全文获取类型
收费全文 | 41433篇 |
免费 | 7733篇 |
国内免费 | 7423篇 |
专业分类
化学 | 30228篇 |
晶体学 | 804篇 |
力学 | 2781篇 |
综合类 | 602篇 |
数学 | 4670篇 |
物理学 | 17504篇 |
出版年
2024年 | 124篇 |
2023年 | 702篇 |
2022年 | 1445篇 |
2021年 | 1579篇 |
2020年 | 1648篇 |
2019年 | 1709篇 |
2018年 | 1507篇 |
2017年 | 1592篇 |
2016年 | 1981篇 |
2015年 | 2207篇 |
2014年 | 2677篇 |
2013年 | 3360篇 |
2012年 | 3866篇 |
2011年 | 3916篇 |
2010年 | 3041篇 |
2009年 | 3142篇 |
2008年 | 3362篇 |
2007年 | 2845篇 |
2006年 | 2606篇 |
2005年 | 2142篇 |
2004年 | 1614篇 |
2003年 | 1415篇 |
2002年 | 1433篇 |
2001年 | 1225篇 |
2000年 | 1016篇 |
1999年 | 800篇 |
1998年 | 507篇 |
1997年 | 452篇 |
1996年 | 415篇 |
1995年 | 324篇 |
1994年 | 331篇 |
1993年 | 263篇 |
1992年 | 209篇 |
1991年 | 170篇 |
1990年 | 176篇 |
1989年 | 120篇 |
1988年 | 104篇 |
1987年 | 89篇 |
1986年 | 88篇 |
1985年 | 68篇 |
1984年 | 40篇 |
1983年 | 45篇 |
1982年 | 21篇 |
1981年 | 20篇 |
1980年 | 17篇 |
1979年 | 28篇 |
1978年 | 12篇 |
1977年 | 11篇 |
1957年 | 8篇 |
1925年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
961.
Song Yun Weizhong Qian Chaojie Cui Yuntao Yu Chao Zheng Yi Liu Qiang Zhang Fei Wei 《Journal of Energy Chemistry》2013,22(4):567-572
For the synthesis of single-walled carbon nanotubes (SWCNTs) from CH4 over a Fe/MgO catalyst, we proposed a coupled Downer-turbulent fluidized-bed (TFB) reactor to enhance the selectivity and yield (or production rate) of SWCNTs. By controlling a very short catalyst residence time (1–3 s) in the Downer, only part of Fe oxides can be reduced to form Fe nano particles (NPs) available for the growth of SWCNTs. The percentage of unreduced Fe oxides increased and the yield of SWCNTs decreased accordingly with the increase of catalyst feeding rate in Downer. SWCNTs were preferentially grown on the catalyst surface and inhibited the sintering of the Fe crystallites which would be formed thereafter in the downstream TFB, evidenced by TEM, Raman and TGA. The coupled Downer-turbulent fluidized-bed reactor technology allowed higher selectivity and higher production rate of SWCNTs as compared to TFB alone. 相似文献
962.
Peirong Chen Ly May Chew Aleksander Kostka Kunpeng Xie Martin Muhler Wei Xia 《Journal of Energy Chemistry》2013,22(2):312-320
Oxygen- and nitrogen-functionalized carbon nanotubes (OCNTs and NCNTs) were applied as metal-free catalysts in selective olefin hydrogenation. A series of NCNTs was synthesized by NH3 post-treatment of OCNTs. Temperature-programmed desorption, N2 physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 °C led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis. 相似文献
963.
Paper-based microfluidic devices have been widely investigated in recent years. Among various detection techniques, colorimetric method plays a very important role in paper-based microfluidic devices. The limitation, however, is also clear: they generally require highly sensitive indicators. In this work, we have developed a novel enrichment-based paper test for the discrimination of heavy-metal ions. Comparing to regular paper-based microfluidic devices, enrichment-based technique showed largely improved sensitivity. Combining with eight pyridylazo compounds and array technologies-based pattern-recognition, we have obtained the discrimination capability of eight different heavy-metal ions at same concentration as low as 50 μM using our enrichment-based pyridylazo compounds array paper. Identification of the heavy-metal ions was readily achieved using a standard chemometric approach. This method can be, of course, used for other analytes as well. 相似文献
964.
Wei-Jun Kong Jun-Yuan Li Feng Qiu Jian-He Wei Xiao-He Xiao Yuguo Zheng Mei-Hua Yang 《Analytica chimica acta》2013
As an edible and medicinal plant, Coix seed is readily contaminated by more than one group of mycotoxins resulting in potential risk to human health. A reliable and sensitive method has been developed to determine seven mycotoxins (aflatoxins B1, B2, G1, G2, zearalenone, α-zearalenol, and β-zearalenol) simultaneously in 10 batches of Coix seed marketed in China. The method is based on a rapid ultrasound-assisted solid–liquid extraction (USLE) using methanol/water (80/20) followed by immunoaffinity column (IAC) clean-up, on-line photochemical derivatization (PCD), and high performance liquid chromatography coupled with fluorescence detection (HPLC-FLD). Careful optimization of extraction, clean-up, separation and detection conditions was accomplished to increase sample throughput and to attain rapid separation and sensitive detection. Method validation was performed by analyzing samples spiked at three different concentrations for the seven mycotoxins. Recoveries were from 73.5% to 107.3%, with relative standard deviations (RSDs) lower than 7.7%. The intra- and inter-day precisions, expressed as RSDs, were lower than 4% for all studied analytes. Limits of detection and quantification ranged from 0.01 to 50.2 μg kg−1, and from 0.04 to 125.5 μg kg−1, respectively, which were below the tolerance levels for mycotoxins set by the European Union. Samples that tested positive were further analyzed by HPLC tandem electrospray ionization mass spectrometry for confirmatory purposes. This is the first application of USLE-IAC-HPLC-PCD-FLD for detecting the occurrence of multi-class mycotoxins in Coix seed. 相似文献
965.
Bai‐Zhan Liu Li Yao Sai‐Jing Zheng Wei‐Miao Wang Xiao‐Lan Zhu Jun Yang 《中国化学会会志》2013,60(8):1055-1061
An efficient and sensitive analytical method based on molecularly imprinted solid‐phase extraction (MISPE) and reverse‐phase ultrasound‐assisted dispersive liquid–liquid microextraction (USA‐DLLME) coupled with LC–MS/MS detection was developed and validated for the analysis of urinary 4‐(methylnitrosamino)‐1‐(3‐pyridyl)‐1‐butanol (NNAL), a tobacco‐specific nitrosamine metabolite. The extraction performances of NNAL on three different solid‐phase extraction (SPE) sorbents including the hydrophilic‐lipophilic balanced sorbent HLB, the mixed mode cationic MCX sorbent and the molecularly imprinted polymers (MIP) sorbent were evaluated. Experimental results showed that the analyte was well retained with the highest extraction recovery and the optimum purification effect on MIP. Under the optimized conditions of MIP and USA‐DLLME, an enrichment factor of 23 was obtained. Good linearity relationship was obtained in the range of 5‐1200 pg/mL with a correlation coefficient of 0.9953. The limit of detection (LOD) was 0.35 pg/mL. The recoveries at three spiked levels ranged between 88.5% and 93.7%. Intra‐ and inter‐day relative standard deviations varied from 3.6% to 7.4% and from 5.4% to 9.7%, respectively. The developed method combing the advantages of MISPE and DLLME significantly improves the purification and enrichment of the analyte and can be used as an effective approach for the determination of ultra‐trace NNAL in complex biological matrices. 相似文献
966.
A new norlabdane diterpenoid, named vitrifolin A, was isolated from the fruits of Vitex trifolia Linn. var. simplicifolia Cham. Its structure was elucidated by mean of spectroscopic methods, including HRESIMS, IR, 1D and 2D NMR. The inhibitory effect of vitrifolin A on nitric oxide production in lipopolysaccarideactivated mouse macrophages was also evaluated. 相似文献
967.
A nano‐crystalline In2O3 was synthesized using calcinations methods and was used as a photocatalyst to degrade sulfan blue (SB) dye. In addition, this study addresses the conditions of the degradation and the factors that influenced the catalysis. In2O3 was prepared by calcining In(OH)3 at heat ranges of 100–700 °C for 24 h. The In2O3 was characterized using field emission scanning electron microscopy (FE‐SEM), an X‐ray diffractometer (XRD), thermogravimetric analysis (TGA), and high‐resolution X‐ray photoelectron spectroscopy (HR‐XPS). The activities of these samples were tested for the photocatalytic degradation of SB dye. The results indicated that the In(OH)3 that was calcined at 300 °C for 24 h had the best performance. 相似文献
968.
Pyrrole was polymerized on the surface of titanium foam using FeCl3 as oxidant and the as-synthesized product could be directly used as electrode for supercapacitor. The globular polypyrrole (PPy) particles were firmly loaded on the substrate with high density. The morphology study of PPy film is observed in SEM images, the XRD, FTIR and UV–vis spectra reveal the structure and crystalline of PPy nanoparticles. The electrochemical properties of PPy modified electrode are investigated by cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) and cycle life techniques. The electrochemical measurements showed such a PPy–Ti electrode had a wide working potential window, a high specific capacitance of 855 F g−1 and excellent cycle stability at a discharge current density of 1 A g−1. 相似文献
969.
Zhao‐Hui Yan Zhu‐Zhen Han Xian‐Qing Hu Qing‐Xin Liu Wei‐Dong Zhang Run‐Hui Liu Hui‐Liang Li 《Helvetica chimica acta》2013,96(1):85-92
Two new sesquiterpenes, 1 and 2 , as well as the five known compounds 3 – 7 , were isolated from the stems of Euonymus alatus. Compounds 2 – 7 have a β‐dihydroagarofuran skeleton. The structures of these compounds were elucidated mainly by spectroscopic methods (1D‐, 2D‐NMR, ESI‐MS, and HR‐ESI‐MS). We also report the X‐ray crystal structure of evonine ( 3 ) for the first time. 相似文献
970.
The synthesis of 1‐arylsulfonyl‐4‐(1′‐N‐hepta‐O‐acetyl‐β‐lactosyl)thiosemicarbazides by reaction of hepta‐O‐acetyl‐α‐D‐lactosyl isothiocyanate with substituted phenylsulfonyl hydrazines has been shown to occur in less than 1 min under microwave activation and 8 min under ultrasound irradiation at room temperature. It is noteworthy that when ultrasound and microwaves (MW) were utilized, a cleaner reaction accompanied with higher yields was observed. 相似文献