures. The novel finding was achieved by building a new cooling unit to a solid-state specialized Universal Chiroptical Spectrophotometer (UCS-1) [R. Kuroda, T. Harada, Y. Shindo, Rev. Sci. Instrum. 72 (2001) 3802.] and by formulating an analytical procedure to obtain artifact-free CD signals based on the Mueller matrix method. The sign inversion is remarkable as the crystal structure hardly changes from 300 to 100 K. The origin of the sign inversion is discussed. 相似文献
114.
115.
Motomasa Yonezumi Reiko Takaku Shokyoku Kanaoka Sadahito Aoshima 《Journal of polymer science. Part A, Polymer chemistry》2008,46(6):2202-2211
Cationic polymerization of α‐methyl vinyl ethers was examined using an IBEA‐Et1.5AlCl1.5/SnCl4 initiating system in toluene in the presence of ethyl acetate at 0 ~ ?78 °C. 2‐Ethylhexyl 2‐propenyl ether (EHPE) had a higher reactivity, compared to corresponding vinyl ethers. But the resulting polymers had low molecular weights at 0 or ?50 °C. In contrast, the polymerization of EHPE at ?78 °C almost quantitatively proceeded, and the number‐average molecular weight (Mn) of the obtained polymers increased in direct proportion to the EHPE conversion with quite narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight ≤ 1.05). In monomer‐addition experiments, the Mn of the polymers shifted higher with low polydispersity as the polymerization proceeded, indicative of living polymerization. In the polymerization of methyl 2‐propenyl ether (MPE), the living‐like propagation also occurred under the reaction conditions similar to those for EHPE, but the elimination of the pendant methoxy groups was observed. The introduction of a more stable terminal group, quenched with sodium diethyl malonate, suppressed this decomposition, and the living polymerization proceeded. The glass transition temperature of the obtained poly(MPE) was 34 °C, which is much higher than that of the corresponding poly(vinyl ether). This poly(MPE) had solubility characteristics that differed from those of poly(vinyl ethers). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2202–2211, 2008 相似文献
116.
117.
Three novel naphthoquinone-based heterocyclic pigments, 2-methyl-3-[(1-methyl-1H-imidazol-2-yl)thio-1,4-naphthalenedione, (4-methyl-4H-1,2,4-triazol-3-yl)thio-1,4-naphthalenedione, and (1-methyl-1H-tetrazol-5-yl)thio]-1,4-naphthalenedione, are synthesized, and their optical properties in both solution and solid states are investigated. Depending on the heteroarylthio ring in the pigment, variation in optical properties is observed, e.g. characteristic colours for each pigment in the solution and solid states. The achiral pigment containing the 1-methyl-1H-tetrazol-5-yl ring exhibits a chiral space group and a CD signal in the solid state. 相似文献
118.
Reaction of 2-propargylphenylcarbamates with diphenyliodonium salts via Meyer-Schuster rearrangement
Hideki Minami Noriko Okamoto Takuya Sueda Takatsugu Sakaguchi Minoru Ishikura Reiko Yanada 《Tetrahedron letters》2017,58(45):4277-4280
The syntheses of 2,3-dihydro-4-quinolones from 2-propargylphenylcarbamates by one-pot tandem process that involves Meyer-Schuster rearrangement or arylative Meyer-Schuster rearrangement/Michael addition of carbamate nitrogen to the resulting vinyl ketones have been developed. Phenylcarbamates tethering tertiary propargyl alcohols underwent arylative Meyer-Schuster rearrangement/Friedel-Crafts alkylation to produce 2,3-dihydroindenones. 相似文献
119.
A secretoglobin 3A2 type C (98–139) peptide was synthesized by native chemical ligation between 115Ile and 116Cys residues using Dawson’s linker. The peptide-N-acyl-benzimidazolinone-glycine amide, a C-terminal thioesters precursor, was provided from 3-amino-4-(methylamino)benzoic acid. In addition, an N-terminal cysteine fragment, the (116–139) peptide, was prepared by ordinary Fmoc-solid phase peptide synthesis. Native chemical ligation of the (98–115) fragment with the Dawson’s linker and the (116–139) peptide smoothly proceeded to give SCGB3A2 type C (98–139) peptide. 相似文献
120.
Evaluation of chemiluminescence reagents for selective detection of reactive oxygen species 总被引:2,自引:0,他引:2
Shinya Yamaguchi Kaname Ohyama Maiko Kohno Akira Takadate Naotaka Kuroda 《Analytica chimica acta》2010,665(1):74-27
In order to evaluate the chemiluminescence (CL) reagents for selective detection of reactive oxygen species (ROS), we comprehensively measured the CL responses of 20 CL reagents (three luminol derivatives, two imidazopyrazinone derivatives, eight lophine derivatives, six acridinium ester derivatives and lucigenin) against six types of ROS (superoxide anion: O2−, hydroxyl radical: OH, hydrogen peroxide: H2O2, hypochlorite anion: ClO−, singlet oxygen: 1O2, and nitric oxide: NO). As a result of the screening, it was found that nine CL reagents selectively detected O2− while one CL reagent selectively detected OH. However, no CL reagent had selectivity on the detection of H2O2, ClO−, 1O2 and NO. Our screening results could help to select the most suitable CL reagent for selective determination of different ROS.As an application study, 4-methoxyphenyl-10-methylacridinium-9-carboxylate (MMAC), one of the acridinium ester derivatives, showed high selectivity on the detection of O2−, and thus was applied to the assay of superoxide dismutase (SOD) activity. The dynamic range and detection limit of the developed CL assay were 0.1-10 and 0.06 U mL−1, respectively. Significant correlation (r = 0.997) was observed between the results by the CL assay using MMAC and the spectrophotometric assay using 2-(4-iodophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium monosodium salt. 相似文献