全文获取类型
收费全文 | 8461篇 |
免费 | 1390篇 |
国内免费 | 664篇 |
专业分类
化学 | 5718篇 |
晶体学 | 87篇 |
力学 | 503篇 |
综合类 | 36篇 |
数学 | 995篇 |
物理学 | 3176篇 |
出版年
2024年 | 22篇 |
2023年 | 163篇 |
2022年 | 286篇 |
2021年 | 284篇 |
2020年 | 366篇 |
2019年 | 303篇 |
2018年 | 274篇 |
2017年 | 259篇 |
2016年 | 421篇 |
2015年 | 428篇 |
2014年 | 467篇 |
2013年 | 594篇 |
2012年 | 785篇 |
2011年 | 750篇 |
2010年 | 529篇 |
2009年 | 488篇 |
2008年 | 552篇 |
2007年 | 418篇 |
2006年 | 457篇 |
2005年 | 330篇 |
2004年 | 262篇 |
2003年 | 219篇 |
2002年 | 173篇 |
2001年 | 140篇 |
2000年 | 146篇 |
1999年 | 174篇 |
1998年 | 154篇 |
1997年 | 127篇 |
1996年 | 132篇 |
1995年 | 112篇 |
1994年 | 96篇 |
1993年 | 80篇 |
1992年 | 78篇 |
1991年 | 77篇 |
1990年 | 44篇 |
1989年 | 38篇 |
1988年 | 39篇 |
1987年 | 35篇 |
1986年 | 28篇 |
1985年 | 21篇 |
1984年 | 20篇 |
1983年 | 21篇 |
1982年 | 9篇 |
1981年 | 14篇 |
1980年 | 9篇 |
1977年 | 6篇 |
1976年 | 11篇 |
1975年 | 9篇 |
1973年 | 8篇 |
1972年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Development and validation of polymerized high internal phase emulsion monoliths coupled with HPLC and fluorescence detection for the determination of trace tetracycline antibiotics in environmental water samples
下载免费PDF全文
![点击此处可从《Journal of separation science》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Fuyou Du Xian Zheng Lin Sun Qun Qin Lin Guo Guihua Ruan 《Journal of separation science》2015,38(21):3774-3780
A polymerized high internal phase emulsion monolith was used as a novel sorbent for solid‐phase extraction coupled with high‐performance liquid chromatography and fluorescence detection for the determination of oxytetracycline, tetracycline, doxycycline, and chlorotetracycline in environmental water samples. The polymerized high internal phase emulsion monolithic column was prepared by the in situ polymerization of the continuous phase of a high internal phase emulsion containing glycidyl methacrylate, styrene, and divinylbenzene in pipette tips, and then functionalized with iminodiacetic acid. The resulting monolith exhibited highly interconnected porosity and large surface areas, making it an excellent candidate as an solid‐phase extraction sorbent for the enrichment of trace tetracycline antibiotics. Several factors affecting the extraction performance of polymerized high internal phase emulsion monoliths, including the pH of sample solution, the eluting solvents, the sample loading flow rate and volume, were investigated, respectively. Under the optimized conditions, the mean recoveries of oxytetracycline, tetracycline, doxycycline, and chlorotetracycline spiked in pond and farm wastewater samples ranged from 78.1 to 119.3% with relative standard deviation less than 15%. The detection limits (S/N = 3) of the proposed method were in the range of 51–137 pg/mL. This study demonstrated that the monolithic polymerized high internal phase emulsion would be promising solid‐phase extraction sorbents in the extraction and proconcentration of trace analytes from complex samples. 相似文献
992.
Hydrophobic terminal group of surfactant initiating micellization as revealed by 1H NMR spectroscopy
The critical aggregation concentration (CAC) of four with three kinds of conventional surfactants, namely, two cationic surfactants [hexadecyltrimethyl ammonium bromide (CTAB) and tetradecyltrimethyl ammonium bromide (TTAB)], one anionic surfactant [sodium dodecyl sulfate (SDS)], and a nonionic surfactant [Triton X-100 (TX-100)], were determined by variation of 1H chemical shifts with surfactant concentrations. Results show that the CAC values of protons at different positions of the same molecule are different, and those of the terminal methyl protons are the lowest, respectively, which suggests that the terminal groups of the alkyl chains aggregates first during micellization. Measurement of the transverse relaxation time (T2) of different protons in SDS also show that the terminal methyl protons start to decrease with the increase in concentration first, which supports the above mentioned tendency. 相似文献
993.
Cai-Na Xu Hua-Yu Tian Yan-Bing Wang Yang Du Jie Chen Lin Lin Zhao-Pei Guo Xue-Si Chen 《中国化学快报》2017,28(4):807-812
Direct administration of drugs and genes to the lungs by pulmonary delivery offers a potential effective therapy for lung cancers.In this study,combined doxorubicin(DOX)and Bcl2 siRNA was employed for cancer therapy using polyethylenimine(PEI)as the carrier of Bcl2 siRNA.Most of the DOX and siRNA possessed high cellular uptake efficiency in B16F10 cells,which was proved by FCM and CLSM analysis. Real-time PCR showed that PEI/Bcl2 siRNA exhibited high gene silencing efficiency with 70% Bcl2 mRNA being knocked down.The combination of DOX and siRNA could enhance the cell proliferation inhibition and the cell apoptosis against B16F10 cells compared to free DOX or PEI/Bcl2 siRNA.Furthermore,the biodistribution of DOX and siRNA via pulmonary administration was studied in mice with B16F10 metastatic lung cancer.The results showed that most of the DOX and siRNA were accumulated in lungs and lasted at least for 3 days,which suggested that combined DOX and siRNA by pulmonary administration may have high anti-tumor effects for metastatic lung cancer treatment in vivo. 相似文献
994.
Ting Wu Chuanjing Zhang Hongxin Ren Yidan Xi Yiping Du 《International Journal of Polymer Analysis and Characterization》2017,22(2):160-168
Solvent effect is one of the important factors in sample preparation which may affect matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra of synthetic polymers. MALDI imaging, a useful imaging tool for discovering biomarkers in tissues, is applied here for better comprehension of solvent effect in polymer analysis by MALDI-TOF mass spectrometry. Nylon-6 was chosen as a model polymer for the study of solvent effect. Its MALDI mass spectra in different solvents were performed. MALDI imaging analysis was performed for studying the incorporation of analytes into matrix crystals in different solvent combinations. Specifically, the colocalization of matrix and analyte was obtained through Pearson’s correlation (PC) coefficient analysis of their MALDI images. The results demonstrated that satisfactory spectra were obtained in higher PC value conditions. PC decreased along with an increase in the ratio of poor solvent, which suggested that we should minimize the poor solvent ratio to obtain better MALDI spectra. 相似文献
995.
Juan Du Zhie Zhou Xueqing Zhang Shuang Wu Jianhua Xiong Wenjun Wang Qiushui Luo 《Journal of Cluster Science》2017,28(6):3149-3158
Biosynthesis of gold nanoparticles (GNPs) by flavonoids from Lilium casa blanca has been developed. Several parameters such as pH, reaction temperature, reaction time and concentration of flavonoids were explored to control the formation of the GNPs. The synthesized GNPs were characterized by UV–Vis spectroscopy, transmission electron microscopy and X-ray diffraction. Stability and catalytic activity of the synthesized GNPs were also discussed. The results showed that the synthesized GNPs were in spherical, about 2.6 nm, with a face centered cubic structure. Synthesized GNPs showed good catalytic activity in the reduction of p-nitrophenol (p-NP) to p-aminphenol (p-AP). This method for synthesis of GNPs is simple, economic, nontoxic and efficient. 相似文献
996.
Bahare Sadeghi Far Gholamhossein Grivani Aliakbar Dehno Khalaji Mahdi Khorshidi Václav Eigner Michal Dušek 《Journal of Cluster Science》2017,28(6):3217-3227
New centrosymmetric trinuclear zinc(II) complex {[Zn(μ-ONN)(μ2-O)(μ-OO)]2Zn} has been synthesized by the reaction of a potentially ONN tridentate Schiff base ligand, and N,N-dimethylethylendiamin, with Zn(OAc)2·2H2O in methanol, in the refluxed conditions and characterized by elemental analysis, FT-IR and UV–Vis spectroscopy. Single crystal X-ray structure analysis reveals a trinuclear complex {[Zn(μ-ONN)(μ2-O)(μ-OO)]2Zn} with zinc(II) ions connected by three different bridges, (μ-ONN) of the Schiff base ligand, μ2-O and μ-OO of the acetate. The complex is centrosymmetric, with one of the Zn atoms located at the inversion center. While the central Zn(II) ion is six-coordinated, the coordination number of the other Zn(II) ions is five. Finally, the {[Zn(μ-ONN)(μ2-O)(μ-OO)]2Zn} complex was thermally decomposed in air at 700 °C resulted in ZnO nano crystalites with the average size of 42 nm. The antibacterial activity of ligand and its zinc(II) complex were tested against gram-positive and gram-negative bacteria. The ligand showed higher activity than its zinc(II) complex. 相似文献
997.
Advanced solvent signal suppression for the acquisition of 1D and 2D NMR spectra of Scotch Whisky
下载免费PDF全文
![点击此处可从《Magnetic resonance in chemistry : MRC》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Will Kew Nicholle G.A. Bell Ian Goodall Dušan Uhrín 《Magnetic resonance in chemistry : MRC》2017,55(9):785-796
A simple and robust solvent suppression technique that enables acquisition of high‐quality 1D 1H nuclear magnetic resonance (NMR) spectra of alcoholic beverages on cryoprobe instruments was developed and applied to acquire NMR spectra of Scotch Whisky. The method uses 3 channels to suppress signals of water and ethanol, including those of 13C satellites of ethanol. It is executed in automation allowing high throughput investigations of alcoholic beverages. On the basis of the well‐established 1D nuclear Overhauser spectroscopy (NOESY) solvent suppression technique, this method suppresses the solvent at the beginning of the pulse sequence, producing pure phase signals minimally affected by the relaxation. The developed solvent suppression procedure was integrated into several homocorrelated and heterocorrelated 2D NMR experiments, including 2D correlation spectroscopy (COSY), 2D total correlation spectroscopy (TOCSY), 2D band‐selective TOCSY, 2D J‐resolved spectroscopy, 2D 1H, 13C heteronuclear single‐quantum correlation spectroscopy (HSQC), 2D 1H, 13C HSQC‐TOCSY, and 2D 1H, 13C heteronuclear multiple‐bond correlation spectroscopy (HMBC). A 1D chemical‐shift‐selective TOCSY experiments was also modified. The wealth of information obtained by these experiments will assist in NMR structure elucidation of Scotch Whisky congeners and generally the composition of alcoholic beverages at the molecular level. 相似文献
998.
Chien-Hong Chen Shih-Hsuan Hung Wan-Ting Du Chung-Hung Hsieh 《Research on Chemical Intermediates》2017,43(6):3621-3631
Oxidative addition of Br2 to [Mn(CO)5]? leads to the formation of [(CO)4MnBr], followed by the ligand exchange of bromide to [S,Se-C6H3-4-Me] 2 2? to form complex (CO)3Mn (µ-? 4-SC6H3-4-(CH3)Se-SeC6H3-4-(CH3)S)Mn(CO)3 (1). A new five-coordinate complex [(CO)3Mn(-S,-Se-C6H3-4-CH3)]? (2) can be synthesized through two different routes: (a) oxidative addition of diselenide [HS,Se-C6H3-4-Me]2 to the [Mn(CO)5]? followed by deprotonation and ligand dissociation to generate complex 2; (b) reduction of diselenide bonds of complex 1 by [BH4]? to produce 2. Drop-wise addition of HBF4·OEt2 at 0 °C results in the formation of complex 1. The X-ray analysis shows that complex 2 has relative short Mn–Se and Mn–S bond distances compare to the published structures of cis-[(CO)4Mn(EPh)2]? (E = S and Se; Liaw et al. in J. Chin. Chem. Soc. 43:427–431, 1996; Liaw et al. in Inorg. Chem. 35:2530, 1996). Interestingly, exposure of the coordinated unsaturated complex 2 under CO(g) atmosphere resulted in complex cis-[(CO)4Mn(-S,-Se-C6H3-4-Me)]? (3) being formed. After purging the solution of complex 3 with N2, it was reconverted completely back to complex 2; this observation was characterized by FTIR. The cyclic voltammetry scan of complex 2 shows a quasi-reversible redox couple with E 1/2 = ?1.94 V and I pa/I pc = 0.68. Ligand [HS, Se-C6H3-4-CH3]2 and complexes 1 and 2 are all characterized by IR, UV–Vis, NMR, EA and X-ray single crystal diffraction. 相似文献
999.
Accreditation and Quality Assurance - The aim of this work was to establish a mathematical model to identify the main source of measurement uncertainty, quantify each uncertainty component, and... 相似文献
1000.
This work was focused on the influence of match degree of structure parameters i.e. molecular size, volume and polarity (denoted as Rd, Vd and Pd) between imprinted cavities in Qu-MIP and Xn on the adsorption selectivity. The results presented that the influence of Rd on the adsorption selectivity was the largest and the most regular, while the influence of Pd was the smallest and the most irregular. Besides, the influence degree of Vd was decreased in general with the increase of Rd. However, as Rd was in the threshold of [0.99, 1.02], Vd would rise to the major influence factor. Furthermore, utilizing data obtained from experiment, the influence authority of Rd, Vd and Pd on the adsorption selectivity was calculated theoretically through multiple linear regression and principal component analysis of IBM SPSS Statistics 20, and results showed the authority order was Rd, Vd and Pd at any circumstance despite the value was different, which was in accordance with the result we directly inducted from the experiment. 相似文献