全文获取类型
收费全文 | 7895篇 |
免费 | 1546篇 |
国内免费 | 969篇 |
专业分类
化学 | 5575篇 |
晶体学 | 116篇 |
力学 | 464篇 |
综合类 | 89篇 |
数学 | 891篇 |
物理学 | 3275篇 |
出版年
2024年 | 32篇 |
2023年 | 239篇 |
2022年 | 391篇 |
2021年 | 378篇 |
2020年 | 454篇 |
2019年 | 425篇 |
2018年 | 357篇 |
2017年 | 330篇 |
2016年 | 452篇 |
2015年 | 452篇 |
2014年 | 486篇 |
2013年 | 655篇 |
2012年 | 733篇 |
2011年 | 723篇 |
2010年 | 516篇 |
2009年 | 474篇 |
2008年 | 454篇 |
2007年 | 405篇 |
2006年 | 340篇 |
2005年 | 305篇 |
2004年 | 256篇 |
2003年 | 208篇 |
2002年 | 187篇 |
2001年 | 156篇 |
2000年 | 112篇 |
1999年 | 143篇 |
1998年 | 108篇 |
1997年 | 94篇 |
1996年 | 95篇 |
1995年 | 77篇 |
1994年 | 66篇 |
1993年 | 46篇 |
1992年 | 43篇 |
1991年 | 47篇 |
1990年 | 42篇 |
1989年 | 26篇 |
1988年 | 22篇 |
1987年 | 18篇 |
1986年 | 16篇 |
1985年 | 13篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 7篇 |
1980年 | 4篇 |
1978年 | 2篇 |
1964年 | 1篇 |
1959年 | 1篇 |
1957年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
31.
Meng Wang 《European Polymer Journal》2007,43(11):4613-4618
In this study the optical property and film morphology of a conjugated polymer, poly(9,9-dihexylfluorene-alt-2,5-dihexyloxybenzene) (PF6OC6), are investigated. It is found that the intensity of the 0-1 emission relative to the 0-0 emission in the PL spectra and the full width at the half-maximum (fwhm) of PL spectra of the PF6OC6 films decrease firstly and then increase with increasing the annealing temperature. The polymer films also exhibit different morphological features after annealing at different temperatures. The optical and morphological results suggest that the vibronic structure of PF6OC6 is closely related to the film morphology, and its formation is enhanced in the amorphous (or less ordered) films and inhibited in the ordered films. 相似文献
32.
33.
Simple and sensitive electrochemical method for the determination of metronidazole, based on a nanostructured film coated glassy carbon electrode (GCE), is described. Multi-walled carbon nanotubes (MWNT) was dispersed into water in the presence of a hydrophobic surfactant to give very stable and homogeneous MWNT suspension, and a MWNT-film coated GCE was achieved via evaporating solvent. Metronidazole yields a well-defined reduction peak whose potential is −0.71 V at the MWNT-film coated GCE in pH 9.0 Britton-Robinson buffer. Compared with bare GCE, the MWNT-film modified GCE significantly enhances the reduction peak current of metronidazole. All the experimental parameters were optimized for the determination of metronidazole. The detection limit is 6×10−9 mol/l at 2 min accumulation. This method has been successfully used to determine metronidazole in the drugs. Furthermore, results obtained by the proposed method have been compared with spectrophotometric method. 相似文献
34.
An enzymatic assay for glucose based on the use of the fluorescent probe for hydrogen peroxide, europium(III) tetracycline (EuTc), is described. The weakly fluorescent EuTc and enzymatically generated H2O2 form a strongly fluorescent complex (EuTc–H2O2) whose fluorescence decay profile is significantly different. Since the decay time of EuTc–H2O2 is in the microseconds time domain, fluorescence can be detected in the time-resolved mode, thus enabling substantial reduction of background fluorescence. The scheme represents the first H2O2-based time-resolved fluorescence assay for glucose not requiring the presence of a peroxidase. The time-resolved assay (with a delay time of 60 s and using endpoint detection) enables glucose to be determined at levels as low as 2.2 mol L–1, with a dynamic range of 2.2–100 mol L–1. The method also was adapted to a kinetic assay in order to cover higher glucose levels (mmol L–1 range). The latter was validated by analyzing spiked serum samples and gave a good linear relationship for glucose levels from 2.5 to 55.5 mmol L–1. Noteworthy features of the assay include easy accessibility of the probe, large Stokes shift, a line-like fluorescence peaking at 616 nm, stability towards oxygen, a working pH of approximately 7, and its suitability for both kinetic and endpoint determination. 相似文献
35.
Jiyun Hu Hamed Mehrabi Yin-Shan Meng Maddison Taylor Jin-Hui Zhan Qigeng Yan Mourad Benamara Robert H. Coridan Hudson Beyzavi 《Chemical science》2021,12(22):7930
Metalation of covalent organic frameworks (COFs) is a critical strategy to functionalize COFs for advanced applications yet largely relies on the pre-installed specific metal docking sites in the network, such as porphyrin, salen, 2,2′-bipyridine, etc. We show in this study that the imine linkage of simple imine-based COFs, one of the most popular COFs, readily chelate transition metal (Ir in this work) via cyclometalation, which has not been explored before. The iridacycle decorated COF exhibited more than 10-fold efficiency enhancement in (photo)catalytic hydrogen evolution from aqueous formate solution than its molecular counterpart under mild conditions. This work will inspire more functional cyclometallated COFs to be explored beyond catalysis considering the large imine COF library and the rich metallacycle chemistry.This study describes cyclometallation as a new metal binding mode for imine-based COFs. The iridacycle decorated COF could be used for catalytic hydrogen evolution from aqueous formate solution with high stability and high efficacy. 相似文献
36.
Basheer C Jayaraman A Kee MK Valiyaveettil S Lee HK 《Journal of chromatography. A》2005,1100(2):137-143
A novel sorbent, dihydroxylated polymethylmethacrylate (DHPMM), coated on hollow-fiber membrane, is used for the polymer-coated hollow-fiber microextraction of trace amounts of natural and synthetic estrogens, such as diethylstilbestrol, estrone, 17beta-estradiol and 17alpha-ethynylestradiol, in aqueous samples. In this procedure, estrogens were extracted using the functionalized polar DHPMM polymer with derivatization using N-methyl-N-(trimethylsilyl)trifluoroacetamide followed by gas chromatography-mass spectrometric analysis. The detection limits for estrogens in aqueous sample were between 0.03 and 0.8 ng l(-1) and the calibration curves were linear over the concentration range 0.05-10 microgl(-1) and had correlation coefficients of >0.994. The relative standard deviations (RSDs) were <15% (n = 3). This simple, accurate, sensitive and selective analytical method is applicable to the determination of trace amounts of estrogens in reservoir and potable water samples. 相似文献
37.
Sinenxan A, a taxoid isolated from callus tissue cultures of Taxus yunnanensis was converted into 13-oxo-7,9-dideoxy-2-debenzoyl-2-acetyl-baccatin IV and 7,9-dideoxy-2-debenzoyl-4-deacetyl-baccatin IV, a key framework of 1,7,9-trideoxypaclitaxel. Several special steps in this transformation are worthy of note: (1) deoxygenation by treatment with hypophosphorous acid at C-14 position; (2) a highly regioselective O-deacetylation of taxanes at C-5 position; and (3) stereoselective reduction of the 13-carbonyl group by transannular assistance from the C-4-hydroxyl. 相似文献
38.
Jie Chen Rong Ji Dai Bin Tong Sheng Yuan Xiao Wei Wei Meng 《中国化学快报》2007,18(1):10-12
The reduction of 4-nitrophenol catalyzed by nitroreductase in the presence of NADH was investigated in this paper.4-Amino- phenol and 4-bydroxylamino-phenol were found in the reductive products.The relationship between reaction time and the reductive ratio were studied.The similar reducing ratios of 4-nitrophenol were obtained under aerobic and anaerobic conditions.The results indicated that an oxygen-insensitive reaction was proceeded in the reduction of 4-nitrophenol and nitroreductase was an oxygen- insensitive enzyme.The reductive products of 4-nitrophenol were determined by HPLC and MS. 相似文献
39.
Yoshikatsu Ito Meng Ji-Ben Shin Suzuki Yoshitaka Kusunaga Teruo Matsuura Keiichi Fukuyama 《Tetrahedron letters》1985,26(17):2093-2096
In contrast to simple imidazoles, 1-methy1–2,4,5-triphenylimidazole () produced stable oxetane photoadducts - with good efficiency upon irradiation in the presence of benzophenone derivatives - in acetonitrile solution. Irradiation in the solid-phase was also studied. The oxetanes - readily underwent cycloreversion by acid catalysis or by heating. 相似文献
40.
Three ion-pair complexes, [RbzPy](+)[Ni(mnt)(2)](-) (mnt(2)(-) = maleonitriledithiolate; [RbzPy](+) = 4-R-benzylpyridinium; R = Br (1), Cl (2), and NO(2) (3)), with unusual magnetic properties have been synthesized and characterized. The crystal structures of 1 and 2 have been solved. The two complexes belong to the P2(1)/c space group with Z = 4 and C(20)H(11)BrN(5)NiS(4), a = 12.0744(17) A, b = 26.369(4) A, c = 7.440(3) A, and beta = 102.63(3) degrees for 1 and C(20)H(11)ClN(5)NiS(4), a = 12.105(2) A, b = 26.218(4) A, c = 7.374(2) A, and beta = 102.55(2) degrees for 2, respectively. The [Ni(mnt)(2)](-) anions in 1-3 form uniformly spaced one-dimensional (1-D) magnetic chains of s = 1/2 at room temperature. The temperature dependences of the susceptibility for 1-3 show that they undergo phase transitions. All three complexes are paramagnetic in their high-temperature (abbreviation HT) phase and diamagnetic in the low-temperature (abbreviation LT) phase because of strong dimerization along the stacking direction. The results of thermal analysis (DSC) further confirm that the phase transition for 1 and 2 is first-order but maybe second-order for 3. The phenomena observed in this study are similar to those of the 1-D radical systems. 相似文献