全文获取类型
收费全文 | 596篇 |
免费 | 20篇 |
国内免费 | 3篇 |
专业分类
化学 | 463篇 |
晶体学 | 7篇 |
力学 | 10篇 |
数学 | 25篇 |
物理学 | 114篇 |
出版年
2023年 | 3篇 |
2022年 | 3篇 |
2021年 | 3篇 |
2020年 | 10篇 |
2019年 | 10篇 |
2018年 | 9篇 |
2017年 | 2篇 |
2016年 | 12篇 |
2015年 | 11篇 |
2014年 | 18篇 |
2013年 | 26篇 |
2012年 | 25篇 |
2011年 | 41篇 |
2010年 | 15篇 |
2009年 | 27篇 |
2008年 | 30篇 |
2007年 | 38篇 |
2006年 | 35篇 |
2005年 | 44篇 |
2004年 | 26篇 |
2003年 | 31篇 |
2002年 | 25篇 |
2001年 | 16篇 |
2000年 | 4篇 |
1999年 | 9篇 |
1998年 | 5篇 |
1997年 | 7篇 |
1996年 | 13篇 |
1995年 | 5篇 |
1994年 | 4篇 |
1993年 | 8篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1986年 | 7篇 |
1985年 | 12篇 |
1984年 | 7篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 4篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1974年 | 4篇 |
1973年 | 7篇 |
1954年 | 1篇 |
排序方式: 共有619条查询结果,搜索用时 6 毫秒
81.
82.
83.
Katsunori Watabe Hisashi Kanda Katsuya Sato Toshiyuki Hobo 《Journal of chromatography. A》1992,590(2):289-296
In continuous counter-current gas-liquid chromatography, which has a high resolving power and is suitable for the large-scale purification of organic solvents, it is very important that the samples that can be applied extend from easily separable to more difficult to separate, such as azeotropes, low-volatility compounds and stereoisomers. A system was designed and constructed for high-temperature operation up to 200°C, and was applied to the separation of dimethyl and diethyl phthalate, trans- and cis-decahydronaphthalene and cis-decahydronaphthalene and tetrahydronaphthalene. It was confirmed that over 99% of purity could be achieved for dimethyl and diethyl phthalate, trans-decahydronaphthalene, and tetrahydronaphthalene. 相似文献
84.
Reconstitution of Biosynthetic Machinery for the Synthesis of the Highly Elaborated Indole Diterpene Penitrem 下载免费PDF全文
Dr. Chengwei Liu Koichi Tagami Dr. Atsushi Minami Tomoyuki Matsumoto Jens Christian Frisvad Hideyuki Suzuki Jun Ishikawa Katsuya Gomi Prof. Dr. Hideaki Oikawa 《Angewandte Chemie (International ed. in English)》2015,54(19):5748-5752
Penitrem A is one of the most elaborated members of the fungal indole diterpenes. Two separate penitrem gene clusters were identified using genomic and RNA sequencing data, and 13 out of 17 transformations in the penitrem biosynthesis were elucidated by heterologous reconstitution of the relevant genes. These reactions involve 1) a prenylation‐initiated cationic cyclization to install the bicyclo[3.2.0]heptane skeleton (PtmE), 2) a two‐step P450‐catalyzed oxidative processes forming the unique tricyclic penitrem skeleton (PtmK and PtmU), and 3) five sequential oxidative transformations (PtmKULNJ). Importantly, without conventional gene disruption, reconstitution of the biosynthetic machinery provided sufficient data to determine the pathway. It was thus demonstrated that the Aspergillus oryzae reconstitution system is a powerful method for studying the biosynthesis of complex natural products. 相似文献
85.
Cover Picture: Reconstitution of Biosynthetic Machinery for the Synthesis of the Highly Elaborated Indole Diterpene Penitrem (Angew. Chem. Int. Ed. 19/2015) 下载免费PDF全文
86.
Saiko KitaharaTakuya Tashiro Yukihiro SugimotoMitsuru Sasaki Hirosato Takikawa 《Tetrahedron letters》2011,52(6):724-726
Sorgomol, isolated from Sorghum bicolor, is the germination stimulant for seeds of root parasitic weeds. The first synthesis of (±)-sorgomol has been achieved by starting from ethyl 2-oxocyclohexanecarboxylate. 相似文献
87.
Regenerative medicine for repairing damaged body tissues has recently become critically important. Cell culture scaffolds are required for the control of cell attachment, proliferation, and differentiation in in vitro cell cultures. A new strategy to control cell adhesion, morphology, and proliferation was developed by culturing mouse osteoblast-like MC3T3-E1 cells on novel cell culture scaffolds fabricated using ordered nanometer-sized pores (100, 300, 500, and 1000 nm). Results of this study indicate that after 72 h of incubation, the number of cells cultured on a silica film with a pore size of 1000 nm was similar to or slightly lower than that cultured on a non-porous control silica film. Films with 100-500 nm pore sizes, however, resulted in the cell growth inhibition. Morphology of the cultured cells revealed increased elongation and the formation of actin stress fibers was virtually absent on macroporous silica films with 100-500 nm pore size. Vinculin molecules expressed in cells cultured on the non-porous silica films showed many clear focal adhesions, whereas focal contacts were insufficiently formed in cells cultured on macroporous films. The influence of hydroxyapatite (HAp) and alumina scaffolds on the behavior of MC3T3-E1 cells was also evaluated. The proliferation rate of MC3T3-E1 cells cultured on HAp films with 1000 nm pore size was increased to approximately 20% above than that obtained of cells cultured on non-porous HAp films. These results demonstrate that the pore size and constituents of films play a role in controlling the morphology and proliferation rate of MC3T3-E1 cells. 相似文献
88.
A Rh-doped SrTiO(3) (SrTiO(3):Rh) photocatalyst electrode that was readily prepared by pasting SrTiO(3):Rh powder onto a transparent indium tin oxide electrode gave a cathodic photocurrent under visible-light irradiation (λ > 420 nm), indicating that the SrTiO(3):Rh photocatalyst electrode possessed p-type semiconductor character. The cathodic photocurrent increased with an increase in the amount of doped Rh up to 7 atom %. The incident-photon-to-current efficiency at 420 nm was 0.18% under an applied potential of -0.7 V vs Ag/AgCl for the SrTiO(3):Rh(7 atom %) photocatalyst electrode. The photocurrent was confirmed to be due to water splitting by analyzing the evolved H(2) and O(2). The water splitting proceeded with the application of an external bias smaller than 1.23 V versus a Pt counter electrode under visible-light irradiation and also using a solar simulator, suggesting that solar energy conversion should be possible with the present photoelectrochemical water splitting. 相似文献
89.
Kawai Y Tsukamoto S Ito J Akimoto K Takahashi M 《Chemical & pharmaceutical bulletin》2011,59(9):1110-1116
The blockade of human ether-a-go-go-related gene (hERG) potassium channels is widely regarded as the predominant cause of drug-induced QT prolongation. The correlation analysis between the inhibition of the hERG channel (hERG inhibition) and physicochemical properties was investigated by use of in-house quinolone antibiotics as model compounds. In order to establish a simple prediction model of hERG inhibition, we focused on the comprehensible physicochemical parameters such as lipophilicity (log P) and basicity (pK(a)). At first, the risk associated with increasing log P and pK(a) was examined by statistical analysis. It was demonstrated that the risk associated with increasing log P and pK(a) by one unit, respectively, almost identically increased. Consequently, equal attention should be paid to both parameters on hERG inhibition. Next, a prediction model of hERG inhibition which was represented by log P and pK(a) was investigated. As a result, we built the stepwise discriminant prediction model which took advantage of the risk judgment by zone classification. In conclusion, the impact of log P and pK(a) on hERG inhibition was clarified relatively and quantitatively. The quantitative risk assessment established based on both parameters, was considered to be a practical and useful tool in avoiding hERG inhibition and in the rational drug design for drug discovery, especially in lead optimization. Moreover, we also carried out a trend analysis using a different derivative and demonstrated that both parameters were equally significant for hERG inhibition. 相似文献
90.
Ishizaki T Teshima K Masuda Y Sakamoto M 《Journal of colloid and interface science》2011,360(1):280-288
Alkyl- and perfluoro-phosphonic acid derived SAMs were successfully formed on Mg alloy by liquid phase method for the first time. The chemical and anticorrosive properties of the prepared SAMs on magnesium alloys were characterized using contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and electrochemical measurements. Water contact angle measurements revealed that the maximum advancing/receding water contact angles of n-octyl (OP: CH(3)(CH(2))(7)PO(OH)(2)), n-dodecyl (DP: CH(3)(CH(2))(11)PO(OH)(2)), n-octadecyl (ODP: CH(3)(CH(2))(17)PO(OH)(2)) phosphonic acid, and 2-(perfluorohexyl)ethyl (PFEP: CF(3)(CF(2))(5)CH(2)CH(2)PO(OH)(2)) phosphonic acid were 105.1/64.7°, 108.3/69.6°, 111.9/75.2°, and 115.2/67.4° respectively. In the case of alkylphosphonic acid SAMs (OP, DP, and ODP), the advancing and receding water contact angles increased with an increase in the preparation time. The angle-resolved XPS (AR-XPS) data revealed that the film thicknesses of the OP, DP, ODP, PFEP on Mg alloy were estimated to be 0.8, 1.2, 1.7, and 1.1 nm, respectively. The XPS O 1s data support that the phosphonic acid derived SAM is covalently bound to the oxide or hydroxide surface of the Mg alloy in a monodenate or bidenate manner. Chemical stability of the alkyl- and perfluoro-phosphonic acid modified Mg alloy surfaces was investigated using aqueous solutions at pH=4.0, 7.0, and 10.0. The contact angles of OP, DP, and PFEP modified Mg surface decreased rapidly within the first 5 min after immersion in all the aqueous solutions and were less than 20°. On the other hand, the contact angles of the ODP modified Mg alloy after immersion in aqueous solutions at pH 4, 7 and 10 for 5 min were 45.1°, 89.3,° and 85.5°, respectively. The ODP modified Mg alloy had highest chemical stability in four types of the phosphonic acid derived SAMs used in this study, indicating that the molecular density of ODP on Mg alloy would be higher than those of OP, DP, PFEP on Mg alloy. The corrosion resistance of ODP modified Mg alloy was investigated by potentiodynamic polarization curve measurements. The ODP modified Mg alloy exhibits protective properties in a solution containing Cl(-) ions compared to unmodified Mg alloy. 相似文献