全文获取类型
收费全文 | 33706篇 |
免费 | 6019篇 |
国内免费 | 7333篇 |
专业分类
化学 | 24800篇 |
晶体学 | 808篇 |
力学 | 2285篇 |
综合类 | 841篇 |
数学 | 3964篇 |
物理学 | 14360篇 |
出版年
2024年 | 114篇 |
2023年 | 585篇 |
2022年 | 1141篇 |
2021年 | 1186篇 |
2020年 | 1263篇 |
2019年 | 1206篇 |
2018年 | 1057篇 |
2017年 | 1252篇 |
2016年 | 1392篇 |
2015年 | 1589篇 |
2014年 | 1877篇 |
2013年 | 2472篇 |
2012年 | 2896篇 |
2011年 | 2940篇 |
2010年 | 2298篇 |
2009年 | 2263篇 |
2008年 | 2659篇 |
2007年 | 2492篇 |
2006年 | 2259篇 |
2005年 | 2056篇 |
2004年 | 1604篇 |
2003年 | 1238篇 |
2002年 | 1212篇 |
2001年 | 990篇 |
2000年 | 1083篇 |
1999年 | 940篇 |
1998年 | 581篇 |
1997年 | 549篇 |
1996年 | 470篇 |
1995年 | 445篇 |
1994年 | 445篇 |
1993年 | 405篇 |
1992年 | 330篇 |
1991年 | 294篇 |
1990年 | 274篇 |
1989年 | 237篇 |
1988年 | 182篇 |
1987年 | 168篇 |
1986年 | 114篇 |
1985年 | 85篇 |
1984年 | 94篇 |
1983年 | 60篇 |
1982年 | 60篇 |
1981年 | 50篇 |
1980年 | 41篇 |
1979年 | 18篇 |
1974年 | 7篇 |
1965年 | 20篇 |
1964年 | 10篇 |
1957年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Petrassi HM Johnson SM Purkey HE Chiang KP Walkup T Jiang X Powers ET Kelly JW 《Journal of the American Chemical Society》2005,127(18):6662-6671
Transthyretin (TTR) amyloidogenesis requires rate-limiting tetramer dissociation and partial monomer denaturation to produce a misassembly competent species. This process has been followed by turbidity to identify transthyretin amyloidogenesis inhibitors including dibenzofuran-4,6-dicarboxylic acid (1). An X-ray cocrystal structure of TTR.1(2) reveals that it only utilizes the outer portion of the two thyroxine binding pockets to bind to and inhibit TTR amyloidogenesis. Herein, structure-based design was employed to append aryl substituents at C1 of the dibenzofuran ring to complement the unused inner portion of the thyroxine binding pockets. Twenty-eight amyloidogenesis inhibitors of increased potency and dramatically increased plasma TTR binding selectivity resulted. These function by imposing kinetic stabilization on the native tetrameric structure of TTR, creating a barrier that is insurmountable under physiological conditions. Since kinetic stabilization of the TTR native state by interallelic trans suppression is known to ameliorate disease, there is reason to be optimistic that the dibenzofuran-based inhibitors will do the same. Preventing the onset of amyloidogenesis is the most conservative strategy to intervene clinically, as it remains unclear which of the TTR misassembly intermediates results in toxicity. The exceptional binding selectivity enables these inhibitors to occupy the thyroxine binding site(s) in a complex biological fluid such as blood plasma, required for inhibition of amyloidogenesis in humans. It is now established that the dibenzofuran-based amyloidogenesis inhibitors have high selectivity, affinity, and efficacy and are thus excellent candidates for further pharmacologic evaluation. 相似文献
992.
锂离子电池正极材料LiMn2O4的低热固相合成与性能表征 总被引:6,自引:0,他引:6
锂离子电池具有比能量高、环境污染小等优点,广泛应用于手提电话、便携式电脑、摄像机等设备中。其正极材料的研究是锂离子电池的研究重点。层状结构的LiCoO2、LiNiO2和尖晶石结构的LiMn2O4是仅有的三种能在3.5V以上电位可嵌入Li的正极材料[1~3]。目前市售的锂离子电池主要采用LiCoO2作正极材料,但由于Co资源缺乏和价格相对昂贵,而锰资源丰富,价格低廉且无毒,对环境友好,因此世界各国都在大力进行以LiMn2O4为正极材料的锂离子电池的实用化研究。LiMn2O4传统的制备方法是高温固相反应合成法[4~7],但由于Mn的变价多,与Li形成贫Li或… 相似文献
993.
Hai-Long Jiang 《Journal of solid state chemistry》2006,179(6):1911-1917
Two new barium zinc selenite and tellurite, namely, BaZn(SeO3)2 and BaZn(TeO3)Cl2, have been synthesized by the solid state reaction. The structure of BaZn(SeO3)2 features double chains of [Zn(SeO3)2]2− anions composed of four- and eight-member rings which are alternatively along a-axis. The double chains of [Zn2(TeO3)2Cl3]3− anions in BaZn(TeO3)Cl2 are formed by Zn3Te3 rings in which each tellurite group connects with three ZnO3Cl tetrahedra. BaZn(SeO3)2 and BaZn(TeO3)Cl2 are wide bandgap semiconductors based on optical diffuse reflectance spectrum measurements. 相似文献
994.
A novel and efficient enantioselective synthesis of both enantiomers of syn-(3-trifluoromethyl)isoserine was achieved. Ring opening of trifluoromethylated cyclic sulfates 3, derived from enantiopure trifluoromethylated vicinal diols 2, with various nucleophiles occurred exclusively at C2 with inversion of chirality. Treatment of 4c and 4d, obtained by nucleophilic opening of 3a and 3b with PhCO2NH4, with (CF3SO2)2O followed by substitution with sodium azide, Jones oxidation, and hydrogenolysis furnished (2S,3S)-(N-benzoyl)-3-(trifluoromethyl)isoserine 9a and (2R,3R)-(N-benzoyl)-3-(trifluoromethyl)isoserine 9b, respectively. 相似文献
995.
The biaryl unit is extensively presented in many classes of natural products, such as polyketides, terpenes, lignanes,coumarins, flavonoids, tannins, and many alkaloids.[1] It has long been recognized that an intramolecular oxidative phenolic or nonphenolic coupling reaction serves as the key step in the biosynthesis of these natural products, and the non-enzymic analogue of this transformation can lead the elegantly simple syntheses of these compounds.[2] During the last decade, a large number of oxidative coupling reagents, such as ferric chloride (FeCl3), phenyliodine(Ⅲ)bis(trifluoroacetate) (PIFA), lead(Ⅳ) tetraacetate [Pb(OAc)4], thallium(Ⅲ) triflouroacetate (TTFA), as well as vanadium oxytrifluoride (VOF3),[3,4] have been developed for this target. However, extensive application of this synthetic potential has been limited by low yields and unexpected side reactions usually encountered. 相似文献
996.
An improved capillary electrophoresis indirect chemiluminescence system was employed for the determination of chlorogenic acid and rutin in cigarette samples. After being separated by capillary electrophoresis, the analyte zones were determined by indirect chemiluminescence of luminol-potassium hexacyanoferrate. In this system, luminol was added into running buffer solution and introduced at the head of separation capillary, and potassium hexacyanoferrate was introduced at the end of the capillary. A high potential buffer reservoir was constructed from a running buffer cell and an electrode buffer one, which were jointed with a frit, in order to avoid luminol electrolysis in high potential reservoir and the excursion of chemiluminescence baseline. A low potential flow reservoir was used to prevent electrode buffer solution from the contamination of chemiluminescence waste. Therefore, the proposed capillary electrophoresis-chemiluminescence system can avoid the electrolysis of chemiluminescence reagent, retain the stability of chemiluminescence baseline and prolong the working time of running and electrode buffer solutions. In addition, the matrix of cigarette sample solutions has also an inhibitory effect on the chemiluminescence intensity in the indirect detection, whereas the influence was not observed in the separation of standard solutions. After the correction of matrix inhibition and the calibration with standard addition method, chlorogenic acid and rutin were determined in four cigarette samples by the improved capillary electrophoresis-chemiluminescence system. 相似文献
997.
ZhuanNiYU XiRong HUANG ShaoFangSONG DanWANG XueMeiLU YueZhongLI YinBoQU PeiJiGAO 《中国化学快报》2003,14(8):836-839
The inhibition of lingninase by hydrogen peroxide in the presence of cationic surfactant CTAB was studied by kinetic speetrophotometdc technique. Results showed that addition of CTAB enhanced the inhibition by H202, but it did not alter the inhibition pattern and the inhibition constant changed little with theco-ncentration of CTAB. Modification of the enzymic protein by the surfactant monomer may be responsible for the above mentioned results. 相似文献
998.
Zhiyong Jiang 《Tetrahedron letters》2007,48(1):51-54
The direct addition of P(O)-H bonds (dialkyl phosphites and diphenyl phosphonite) across various activated alkenes was catalyzed effectively by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). This is a mild, rapid and efficient protocol to generate P-C bonds. This simple procedure allows a series of dialkyl alkylphosphonates and trisubstituted phosphine oxides to be prepared in high yields. Further investigation resulted in a convenient one-pot, three-component reaction containing diphenyl phosphonite, malononitrile and an aldehyde. 相似文献
999.
A water-soluble hyperbranched polymer (WHBP), obtained from a second generation of hyperbranched polyester and maleic anhydride, was studied. Its effects on the properties of acrylic latexes, which were based on emulsion polymerization of butyl acrylate (BA), methyl methacrylate (MMA), acrylic acid (AA) and WHBP, and latex film were discussed. The characteristics of WHBP were determined by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared (FTIR) and gel permeation chromatography (GPC). Particle size and morphology of latex particles were confirmed by dynamic light scattering (DLS) and transmission electron microscope (TEM). The investigation showed that WHBP could be used in emulsion polymerization, and that latex of poly(BA-MMA-WHBP) was more stable than that of poly(BA-MMA-AA). The hardness of latex film increased from 2B to HB when WHBP was used. 相似文献
1000.
A series of [tetra-α-(2,2,4-tirmethyl-3-pentoxy) phthalocyaninato] metal complexes(M=Co, Ni, Cu, Zn)were prepared by cyclotetramerization of 3-(2,2,4-tirmethyl-3-pentoxy)phthalonitrile with corresponding anhydrous metal salts, using 1.8-diazabicyclo[5.4.0] undec-7-ene (DBU) as the catalyst. HPLC analysis shows that one isomer predominates in the product of nickel complex, while at least two main constitutional isomers exist in the product of other metal complexes. The complexes (in the form of mixture of constitutional isomers) were characterized by elemental analyses, MS, IR and UV-Vis spectroscopy. 相似文献