全文获取类型
收费全文 | 548篇 |
免费 | 37篇 |
国内免费 | 2篇 |
专业分类
化学 | 430篇 |
晶体学 | 7篇 |
力学 | 17篇 |
数学 | 16篇 |
物理学 | 117篇 |
出版年
2023年 | 9篇 |
2022年 | 11篇 |
2021年 | 13篇 |
2020年 | 15篇 |
2019年 | 18篇 |
2018年 | 16篇 |
2017年 | 11篇 |
2016年 | 17篇 |
2015年 | 15篇 |
2014年 | 23篇 |
2013年 | 19篇 |
2012年 | 42篇 |
2011年 | 49篇 |
2010年 | 34篇 |
2009年 | 34篇 |
2008年 | 36篇 |
2007年 | 36篇 |
2006年 | 38篇 |
2005年 | 30篇 |
2004年 | 27篇 |
2003年 | 11篇 |
2002年 | 12篇 |
2001年 | 7篇 |
2000年 | 8篇 |
1999年 | 3篇 |
1998年 | 8篇 |
1996年 | 4篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1987年 | 5篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 1篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1972年 | 2篇 |
1971年 | 1篇 |
排序方式: 共有587条查询结果,搜索用时 109 毫秒
1.
2.
Joji Ohshita Ryosuke Taketsugu Yuki Nakahara Atsutaka Kunai 《Journal of organometallic chemistry》2004,689(20):3258-3264
Selective dehydrogenative coupling of di- and trihydrosilanes with alcohols catalyzed by PdCl2 or NiCl2 afforded alkoxyhydro- and dialkoxyhydrosilanes in good yield. Further treatment of the resulting alkoxyhydrosilanes with carbon tetrachloride or allyl bromide in the presence of the same catalyst led to the formation of alkoxychloro- and alkoxybromosilanes, respectively. Similar reactions of dialkoxyhydrosilanes with carbon tetrachloride afforded dialkoxychlorosilanes in good yield, although contamination of small amounts of trialkoxysilanes and alkoxydichlorosilanes was detected in the products. Selective substitution of the alkoxyhalosilanes with nucleophiles is also reported. 相似文献
3.
Ryosuke Sakai Issei Otsuka Toshifumi Satoh Ryohei Kakuchi Harumi Kaga Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):325-334
The asymmetric polymerization of 4′‐isocyanatobenzo‐18‐crown‐6 with the lithium amide of (S)‐(2‐methoxymethyl)pyrrolidine successfully proceeded to afford end‐functionalized poly(4′‐isocyanatobenzo‐18‐crown‐6) with (S)‐(2‐methoxymethyl)pyrrolidine (polymer 2 ). In the circular dichroism (CD) spectrum of 2 , a clear positive Cotton effect was observed in the range of 240–350 nm corresponding to the absorption of the polymer backbone, indicating that 2 partially formed a one‐handed helical structure, which was preserved by the chirality of (S)‐(2‐methoxymethyl)pyrrolidine bonding to the terminal end in 2 . In the titration experiments for the CD intensity of 2 in the presence of D ‐ and L ‐Phe·HClO4 (where Phe is phenylalanine), a small but remarkable difference was observed in the amount of the chiral guest needed for saturation of the CD intensity and in the saturated CD intensity, indicating that the extremely stable, one‐handed helical part should exist in the main chain of 2 , which was not inverted even when the unfavorable chiral guest for the predominant helical sense, L ‐Phe·HClO4, was added. In addition, helical polymer 2 exhibited a chiral discrimination ability toward racemic guests; that is, the guests were extracted from the aqueous phase into the organic phase with enantiomeric excess. The driving force of the chiral discrimination ability of 2 should certainly be attributed to the one‐handed helical structure in 2 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 325–334, 2006 相似文献
4.
Takahiro Gunji Ryosuke Shimano Koji Arimitsu Yoshimoto Abe 《Journal of polymer science. Part A, Polymer chemistry》2006,44(8):2542-2550
Tetraethoxysilane (TEOS) and polyethoxysiloxanes (PEOSs; prepared by the acid‐catalyzed hydrolytic polycondensation of TEOS) were subjected to the sol–gel process in the presence of cetyltrimethylammonium bromide (CTAB), respectively. The PEOSs with Mw 700–26,000, as prepared by sol–gel coating of TEOS and PEOS under various conditions, were used. Uniform and crack‐free thin films of thickness 276–613 nm were prepared by spin‐coating of a PEOS solution containing CTAB. When the coating films were sintered at 400 °C, the combustion of ethoxy groups and CTAB took place to provide porous silica thin films. The structure of the thin films was found to be dependent on the molecular weight of PEOS and the molar ratio of CTAB/Si: lamellar or hexagonal phase was observed for Mw less than 15,000 and for CTAB/Si molar ratios greater than 0.10. Honeycomb structures were observed for Mw less than 5000 and for CTAB/Si molar ratios of 0.15. The honeycomb structure was also observed by atomic force microscopy and transmission electron microscope. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2542–2550, 2006 相似文献
5.
Hosono E Fujihara S Honma I Zhou H 《Journal of the American Chemical Society》2005,127(39):13458-13459
We first fabricated the superhydrophobic film with a water contact angle of 178 degrees based on a perpendicular nanopin fractal structure by a bottom-up process. Until now, only materials with an original water contact angle larger than 90 degrees , which is classified as hydrophobicity, could be used to fabricate the superhydrophobic film (>170 degrees ) according to the possible fractal structure by a top-down process. Now, in this work, a water contact angle of about 178 degrees can be achieved using a lauric acid-coated film with an original contact angle of 75 degrees , which is classified as hydrophilicity, based on an ideal fractal structure for the superhydrophobic surface which is fabricated by the nanosize pin with 6.5 nm diameter. 相似文献
6.
[reaction: see text] Catalytic, enantioselective Mannich-type reactions of alpha-imino esters bearing readily removable substituents on nitrogen are described. Several N-carbamate-protected alpha-imino esters, which are readily prepared from 2-bromoglycine esters using a polymer-supported amine, reacted with silicon enolates to afford the desired adducts in high yields with high enantioselectivity using a copper(II)-diamine complex. Easy deprotection of the product amine and transformation to free alpha-amino acid derivatives have also been demonstrated. 相似文献
7.
Mitamura K Setaka M Shimada K Honma S Namiki M Koh E Mizokami A 《Biomedical chromatography : BMC》2005,19(10):796-801
A promising liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS) for analysis of the sulfates of 5alpha-androgen, androsterone and epiandrosterone (A-S and EpiA-S) in human serum was developed. The method was used to assess one of the markers of 5alpha-reductase activity of males including patients with prostate cancer (PC). After deproteinization with acetonitrile, the androgen sulfates and the internal standard, [7,7,16,16-2H4]dehydroepiandrosterone-S, were extracted from human serum using a solid-phase extraction cartridge and washed with hexane. The extract was reconstituted and applied to the LC/ESI-MS system operated in the selected ion monitoring mode. The method was validated over the range 0.02-5 microg/mL (A-S) and 0.005-1.5 microg/mL (EpiA-S) using 10 microL of human serum. The method was a concise procedure without chemical or enzymatic hydrolysis of the conjugates, purification by high-performance liquid chromatography and/or derivatization, and proved to be satisfactory in its reproducibility and accuracy. The levels of these androgen sulfates tended to decrease during aging, and the A-S levels in the sera obtained from both healthy males and patients with PC were correlated with their EpiA-S levels. 相似文献
8.
Motozaki T Sawamura K Suzuki A Yoshida K Ueki T Ohara A Munakata R Takao K Tadano K 《Organic letters》2005,7(11):2265-2267
[reaction: see text]. We have completed the total synthesis of natural (+)-tubelactomicin A (1), a 16-membered macrolide antibiotic. This Letter presents a highly efficient synthesis of the upper-half segment (C14-C24) and the completion of the total synthesis featuring a high-yielding Stille coupling for the connection of the upper-half and lower-half segments and Mukaiyama macrolactonization for the construction of the entire structure of 1. 相似文献
9.
Akiko Sekihara Hidekazu Honma Tadahiro Fukuju Kiminori Maeda Hisao Murai 《Research on Chemical Intermediates》1998,24(8):859-877
Photooxidation (charge transfer) reactions of carbazole derivatives by maleic anhydride (MA) in alcoholic media are studied
by a time-resolved cw-ESR (TRESR) and Fourier transform ESR (FTESR) techniques. The CIDEP spectra observed in the systems
(methyl-, ethyl-, and phenyl-substituted carbazoles with MA) remarkably depend on the MA concentration. Under the high concentration
conditions, an emissive TM (triplet mechanism) polarization with a slight A/E (absorption/emission) pattern of the RPM (radical
pair mechanism) is observed. In the low concentration of MA, a TM-like absorptive polarization is superimposed on the A/E
pattern of the RPM. Since this reaction takes place exclusively through the triplet state, this spectral phase reveals that
the singlet state of the radical-ion pair (RIP) has an energy higher than that of the triplet state, in other words, the sign
of the apparent exchange interaction of the present RIP systems is positive. The total absorptive polarization observed in
the low concentration of MA is tentatively explained by the polarization transfer from the excited triplet state of carbazoles
in thermal equilibrium. 相似文献
10.
Keiichi Satoh Zhang Xiang-Yu Masashi Miya-iri Akiko Honma Kiyoshi Sawada 《Monatshefte für Chemie / Chemical Monthly》2006,137(11):1375-1383
Summary. The ion-pair solvent extraction behavior of ethylenediaminetetraacetate (EDTA) anion by various tetraalkylammonium ions was investigated at 25.0 ± 0.1°C. The extraction of EDTA exceeded 90% from the basic aqueous solution into the organic solvents such as n-hexane and benzene derivatives containing tri-n-octylmethylammonium chloride, but EDTA was hardly extracted from acidic solution. Among the chemical species of EDTA in aqueous solution, edta
4− is the most extractable one. On the other hand, the extraction of EDTA was less than 1% into chloroform and 1,2-dichloroethane even from the basic aqueous solution. The effect of the structure
of alkylammonium ion was also examined. Tetra-n-hexylammonium and tetra-n-octylammonium ions could not extract EDTA even from the basic aqueous solution, while the use of tri-n-octylmethylammonium and di-n-lauryldimethylammonium ions enhances the extraction of EDTA. These results suggest that the steric hindrance in the ion-pair of alkylammonium and EDTA anion in the organic phase affects the extractability of EDTA containing ion-pair. The solution structure of ion-pair in the organic phase was calculated by MMFF force field and the steric
effect in the ion-pair was also suggested. From the extraction constants obtained, the possibility of the extraction separation
of EDTA has been shown.
Present address: Chemistry Department, Heilongjiang University, Harbin, China 相似文献