全文获取类型
收费全文 | 20044篇 |
免费 | 3574篇 |
国内免费 | 2419篇 |
专业分类
化学 | 14548篇 |
晶体学 | 245篇 |
力学 | 1224篇 |
综合类 | 186篇 |
数学 | 2066篇 |
物理学 | 7768篇 |
出版年
2024年 | 20篇 |
2023年 | 451篇 |
2022年 | 437篇 |
2021年 | 654篇 |
2020年 | 811篇 |
2019年 | 778篇 |
2018年 | 642篇 |
2017年 | 612篇 |
2016年 | 951篇 |
2015年 | 928篇 |
2014年 | 1084篇 |
2013年 | 1403篇 |
2012年 | 1843篇 |
2011年 | 1935篇 |
2010年 | 1278篇 |
2009年 | 1144篇 |
2008年 | 1329篇 |
2007年 | 1315篇 |
2006年 | 1175篇 |
2005年 | 1042篇 |
2004年 | 740篇 |
2003年 | 651篇 |
2002年 | 574篇 |
2001年 | 434篇 |
2000年 | 414篇 |
1999年 | 474篇 |
1998年 | 356篇 |
1997年 | 362篇 |
1996年 | 280篇 |
1995年 | 288篇 |
1994年 | 294篇 |
1993年 | 244篇 |
1992年 | 198篇 |
1991年 | 198篇 |
1990年 | 177篇 |
1989年 | 112篇 |
1988年 | 87篇 |
1987年 | 90篇 |
1986年 | 59篇 |
1985年 | 44篇 |
1984年 | 42篇 |
1983年 | 24篇 |
1982年 | 25篇 |
1981年 | 18篇 |
1980年 | 13篇 |
1975年 | 2篇 |
1957年 | 4篇 |
1936年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 187 毫秒
991.
Qingxiang Wang Yingtao Ding Feng Gao Shulian Jiang Bin Zhang Jiancong Ni Fei Gao 《Analytica chimica acta》2013
A novel DNA biosensor was fabricated through a facile sulfamide coupling reaction. First, the versatile sulfonic dye molecule of 1-amino-2-naphthol-4-sulfonate (AN-SO3−) was electrodeposited on the surface of a glassy carbon electrode (GCE) to form a steady and ordered AN-SO3− layer. Then the amino-terminated capture probe was covalently grafted to the surface of SO3−-AN deposited GCE through the sulfamide coupling reaction between the amino groups in the probe DNA and the sulfonic groups in the AN-SO3−. The step-by-step modification process was characterized by electrochemistry and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. Using Ru(NH3)63+ as probe, the probe density and the hybridization efficiency of the biosensor were determined to be 3.18 × 1013 strands cm−2 and 86.5%, respectively. The hybridization performance of the biosensor was examined by differential pulse voltammetry using Co(phen)33+/2+ (phen = 1,10-phenanthroline) as the indicator. The selectivity experiments showed that the biosensor presented distinguishable response after hybridization with the three-base mismatched, non-complementary and complementary sequences. Under the optimal conditions, the oxidation peak currents of Co(phen)33+/2+ increased linearly with the logarithm values of the concentration of the complementary sequences in the range from 1.0 × 10−13 M to 1.0 × 10−8 M with a regression coefficient of 0.9961. The detection limit was estimated to be 7.2 × 10−14 M based on 3σ. 相似文献
992.
Determination of Pd,Rh, Pt,Au in road dust by electrothermal vaporization inductively coupled plasma mass spectrometry with slurry sampling 总被引:1,自引:0,他引:1
Inductively coupled plasma mass spectrometry coupled with ultrasonic slurry sampling electrothermal vaporization (USS-ETV-ICP-MS) has been applied to determine Pd, Rh, Pt and Au in 0.5% m/v slurries of several road dust samples. 2% m/v ammonium pyrrolidine dithiocarbamate (APDC) was used as the modifier to enhance the ion count. The influence of instrument operating conditions, slurry preparation and interferences on the ion count was reported. This method has been applied to the determination of Pd, Rh, Pt and Au in BCR 723 Road Dust and NIST SRM 2709 San Joaquin Soil reference materials and two road dust samples collected locally. The analysis results of the standard reference materials agreed with the certified values. Precision between sample replicates was better than 10% for all the determinations. The method detection limits estimated from standard addition curves were 0.9, 0.4, 0.6 and 0.4 ng g−1 for Pd, Rh, Pt and Au, respectively, in original dust samples. 相似文献
993.
Yanlong He Jianniao TianJuanni Zhang Sheng ChenYixuan Jiang Yanchun ZhaoShulin Zhao 《Analytica chimica acta》2013
In this work, an ultrasensitive fluorescent polarization immunoassay (FPIA) method based on the quantum dot/aptamer/antibody/gold nanoparticles ensemble has been developed for the detection of adenosine triphosphate (ATP). DNA hybridization is formed when ATP is present in the PBS solution containing the DNA-conjugated quantum dots (QDs) and antibody-AuNPs. The substantial sensitivity improvement of the antibody-AuNPs-enhanced method is mainly attributed to the slower rotation of fluorescent unit when QDs-labeled oligonucleotides hybridize with antibody modified the gold nanoparticle. As a result, the fluorescent polarization (FP) values of the system increase significantly. Under the optimal conditions, a linear response with ATP concentration is ranged from 8 × 10−12 M to 2.40 × 10−4 M. The detection limit reached as low as 1.8 pM. The developed work provides a sensitive and selective immunoassay protocol for ATP detection, which could be applied in more bioanalytical systems. 相似文献
994.
Jian‐You Li Ying Peng Ling‐Zhi Li Pin‐Yi Gao Chang Gao Su‐Xia Xia Shao‐Jiang Song 《Helvetica chimica acta》2013,96(2):313-319
Two new abietane‐type diterpenoids, named triptobenzene R ( 1 ) and triptobenzene S ( 2 ), together with three known abietane‐type diterpenoids, triptophenolide ( 3 ), triptonodiol ( 4 ), and triptonoterpene methyl ether ( 5 ), were isolated from the roots of Tripterygium wilfordii Hook . f. Their structures and relative configurations were established by detailed spectral studies, including 1D‐ and 2D‐NMR (HSQC, HMBC, and NOESY), and HR‐ESI‐TOF‐MS, and by comparison with published data. Their absolute configurations were assigned by the CD technique, applied for the first time to abietane diterpenes from Tripterygium wilfordii. Compound 2 is the first abietane‐type norditerpenoid isolated from the genus Tripterygium. 相似文献
995.
Li‐Jun Yang Kun Jiang Jun‐Jie Tan Shi‐Jin Qu Hong‐Feng Luo Chang‐Heng Tan Da‐Yuan Zhu 《Helvetica chimica acta》2013,96(1):119-123
Chemical investigation on the stem and root of Melicope pteleifolia afforded three new prenylated benzene metabolites as racemic mixtures, named pteleifolins A–C ( 1 – 3 , resp.). Their gross structures were elucidated on the basis of spectroscopic analysis, especially 2D‐NMR experiments. An enantiomer resolution of (±)‐ 1 using chiral HPLC was performed, and the absolute configuration of the enantiomers were determined to be (+)‐(S)‐ 1 and (?)‐(R)‐ 1 by means of circular‐dichroism analysis. 相似文献
996.
The anion derived from diethyl malonate reacts with a series of halides readly under microwave irradiation, and the isolated yield of alkylated products varying from 64% to 86%. 相似文献
997.
Tetrachloro-1, 2-benzoquinone and 2, 3-dichloro-1, 4-naphthoquinone react with a series of aryl and alkyl selenolate, generated either by the reaction of Grignard reagents and selenium powder or by the reduction of diselenides with NaBH4, to give 3, 6-diarylseleno-2, 5-dichloro-1, 4-benzoquinones 3 and 2, 3-diarylseleno-1, 4-naphthoquinones 4 in good yields. 相似文献
998.
Abstract A novel 1,1,10,10,19,19-hexamethyl-5,14,23-trimethoxy[3.3.3]metacyclophane (2) was prepared in 25% yield by Friedel–Crafts cyclization of 4-(2-methoxyphenyl)-2-methylbutan-2-ol (1) at ? 78 °C using TiCl4 as Lewis acid catalyst in anhydrous dichloromethane. The structure of cyclophane 2 was determined by single-crystal X-ray diffraction, and the impact of substrate concentration on the yield of macrocycle 2 was also examined. The study on the effect of substituents at the phenyl ring showed that the methoxy group in 1 is crucial for its trimerization to give the hexamethyl[3.3.3]metacyclophane derivative. Demethylation of 2 with BBr3 gave 1,1,10,10,19,19-hexamethyl-5,14,23-trihydroxy[3.3.3]metacyclophane (4) in 96% yield, and its three hydroxyl groups provide the possible modification sites for further construction of supramolecular assemblies. 相似文献
999.
Bei‐Bei Zhang Qian Jiang Zhi‐Xin Liao Chao Liu Shi‐Jun Liu 《Helvetica chimica acta》2013,96(7):1281-1289
Phytochemical investigation of the EtOH extract of Euphorbia sieboldiana led to the isolation of four new oleanane‐type triterpenoids, (1β,2α,3β,19β)‐1,2,3,19‐tetrahydroxyolean‐12‐en‐28‐oic acid, (1β,3β,19β)‐1,3,19‐trihydroxyolean‐12‐en‐28‐oic acid, (1β,2α,3β,16β,19β)‐1,2,3,16,19‐pentahydroxyolean‐12‐en‐28‐oic acid, and (1β,2α,3β,19β,23)‐1,2,3,19,23‐pentahydroxyolean‐12‐en‐28‐oic acid, along with 16 known compounds. Their structures were established by extensive 1D‐ and 2D‐NMR, as well as other spectral analyses. Biological evaluation of the four new triterpenoids revealed potent cytotoxic activities against HeLa and Hep‐G2 cells. 相似文献
1000.
Hua‐Wei Li Sabyasachi Kar Pinghui Jiang 《International journal of quantum chemistry》2013,113(10):1493-1497
The effects of Debye plasma on the frequency‐dependent polarizabilities of Li and Na atoms are investigated using symplectic algorithm within the framework of the pseudostate summation technique. Dynamic dipole polarizabilities of Li (2s 2S) and Na(3s 2S) as functions of scaled number density of the plasma electrons for arbitrary plasma temperature are presented. Screening effects on the resonance frequencies are also presented. In free‐atomic cases, our calculated results are comparable with the reported theoretical and experimental predictions. © 2012 Wiley Periodicals, Inc. 相似文献