全文获取类型
收费全文 | 1513篇 |
免费 | 162篇 |
国内免费 | 199篇 |
专业分类
化学 | 1150篇 |
晶体学 | 28篇 |
力学 | 108篇 |
综合类 | 21篇 |
数学 | 175篇 |
物理学 | 392篇 |
出版年
2024年 | 3篇 |
2023年 | 30篇 |
2022年 | 21篇 |
2021年 | 59篇 |
2020年 | 55篇 |
2019年 | 64篇 |
2018年 | 32篇 |
2017年 | 40篇 |
2016年 | 56篇 |
2015年 | 75篇 |
2014年 | 74篇 |
2013年 | 99篇 |
2012年 | 143篇 |
2011年 | 159篇 |
2010年 | 85篇 |
2009年 | 81篇 |
2008年 | 94篇 |
2007年 | 83篇 |
2006年 | 74篇 |
2005年 | 79篇 |
2004年 | 57篇 |
2003年 | 40篇 |
2002年 | 56篇 |
2001年 | 28篇 |
2000年 | 35篇 |
1999年 | 26篇 |
1998年 | 35篇 |
1997年 | 31篇 |
1996年 | 36篇 |
1995年 | 26篇 |
1994年 | 21篇 |
1993年 | 17篇 |
1992年 | 7篇 |
1991年 | 15篇 |
1990年 | 12篇 |
1989年 | 8篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1981年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有1874条查询结果,搜索用时 234 毫秒
41.
YipingZhang DongjieWang JinhuaFei XiaomingZheng 《天然气化学杂志》2003,12(2):145-149
Mo/HZSM-5 is a good catalyst for methane aromatization, and the reaction performance of Mo/HZSM-5 and Cu modified Mo/HZSM-5 catalysts under various pretreatment conditions has been studied. The results indicate that the catalyst presented a distinguished catalytic activity, benzene selectivity and a high stability when the bed temperature was raised in N2 atmosphere. 相似文献
42.
Yulu Yang Mingguang Wu Xingwang Zhu Hui Xu Si Ma Yongfeng Zhi Hong Xia Xiaoming Liu Jun Pan Jie-Yinn Tang Siang-Piao Chai Leonardo Palmisano Francesco Parrino Junli Liu Jianzhong Ma Ze-Lin Wang Ling Tan Yu-Fei Zhao Yu-Fei Song Pardeep Singh Pankaj Raizada Deli Jiang Di Li R. A. Geioushy Jizhen Ma Jintao Zhang Song Hu Rongjuan Feng Gang Liu Minghua Liu Zhenhua Li Mingfei Shao Neng Li Jiahe Peng Wee-Jun Ong Nikolay Kornienko Zhenyu Xing Xiujun Fan Jianmin Ma 《中国化学快报》1990,30(12):2065-2088
This roadmap demonstrates a series of two-dimensional nanomaterials, such as graphene, black phosphorus, oxides, layered double hydroxides, chalcogenides, bismuth-based layered compounds, MXenes, metal organic frameworks, covalent organic frameworks, and others, for environmental catalysis. 相似文献
43.
铬天青S共振光散射法测定脱氧核糖核酸 总被引:3,自引:0,他引:3
介绍在阳离子表面活性剂十六烷基三甲基溴化铵(CTMAB)存在下阴离子染料铬天青S(CAS)共振光散射(RLS)法测定脱氧核糖核酸(DNA)的方法。在pH=5.27的六次甲基四铵一盐酸缓冲溶液中,研究了CAS—CT-MAB—yDNA体系的RLS光谱特征、影响因素和最佳反应条件。在最佳条件下,体系的RLS强度增加值△I与yDNA的浓度在50~800μg/L和1000~2000μg/L呈线性关系,其线性回归方程分别为△I=0.48c 2.56和△I=0.14c 17.86,相关系数分别为0.9997和0.9991,检出限为4.3ng/mL。该方法简便、快速,应用于合成样品中yDNA的测定,测定结果的相对标准偏差为2.93%~4.71%,回收率为97.8%~105.2%。 相似文献
44.
The catalytic effect of chiral Lewis acids on the hetero-Diels-Alder reaction between aldehydes and Danishefsky's diene (1) has been investigated. A variety of combinations of different ligands and Lewis acids have been examined as catalysts for the hetero-Diels-Alder reaction between benzaldehyde and 1, and it has been found that the readily accessible Ti(IV)-H(8)-BINOL (TiHBOL) complex is a very effective catalyst for the reaction, leading to products with very high enantioselectivity (up to 99% ee) and yield (92%). The hetero-Diels-Alder reaction of other aldehydes with 1 under the catalysis of TiHBOL is a general reaction which proceeds well with very high enantioselectivity and isolated yield for various aldehydes at 0 degrees C to room temperature. Based on the experimental results, the proposed mechanism of the hetero-Diels-Alder reaction and the dihedral angle effects of ligands are discussed. 相似文献
45.
DNA repair has received heightened attention in recent years as ozone depletion threatens to significantly increase DNA damage by UVB radiation[1—6]. The major lesions formed in DNA by this radiation are cis-syn cyclobutane pyrimidine dimers, which are created by the linkage of two neighboring pyrimidine bases in DNA via C5-C5 and C6-C6 atoms by [2+2] cycloaddition[2,5—8]. This potentially lethal or mutagenic damage can be repaired either by the removal of the damaged bases by excisio… 相似文献
46.
Wanlong Xiao Yuhao Mo Jing Guo Zhishan Su Shunxi Dong Xiaoming Feng 《Chemical science》2021,12(8):2940
New types of C2-symmetric chiral macrodiolides are readily obtained via chiral N,N′-dioxide-scandium(iii) complex-promoted asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles. This protocol provides an array of enantioenriched macrodiolides with 16, 18 or 20-membered rings in moderate to good yields with high diastereoselectivities and excellent enantioselectivities through adjusting the length of the tether at the C3 position of indoles. Density functional theory calculations indicate that the formation of macrocycles is more favorable than that of 9-membered-ring lactones in terms of kinetics and thermodynamics. The potential utility of these intriguing chiral macrodiolide molecules is demonstrated in the enantiomeric recognition of aminols and chemical recognition of metal ions.An asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles was achieved by using a chiral N,N′-dioxide-scandium(iii) complex. 相似文献
47.
Chaoran Xu Jianglin Qiao Shunxi Dong Yuqiao Zhou Xiaohua Liu Xiaoming Feng 《Chemical science》2021,12(15):5458
Heterocycles have been widely used in organic synthesis, agrochemical, pharmaceutical and materials science industries. Catalytic three-component ylide formation/cycloaddition enables the assembly of complex heterocycles from simple starting materials in a highly efficient manner. However, asymmetric versions remain a yet-unsolved task. Here, we present a new bimetallic catalytic system for tackling this challenge. A combined system of Rh(ii) salt and chiral N,N′-dioxide–Sm(iii) complex was established for promoting the unprecedented tandem carbonyl ylide formation/asymmetric [4 + 3]-cycloaddition of aldehydes and α-diazoacetates with β,γ-unsaturated α-ketoesters smoothly, affording various chiral 4,5-dihydro-1,3-dioxepines in up to 97% yield, with 99% ee. The utility of the current method was demonstrated by conversion of products to optically active multi-substituted tetrahydrofuran derivatives. A possible reaction mechanism was provided to elucidate the origin of chiral induction based on experimental studies and X-ray structures of catalysts and products.Catalytic asymmetric tandem carbonyl ylide formation/[4 + 3]-cycloaddition of β,γ-unsaturated α-ketoesters, aldehydes and α-diazoacetates was achieved by using a bimetallic rhodium(ii)/chiral N,N′-dioxide–Sm(iii) complex catalyst. 相似文献
48.
不同软段结构聚氨酯-酰亚胺嵌段共聚物的合成及热性能研究 总被引:4,自引:2,他引:4
用二步法合成了不同软段 (PPO ,PEG ,PEPA)聚氨酯 酰亚胺 (PUI)嵌段共聚物 ,FTIR光谱表征了所有合成PUI分子主链均含有酰亚胺链段 ,并研究了PUI嵌段共聚物的热性能受软段类型及长度的影响 .DSC研究表明聚酯型PUI的软硬段之间的相容性比聚醚型PUI好 ,随相同软段分子量的增加 ,PUI体系的软硬段兼容性变差 ,并显示了相分离的特征 ;热失重 (TGA)研究得出不同软段的PUI样品的热稳定性大小顺序为 :PEPA PUI >PEG PUI>PPO PUI ;动态力学 (DMTA)研究给出了所合成的PUI样品在 5 0~ 2 0 0℃范围内均出现了较长的模量平台显示出有较好的耐热性 ,且随硬段含量的升高其储能模量不断增强 相似文献
49.
Hu Chuanjiang Duan Chunying Meng Qingjin Liu Yongjiang Lu Changsheng Reng Xiaoming Chen Yijun Cao Mi 《Transition Metal Chemistry》2000,25(2):141-144
The mixed-valence molybdovanadate compound Na2(NH4)4[VIVVV
8Mo)O28] · 10H2O [Vanadata(6-)tetradeca--oxotetra-3-oxodi-6-oxoheptaoxo(oxomolybdate) nonatetrammonium disodium, decahydrate] has been synthesized from sodium molybdate(VI) dihydrate and sodium metavanadate dihydrate in aqueous solution by adding NH2OH · HCl. The molecular structure has been determined by X-ray diffraction and is based on the isopolydecavanadate structure. The molybdate atom is crystallographically disordered over 6MO6 octahedral sites. The e.s.r. spectrum clearly indicates that one vanadium atom has the oxidation number +4. 相似文献
50.
The mass spectrometry of a group of inorganic oxidizers was studied using the electrospray ionization technique. It was found that a series of cluster ions were predominant in both positive- and negative-ion mode, allowing for the characterization of the investigated oxidizers. The identity of the recorded cluster ions was further confirmed by using some isotopically labeled compounds and tandem mass spectrometry with collision-induced dissociation. The use of electrospray ionization mass spectrometry for positive identification of major oxidizer components in explosive formulations was demonstrated by three samples of forensic interest. 相似文献