全文获取类型
收费全文 | 2446篇 |
免费 | 292篇 |
国内免费 | 150篇 |
专业分类
化学 | 1855篇 |
晶体学 | 23篇 |
力学 | 107篇 |
综合类 | 1篇 |
数学 | 238篇 |
物理学 | 664篇 |
出版年
2024年 | 4篇 |
2023年 | 95篇 |
2022年 | 109篇 |
2021年 | 113篇 |
2020年 | 162篇 |
2019年 | 172篇 |
2018年 | 159篇 |
2017年 | 110篇 |
2016年 | 171篇 |
2015年 | 161篇 |
2014年 | 185篇 |
2013年 | 236篇 |
2012年 | 262篇 |
2011年 | 250篇 |
2010年 | 163篇 |
2009年 | 124篇 |
2008年 | 133篇 |
2007年 | 107篇 |
2006年 | 60篇 |
2005年 | 34篇 |
2004年 | 18篇 |
2003年 | 9篇 |
2002年 | 16篇 |
2001年 | 4篇 |
2000年 | 10篇 |
1998年 | 6篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1993年 | 2篇 |
1991年 | 1篇 |
1990年 | 6篇 |
1986年 | 1篇 |
1985年 | 2篇 |
排序方式: 共有2888条查询结果,搜索用时 46 毫秒
41.
Metal binding of organic ligands can definitely affect its environmental behavior in waters, while information on the binding heterogeneity with different organic ligands is still lacked till now. In this study, the binding of zinc with organic matters associated with cyanobacterial blooms, including dissolved organic matters (DOM) and attached organic matters (AOM), were studied by using fluorescence quenching titration combined with two-dimensional correlation spectroscopy (2D-COS). Metal-induced fluorescent quenching was obviously observed both for DOM and AOM, indicating the formation of metal-ligand complexes. Compared with the one-dimensional spectra, 2D-COS revealed the sequences of metal-ligand interaction with the following orders: 276 nm > 232 nm for DOM and 232 nm > 276 nm for AOM. Furthermore, the modified Stern-Volmer model showed that the binding constant (log KM) of 276 nm in DOM was higher than that of 232 nm (4.93 vs. 4.51), while AOM was characterized with a high binding affinity for 232 nm (log KM: 4.83). The ranks of log KM values were consistent with the sequential orders derived from 2D-COS results both for the two samples. Fluorescence quenching titration combined with 2D-COS was an effective method to characterize the metal-ligand interaction. 相似文献
42.
文章合成了Lu(NO3)3(C2H5O2N)4.H2O,用红外和元素分析对其进行了表征。用高精度全自动绝热量热仪,测定了该配合物80-382 K温区的热容, 利用实验热容数据, 根据热容与焓、熵的热力学关系, 求出了配合物85-350 K温区内每隔5 K相对于298.15K的标准热力学函数(HT - H298.15)m和(ST - S298.15)m.在80-350 K温度区间内,配合物的热容随温度升高而增大,没有相转移点和热力学吸收峰的出现,该配合物在此温度区间内是稳定存在的。 相似文献
43.
Research on Chemical Intermediates - The electronic parameters of two azole molecules, namely benzoxazole (BOX) and benzothiazole (BTH), have been studied using DFT/B3LYP, MP2, and HF methods with... 相似文献
44.
45.
Wrinkled Graphene Monoliths as Superabsorbing Building Blocks for Superhydrophobic and Superhydrophilic Surfaces 下载免费PDF全文
Li‐Bing Lv Tian‐Lu Cui Bing Zhang Hong‐Hui Wang Prof. Xin‐Hao Li Prof. Jie‐Sheng Chen 《Angewandte Chemie (International ed. in English)》2015,54(50):15165-15169
Superhydrophobic and superhydrophilic surfaces are of great interest because of a large range of applications, for example, as antifogging and self‐cleaning coatings, as antibiofouling paints for boats, in metal refining, and for water–oil separation. An aqueous ink based on three‐dimensional graphene monoliths (Gr) can be used for constructing both superhydrophobic and superhydrophilic surfaces on arbitrary substrates with different surficial structures from the meso‐ to the macroscale. The surface wettability of a Gr‐coated surface mainly depends on which additional layers (air for a superhydrophobic surface and water for a superhydrophilic surface) are adsorbed on the surface of the graphene sheets. Switching a Gr‐coated surface between being superhydrophobic and superhydrophilic can thus be easily achieved by drying and prewetting with ethanol. The Gr‐based superhydrophobic membranes or films should have great potential as efficient separators for fast and gravity‐driven oil–water separation. 相似文献
46.
47.
48.
49.
Simultaneous chemical fingerprint and quantitative analysis of Rhizoma Smilacis Glabrae by accelerated solvent extraction and high‐performance liquid chromatography with tandem mass spectrometry 下载免费PDF全文
Weiquan Dai Weiquan Zhao Fangyuan Gao Jingjing Shen Diya Lv Yunpeng Qi Guorong Fan 《Journal of separation science》2015,38(9):1466-1475
Rhizoma Smilacis Glabrae (RSG) is a well‐known herbal medicine with the homology of medicine and food. In this study, simultaneous chemical fingerprint and quantitative analysis of the bioactive flavonoid components of RSG were developed using accelerated solvent extraction and high‐performance liquid chromatography coupled with ion trap tandem mass spectrometry. The operational parameters of accelerated solvent extraction including extraction solvent, extraction temperature, static extraction time, solid‐to‐liquid ratio, and extraction cycles were optimized. Hierarchical cluster analysis, similarity analysis, and principal component analysis were performed to evaluate the similarity and variation of the samples collected from several provinces in China. Subsequently, high‐performance liquid chromatography fingerprints were established for the discrimination of 16 batches of RSG samples, and the major six flavonoids, namely, toxifolin, neoastilbin, astilbin, neoisoastilbin, isoastilbin, and engeletin were then quantitatively determined. The calibration curves for all the six analytes showed good linearity (r2 > 0.999), and the limits of detection and quantification were less than 0.10 and 0.27 μg·mL?1, respectively. Therefore, the proposed extraction and determination methods were proved to be robust and reliable for the quality control of RSG. 相似文献
50.
全/多卤代有机污染物大多具有生态毒性、生物蓄积性、环境持久性及长距离迁移性,不仅危害环境与生态安全,而且可经食物链传递威胁人类健康。由于卤原子是吸电子基团且取代数目多,这类物质的最高占据分子轨道能较低,难于被氧化降解,相反较易被还原法脱卤降解。随卤原子取代数减少,脱卤产物难被进一步还原,而其毒性甚至高于母体污染物。注意到低卤代有机物更容易发生氧化降解,一些研究构建了还原-氧化接力降解体系,即先利用还原法将全/多卤代有机污染物还原为低卤代产物,再利用氧化法降解这些中间产物,从而实现深度/完全脱卤和矿化。本文根据催化反应类型对还原-氧化联用法进行了归纳,分类介绍了基于传统化学催化、光催化、电化学、光电化学及机械化学等构建还原-氧化协同降解体系的原理及应用,以期为开发高效的处置技术提供思路和建议。 相似文献