全文获取类型
收费全文 | 8817篇 |
免费 | 885篇 |
国内免费 | 913篇 |
专业分类
化学 | 4266篇 |
晶体学 | 72篇 |
力学 | 275篇 |
综合类 | 74篇 |
数学 | 541篇 |
物理学 | 1807篇 |
综合类 | 3580篇 |
出版年
2024年 | 21篇 |
2023年 | 89篇 |
2022年 | 192篇 |
2021年 | 198篇 |
2020年 | 251篇 |
2019年 | 238篇 |
2018年 | 180篇 |
2017年 | 198篇 |
2016年 | 335篇 |
2015年 | 384篇 |
2014年 | 456篇 |
2013年 | 589篇 |
2012年 | 601篇 |
2011年 | 595篇 |
2010年 | 583篇 |
2009年 | 515篇 |
2008年 | 680篇 |
2007年 | 624篇 |
2006年 | 530篇 |
2005年 | 492篇 |
2004年 | 404篇 |
2003年 | 355篇 |
2002年 | 345篇 |
2001年 | 338篇 |
2000年 | 234篇 |
1999年 | 211篇 |
1998年 | 139篇 |
1997年 | 124篇 |
1996年 | 116篇 |
1995年 | 84篇 |
1994年 | 72篇 |
1993年 | 71篇 |
1992年 | 67篇 |
1991年 | 67篇 |
1990年 | 45篇 |
1989年 | 41篇 |
1988年 | 33篇 |
1987年 | 30篇 |
1986年 | 21篇 |
1985年 | 16篇 |
1984年 | 9篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1935年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
841.
A Molecular Copper Catalyst for Electrochemical Water Reduction with a Large Hydrogen‐Generation Rate Constant in Aqueous Solution 下载免费PDF全文
Peili Zhang Prof. Mei Wang Yong Yang Tianyi Yao Prof. Licheng Sun 《Angewandte Chemie (International ed. in English)》2014,53(50):13803-13807
The copper complex [(bztpen)Cu](BF4)2 (bztpen=N‐benzyl‐N,N′,N′‐tris(pyridin‐2‐ylmethyl)ethylenediamine) displays high catalytic activity for electrochemical proton reduction in acidic aqueous solutions, with a calculated hydrogen‐generation rate constant (kobs) of over 10000 s?1. A turnover frequency (TOF) of 7000 h?1 cm?2 and a Faradaic efficiency of 96 % were obtained from a controlled potential electrolysis (CPE) experiment with [(bztpen)Cu]2+ in pH 2.5 buffer solution at ?0.90 V versus the standard hydrogen electrode (SHE) over two hours using a glassy carbon electrode. A mechanism involving two proton‐coupled reduction steps was proposed for the dihydrogen generation reaction catalyzed by [(bztpen)Cu]2+. 相似文献
842.
Highly Efficient Orange and Warm White Phosphorescent OLEDs Based on a Host Material with a Carbazole–Fluorenyl Hybrid 下载免费PDF全文
Xiaoyang Du Yun Huang Dr. Silu Tao Xiaoxia Yang Chuan Wu Huaixin Wei Dr. Mei‐Yee Chan Dr. Vivian Wing‐Wah Yam Prof. Chun‐Sing Lee 《化学:亚洲杂志》2014,9(6):1500-1505
A new carbazole–fluorenyl hybrid compound, 3,3′(2,7‐di(naphthaline‐2‐yl)‐9H‐fluorene‐9,9‐diyl)bis(9‐phenyl‐9H‐carbazole) (NFBC) was synthesized and characterized. The compound exhibits blue‐violet emission both in solution and in film, with peaks centered at 404 and 420 nm. In addition to the application as a blue emitter, NFBC is demonstrated to be a good host for phosphorescent dopants. By doping Ir(2‐phq)3 in NFBC, a highly efficient orange organic light‐emitting diode (OLED) with a maximum efficiency of 32 cd A?1 (26.5 Lm W?1) was obtained. Unlike most phosphorescent OLEDs, the device prepared in our study shows little efficiency roll‐off at high brightness and maintains current efficiencies of 31.9 and 26.8 cd A?1 at a luminance of 1000 and 10 000 cd m?2, respectively. By using NFBC simultaneously as a blue fluorescence emitter and as a host for a phosphorescent dopant, a warm white OLED with a maximum efficiency of 22.9 Lm W?1 (21.9 cd A?1) was also obtained. 相似文献
843.
Dr. Hong‐Jay Lo M. Sc. Chin‐Yin Lin Dr. Mei‐Chun Tseng Prof. Rong‐Jie Chein 《Angewandte Chemie (International ed. in English)》2014,53(34):9026-9029
A hydroxy‐directed alkylation of an N,N‐diethylarylamide using CIPE‐assisted α‐silyl carbanions (CIPE=complex‐induced proximity effect) has been developed using a simple reagent combination of LDA (lithium diisopropylamide) and chlorosilane. A study of the mechanism, and the application of the procedure to an anionic Snieckus–Fries rearrangement for a highly efficient synthesis of the potent phosphatidylinositol 3‐kinase (PI3K) inhibitor LY294002, are reported. 相似文献
844.
Reactivity of Oxygen Radical Anions Bound to Scandia Nanoparticles in the Gas Phase: CH Bond Activation 下载免费PDF全文
Li‐Hua Tian Jing‐Heng Meng Dr. Xiao‐Nan Wu Dr. Yan‐Xia Zhao Dr. Xun‐Lei Ding Prof. Dr. Sheng‐Gui He Dr. Tong‐Mei Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):1167-1175
The activation of C?H bonds in alkanes is currently a hot research topic in chemistry. The atomic oxygen radical anion (O?.) is an important species in C?H activation. The mechanistic details of C?H activation by O?. radicals can be well understood by studying the reactions between O?. containing transition metal oxide clusters and alkanes. Here the reactivity of scandium oxide cluster anions toward n‐butane was studied by using a high‐resolution time‐of‐flight mass spectrometer coupled with a fast flow reactor. Hydrogen atom abstraction (HAA) from n‐butane by (Sc2O3)NO? (N=1–18) clusters was observed. The reactivity of (Sc2O3)NO? (N=1–18) clusters is significantly sizedependent and the highest reactivity was observed for N=4 (Sc8O13?) and 12 (Sc24O37?). Larger (Sc2O3)NO? clusters generally have higher reactivity than the smaller ones. Density functional theory calculations were performed to interpret the reactivity of (Sc2O3)NO? (N=1–5) clusters, which were found to contain the O?. radicals as the active sites. The local charge environment around the O?. radicals was demonstrated to control the experimentally observed size‐dependent reactivity. This work is among the first to report HAA reactivity of cluster anions with dimensions up to nanosize toward alkane molecules. The anionic O?. containing scandium oxide clusters are found to be more reactive than the corresponding cationic ones in the C?H bond activation. 相似文献
845.
Ivanei Ferreira Pinheiro Ana Rita Morales Lucia H. Mei 《Cellulose (London, England)》2014,21(6):4381-4391
In this work, polymeric biocomposites of poly (butylene adipate-co-terephthalate), PBAT, were reinforced with Munguba fibers (Pseudobombax munguba). This tree is found in great abundance in the marshy areas of the Amazon forest. The motivation for using this fiber in polymer composites comes from the fact that although research for this fiber has not been reported in the scientific literature, it is commonly used by the local population because its bark is strong and flexible. Most important is that the extraction of Munguba fibers does not damage the supplier tree because as it is extracted from the bark, its regeneration starts as it is removed. The fibers were chemically treated by mercerization/acetylation and evaluated by Fourier transform infrared spectroscopy, thermogravimetric analysis and tensile tests. The Munguba fiber presented mechanical properties similar to those of other natural fibers traditionally used in composites, and the chemical treatment provided improvements of its thermal stability and stiffness. The biocomposites showed a better elastic modulus in relation to the pure PBAT. The addition of fibers caused changes in the T g, T m and T c of PBAT as observed by differential scanning calorimetry analysis. The Russel, Halpin-Tsai and Maxwell models were employed to provide the theoretical elastic modulus of the biocomposites. 相似文献
846.
Sheng-ming Xie Xin-huan Zhang Bang-jin Wang Mei Zhang Jun-hui Zhang Li-ming Yuan 《Chromatographia》2014,77(19-20):1359-1365
Metal–organic frameworks (MOFs) have received great attention as stationary phases in chromatographic separation technology because of their unusual properties such as high surface areas, fascinating structures, and excellent chemical and thermal stability. A chiral MOF, [(CH3)2NH2][Cd(bpdc)1.5]·2DMA, possesses a unique chiral nanotube motif built from the covalent linkage of homochiral nanotubes made up of octuple helices. Here, we report the fabrication of a three-dimensional (3D) chiral nanoporous MOF-coated capillary column (2 m long × 75 μm i.d.) for capillary gas chromatographic separation of racemates, Grob’s test mixture, normal alkanes, normal alcohols, and isomers. The MOF-coated capillary column offered good separation efficiency (2,180 plates m?1), which was measured using n-dodecane as the analyte at 120 °C. The relative standard deviations of repeatability for citronellal on MOF-coated capillary column were 0.23 and 2.1 % for retention time and peak area, respectively. The results demonstrated that the capillary column exhibited excellent selectivity and separation ability toward Grob’s test mixture, normal alkanes, normal alcohols and isomers, especially for racemates. 相似文献
847.
Rapid analysis of phthalic acid esters in environmental water using fast elution gas chromatography with mass spectrometry and adaptive library spectra 下载免费PDF全文
A method for the fast determination of the components in a complex sample by using gas chromatography with mass spectrometry was developed and used for the quantitative analysis of phthalic acid esters in environmental water. In the method, the adaptively corrected mass spectra were used to compensate for the differences between the library spectra and the measured ones in the experiment. The correction was obtained by the iterative transformation of the library spectra using iterative target transformation factor analysis, and the resolution was performed by non‐negative immune algorithm using the corrected spectra. Rapid analysis of 16 phthalic acid esters in water samples was achieved using fast elution gas chromatography with mass spectrometry measurements. The results show that the mass spectra and chromatographic profiles of the phthalic acid esters can be obtained from the overlapping signal of 13 min elution, and accurate quantitative analysis can be obtained. The recoveries of the phthalic acid esters obtained by standard addition are between 90.3 and 107.4%, and the relative standard deviations obtained in repeated measurements are less than 9%. 相似文献
848.
Tao Jing Yusun Zhou Wei Wu Min Liu Yikai Zhou Surong Mei 《Journal of separation science》2014,37(20):2940-2946
In this study, we developed a simple and selective spin column extraction technology utilizing hydrophilic molecularly imprinted polymers as the sorbents for extracting nitrophenol pollutants in water samples (the East Lake, the Yangtze River, and wastewater). The whole procedure was achieved by centrifugation of the spin column, and multiple samples were simultaneously processed with a low volume of solvent and without evaporation. Under the optimized condition, recoveries of nitrophenol compounds on the spin column packed with hydrophilic molecularly imprinted polymers ranged from 87.3 to 92.9% and an excellent purification effect was obtained. Compared with activated carbon, multi‐walled carbon nanotubes, LC‐C18 sorbents, hydrophilic molecularly imprinted polymers exhibited a highly selective recognition ability for nitrophenol compounds and satisfactory sample extraction efficiency. Subsequently, the spin column extraction coupled with high‐performance liquid chromatography was established, which was found to be linear in the range of 2–1000 ng/mL for 2,4‐dinitropehnol and 2‐nitrophenol, and 6–1000 ng/mL for 4‐nitrophenol with correlation coefficients greater than 0.998. The detection limits ranged from 0.3–0.5 ng/mL. It is shown that the proposed method can be used for the determination of trace nitrophenol pollutants in complex samples, which is not only beneficial for water quality analysis but also for environmental risk assessment. 相似文献
849.
A special multifunctional ionic liquid compound (1‐methyl‐3‐(2‐(thiocarboxyoxy)‐ethyl)‐2H‐imidazole‐1,3‐diium bromide (SHIL)) is used as the chemical bridge to link lanthanide beta‐diketonates and polymer resin, which are designated as Ln(L)4‐SHIL‐WR/MR (Ln = Eu, Tb, Sm; L = thenoyltrifluoroacetonate (TTA), acetylacetonate (AA), dibenzoylmethane (DBM); WR = Wang resin, MR = Merrifield resin). Among SHIL and polymer resin are assembled to form covalently bonded system through condensation reaction. Then tetrakis lanthanide beta‐diketonates are linked to SHIL through ion‐exchange reaction. Physical characterization and especially the photoluminescent performance of the multicomponent hybrids are studied. The hybrid materials possess good stability and excellent luminescent property. The results provide useful path to obtain luminescent hybrids for further practical application. 相似文献
850.
Cheng-Fang Wang Li Fan Mei Tian Shu-Shan Du Zhi-Wei Deng Jiang-Bin Feng 《Natural product research》2015,29(14):1380-1383
This work aimed to investigate benzophenanthridine from the roots of Zanthoxylum nitidum (Roxb.) DC. var. fastuosum How ex Huang for the first time. Thirteen benzophenanthridines were isolated, and our results of the cytotoxic activities indicated that compound 6 exhibited the best potency against A549, Hela, SMMC-7721 and EJ, with the IC50 values of 27.50, 37.50, 16.95 and 60.42 μM, respectively. Compounds 7 and 11 also showed strong cytotoxicity when tested against the four human cancer cell lines (A549, Hela, SMMC-7721 and EJ), while only compounds 12 and 13 displayed cytotoxicity in inhibiting BALL-1 proliferation among all the compounds. These results suggested that benzophenanthridines may become a valid alternative of potential basis for new anti-proliferative agents. 相似文献