全文获取类型
收费全文 | 10828篇 |
免费 | 612篇 |
国内免费 | 2076篇 |
专业分类
化学 | 10007篇 |
晶体学 | 185篇 |
力学 | 148篇 |
综合类 | 90篇 |
数学 | 1350篇 |
物理学 | 1736篇 |
出版年
2024年 | 8篇 |
2023年 | 112篇 |
2022年 | 247篇 |
2021年 | 244篇 |
2020年 | 244篇 |
2019年 | 252篇 |
2018年 | 224篇 |
2017年 | 280篇 |
2016年 | 298篇 |
2015年 | 247篇 |
2014年 | 320篇 |
2013年 | 817篇 |
2012年 | 573篇 |
2011年 | 720篇 |
2010年 | 615篇 |
2009年 | 818篇 |
2008年 | 795篇 |
2007年 | 753篇 |
2006年 | 708篇 |
2005年 | 643篇 |
2004年 | 653篇 |
2003年 | 489篇 |
2002年 | 450篇 |
2001年 | 332篇 |
2000年 | 350篇 |
1999年 | 260篇 |
1998年 | 219篇 |
1997年 | 242篇 |
1996年 | 208篇 |
1995年 | 229篇 |
1994年 | 207篇 |
1993年 | 173篇 |
1992年 | 157篇 |
1991年 | 115篇 |
1990年 | 87篇 |
1989年 | 88篇 |
1988年 | 56篇 |
1987年 | 30篇 |
1986年 | 45篇 |
1985年 | 23篇 |
1984年 | 27篇 |
1983年 | 11篇 |
1982年 | 20篇 |
1981年 | 29篇 |
1980年 | 19篇 |
1979年 | 20篇 |
1978年 | 18篇 |
1977年 | 7篇 |
1976年 | 12篇 |
1974年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
891.
892.
5-卤代1,2,3,-三唑互变异构的密度泛函理论研究 总被引:4,自引:1,他引:3
用密度泛函B3LYP/6-311 G**方法,对气相和水相中的1,2,3三,-唑及5-卤(-F、C l和-B r)代1,2,3,-三唑互变异构体进行了几何构型全自由度优化,获得了它们在气相和水相中的几何结构和电子结构。计算结果显示,在气相和水相中1,2,3三-唑和5-卤代1,2,3三-唑的N2-H型要比对应的N1-H型和N3-H型稳定。讨论了不同的取代基团和溶剂化效应对互变异构体的几何结构、能量和电荷分布以及互变异构反应活化能的影响带。并进一步研究了N1-H、N2-H和N3-H型三唑之间的互变异构机理:(a)分子内质子转移;(b)水助质子转移。计算结果表明,途径(b)所需要的活化能较小,为120.06KJ/mol,途径(a)为204.12KJ/mol。 相似文献
893.
根据p53基因的序列设计并合成了能特异性检测p53 mRNA的分子信标(MB), 发展了一种快速定量测定细胞内总RNA提取物中p53 mRNA的方法. 采用鼻咽癌(CNE2)细胞系和经RNA干扰技术降低p53基因表达的CNE2-p53RNAi细胞系, 抽提总RNA并用MB检测, 验证了MB的检测对象是p53 mRNA. 将该方法应用于多种肿瘤细胞内p53基因表达水平的分析, 表达变化趋势与经典的mRNA分析方法RT-PCR检测结果相符. 在此基础上, 用MB对5-氟尿嘧啶(5-Fu)处理的肺腺癌细胞(A549)进行了p53 mRNA的体外定量检测, 结果表明采用MB能够快速地获知该药物对细胞内p53 mRNA表达影响的信息. 相似文献
894.
1INTRODUCTION Antipyrine(2,3-dimethyl-1-phenyl-5-pyrazolone)and its derivatives exhibit a wide range of biological activities and applications[1~3].Antipyrine shows mi-nimal protein binding and is rapidly and completely absorbed from the gastrointestinal tract and exten-sively metabolized by the cytochrome P450liver en-zymes[4].Estimates of half-life and systemic cleara-nce of antipyrine have been used for the in vivo asse-ssment of hepatic drug oxidation in different spe-cies[5].Owing to… 相似文献
895.
1INTRODUCTION Pyrazolo[1,5-a]pyrimidine derivatives have shown various biological activities in the terms of antibac-terial,antischistosomal and xanthine oxidase inhibi-tors[1~5].The enaminones are highly reactive inter-mediates and have been extensively used as build-ing blocks in organic synthesis especially in the he-terocyclic compounds[6~8].In addition,a great deal of interest has been focused on the synthesis of py-razolo[1,5-a]pyrimidine through versatile enamino-nes because of thei… 相似文献
896.
LU Ya-Lin GONG Xue-Dong JU Xue-Hai MA Xiu-Fang XIAO He-Ming ② 《结构化学》2006,25(8):1004-1010
1 INTRODUCTION Triazole, a five-membered heterocyclic compound with three nitrogen atoms, is an important interme- diate product of medicine and chemical industry as well as insecticide [1]. Due to its small volume and high nitrogenous density, triazole holds more and more attraction for the material researchers, espe- cially the researchers of high-energy insensitive explosive. It is reported that its nitro and amino deri- vatives are a sort of important high-energy mate- rials[2]. Previ… 相似文献
897.
DENG Yi-Fang KUANG Dai-Zhi ZHANG Chun-Hua CHEN Man-Sheng PENG Yun-Lin YANG Ying-Qun LI Wei 《结构化学》2006,25(8)
The title complex [Zn(L)(phen)(CH3OH)] (L= C8H6BrO4NS, aminomethanesulfonic acid 5-bromo-salicylaldelyde schiff base; phen = 1,10-phenanthroline) has been synthesized and characterized by X-ray diffraction method. The crystal belongs to monoclinic, space group P21/c with a = 1.8712(3), b = 1.38008(19), c = 0.83685(12) nm, β = 97.791 (2)°, Mr = 569.72, V = 2.1411(5)nm3,Z= 4, Dc = 1.767 g/cm3, μ = 3.151 mm-1, F(000) = 1144, the final R = 0.0402 and wR = 0.0885. The central Zn(Ⅱ) is six-coordinated by one nitrogen and two oxygen atoms from the Schiff base, two nitrogen atoms from 1,10-phenanthroline and one oxygen from methanol to form a distorted octahedral coordination geometry. 相似文献
898.
One-dimensional Zigzag Chain Composed of HgI2 Unit and 2,5-Bis(4-pyridyl)- 1,3,4-thiadiazole: [HgI2(C12H8N4S)] 总被引:1,自引:1,他引:0
CHEN Li-Juan MENG Ze-Rong ZHANG Quan-Zheng WU Xiao-Yuan LU Can-Zhong② 《结构化学》2006,25(10):1189-1192
1 INTRODUCTION Much interest has been focused on the design and syntheses of supramolecular coordination polymers with novel topologies and structural motifs because of their encouraging potential applications in the fields of nonlinear optics, catalysis and separation, magnetism and molecular recognition[1, 2]. In princi- ple, control over the type and topology of the coor- dination polymers can be achieved by careful choice of ligand, metal coordination geometry preference, inorganic cou… 相似文献
899.
Synthesis and Crystal Structural Characterization of a Thiosemicarbazone Derived from 4-Acylpyrazolone 总被引:1,自引:0,他引:1
LIU Guang-Feia LIU Langa HU Xina JIA Dian-Zenga② YU Kai-Beib a 《结构化学》2006,25(10):1233-1237
1 INTRODUCTION Pyrazol-5-one derivatives form an important class of organic compounds due to their structural che- mistry and biological activities as analgesic, antipy- retic, anti-inflammatory and hyperglycemic agents[1~4]. Even the simplest pyrazol-5-one derivatives like antipyrine and amidopyrine are widely used in anal- gesic medicine[5, 6]. On the other hand, thiosemicar- bazones, especially heterocyclic thiosemicarbazones, have been the subject of extensive investigations be- cause… 相似文献
900.
A novel organotin complex [Ph3Sn(C2H5OH)(OCOC5H3NBr)SnPh3(OCOC5H3NBr)]has been synthesized by the reaction of 5-bromonicotinic acid with triphenyltin hydroxide in ethanol and characterized by elemental analysis, IR and 1H NMR. The crystal structure was determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 15.564(2), b = 24.975(4), c = 12.2973(19) (A), β = 92.224(2)°, Z = 4, V = 4776.5(13) (A)3, Dc = 1.596g/cm3, μ(MoKα) = 2.765 mm-1, F(000) = 2264, R = 0.0385 and wR = 0.0667. In the molecular structure of the title complex, the tin atoms are five-coordinated in a trigonal bipyramidal geometry. 相似文献