全文获取类型
收费全文 | 8718篇 |
免费 | 1639篇 |
国内免费 | 1680篇 |
专业分类
化学 | 6568篇 |
晶体学 | 195篇 |
力学 | 511篇 |
综合类 | 137篇 |
数学 | 1064篇 |
物理学 | 3562篇 |
出版年
2024年 | 34篇 |
2023年 | 166篇 |
2022年 | 329篇 |
2021年 | 354篇 |
2020年 | 390篇 |
2019年 | 368篇 |
2018年 | 350篇 |
2017年 | 369篇 |
2016年 | 406篇 |
2015年 | 508篇 |
2014年 | 542篇 |
2013年 | 657篇 |
2012年 | 783篇 |
2011年 | 875篇 |
2010年 | 689篇 |
2009年 | 527篇 |
2008年 | 676篇 |
2007年 | 572篇 |
2006年 | 515篇 |
2005年 | 444篇 |
2004年 | 353篇 |
2003年 | 330篇 |
2002年 | 397篇 |
2001年 | 308篇 |
2000年 | 202篇 |
1999年 | 174篇 |
1998年 | 103篇 |
1997年 | 83篇 |
1996年 | 91篇 |
1995年 | 83篇 |
1994年 | 61篇 |
1993年 | 44篇 |
1992年 | 46篇 |
1991年 | 37篇 |
1990年 | 44篇 |
1989年 | 27篇 |
1988年 | 19篇 |
1987年 | 19篇 |
1986年 | 9篇 |
1985年 | 18篇 |
1984年 | 12篇 |
1983年 | 9篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1971年 | 1篇 |
1957年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
61.
微波作用下2,5-二取代-1,3,4-噁二唑的合成 总被引:2,自引:0,他引:2
2 ,5 二取代 1 ,3 ,4 二唑可用作药品 ,光敏物质 ,闪烁体 ,激光材料 ,高分子液晶单体等[1- 5] 。一种是以芳香酸与水合肼作为原料用多聚磷酸作为脱水环合剂来合成此类化合物[6 ] ,另一种是由芳香酸转变为芳香酰氯或酯 ,再与水合肼反应得到单酰肼或二酰肼 ,最后用三氯氧磷[7] ,五氧化二磷和五氯化磷[8] ,一氯三甲硅[9] 脱水环合 ;此外 ,用水合肼和尿素合成得到的氨基脲代替水合肼 ,与芳香酸缩合合成二唑[10 ] ,这些方法共同的缺陷是 :环合时间较长 ,少者 4~ 5h ,多则 8h。近年来 ,微波技术在有机合成及其杂环化合物的合成中得到了广… 相似文献
62.
Chun‐Xiang Wang Chen‐Xia Du Zhi‐Feng Li 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(10):m488-m490
In the title compound, [Zn(C17H10N5O)2(H2O)2]·4H2O, cyclic water hexamers forming one‐dimensional metal–water chains are observed. The water clusters are trapped by the co‐operative association of coordination interactions and hydrogen bonds. The ZnII ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two O atoms and two N atoms from two 2′‐(4,5‐diazafluoren‐9‐ylidene)picolinohydrazidate ligands and two water molecules. 相似文献
63.
Cu(I)/Diamine-catalyzed Aryl-alkyne Coupling Reactions 总被引:1,自引:0,他引:1
Ye Feng WANG Wei DENG Lei LIU Qing Xiang GUO 《中国化学快报》2005,16(9):1197-1200
Arylalkynes are important building blocks for the synthesis of natural products,pharmaceuticals,and artificial molecular devices1.They are often synthesized via the Pd-catalyzed Sonogashira coupling reactions between aryl halides and terminal alkynes2,3.Unfortunately,it remains difficult to apply the Sonogashira reaction to industrial scale and/or pharmaceutical synthesis,due to the high cost of Pd and the difficulty in removing the toxic Pd residues from the reaction products.Thus it is wor… 相似文献
64.
Xiang‐Gao Meng Chun‐Shan Zhou Li Wang Chang‐Lin Liu 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):o667-o670
5‐Sulfosalicylic acid (5‐SSA) and 3‐aminopyridine (3‐APy) crystallize in the same solvent system, resulting in two kinds of 1:1 proton‐transfer organic adduct, namely 3‐aminopyridinium 3‐carboxy‐4‐hydroxybenzenesulfonate monohydrate, C5H7N2+·C7H5O6S−·H2O or 3‐APy·5‐SSA·H2O, (I), and the anhydrous adduct, C5H7N2+·C7H5O6S− or 3‐APy·5‐SSA, (II). Both compounds have extensively hydrogen‐bonded three‐dimensional layered polymer structures, with interlayer homo‐ and heterogeneous π–π interactions in (I) and (II), respectively. 相似文献
65.
Lijun X Bochu W Zhimin L Chuanren D Qinghong W Liu L 《Colloids and surfaces. B, Biointerfaces》2005,40(1):25-29
We studied the LAS degradation of immobilized Pseudomonas aeruginosa with low-intensity ultrasonic and the influence of original LAS concentration, pH, rotary velocity and different conditions of low-intensity ultrasonic irradiation on the degradation of LAS. In our experiment, the degradation rate of LAS was the main index. We found that low-intensity ultrasonic irradiation could improve the metabolism of microorganism cells and promote the LAS biodegradation of immobilized cells. In the experiment, 50 mg/l LAS were used to simulate wastewater, and low-intensity ultrasonic was considered. We found the influence was obvious, and the optimal degradation rate was acquired when the conditions of ultrasonic were frequency 24 kHz, power 8 W, stimulation time 5 s, intermissive time 30 s, and total time 10 min. The LAS degradation rate of immobilized cells with ultrasonic were respectively 40% and 9.5% higher than that of the suspending cells and immobilized cells without irradiation. 相似文献
66.
用TRP技术研究了以全硅MCM-41(Si-MCM-41)和HNO3交换的全硅MCM-41(H-MCM-41)为载体制备的Ni-Mo、Co-Mo和Ni-W加氢脱硫(HDS)催化剂的还原性能,并以0.8(wt)%二苯并噻吩(DBT)的十氢萘溶液为模型化合物,在高压固定床反应器上考察了上述催化剂的加氢脱硫(HDS)反应性能。结果表明,Si-MCM-41经稀HNO3交换后,所担载的Ni-Mo和Ni-W催化剂还原性能、HDS活性和加氢活性有显著变化,但对Co-Mo催化剂影响不大。这说明在Ni-Mo/H-MCM-41和Ni-W/H-MCM-41中可能存在氢溢流现象,DBT的HDS活性与载体表面酸性和氢溢流有关。 相似文献
67.
Huang S Xiao Z Wang F Zhou J Yuan G Zhang S Chen Z Thiel W von Ragué Schleyer P Zhang X Hu X Chen B Gan L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5449-5456
[60]Fullerene mixed peroxides C60(O)(OOtBu)4 exhibit chemo- and regioselective reactions under mild conditions. The epoxy moiety is opened by ferric chloride to form vicinal hydroxy chloride C60Cl(OH)(OOtBu)4. BF3 is also effective in opening the epoxy moiety. The O-O bond of the fullerene mixed peroxide is cleaved by aluminum chloride to form both [5,6]- and [6,6]-fullerene hemiketals (oxohomo[60]fullerenes). A Hock-type rearrangement is proposed for the formation of the hemiketals, in which a fullerene C-C bond is cleaved. Lewis acids and/or visible light can initiate isomerization of the hemiketal isomers. Single-crystal X-ray analysis and theoretical calculations confirmed the results. 相似文献
68.
聚1-氨基蒽醌在二次锂电池正极材料中的应用 总被引:4,自引:0,他引:4
采用化学方法合成聚1-氨基蒽醌并用于二次锂电池正极材料,通过红外光谱、扫描电镜、粒度测试、循环伏安以及充放电测试等方法对材料的官能团结构、微观形貌、颗粒大小以及电化学性能等进行了研究与分析.实验表明,与金属锂组成二次锂电池后,聚1-氨基蒽醌达到了218.3 mAh•g-1的首次放电容量,经过25次循环后仍可保持较高的充放电效率.由于材料具有较高的能量密度且不含对环境有污染的元素S,因此是二次锂电池非常有希望的正极材料. 相似文献
69.
Cabeza A Ouyang X Sharma CV Aranda MA Bruque S Clearfield A 《Inorganic chemistry》2002,41(9):2325-2333
Nitrilotris(methylenephosphonic acid) (NTP, [N(CH(2)PO(3)H(2))(3)]) recently has been found to form three-dimensional porous structures with encapsulation of templates as well as layered and linear structures with template intercalation. It was, therefore, of interest to examine the type of organic-inorganic hybrids that would form with metal cations. Mn(II) was found to replace two of the six acid protons, while a third proton bonds to the nitrilo nitrogen, forming a zwitter ion. Two types of compounds were obtained. When the ratio of acid to Mn(II) was less than 10, a trihydrate, Mn[HN(CH(2)PO(3)H)(3)(H(2)O)(3)] (2) formed. Compound 2 is monoclinic P2(1)/c, with a = 9.283(2) A, b = 16.027(3) A, c = 9.7742(2) A, beta = 115.209(3) degrees, V = 1315.0(5) A(3), and Z = 4. The Mn atoms form zigzag chains bridged by two of the three phosphonate groups. The third phosphonate group is only involved in hydrogen bonding. The metal atoms are octahedrally coordinated with three of the sites occupied by water molecules. Adjacent chains are hydrogen-bonded to each other through POH and HN donors, and the additional participation of all the water hydrogens in H-bonding results in a corrugated sheet-like structure. Use of excess NTP at a ratio to metal of 10 to 1 yields an anhydrous compound Mn[HN(CH(2)PO(3)H)(3)] (1), P2(1)/n, a = 9.129(1) A, b = 8.408(1) A, c = 13.453(1) A, beta = 97.830(2) degrees, V = 1023.0(2) A(3), and Z = 4. Manganese is five coordinate forming a distorted square pyramid with oxygens from five different phosphonate groups. The sixth oxygen is 2.85 A from an adjacent Mn, preventing octahedral coordination. All the protonated atoms, three phosphonate oxygens and N, form moderately strong hydrogen bonds in a compact three-dimensional structure. The open-structured trihydrate forms a series of isostructural compounds with other divalent transition metal ions as well as with mixed-metal compositions. This is indicative that the hydrogen bonding controls the type of structure formed irrespective of the cation. 相似文献
70.
The Chemical Speciation and Behavior of Mercury and Selenium in the Insoluble Fraction of Striped Dolphin Liver 总被引:1,自引:0,他引:1
XiaoRongHU HuiLI YongXiangZHANG 《中国化学快报》2004,15(3):326-329
Most of the mercury and selenium exist in the insoluble fraction of dolphin liver. After the insoluble fraction was digested by alkaline protease in the presence of 1% SDS, approximately 50% of Hg and Se consisted in the supernatant and the others in the residue. Gel filtration chromatography of the hydrolysate showed that 96% of Hg and 87% of Se were combined with the high molecular weight proteins stably, which cannot be substituted by the complex reagents.Mercury and selenium in the residue were confirmed as HgSe crystal. 相似文献