全文获取类型
收费全文 | 2112篇 |
免费 | 68篇 |
国内免费 | 12篇 |
专业分类
化学 | 1528篇 |
晶体学 | 28篇 |
力学 | 27篇 |
综合类 | 1篇 |
数学 | 115篇 |
物理学 | 493篇 |
出版年
2021年 | 12篇 |
2020年 | 17篇 |
2019年 | 33篇 |
2018年 | 25篇 |
2017年 | 22篇 |
2016年 | 35篇 |
2015年 | 34篇 |
2014年 | 35篇 |
2013年 | 137篇 |
2012年 | 87篇 |
2011年 | 122篇 |
2010年 | 63篇 |
2009年 | 73篇 |
2008年 | 102篇 |
2007年 | 113篇 |
2006年 | 108篇 |
2005年 | 114篇 |
2004年 | 108篇 |
2003年 | 85篇 |
2002年 | 70篇 |
2001年 | 44篇 |
2000年 | 37篇 |
1999年 | 29篇 |
1998年 | 36篇 |
1997年 | 32篇 |
1996年 | 24篇 |
1995年 | 17篇 |
1994年 | 24篇 |
1993年 | 17篇 |
1992年 | 23篇 |
1991年 | 21篇 |
1990年 | 16篇 |
1989年 | 22篇 |
1988年 | 28篇 |
1987年 | 17篇 |
1986年 | 12篇 |
1985年 | 27篇 |
1984年 | 46篇 |
1983年 | 21篇 |
1982年 | 28篇 |
1981年 | 21篇 |
1980年 | 29篇 |
1979年 | 28篇 |
1978年 | 32篇 |
1977年 | 28篇 |
1976年 | 22篇 |
1975年 | 14篇 |
1974年 | 10篇 |
1972年 | 9篇 |
1967年 | 10篇 |
排序方式: 共有2192条查询结果,搜索用时 156 毫秒
1.
2.
Minoru Koyama Dr. Takafumi Kawakami Dr. Takashi Okazoe Prof. Dr. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10913-10917
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield. 相似文献
3.
Hiroyuki Saimoto Tomoyuki Onitsuka Satoko Okabe Minoru Morimoto 《Tetrahedron letters》2004,45(48):8777-8780
Treatment of 1,3-dihydroxyacetone and acrolein with aqueous KOH gave a tetrahydrofuran derivative, 1,4-dihydroxy-3,7-dioxabicyclo[3.3.0]octane, in 80% yield. Similarly, 6-alkyl substituted 1,4-dihydroxy-3,7-dioxabicyclo[3.3.0]octanes were obtained by reaction of 1,3-dihydroxyacetone with various α,β-unsaturated aldehydes. In the cases of long chain alkenals, the reaction was effectively accelerated in the presence of organic co-solvent. On the other hand, the corresponding tricyclic products were synthesized by reaction of 1,3-dihydroxyacetone with cyclic enones, such as 2-cyclopentenone and 2-cyclohexenone. This method was successfully applied to the reaction of a tetrulose in the absence of any protecting groups. 相似文献
4.
Yusong Wu Toshihiro Seo Shiro Maeda Takashi Sasaki Satoshi Irie Kensuke Sakurai 《Journal of Polymer Science.Polymer Physics》2004,42(22):4107-4115
Two benzoyl substituted chitosan derivatives, 3,6‐O‐dibenzoylchitosan (DBC) and 2‐N‐3,6‐O‐tribenzoylchitosan (TBC), were prepared, and their optical activities in organic solvent were investigated by circular dichroism (CD). For TBC, two splitting bands (a negative one at 288 nm and a positive one at 274 nm) corresponding to the 1Lb transition of the benzoyl group were observed in chloroform and dichloromethane, while only a negative CD band was recorded in N, N‐dimethylformamide (DMF). These results indicated that the transition moments of benzoyl groups were orderly arranged along the helical polymer chain when TBC was dissolved in a solvent with low polarity, but the same ordered structure did not appear in a polar solvent of DMF. For DBC, only negative CD signals corresponding to the 1Lb transition of the benzoyl group were observed, regardless of the solvent property, which indicated that the chromophores were not arranged in an ordered fashion with appropriate geometry to interact with one another to induce bi‐signate CD signals. Adding methanol or DMF to the solution of TBC/chloroform resulted in a progressive decrease of the intensity of the positive split band at 274 nm. The intensity of the positive band was weakened upon heating a solution of TBC/chloroform from 20 to 60 °C. The results suggested that the ordered arrangement of the chromophores in the TBC system was dependent on solvent and sensitive to temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4107–4115, 2004 相似文献
5.
K. Sakurai Y. Kondo K. Miyazaki T. Okamoto S. Irie T. Sasaki 《Journal of Polymer Science.Polymer Physics》2004,42(13):2595-2603
Aiming to develop a high‐performance fiber‐reinforced rubber from styrene–butadiene rubber (SBR), we applied a special technique using electron‐beam (EB)‐irradiation‐induced graft polymerization to ultrahigh‐molecular‐weight‐polyethylene (UHMWPE) fibers. The molecular interaction between the grafted UHMWPE fibers and an SBR matrix was studied through the evaluation of the adhesive behavior of the fibers in the SBR matrix. Although UHMWPE was chemically inert, two monomers, styrene and N‐vinyl formamide (NVF), were examined for graft polymerization onto the UHMWPE fiber surface. Styrene was not effective, but NVF was graft‐polymerized onto the UHMWPE fibers with this special method. A methanol/water mixture and dioxane were used as solvents for NVF, and the effects of the solvents on the grafting percentage of NVF were also examined. The methanol/water mixture was more effective. A grafting percentage of 16.4% was the highest obtained. This improved the adhesive force threefold with respect to that of untreated UHMWPE fibers. These results demonstrated that EB irradiation enabled graft polymerization to occur even on the inert surface of UHMWPE fibers. However, the mechanical properties of the fibers could be compromised according to the dose of EB irradiation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2595–2603, 2004 相似文献
6.
Application of the 19F NMR technique to observe binding of the general anesthetic halothane to human serum albumin. 总被引:1,自引:0,他引:1
Kazuaki Shikii Satoshi Sakurai Hiroaki Utsumi Hiroko Seki Mitsuru Tashiro 《Analytical sciences》2004,20(10):1475-1477
19F NMR techniques were employed to characterize the binding property of the widely used general anesthetic halothane with human serum albumin (HSA). It was found that 19F(1H) NOE and 2D 1H-19F HOESY experiments detected intermolecular NOEs between halothane 19F and HSA protons. Measurements of the diffusion coefficients for halothane were also carried out by 1H and 19F NMR, indicating the interaction of halothane with HSA. The present results indicate that these techniques are very suitable to identify a fluorine-containing ligand binding with a protein receptor in the drug-discovery process. 相似文献
7.
Yasushi Seike Ryoko Fukumori Yukiko Senga Hiroki Oka Kaoru Fujinaga Minoru Okumura 《Analytical sciences》2004,20(1):139-142
A new and simple method for the determination of hydroxylamine in environmental water, such as fresh rivers and lakes using hypochlorite, followed by its gas choromatographic detection, has been developed. A glass vial filled with sample water was sealed by a butyl-rubber stopper and aluminum cap without head-space, and then sodium hypochlorite solution was injected into the vial through a syringe to convert hydroxylamine to nitrous oxide. The head-space in the glass vial was prepared with 99.9% grade N2 using a gas-tight syringe. After the glass vial was shaken for a few minutes, nitrous oxide in the gas-phase was measured by a gas chromatograph with an electron-capture detector. The dissolved nitrous oxide in the liquid-phase was calculated according to the solubility formula. The proposed method was applied to the analysis of fresh-water samples taken from Iu river and Hii river, flowing into brackish Lakes Nakaumi and Shinji, respectively. 相似文献
8.
Minoru Itoh 《Mathematische Zeitschrift》2004,246(1-2):125-154
9.
10.