全文获取类型
收费全文 | 2005篇 |
免费 | 60篇 |
国内免费 | 7篇 |
专业分类
化学 | 1525篇 |
晶体学 | 22篇 |
力学 | 22篇 |
数学 | 84篇 |
物理学 | 419篇 |
出版年
2023年 | 7篇 |
2022年 | 18篇 |
2021年 | 24篇 |
2020年 | 35篇 |
2019年 | 36篇 |
2018年 | 27篇 |
2017年 | 8篇 |
2016年 | 46篇 |
2015年 | 34篇 |
2014年 | 39篇 |
2013年 | 112篇 |
2012年 | 86篇 |
2011年 | 121篇 |
2010年 | 46篇 |
2009年 | 73篇 |
2008年 | 106篇 |
2007年 | 112篇 |
2006年 | 124篇 |
2005年 | 122篇 |
2004年 | 129篇 |
2003年 | 119篇 |
2002年 | 106篇 |
2001年 | 62篇 |
2000年 | 46篇 |
1999年 | 31篇 |
1998年 | 16篇 |
1997年 | 22篇 |
1996年 | 21篇 |
1995年 | 21篇 |
1994年 | 12篇 |
1993年 | 20篇 |
1992年 | 14篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1989年 | 16篇 |
1988年 | 25篇 |
1987年 | 14篇 |
1986年 | 18篇 |
1985年 | 22篇 |
1984年 | 30篇 |
1983年 | 12篇 |
1982年 | 10篇 |
1981年 | 10篇 |
1980年 | 15篇 |
1979年 | 16篇 |
1978年 | 14篇 |
1977年 | 11篇 |
1975年 | 9篇 |
1974年 | 11篇 |
1973年 | 9篇 |
排序方式: 共有2072条查询结果,搜索用时 15 毫秒
21.
M Sugiyama T Sakamoto K Tabata K Endo K Ito M Kobayashi H Fukumi 《Chemical & pharmaceutical bulletin》1989,37(8):2122-2131
Thiazolo[3,2-a]thieno[3,2-d]-, [3,4-d]- and [2,3-d]pyrimidin-5-one derivatives (6, 11 and 16), and polymethylene condensed thieno[3,2-d]-, [3,4-d]- and [2,3-d]pyrimidin-5-one derivatives (19-21), in which the oxygen atom of the oxazolidine moiety in 3 was replaced by a sulfur atom or methylene groups, were synthesized and evaluated for gastric antisecretory activity in pylorus-ligated rats. The structure-activity relationships of these compounds are discussed. 相似文献
22.
Y Nishioka S Kyotani M Okamura M Miyazaki Y Sakamoto M Morita K Okazaki S Ohnishi Y Yamamoto K Ito 《Chemical & pharmaceutical bulletin》1992,40(1):267-268
Hepatic artery of dogs was embolized with cisplatin (CDDP) albumin microspheres containing chitin and chitosan to investigate the in vivo CDDP release kinetics from CDDP albumin microspheres, the CDDP cumulative characteristics in the liver, and the influence of microsphere administration on hepatic tissue. Results showed that changes in blood CDDP content were dependent on CDDP albumin microsphere type and that release kinetics were better sustained when chitin was added to the microspheres or when the microspheres were treated with chitosan. In particular, the administration of CDDP in the chitin-containing CDDP chitosan albumin microspheres showed a blood CDDP content of approximately 0.26 micrograms Pt/ml 14 d after administration. The administration of chitin-containing or chitosan treated CDDP microspheres showed a CDDP content in the hepatic tissue of 0.14 to 0.23 micrograms Pt/g 28 d after administration. They also showed better control of CDDP release than those without chitin or chitosan treatment. No CDDP influence on hepatic tissue was observed. We conclude that, even in vivo, chitin and chitosan are effective embolic materials. 相似文献
23.
Applicability of headspace solid-phase microextraction to the determination of multi-class pesticides in waters 总被引:8,自引:0,他引:8
The applicability of headspace solid-phase microextraction (HS-SPME) to pesticide determination in water samples was demonstrated by evaluating the effects of temperature on the extraction of the pesticides. The evaluations were performed using an automated system with a heating module. The 174 pesticides that are detectable with gas chromatograph were selected objectively and impartially based on their physical properties: vapor pressure and partition coefficient between octanol and water. Of the 174 pesticides, 158 (90% of tested) were extracted with a polyacrylate-coated fiber between 30 and 100 degrees C and were determined with gas chromatograph-mass spectrometry. The extraction-temperature profiles of the 158 extracted pesticides were obtained to evaluate the effects of temperature on the extraction of pesticides. The pesticides were classified into four groups according to the shape of their extraction-temperature profiles. The line of demarcation between extractable pesticides and non-extractable pesticides could be drawn in the physical property diagram (a double logarithmic plot of their vapor pressure and partition coefficient between octanol and water). The plot also revealed relationships between classified extraction features and their physical properties. The new method for multi residue screening in which the analytes were categorized into sub-groups based on extraction temperature was developed. In order to evaluate the quantitivity of the developed method, the 45 pesticides were chosen among the pesticides that are typically monitored in waters. Linear response data for 40 of the 45 was obtained in the concentration range below 5 microg/l with correlation coefficients ranging between 0.979 and 0.999. The other five pesticides had poor responses. Relative standard deviations at the concentration of the lowest standard solution for each calibration curve of the pesticides ranged from 3.6 to 18%. The value of 0.01 microg/l in the limits of detection for 17 pesticides was achieved only under the approximate conditions for screening, not under the individually optimized conditions for each pesticide. Recoveries of tested pesticides in actual matrices were essentially in agreement with those obtained by solid-phase extraction. 相似文献
24.
Winny Dong Jeffrey Sakamoto Bruce Dunn 《Journal of Sol-Gel Science and Technology》2003,26(1-3):641-644
The electrochemical properties of high surface area transition metal oxide aerogels are extremely interesting because aerogels serve to amplify surface effects. As a result, the electrochemical properties are dominated by surfaces rather than by bulk behavior. In the case of vanadium oxide aerogels this leads to extraordinary electrochemical properties, including an extremely high capacity for lithium and electrochemical responses that are both battery-like and capacitor-like. By exploiting sol-gel synthesis, it is possible to synthesize nanocomposite electrodes in which aerogels are in intimate contact with carbon nanotubes. The resulting nanocomposites exhibit superior electrochemical properties, especially at high discharge. 相似文献
25.
Toshio Koizumi Jun Sakamoto Yasuhiko Gondo Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2002,40(14):2487-2494
The palladium(0)‐catalyzed polyaddition of bifunctional vinyloxiranes [1,4‐bis(2‐vinylepoxyethyl)benzene ( 1a ) and 1,4‐bis(1‐methyl‐2‐vinylepoxyethyl)benzene ( 1b )] with 1,3‐dicarbonyl compounds [methyl acetoacetate ( 4 ), dimethyl malonate ( 6 ), and Meldrum's acid ( 8 )] was investigated under various conditions. The polyaddition of 1 with 4 was carried out in tetrahydrofuran with phosphine ligands such as PPh3 and 1,2‐bis(diphenylphosphino)ethane (dppe). Polymers having hydroxy, ketone, and ester groups in the side groups ( 5 ) were obtained in good yields despite the kinds of ligands employed. The number‐average molecular weight value of 5b was higher than that of 5a . The polyaddition of 1b and 6 was affected by the kinds of ligands employed. The corresponding polymer 7b was not obtained when PPh3 and 1,2‐bis(diphenylphosphino)ferrocene were used. The polyaddition was carried out with dppe as the ligand and gave polymer 7b in a good yield. The molecular weight of the polymer obtained from 1b and 8 was much higher than those of polymers 5b and 7b . The polyaddition with Pd2(dba)3 · CHCl3/dppe as a catalyst (where dba is dibenzylideneacetone) produced polymer 9b in a 92% yield (number‐average molecular weight = 45,600). The stereochemistries of all the obtained polymers were confirmed as an E configuration by the coupling constant of the vinyl proton. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2487–2494, 2002 相似文献
26.
(+)-Biotin (1) was synthesized in 25% overall yield over 11 steps from L-cysteine. The contiguous asymmetric centers at C-3a and C-6a were formed through a novel and highly stereoselective Lewis base-catalyzed cyanosilylation of alpha-amino aldehyde 3 to provide anti-O-TMS-cyanohydrin 4 with high stereoselectivity and in high yield (anti/syn = 92:8, 96%). Treatment of 4 with a di-Grignard reagent, 1,4-bis(bromomagnesio)butane, followed by carbon dioxide, efficiently installed the 4-carboxybutyl chain at C-4 to give keto acid 5. The final cyclization to bicyclic compound 7b, a precursor to 1, was realized by a palladium-catalyzed intramolecular allylic amination of cis-allylic carbonate 6b that was elaborated from 5. 相似文献
27.
Aldehyde-2,4-dinitrophenylhydrazones exist as (E)- and (Z)-geometrical isomers, and adventitious isomerization during sample preparation can cause analytical errors. Purified alkenal-2,4-dinitrophenylhydrazone derivatives comprise only the (E)-isomer. However, partial isomerization to the (Z)-isomer occurs upon addition of acid to attain an equilibrium isomer ratio. The UV-visible spectral properties of the isomers differ; the (Z)-isomer exhibiting a 6-10 nm lower absorption maximum compared to the (E)-isomer. Alkenal-2,4-dinitrophenylhydrazones having a CC double bond at the 2- or 3-position of the alkenal exhibited similar absorption maxima with an equilibrium isomer ratio (0.035) that was much lower than those of other alkenals. The CC double bond at the 3-position migrates to a position of conjugation with the CN double bond during hydrazone synthesis to form a stabilized molecular structure. Alkenal-2,4-dinitrophenylhydrazones having a double bond at the 4-position or greater exhibited a similar absorption maxima equilibrium isomer ratio (0.14) to alkanal-2,4-dinitrophenylhydrazones. The quantitative analysis of carbonyl compounds in air or water using DNPH is usually conducted in the presence of an acid catalyst. Consequently, the solution of the direct extract prepared for HPLC or GC analysis contains both (E)- and (Z)-isomers. 相似文献
28.
Ochiai M Suefuji T Miyamoto K Tada N Goto S Shiro M Sakamoto S Yamaguchi K 《Journal of the American Chemical Society》2003,125(3):769-773
Reported here for the first time are the synthesis and characterization of supramolecular complexes between diaryl-lambda(3)-iodanes and 18-crown-6 (18C6). Slow evaporation of solvents afforded 1:1 and 2:1 complexes between Ph(2)IBF(4) and 18C6 as stable crystals, depending on the conditions. X-ray crystal structures of these complexes indicated that each iodine atom contacts with the three adjacent oxygen atoms of 18C6 through two hypervalent secondary bonding and a weak interaction. (1)H NMR analyses and CSI-MS spectra showed that, in dichloromethane solution, Ph(2)IBF(4) exclusively forms the 1:1 complex with 18C6 (binding constant K(a), 1.02 x 10(3) M(-)(1)). The binding constants decrease with the increased solvent donor ability (Gutmann's DN). Changing the heteroatom ligand from BF(4) to the less nucleophilic PF(6) and AsF(6) increased the binding constant by about six times. Substitution of an electron-withdrawing group onto the para position of Ph(2)IBF(4) tends to increase in the complex stability. A linear Hammett relationship (rho = 0.59) between log K(a) and sigma(p)(+) values of substituents indicates that the diaryl-lambda(3)-iodanes with electropositive iodine(III) interact more efficiently with 18C6. Decreased binding magnitude was measured with 15C5, dibenzo-18C6, dibenzo-21C7, and dibenzo-30C10. 相似文献
29.
R. Sakamoto 《Colloid and polymer science》1984,262(10):788-792
Solvent effects on the phase separation of poly(-benzyl L-glutamate) to liquid crystal and isotropic solution have been observed in various helicogenic solvents. The temperature-composition phase diagrams have been determined for each solution. The critical concentrations,
2
*
, at which the phase separation occours have been compared in various solvents. In dimethylformamide in which the polymer is molecularly dispersed, the observed
2
*
value has agreed with that calculated by Flory's theory. In some solvents in which the polymer aggregates in a head-to-tail mode such as chloroform, the observed
2
*
values have been considerably small. It is assumed that the polymer aggregates behave as longer particles than the original particles. In dioxane in which the polymer aggregates highly both in a head-to-tail and a side-by-side modes, the
2
*
value has been a little larger than that in chloroform. In this case the relationship between the aggregation and the liquid crystal formation is so complicated that further investigation is necessary. In aromatic solvents such asm-cresol that dissolves the polymer almost molecularly, the
2
*
is smaller than that in dimethylformamide. Therefore, the intermolecular interactions between the phenyl groups in the side groups of the polymer and those in solvent molecules must be considered.The author is grateful to Mr. K. Sano and Mr. M. Watanabe for their observation of the liquid crystal formation. 相似文献
30.
Tatsuro Ouchi Hirotoshi Fujie Satoshi Jokei Yoshiomi Sakamoto Hidenori Chikashita Takeshi Inoi Otto Vogl 《Journal of polymer science. Part A, Polymer chemistry》1986,24(9):2059-2074
Acryloyl-type polymer fixing 1-β-carbonylethyl-5-fluorouracil residues through D -glucofuranoses via ester bonds was synthesized by means of polymerization of the corresponding monomer and polymer reaction. In order to provide the water-soluble objective polymer, the copolymerization of the acryloyl-type monomer with acrylamide was carried out. The extent of release of 5-FU residues from the copolymer was investigated in the enzyme or nonenzyme system in vitro. Furthermore, the antitumor activities of the water-insoluble homopolymer and water-soluble copolymer obtained were tested in vivo. 相似文献