全文获取类型
收费全文 | 1099篇 |
免费 | 24篇 |
国内免费 | 7篇 |
专业分类
化学 | 878篇 |
晶体学 | 9篇 |
力学 | 12篇 |
数学 | 58篇 |
物理学 | 173篇 |
出版年
2022年 | 12篇 |
2021年 | 8篇 |
2020年 | 11篇 |
2019年 | 8篇 |
2018年 | 17篇 |
2017年 | 7篇 |
2016年 | 14篇 |
2015年 | 14篇 |
2014年 | 20篇 |
2013年 | 60篇 |
2012年 | 51篇 |
2011年 | 56篇 |
2010年 | 25篇 |
2009年 | 34篇 |
2008年 | 60篇 |
2007年 | 65篇 |
2006年 | 65篇 |
2005年 | 73篇 |
2004年 | 54篇 |
2003年 | 50篇 |
2002年 | 49篇 |
2001年 | 18篇 |
2000年 | 11篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 7篇 |
1996年 | 11篇 |
1995年 | 10篇 |
1994年 | 14篇 |
1993年 | 10篇 |
1992年 | 17篇 |
1991年 | 14篇 |
1990年 | 14篇 |
1989年 | 13篇 |
1988年 | 15篇 |
1987年 | 16篇 |
1986年 | 10篇 |
1985年 | 14篇 |
1984年 | 22篇 |
1983年 | 10篇 |
1982年 | 17篇 |
1980年 | 17篇 |
1979年 | 14篇 |
1978年 | 6篇 |
1977年 | 15篇 |
1976年 | 8篇 |
1975年 | 10篇 |
1974年 | 8篇 |
1973年 | 5篇 |
1971年 | 7篇 |
排序方式: 共有1130条查询结果,搜索用时 234 毫秒
21.
The removal of excess reagent extracted into an organic phase in the solvent extraction of a metal complex anion with a quaternary ammonium ion is discussed. With a given chelating ligand (HO—R—SO3H), the order of extractability is HO—R—SO3- > M(OR—SO3)n- > X- > -O—R—SO3- when an anion such as nitrate or halide is added. If suitable amounts of the anion are added, only the excess of reagent can be removed. The principle is applied to the extraction with zephiramine of the cobalt complex anion formed with 2-nitroso-1-naphthol-4-sulfonic acid. Micro amounts of cobalt in pure nickel salts were determined spectrophotometrically. 相似文献
22.
T Nishi F Saito H Nagahori M Kataoka Y Morisawa Y Yabe M Sakurai S Higashida M Shoji Y Matsushita 《Chemical & pharmaceutical bulletin》1990,38(1):103-109
Syntheses and biological activities of dipeptide renin inhibitors that contain statine analogues are described. The key steps of the synthetic approach to dipeptide renin inhibitors are the asymmetric synthesis of 2(R)-substituted-3-aminocarbonylpropionic acids and the diastereoselective syntheses of (3S,4S)-statine analogues. These inhibitors (2,14-40) inhibited human renin in the 3-140 nM range. Inhibitor ES 6864 (2) was found to be a highly potent inhibitor of human renin (IC50: 4.6 x 10(-9) M) and showed high enzyme specificity. Oral administration of ES 6864 at 3 mg/kg to conscious, sodium-depleted marmosets inhibited plasma renin activity (PRA) more than 80% after 1 h. 相似文献
23.
T Hachiya E Hagami Y Shoji Y Aizawa I Kanno K Uemura M Handa J Mori A Fukagawa 《Radioisotopes》1989,38(9):377-380
In the unit housing of a compact cyclotron and positron emission CT (PET), positron emitting gas such as 15O, 11C, C15O2, C15O etc. is supplied from a cyclotron to a PET room through a transportation pipe with an appropriate shield to reduce positron annihilation radiation. Using lead or concrete shield blocks with various thicknesses, radiation leakage through the shield was measured by an ionization chamber type survey meter during continuous and constant supply of 15O gas of 1.85 GBq/min concentration which is the maximum dose for clinical use. The leakage radiation measured was 213.7, 56.0, 15.3, 5.0 muSv/week for lead shield with 1, 2, 3, and 4 cm thickness, respectively, and 193.3, 30.5 and 5.1 muSv/week for concrete shields with thickness of 10, 20, and 30 cm, respectively. The present study shows that to keep less than 300 muSv/week, which is the permissible dose rate of the boundary zone around the radiation controlled area by Japan Science and Technology Agency, it is required to use more than 8 mm thick lead shield or 7 cm thick concrete for continuous supply of 1.85 GBq/min 15O gas. 相似文献
24.
Yoshimoto S Ohashi F Ohnishi Y Nonami T 《Chemical communications (Cambridge, England)》2004,(17):1924-1925
Nanocomposites consisting of conducting polyaniline and clay minerals were successfully synthesized from mechanochemically intercalated anilinium fluoride; the nanocomposites prepared by the mechanochemical intercalation method contained much more polyaniline in the clay layers than those prepared by a conventional solution method. 相似文献
25.
Takafumi Ohta Kohji Shikinami Yukiyo Iga Shoji Takitani 《Fresenius' Journal of Analytical Chemistry》1990,336(5):385-388
Summary Chelex resins in several metal forms were tested for selective uptake of o-nitrosonaphthols and o-nitrosophenols from aqueous solution. Cu-Chelex was the most efficient resin over a wide pH range, and the taken-up nitroso compounds were effectively eluted with concentrated ammonia: acetonitrile (4:1, v/v) after washing the resin with acetonitrile to eliminate non-specific binding. The upper and lower limits of uptake capacity of the resin for 1-nitroso-2-naphthol were 0.5 mol/100 mg and 1.25 mol/100 mg, respectively. A preliminary recovery experiment using urine and cucumber juice showed that Cu-Chelex would be useful for screening of o-nitroso derivatives of phenolic substances in complicated samples such as biological fluids and foods. 相似文献
26.
Ishii K Takeuchi S Shimizu S Kobayashi N 《Journal of the American Chemical Society》2004,126(7):2082-2088
In this study, we have investigated the singlet oxygen ((1)Delta(g)) generation mechanism using phthalocyaninatosilicon (SiPc) covalently linked to nitroxide radicals (NRs), and we succeeded in increasing the singlet oxygen quantum yield (Phi(Delta)) by linking the NRs. This originates from both an increase in the triplet quantum yield and excited-state lifetimes long enough to utilize photochemical reactions. Because the electron exchange interactions with paramagnetic species were known to result only in very fast excited-state relaxation, leading to a decrease in photochemical reaction yields, this increase in Phi(Delta) is an unusual and precious example for increasing photochemical reaction yields by electron exchange interactions with paramagnetic species. In addition, our experiments and theoretical analyses show that the spin-selective energy transfer rate constant is not influenced by linking the NRs and can be evaluated by the product of spin-statistical factors and matrix elements between the initial and final states. 相似文献
27.
Shoji M Imai H Shiina I Kakeya H Osada H Hayashi Y 《The Journal of organic chemistry》2004,69(5):1548-1556
An oxidative dimerization reaction, involving the three successive steps of oxidation, 6 pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6 pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6 pi-electrocyclization. 相似文献
28.
Hitoshi?MatsukiEmail author Michio?Yamanaka Hiroshi?Kamaya Shoji?Kaneshina Issaku?Ueda 《Colloid and polymer science》2005,283(5):512-520
The dissociation equilibrium between uncharged local anesthetic lidocaine (LC) and charged local anesthetic LC (LCH+) in a surface-adsorbed film was investigated by measuring the surface tension and pH of aqueous solutions of a mixture of hydrochloric acid and LC. The surface tension values decreased slightly with increasing total molality mt at 0X20.5, where X2 is the mole fraction of LC in the mixture, while they decreased rapidly with increasing mt at 0.5<X21. It was shown from the pH measurements that almost all LC molecules were changed into LCH+ ions by protonation at 0X20.5 and both forms coexisted only at 0.5<X21. The quantities of the respective LC and LCH+ transferred from the aqueous solution to the adsorbed film, i.e., their surface densities, were calculated by applying the thermodynamic equations derived to the surface tension and pH data. A greater quantity of LC than LCH+ existed in the adsorbed film at the coexisting composition. The partitioning behavior of LC and LCH+ in the adsorbed film was characterized by three composition regions: (1) slight partitioning of low surface-active LCH+ in the region at 0X20.5, (2) preferential partitioning of LC at 0.5<X2<around 0.7, and (3) negative partitioning of LCH+ at around 0.7X21. The present results clearly indicate that uncharged local anesthetics transfer into hydrophobic environments such as cell membranes more than charged ones. 相似文献
29.
Andrzej W. Trochimczuk Shoji AokiKazunori Yamabe Akinori Jyo 《European Polymer Journal》2002,38(5):941-945
Four porous vinylnaphthalene/divinylnaphthalene (VN/DVN) polymers having three different nominal crosslinking degrees (60, 80 and 100 wt.%) have been synthesized using the suspension polymerization method in the presence of toluene and decane.The use of various crosslinking levels and inert diluents was aimed at changing the extent of polymeric network-diluent interactions. The resultant polymers have specific surface area in the range 450-700 m2/g depending on the DVN content. Two sets of pores were detected in all resins: one with the diameter of ≈2 nm and the second one in the range of 30-40 nm. Their sorptive properties have been studied using dilute (0.5 mmol/l) solutions of phenol and its derivatives (o-chlorophenol, 2-methylphenol, o-nitrophenol, m-nitrophenol and p-nitrophenol). It has been found that sorption, at low equilibrium concentration, follows the order: o-nitrophenol > o-chlorophenol > m-nitrophenol > o-methylphenol > p-nitrophenol > phenol. Full characteristics of the porous structure of resultant polymers was obtained by nitrogen adsorption at 77 K and their surface properties analyzed using Inverse Gas Chromatography. 相似文献
30.
Ken-ichi Sato Shoji Akai Akira Yoshitomo Yoshimitsu Takai 《Tetrahedron letters》2004,45(44):8199-8201
The merits of an indirect protecting method for hydroxyl groups using allyl groups via allyloxycarbonyl groups in the synthesis of antennary β-d-mannopyranosyl disaccharides from β-d-galactopyranosyl disaccharides were studied. Regioselective allyloxycarbonylation and conversion reactions involving simultaneous double SN2 nucleophilic substitution at C-2′ and C-4′ of benzyl O-[β-d-galactopyranosyl]-(1-4)-3,6-di-O-benzyl-2-deoxy-2-N-phthalimido-β-d-glucopyranoside were examined for comparison with the direct allylation method. The required β-d-mannopyranosyl disaccharide having proper protecting groups was obtained using this indirect method in 52% yield. In contrast, the reported direct allylation method using methyl O-(β-d-galactopyranosyl) disaccharide gave the corresponding β-d-mannopyranosyl disaccharide in only 7.5% yield. 相似文献