全文获取类型
收费全文 | 1053篇 |
免费 | 20篇 |
国内免费 | 2篇 |
专业分类
化学 | 831篇 |
晶体学 | 13篇 |
力学 | 6篇 |
数学 | 33篇 |
物理学 | 192篇 |
出版年
2023年 | 6篇 |
2022年 | 6篇 |
2020年 | 9篇 |
2019年 | 10篇 |
2018年 | 9篇 |
2017年 | 5篇 |
2016年 | 18篇 |
2015年 | 14篇 |
2014年 | 21篇 |
2013年 | 47篇 |
2012年 | 44篇 |
2011年 | 71篇 |
2010年 | 27篇 |
2009年 | 34篇 |
2008年 | 67篇 |
2007年 | 47篇 |
2006年 | 68篇 |
2005年 | 54篇 |
2004年 | 46篇 |
2003年 | 41篇 |
2002年 | 44篇 |
2001年 | 26篇 |
2000年 | 15篇 |
1999年 | 21篇 |
1998年 | 17篇 |
1997年 | 10篇 |
1996年 | 12篇 |
1995年 | 15篇 |
1994年 | 15篇 |
1993年 | 15篇 |
1992年 | 20篇 |
1991年 | 11篇 |
1990年 | 9篇 |
1989年 | 18篇 |
1988年 | 14篇 |
1987年 | 14篇 |
1986年 | 21篇 |
1985年 | 29篇 |
1984年 | 7篇 |
1983年 | 12篇 |
1982年 | 8篇 |
1981年 | 15篇 |
1980年 | 8篇 |
1979年 | 7篇 |
1978年 | 7篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1974年 | 6篇 |
1939年 | 3篇 |
1938年 | 3篇 |
排序方式: 共有1075条查询结果,搜索用时 0 毫秒
101.
102.
103.
We describe here the first case of the finding of xanthoanthrafil, a phosphodiesterase-5 inhibitor, in a dietary supplement. A methanol extract of the supplement product was first analyzed by TLC and HPLC. The results indicated that the extract contained an unknown compound. The molecular weight of the compound was 389 and the accurate mass showed its elemental composition to be C(19)H(23)N(3)O(6). Combined with this data, NMR analysis revealed the planar structure of the unknown compound to be N-(3,4-dimethoxybenzyl)-2-(1-hydroxypropan-2-ylamino)-5-nitrobenzamide. The R-configuration of this compound had been synthesized as a phosphodiesterase-5 inhibitor, formerly reported as FR226807 by Fujisawa Pharmaceutical Co., Ltd. The absolute configuration of the isolated compound was estimated to have R-configuration by its optical rotation. Considering its general properties, this compound is renamed as (R)-xanthoanthrafil with the agreement of Astellas Pharma Inc. which is the successor of Fujisawa Pharmaceutical Co., Ltd. Quantitative analysis revealed that the content of (R)-xanthoanthrafil in the product was about 31 mg/capsule. 相似文献
104.
Noboru Sato Yuichi Funato Yasuyuki Fukushima Takeshi Momose Mitsuo Koshi Yukihiro Shimogaki 《国际化学动力学杂志》2020,52(6):359-367
We established a gas-phase, elementary reaction model for chemical vapor deposition of silicon carbide from methyltrichlorosilane (MTS) and H2, based on the model developed at Iowa State University (ISU). The ISU model did not reproduce our experimental results, decomposition behavior of MTS in the gas phase in an environment with H2. Therefore, we made several modifications to the ISU model. Of the reactions included in existing models, 236 were lacking in the ISU model, and thus were added to the model. In addition, we modified the rate constants of the unimolecular reactions and the recombination reactions, which were treated as a high-pressure limit in the ISU model, into pressure-dependent rate expressions based on the previous reports (to yield the ISU+ model), for example, H2(+M) → H + H(+M), but decomposition behavior remained poorly reproducible. To incorporate the pressure dependencies of unimolecular decomposition rate constants, and to increase the accuracies of these constants, we recalculated the rate constants of five unimolecular decomposition reactions of MTS using the Rice-Ramsperger-Kassel-Marcus method at the CBS-QB3 level. These chemistries were added to the ISU+ model to yield the UT2014 model. The UT2014 model reproduced overall MTS decomposition. From the results of our model, we confirmed that MTS mainly decomposes into CH3 and SiCl3 at the temperature around 1000°C as reported in the several studies. 相似文献
105.
3-Succinylaconitine was conjugated with bovine serum albumin (BSA) for use as an immunogen for the preparation of a monoclonal antibody (MAb) against aconitine (Aco). Splenocytes from mice immunized with the Aco-BSA conjugate were fused with an aminopterin-sensitive mouse myeloma cell line, P3-X63-Ag8-653, and a hybridoma secreting a MAb against Aco was successfully obtained. The MAb cross-reacted with mesaconitine, hypaconitine and jesaconitine, which are Aco-type alkaloids, but not with any other compounds examined. The full measurement range of an enzyme-linked immunosorbent assay (ELISA) developed using the new MAb extended from 100 ng mL−1 to 1.5 μg mL−1 of Aco. The concentrations of Aco-type alkaloids in various Aconiti radixes assayed using the new ELISA method showed good agreement with previous reports. 相似文献
106.
Prof. Isao Fujii Dr. Makoto Hashimoto Kaori Konishi Akiko Unezawa Haruka Sakuraba Kenta Suzuki Harue Tsushima Miho Iwasaki Satsuki Yoshida Akane Kudo Rina Fujita Aika Hichiwa Koharu Saito Dr. Takashi Asano Dr. Jun Ishikawa Dr. Daigo Wakana Dr. Yukihiro Goda Ayumi Watanabe Mamoru Watanabe Yui Masumoto Dr. Junichiro Kanazawa Dr. Hajime Sato Prof. Masanobu Uchiyama 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(22):8542-8548
Shimalactones A and B are neuritogenic polyketides possessing characteristic oxabicyclo[2.2.1]heptane and bicyclo[4.2.0]octadiene ring systems that are produced by the marine fungus Emericella variecolor GF10. We identified a candidate biosynthetic gene cluster and conducted heterologous expression analysis. Expression of ShmA polyketide synthase in Aspergillus oryzae resulted in the production of preshimalactone. Aspergillus oryzae and Saccharomyces cerevisiae transformants expressing ShmA and ShmB produced shimalactones A and B, thus suggesting that the double bicyclo-ring formation reactions proceed non-enzymatically from preshimalactone epoxide. DFT calculations strongly support the idea that oxabicyclo-ring formation and 8π-6π electrocyclization proceed spontaneously after opening of the preshimalactone epoxide ring through protonation. We confirmed the formation of preshimalactone epoxide in vitro, followed by its non-enzymatic conversion to shimalactones in the dark. 相似文献
107.
Masahiko Matsukata Ken-ichi Sawamura Tsutomu Shirai Mitsuko Takada Yasushi Sekine Eiichi Kikuchi 《Journal of membrane science》2008,316(1-2):18-27
Controlling the growth of zeolite crystals on a porous alumina support is essential for preparing a compact zeolite membarne. First, mordenite seed crystals applied on a nonporous -alumina disk were grown and morphological change of mordenite crystals were observed in the course of growth. Then, mordenite membranes were synthesized on a porous -alumina tube under the same conditions employed in the study using the alumina disks. We found that seed crystal growth was widely controllable by changing water content in reaction solution, which resulted in better control of the morphology of mordenite crystals for synthesizing a thin compact mordenite membrane. Separation properties for mordenite membranes were studied in water–hydrogen binary system at 473 K with 10 kPa of water partial pressure, where no capillary condensation was expected in non-zeolitic pores. Separation factor for a mordenite membrane with a few defects was poor; however, a defect-free mordenite membrane prepared under a suitable condition highly separated steam from hydrogen. 相似文献
108.
Fukui K Takada Y Sumiyoshi T Imai T Takahashi K 《The journal of physical chemistry. B》2006,110(32):16111-16116
The fragmentation of peptides and oligosaccharides in the gas phase was investigated by means of electrospray ionization Fourier transform ion cyclotron resonance (FTICR) mass spectrometry coupled with dissociation by a laser-cleavage infrared multiphoton dissociation (IRMPD) technique. In this technique, an IR free-electron laser is used as a tunable source of IR radiation to cause cleavage of the ionized samples introduced into the FTICR cell. The gas-phase IRMPD spectra of protonated peptides (substance P and angiotensin II) and two sodiated oligosaccharides (sialyl Lewis X and lacto-N-fucopentaose III) were obtained over the IR scan range of 5.7-9.5 microm. In the IRMPD spectra for the peptide, fragment ions are observed as y/b-type fragment ions in the range 5.7-7.5 microm, corresponding to cleavage of the backbone of the parent amino acid sequence, whereas the spectra of the oligosaccharides have major peaks in the range 8.4-9.5 microm, corresponding to photoproducts of the B/Y type. 相似文献
109.
Yan C Zhang Y Hu Y Ozaki Y Shen D Gan Z Yan S Takahashi I 《The journal of physical chemistry. B》2008,112(11):3311-3314
The structure evolution of poly(butylene adipate) (PBA) during isothermal melt crystallization and phase transition processes is investigated by Fourier transform infrared spectroscopy (FTIR). Detailed IR spectra analysis and band assignment are performed to disclose the bands sensitive to the alpha-form crystalline order of PBA. It is revealed from the in situ IR study that the functionalities within PBA chains alter simultaneously during the melt crystallization process. From the analysis of the spectral changes, it is found that band shifts take place during the phase transition process of PBA from its metastable beta-form crystal to the stable alpha-form. Notable band shifts in the 1300-1100 cm(-1) region indicate that the twist of polymer chains in the alpha-form is located in the C-O-C and C-O linkages. Moreover, the results elucidated that the different segments of molecular chains tune up their conformations synchronously during the beta to alpha crystal transition process of PBA. It is suggested that the betaalpha phase transition process proceeds randomly throughout the solid at a constant rate. 相似文献
110.
Tachi T Hase T Okamoto Y Kaji N Arima T Matsumoto H Kondo M Tokeshi M Hasegawa Y Baba Y 《Analytical and bioanalytical chemistry》2011,401(7):2301-2305
Microchip analysis is a promising method for therapeutic drug monitoring. This led us to evaluate a microchip-based fluorescence
polarization immunoassay (FPIA) system for point-of-care testing on patients being treated with theophylline. The sera were
collected from 20 patients being treated with theophylline. Fluorescence polarization was measured on the microchip and theophylline
concentrations in serum were obtained. Regression analysis of the correlations was done between the results given by the microchip-based
FPIA and the conventional cloned enzyme donor immunoassay (CEDIA), and between the results given by the microchip-based FPIA
and the conventional particle-enhanced turbidimetric inhibition immunoassay (PETINIA). We successfully carried out a quantitative
analysis of theophylline in serum at values near its therapeutic range in 65 s. The results obtained by the microchip-based
FPIA correlated well with CEDIA and PETINIA results; the correlation coefficients (R
2) were 0.986 and 0.989, respectively. The FPIA system is a simple and rapid method for point-of-care testing of drugs in serum,
and its accuracy is the same as the conventional CEDIA and PETINIA. It is essential to use real samples from patients and
to confirm good correlations with conventional methods for a study on the realization of microchip. 相似文献