全文获取类型
收费全文 | 3302篇 |
免费 | 275篇 |
国内免费 | 465篇 |
专业分类
化学 | 3731篇 |
晶体学 | 16篇 |
力学 | 18篇 |
综合类 | 30篇 |
数学 | 23篇 |
物理学 | 224篇 |
出版年
2024年 | 6篇 |
2023年 | 28篇 |
2022年 | 57篇 |
2021年 | 99篇 |
2020年 | 172篇 |
2019年 | 128篇 |
2018年 | 108篇 |
2017年 | 120篇 |
2016年 | 131篇 |
2015年 | 137篇 |
2014年 | 155篇 |
2013年 | 306篇 |
2012年 | 192篇 |
2011年 | 164篇 |
2010年 | 148篇 |
2009年 | 158篇 |
2008年 | 163篇 |
2007年 | 153篇 |
2006年 | 149篇 |
2005年 | 151篇 |
2004年 | 166篇 |
2003年 | 155篇 |
2002年 | 109篇 |
2001年 | 80篇 |
2000年 | 77篇 |
1999年 | 78篇 |
1998年 | 88篇 |
1997年 | 59篇 |
1996年 | 85篇 |
1995年 | 58篇 |
1994年 | 63篇 |
1993年 | 58篇 |
1992年 | 49篇 |
1991年 | 32篇 |
1990年 | 24篇 |
1989年 | 18篇 |
1988年 | 17篇 |
1987年 | 11篇 |
1986年 | 17篇 |
1985年 | 12篇 |
1984年 | 15篇 |
1983年 | 9篇 |
1982年 | 11篇 |
1981年 | 7篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有4042条查询结果,搜索用时 15 毫秒
71.
Alastair C. Lewis Sarah A. Askey Krystyna M. Holden Keith D. Bartle Michael J. Pilling 《Journal of separation science》1997,20(2):109-114
The composition and concentration of polycyclic aromatic compounds (PAC) in fuels. Theier combustion products and in the atmosphere remains a topic of considerable interest. Despite the wealth of literature on the identification of PAC, speciation at low concentrations remains difficult due to instrument limitation and the complexity of fuel and environmental samples. Consequently on line sample preparation procedures (SPE, SFE, LC, etc.) are becomeing an increasingly important step in the analysis procedure particularly where sample clean-up and fractionation are essential for improving analytical resolution. In this study a normal phase high pressure analytical resolution. In this study a normal phase high pressure liquid chromatography-gas chromatography (LC-GC) system has been developed to provide quantitative analysis of samples, as diverse as coal liquids, petroleum fuels, diesel exhaust particulates, and urban air particulates. Separation and identification of parent and alkylated PAH, hetercycline nitro-and oxy-PAC can be achieved by direct coupling to an atomic emission detector and a bech top mass spectrometer. For both systems the primary LC separation combined with the large sample volume transferred to GC vastly improves detection limits. Furthermore the complimentary nature of the two detectors used enables the positive indentification of many unknowns. 相似文献
72.
Ammonium acetate was found to catalyze efficiently the selective deprotection of aromatic acetates in the presence of various sensitive functionalities in aqueous methanol under neutral conditions at room temperature to yield the corresponding phenols in excellent yields. The method has been utilized for deprotection of acetates of several naturally occurring bioactive phenolic compounds and for preparation of venkatasin, a natural coumarino-lignan, from the anticancer compound cleomiscosin A. 相似文献
73.
Aromatic peptide nucleic acid analogs having an N-(2-aminobenzyl)glycine backbone (APNA 1) were previously identified as promising new leads for the design of polyaromatic DNA mimics. Structural modifications of 1, which lock the aromatic backbone into a unique conformation, while maintaining the same space distribution between the nucleobases as in 1, were investigated. The electrostatic potential of the aromatic backbone was also modified in an attempt to improve the solubility of these compounds in aqueous media and to evaluate how the quadrapole of the aromatic backbone may influence the biophysical properties of the APNA oligomers. PNA hexamers containing a single monomer insert of each new APNA monomer were used to explore the hybridization properties of these analogs with poly rA and poly dA. Preliminary results indicated that these modifications do not seriously alter the molecular recognition properties of APNAs towards DNA and RNA. 相似文献
74.
Summary The method for the contraction and expansion of graphs is used to treat the subspectrality of benzenoid hydrocarbons in relation to eigenvalues ±1. Counts of benzenoid hydrocarbons together with degeneracies of eigenvalues have been carried out for all species having h 7 hexagons. In addition, twelve homologous series are evaluated, and the closed results for the distribution of eigenvalues ± 1 and degeneracies in terms of the number of repeated units are tabulated. This method is universal and applicable to cases sharing other eigenvalues and to nonbenzenoid systems.Also known as Yuan-sun Kiang 相似文献
75.
The electron capture detector (ECD) response to numerous aromatic hydrocarbons of low electron affinity (EA) is shown to be detrimentally affected by two processes which compete with and typically overwhelm the electron capture reactions of these molecules. It is shown that the effects of these two undesired reactions can be eliminated by the permanent addition of trimethylamine and one of several alkyl monochlorides to the detector make-up gas. These modifications of the detector gas result in greatly increased sensitivity, increased linearity, and increased reproducibility of response. A kinetic model for the ECD responses of low EA resonance capture molecules is developed which appears to explain these improvements. 相似文献
76.
建立了测定尿液中3种羟基多环芳烃的氮化碳复合材料磁性固相萃取结合高效液相色谱-荧光检测法。所构筑的磁性氮化碳材料,经扫描电子显微镜、X射线衍射仪、振动样品磁强计和比表面积分析仪表征后,用于尿液中3种羟基多环芳烃的富集净化。考察了吸附剂用量、吸附时间、洗脱溶液和洗脱体积(单次洗脱体积×洗脱次数)对萃取效率的影响。结合高效液相色谱-荧光分析,在0.25~250 μg/L范围内线性关系良好(相关系数r=0.999),3种羟基多环芳烃的检出限和定量限分别为0.08和0.25 μg/L,回收率为90.1%~102%,日内和日间精密度分别为1.5%~7.7%和2.2%~8.7%。该本方法简单、快速、高效,可用于尿液中羟基多环芳烃的分析。 相似文献
77.
Ju-Won Tae Byung-Sik Jang Kyung-Hoon Kim Dae-Won Park 《Reaction Kinetics and Catalysis Letters》2005,84(1):167-174
Summary The addition of carbon dioxide to phenyl glycidyl ether (PGE) was investigated in a semi-batch reactor using immobilized quaternary ammonium chloride catalysts. Five different catalysts were prepared with the following supports : (1) soluble poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC) [C1], (2) insoluble poly(ST-DVB-VBC) [C2], (3) macroporous poly(ST-DVB-VBC) [C3], (4) poly(ST-<Emphasis Type=Italic>co</Emphasis>-VBC)-MMT [C4] (5) modified MCM-41 [C5]. The addition of carbon dioxide to PGE can be considered as a pseudo-first order process with respect to the concentration of PGE. The pseudo-first order rate constant for the catalysts decreased in the series C1>C3>C2>C4>C5. The activation energy for C1 to C5 catalysts was 8.6, 20.9, 19.9, 23.9, and 26.8 kJ/mol, respectively. The immobilized catalysts can be reused in least 4 successive runs without any considerable loss of their initial reactivities. 相似文献
78.
A novel cross-linking process using two high molecular weight aromatic poly(thioether)s,which were synthesized by the reactions of 4,4′-thiobisbenzenethiol with 4,4′-difluorobenzophenone and 4,4′-difluorodiphenylsulfone,respectively, and commercially available lower molecular weight poly(p-phenylene sulfide)was investigated.These reactions were carried out in bulk by the addition of silver tetrafluroborate andα,α′-dibromo-p-xylene at 190℃over a period of 45 min. Furthermore,the same procedure could be modified to cross-link compression-molded films of these three polymers.The thermal and solubility behaviors of these polymers before and after cross-linking reactions,are presented. 相似文献
79.
Jiang Ke QIN Xian Zhang BU Yu Fang WANG Zhi Yun DU Xing Yuan WANG Zhi Shu HUANG Lin MA Lin Kun AN Lian Quan GU 《中国化学快报》2005,16(11):1451-1454
The reactions of tanshinone IIA with aromatic aldehydes have been investigated and several 2, T-(substituted arylmethylene) bis (1,6,6-trimethyl-6,7,8,9-tetrahydrophenanthro[1,2-b]- furan- 10, 11-dione) derivatives were obtained, 相似文献
80.
Application of matrix solid-phase dispersion in the analysis of priority polycyclic aromatic hydrocarbons in fish samples 总被引:1,自引:0,他引:1
The performance of matrix solid-phase dispersion (MSPD) for the extraction of polycyclic aromatic hydrocarbons (PAHs) in fish tissue is described. The suitability of different solid supports was tested as well as the influence on the extraction efficiency of the natural fat content in samples. Under optimal conditions 0.6-0.8 g of tissue sample, are dispersed with 2 g of octadecylsiloxane (C18) and 0.5 g of anhydrous sodium sulphate and transferred to the top of a polyethylene solid-phase extraction cartridge which already contains 2 g of florisil and 1 g of C18. Cartridges were eluted with acetonitrile. The analysis of the extracts was carried out by high-performance liquid chromatography (HPLC) coupled with fluorescence detection. The proposed method provides detection limits between 0.04 and 0.32 ng/g for the different considered PAHs, below the maximum levels established by the some regulatory bodies for the six PAHs after recent oil spill episodes and European Union regulations. Recoveries over 80% were obtained for all compounds. Accuracy validation was carried out using the US National Institute of Standards and Technology (NIST) SRM 2977 reference material. 相似文献