全文获取类型
收费全文 | 20136篇 |
免费 | 3313篇 |
国内免费 | 2394篇 |
专业分类
化学 | 14068篇 |
晶体学 | 180篇 |
力学 | 1152篇 |
综合类 | 124篇 |
数学 | 2782篇 |
物理学 | 7537篇 |
出版年
2024年 | 86篇 |
2023年 | 435篇 |
2022年 | 658篇 |
2021年 | 735篇 |
2020年 | 868篇 |
2019年 | 790篇 |
2018年 | 714篇 |
2017年 | 673篇 |
2016年 | 996篇 |
2015年 | 978篇 |
2014年 | 1108篇 |
2013年 | 1487篇 |
2012年 | 1717篇 |
2011年 | 1788篇 |
2010年 | 1248篇 |
2009年 | 1142篇 |
2008年 | 1275篇 |
2007年 | 1125篇 |
2006年 | 1004篇 |
2005年 | 906篇 |
2004年 | 728篇 |
2003年 | 626篇 |
2002年 | 705篇 |
2001年 | 560篇 |
2000年 | 453篇 |
1999年 | 441篇 |
1998年 | 354篇 |
1997年 | 324篇 |
1996年 | 333篇 |
1995年 | 302篇 |
1994年 | 239篇 |
1993年 | 166篇 |
1992年 | 168篇 |
1991年 | 161篇 |
1990年 | 123篇 |
1989年 | 95篇 |
1988年 | 55篇 |
1987年 | 57篇 |
1986年 | 74篇 |
1985年 | 47篇 |
1984年 | 32篇 |
1983年 | 26篇 |
1982年 | 15篇 |
1981年 | 11篇 |
1980年 | 4篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1969年 | 1篇 |
1959年 | 1篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
991.
Harry R. Chobanian Ping Liu Marc D. Chioda Yan Guo Linus S. Lin 《Tetrahedron letters》2007,48(7):1213-1216
We report an expedient method for the heteroarylation of acetone under tin-free conditions. The coupling is performed using the commercially available enol silane of acetone (2-trimethylsilyloxypropene) and a corresponding aryl bromide, chloride or triflate under microwave-assisted conditions, with tris(dibenzylideneacetone)dipalladium (Pd2(dba)3) or palladium acetate (Pd(OAc)2) and 2-(2′,6′-dimethoxybiphenyl)dicyclohexylphosphine (S-Phos) as the catalyst system. 相似文献
992.
Pd-catalyzed aerobic oxidative coupling of anilides with olefins was achieved through selective C-H bond activation. Compared to the previous studies, not only did we successfully use molecular oxygen to replace the chemical oxidant, but we also obtained improved yields for a number of substrates. The reaction tended to give high yields for electron-rich anilides and electron-deficient olefins, with a best yield up to 91%. 相似文献
993.
A short and efficient route to the synthesis of 4-oxa-tricyclo[4.3.1.0]decan-2-one scaffold 12 in good yield is reported. Essential to the synthesis was the implementation of selective protection of the catechol system in xanthone 2 with Ph2CCl2 and MOM groups. Subsequently, a biomimetic tandem Claisen/Diels-Alder reaction occurred to produce the desired tricyclic scaffold 11a as a single isomer. A rationalization of the excellent region and stereoselectivity of this transformation was also proposed. 相似文献
994.
A series of salicylanilides (1a-h) bearing varied substituents at the 3'- or 4'-position of the anilino moiety (substituent = p-OCH3, p-CH3, m-CH3, H, p-Cl, m-Cl, p-CO2CH3, and p-CN) were synthesized. In acetonitrile all of the substituted salicylanilides 1a-h predominantly adopt the "closed-ring" conformation facilitated by a strong intramolecular OH...O=C hydrogen bond. In the presence of H2PO4-, the conformation of 1a-h was found to be modulated by the substituent. With our proposed proton-transfer fluorescence probing method, we were able to show that the conformation of 1a-f bearing a not highly electron-withdrawing substituent was switched to the "open-ring" form by H2PO4-, whereas 1h bearing a highly electron-withdrawing substituent, p-CN, remained in the "closed-ring" conformation. The significance of these findings for understanding, from a molecular structural point of view, the mechanism of salicylanilide-based inhibitors for inhibiting the protein tyrosine kinase epidermal growth factor receptor was discussed. 相似文献
995.
ZnO nanocrystals, nanorods, and tablets were prepared at 110, 140, and 180 degrees C in a water-ethanol system. Nanorods (~2 x 40 nm) arranged in serpentine morphologies formed by the oriented coalescence of anhedral ZnO nanocrystals (~3.5 nm diameter), while tabular ZnO grew by [1210] textural attachment of the nanorods. The development of these crystal habits is believed to proceed via a dissolution and growth mechanism mediated by a transient amorphous phase. Materials synthesized at intermediate temperatures (125 and 160 degrees C) possessed microstructures containing mixed crystal forms in the expected orientation relationship. Photoluminescent spectra of the nanocrystals and nanorods showed blue shifts of 0.16 and 0.13 eV with respect to the bulk ZnO band gap (3.26 eV) due to quantum confinement, with the narrow emission peaks typical of particles possessing uniform size and shape. The larger tablets displayed a less energetic emission (3.10 eV) ascribed to exciton-exciton collisions. 相似文献
996.
A novel surface ionization source for ion mobility spectrometer 总被引:1,自引:0,他引:1
A surface ionization (SI) source is designed and prepared for ion mobility spectrometer (IMS). The source acts not only as an emitter but also an ion injector which can inject ions periodically into the drift region of drift tube. Using the dual-role source, the dimension of the drift tube can be decreased and the circuit for high voltage can be simplified efficiently. The IMS with the SI source has a response range of ∼4 orders of magnitude and a good reproducibility to tri-ethylamine. Compared with radioactive ionization (RI), the ultra-short time for ion injection and the zero level base line of ion mobility spectrum are characteristics of the surface ionization. 相似文献
997.
Preparation of a multi-hapten antigen and broad specificity polyclonal antibodies for a multiple pesticide immunoassay 总被引:4,自引:0,他引:4
A multi-determinant artificial antigen was prepared by haptens of four pesticides (chlorpyrifos, triazophos, carbofuran and parathion methyl) conjugating to the carrier protein BSA in turn. Male New Zealand white rabbits were immunized with this multi-determinant immunogen to produce the polyclonal antibodies (PAbs), which can recognize the four pesticides. The PAbs displayed high level for each relative hapten-OVA conjugate, with the favorable titers of 4.49 × 104, 8.98 × 104, 2.24 × 104 and 1.86 × 104, for CHBu-OVA, THHe-OVA, BFNB-OVA and MP5-OVA, respectively. Characterization studies of the PcAbs showed that it has high affinity and specificity to the four relative pesticides. An indirect competitive ELISA was developed for multi-residue determination. The I50 value for the four pesticides was 0.290, 0.065, 0.582 and 2.824 μg mL−1, with the detection limit (I10) of 0.022, 0.005, 0.015 and 0.115 μg mL−1 for carbofuran, triazophos, chlorpyrifos and parathion methyl, respectively. The linear rang was 0.016-2.000, 0.005-0.500, 0.010-2.000 and 0.063-5.000 μg mL−1, respectively, for carbofuran, triazophos, chlorpyrifos and parathion methyl. Results indicated that, this study provided a new strategy to develop immunoassays through artificial antigen design for pesticides multi-residue determination. 相似文献
998.
In this paper, the synthetic route of a potential antitumor reagent, benzo[b][1,10] phenanthrolin-7(12H)-one (BPO), was improved. A sulfonic group was introduced to BPO to form a new compound, 7-oxobenzo[b][1,10]phenan-throline-12(7H)-sulfonic acid (OPSA), in order to enhance its water-solubility. The molecular structure of OPSA has been confirmed by IR, UV, MS, 1H NMR and elements analysis. It was proved in our experiments that DNA could quench the fluorescence of OPSA and the maximum quenched intensity appeared at 408 nm (λex = 284 nm). The quenched fluorescence intensity was proportional to the concentration of DNA. Based on this phenomenon, OPSA had been used as the fluorescent probe for detection of calf thymus DNA (ct-DNA) and the corresponding linear response range was from 1.0 to 150.0 μg mL−1 and the limit of detection (LOD) was 3.8 ng mL−1. Its interaction with ct-DNA was investigated by fluorescence, absorption and viscosity measurements. When binding to ct-DNA, OPSA showed obvious fluorescence quenching and the quenched intensity was stable with the presence and absence of NaCl. The absorption spectra of OPSA had no evidence of increasing or decreasing when ct-DNA was added. The viscosity of OPSA and ct-DNA mixture showed no obvious change comparing with the viscosity of ct-DNA along. The results suggested that the interaction between OPSA and ct-DNA was groove binding in nature. Scatchard plots constructed from fluorescence titration data gave a binding constant of 8.9 × 105 L mol−1 and a binding site size of 0.35 base pairs per bound drug molecule. 相似文献
999.
Huang LF Wu MJ Zhong KJ Sun XJ Liang YZ Dai YH Huang KL Guo FQ 《Analytica chimica acta》2007,588(2):216-223
In this paper, chromatographic fingerprint was firstly used for quality control of tobacco flavors. Based on gas chromatography-mass spectrometry (GC-MS) and combined chemometrics methods, a simple, reliable and reproducible method for developing chromatographic fingerprint of coffee flavor, one of tobacco flavors, was described. Six coffee flavor samples obtained from different locations were used to establish the fingerprint. The qualitative and quantitative analysis of coffee flavor sample from Shenzhen was completed with the help of subwindow factor analysis (SFA). Fifty-two components of 68 separated constituents in coffee flavor sample from Shenzhen, accounting for 88.42% of the total content, were identified and quantified. Then, spectral correlative chromatography (SCC) was used to extract the common peaks from other five studied coffee flavor samples. Thirty-eight components were found to exist in all six samples. Finally, the method validation of fingerprint analysis was performed based on the relative retention time and the relative peak area of common peaks, sample stability and similarity analysis. The similarities of six coffee flavor samples were more than 0.9104 and showed that samples from different locations were consistent to some extent. The developed chromatographic fingerprint was successfully used to differentiate coffee flavor from coco flavor and some little difference sample prepared with coffee flavor and coco flavor by both similarity comparison and principal component projection analysis. The developed method can be used for quality control of coffee flavor. 相似文献
1000.
Yaping Guo 《European Polymer Journal》2007,43(6):2292-2297
Polyaniline (PANI) nanofibers with interconnected network-like structures were electropolymerized on stainless steel substrates by galvanostatic electrolysis. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy (UV-vis) and Fourier transform infrared spectroscopy (FTIR). The results show that PANI and gels (mixtures of oligomer, dopant and aniline) form simultaneously during the electrochemical deposition. The gels play an important role in the formation of PANI nanofibers. The PANI formed in the early stage of polymerization is subject to secondary growth along one dimension, since the nucleation sites are suppressed by the wrapped gels. The dendritic degree of PANI nanofibers is related to dopants, and the order is as follows: PANI-H3PO4 > PANI-H2SO4 > PANI-HNO3. No nanofibers are obtained using CH3COOH as dopants due to the high solubility of PANI-CH3COOH. 相似文献