全文获取类型
收费全文 | 619篇 |
免费 | 9篇 |
国内免费 | 5篇 |
专业分类
化学 | 455篇 |
晶体学 | 12篇 |
力学 | 5篇 |
数学 | 20篇 |
物理学 | 141篇 |
出版年
2022年 | 4篇 |
2021年 | 4篇 |
2019年 | 8篇 |
2016年 | 6篇 |
2015年 | 6篇 |
2014年 | 12篇 |
2013年 | 19篇 |
2012年 | 28篇 |
2011年 | 42篇 |
2010年 | 22篇 |
2009年 | 15篇 |
2008年 | 36篇 |
2007年 | 40篇 |
2006年 | 33篇 |
2005年 | 30篇 |
2004年 | 32篇 |
2003年 | 33篇 |
2002年 | 30篇 |
2001年 | 3篇 |
2000年 | 5篇 |
1999年 | 8篇 |
1998年 | 4篇 |
1997年 | 7篇 |
1996年 | 4篇 |
1995年 | 5篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 8篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1985年 | 7篇 |
1984年 | 12篇 |
1983年 | 6篇 |
1982年 | 9篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 18篇 |
1978年 | 11篇 |
1977年 | 7篇 |
1976年 | 6篇 |
1975年 | 6篇 |
1974年 | 9篇 |
1973年 | 15篇 |
1970年 | 6篇 |
1969年 | 5篇 |
1967年 | 6篇 |
1965年 | 5篇 |
排序方式: 共有633条查询结果,搜索用时 62 毫秒
111.
112.
Ohishi Y Kimura K Yamaguchi M Uchida N Kanayama T 《The Journal of chemical physics》2008,128(12):124304
We report the formation of icosahedral B(12)H(8) (+) through ion-molecule reactions of the decaborane ion [B(10)H(x)(+) (x=6-14)] with diborane (B(2)H(6)) molecules in an external quadrupole static attraction ion trap. The hydrogen content n of B(12)H(n)(+) is determined by the analysis of the mass spectrum. The result reveals that B(12)H(8)(+) is the main product. Ab initio calculations indicate that B(12)H(8)(+) preferentially forms an icosahedral structure rather than a quasiplanar structure. The energies of the formation reactions of B(12)H(14)(+) and B(12)H(12)(+) between B(10)H(x)(+) (x=6,8) ions, which are considered to be involved in the formation of B(12)H(n)(+), and a B(2)H(6) molecule are calculated. The calculations of the detachment pathway of H(2) molecules and H atoms from the product ions, B(12)H(14)(+) and B(12)H(12) (+), indicate that the intermediate state has a relatively low energy, enabling the detachment reaction to proceed owing to the sufficient reaction energy. This autodetachment of H(2) accounts for the experimental result that B(12)H(8)(+) is the most abundant product, even though it does not have the lowest energy among B(12)H(n)(+). 相似文献
113.
Honda S Akiba T Kato YS Sawada Y Sekijima M Ishimura M Ooishi A Watanabe H Odahara T Harata K 《Journal of the American Chemical Society》2008,130(46):15327-15331
What is the smallest protein? This is actually not such a simple question to answer, because there is no established consensus among scientists as to the definition of a protein. We describe here a designed molecule consisting of only 10 amino acids. Despite its small size, its essential characteristics, revealed by its crystal structure, solution structure, thermal stability, free energy surface, and folding pathway network, are consistent with the properties of natural proteins. The existence of this kind of molecule deepens our understanding of proteins and impels us to define an "ideal protein" without inquiring whether the molecule actually occurs in nature. 相似文献
114.
Ishizaka T Okada S Tokuyama E Mukai J Uchida T 《Chemical & pharmaceutical bulletin》2008,56(10):1389-1394
The objective of the study was to evaluate the bitterness, grittiness and uniformity of drug loading as measures of the quality of 12 formulations of clarithromycin dry syrup (CAMDS), comprising one branded and 11 generic products. Some of the generic CAMDS formulations were more bitter than the branded product while others had similar bitterness when tested as aqueous suspensions. Only one generic product was less bitter than the branded product when tested as a suspension in acidic sports drink. The usual dissolution test described in JP XV could not be used to evaluate the bitterness of the products. A brief dissolution test using only 12.5 ml of water was used to evaluate the bitterness of the products in aqueous suspensions. There were considerable variances in the grittiness of the various products, which were independent of particle size. Changes in grittiness level seemed to be correlated with changes in the intensity of bitterness due to the disintegration of the formulation. Finally, there was less variation in the uniformity of drug loading for the branded product than for the generic products. These data may be useful when selecting which CAMDS formulation to prescribe. 相似文献
115.
Soh N Ariyoshi T Fukaminato T Nakajima H Nakano K Imato T 《Organic & biomolecular chemistry》2007,5(23):3762-3768
A swallow-tailed perylene derivative including a triphenylphosphine moiety was synthesized and applied to the detection and the live-cell imaging of lipid hydroperoxides. The novel probe, named Spy-LHP, reacted rapidly and quantitatively with lipid hydroperoxides to form the corresponding oxide, Spy-LHPOx, which emits extremely strong fluorescence (Phi approximately 1) in the visible range (lambda(em) = 535 nm, 574 nm). Spy-LHP was highly selective for lipid hydroperoxides, and the addition of other reactive oxygen species (ROS) including hydrogen peroxides, hydroxyl radical, superoxide anion, nitric oxide, peroxynitrite, and alkylperoxyl radical, caused no significant increase in the fluorescence intensity. The probe exhibited good localization to cellular membranes and was successfully applied to the confocal laser scanning microscopy (CLSM) imaging of lipid hydroperoxides in live J774A.1 cells, in which lipid peroxidation was proceeded by the stimulation of 2,2-azobis(2-amidinopropane)dihydrochloride (AAPH). These findings establish Spy-LHP as a promising new tool for investigating the physiology of lipid hydroperoxides. 相似文献
116.
Soh N Yoshida K Nakajima H Nakano K Imato T Fukaminato T Irie M 《Chemical communications (Cambridge, England)》2007,(48):5206-5208
A fluorescent photochromic compound, composed of diarylethene, fluorescein and succinimidyl ester units, was developed for the controllable fluorescent labeling of biomolecules based on a small molecule. 相似文献
117.
Zhang R Nakajima H Soh N Nakano K Masadome T Nagata K Sakamoto K Imato T 《Analytica chimica acta》2007,600(1-2):105-113
A rapid and sensitive immunoassay based on a sequential injection analysis (SIA) using magnetic microbeads for the determination of alkylphenol polyethoxylates (APnEOs) is described. An SIA system was constructed from a syringe pump, a switching valve, a flow-through type immunoreaction cell equipped with a photon counting unit and a neodymium magnet. Magnetic beads, to which an anti-APnEOs monoclonal antibody was immobilized, were used as a solid support in an immunoassay. The introduction, trapping and release of the magnetic beads in and from the immunoreaction cell were controlled by means of a neodymium magnet and adjusting the flow of a carrier solution. The immunoassay was based on an indirect competitive immunoreaction of an anti-APnEOs monoclonal antibody immobilized on the magnetic beads with a sample APnEOs and a horseradish peroxidase (HRP)-labeled APnEOs in the same sample solution, and was based on the subsequent chemiluminscence reaction of HRP on the magnetic microbeads with a luminol solution containing hydrogen peroxide and p-iodophenol. The anti-APnEOs antibody was immobilized on the magnetic microbeads by coupling the antibody with the magnetic beads after activation of a carboxylate moiety on the surface of the magnetic beads that had been coated with a polylactic acid film. The antibody immobilized magnetic beads were introduced in the immunoreaction cell and trapped in it by the neodymium magnet, which was equipped beneath the immunoreaction cell. An APnEOs sample solution containing the HRP-labeled APnEOs at a constant concentration, and a luminol solution containing hydrogen peroxide and p-iodophenol were sequentially introduced into the immunoreaction cell, according to an SIA programmed sequence. Chemiluminescence emission was monitored by means of a photon counting unit located at the upper side of the immunoreaction cell by collecting the emitted light with a lens. A typical sigmoidal calibration curve was obtained, when the logarithm of the concentration of APnEOs was plotted against the chemiluminescence intensity as the number of photons in 100 ms using standard APnEOs sample solutions at various concentrations (0–1000 ppb) under optimum conditions. The lower detection limit defined as IC80 is ca 10 ppb. The time required for analysis is less than 15 min per a sample. The present method was successfully applied to the determination of APnEOs in river water. 相似文献
118.
Twelve "health foods" products containing chondroitin sulfate (CS) were purchased from the Japanese market and the origin of the CS was investigated by conducting disaccharide compositional analysis after enzymatic depolymerization and by 1H-NMR spectroscopy. Nine of the 12 products had labels indicating that the origin of the CS was shark cartilage. However, two of them were found to contain mammalian CS. Next, we compared the ratio of the sulfate group to the galactosamine residue after the acid hydrolysis of CS. The results suggest that all of the CS from sharks had a ratio of more than 1.0, while the CS from mammals had a ratio of less than 1.0. Since this comparative analysis does not require expensive purified enzyme, it would be an economical way to identify the origin of CS in "health foods." Being able to determine the origin of the ingredients in natural products is very important for ensuring their quality, safety, and efficacy. Therefore, we think that regulatory requirements for accurately indicating the origin of "health foods" and effective enforcement of these requirements are needed. 相似文献
119.
Masato Tazaki Toshihiko Hieda Hironori Maeda Shizuo Nagahama Akinori Jyo 《Heteroatom Chemistry》1998,9(3):281-287
Lithiated furans have been found to cleave the S–S bond of polymerization-resistant 1,2-dithiolanes to give the ring opened products in good yields. In the case of lithiated benzofuran, the excess reagent reacted with the normal product to give a mixture. Lithiated dihydrofuran and dihydropyran gave the corresponding ring-opened products that rearranged to spiro-1,3-dithianes during acidic workup. The reaction was applied to the selective synthesis of substrates for intramolecular Diels-Alder reactions. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:281–287, 1998 相似文献
120.