全文获取类型
收费全文 | 4121篇 |
免费 | 1212篇 |
国内免费 | 291篇 |
专业分类
化学 | 219篇 |
晶体学 | 31篇 |
力学 | 449篇 |
综合类 | 23篇 |
数学 | 244篇 |
物理学 | 2734篇 |
无线电 | 1924篇 |
出版年
2024年 | 13篇 |
2023年 | 43篇 |
2022年 | 64篇 |
2021年 | 90篇 |
2020年 | 97篇 |
2019年 | 81篇 |
2018年 | 85篇 |
2017年 | 114篇 |
2016年 | 172篇 |
2015年 | 135篇 |
2014年 | 281篇 |
2013年 | 279篇 |
2012年 | 309篇 |
2011年 | 323篇 |
2010年 | 270篇 |
2009年 | 280篇 |
2008年 | 380篇 |
2007年 | 343篇 |
2006年 | 331篇 |
2005年 | 252篇 |
2004年 | 236篇 |
2003年 | 203篇 |
2002年 | 169篇 |
2001年 | 162篇 |
2000年 | 132篇 |
1999年 | 105篇 |
1998年 | 86篇 |
1997年 | 86篇 |
1996年 | 107篇 |
1995年 | 70篇 |
1994年 | 75篇 |
1993年 | 43篇 |
1992年 | 47篇 |
1991年 | 32篇 |
1990年 | 35篇 |
1989年 | 15篇 |
1988年 | 16篇 |
1987年 | 18篇 |
1986年 | 9篇 |
1985年 | 9篇 |
1984年 | 11篇 |
1983年 | 3篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有5624条查询结果,搜索用时 78 毫秒
81.
The hydrolysis reaction of
,
and
,
-dipalmitoylphosphatidylcholine (DPPC) catalized by bee venom phospholipase A2 was studied in spreading monolayer at the water/air interface. DPPC and the hydrolysis products, palmitic acid and
-lysophosphatidylcholine, palmitoyl were characterized at the interface by means of surface pressure, surface potential and ellipsometric measurements. Furthermore, mixed monolayers of reagents and products were investigated to ascertain their miscibility. The results show that the hydrolysis reaction can be followed by the decrease of surface pressure with time on subphases containing β-cyclodextrin, a well-known complexing agent of many amphiphilic compounds. The order of the reaction, the kinetic constant and other kinetic parameters are deduced. 相似文献
82.
In this paper the formation mechanism of iron macro-spheres in
a plasma medium is dealt with, including the conditions under which such
spheres are formed. The geometry of the spheres referred to above
depends on the main technological parameters involved in the production
of pores. Conditions under which pores occur within macro-spheres are
also established. The radii of these pores are sensitive to the velocity
distribution within the plasma jet section 相似文献
83.
This work describes a hybrid procedure for eliminating major interference sources in aqueous near-infrared (NIR) spectra, that include aqueous influence, noise, and systemic variations irrelevant to concentration. The scheme consists of two parts: extension of wavelet prism (WPe) and orthogonal signal correction (OSC). First, WPe is employed to remove variations due to aqueous absorbance and noise; then OSC is applied to remove systemic spectral variations irrelevant to concentration. Although water possesses strong absorption bands that overshadow and overlap the absorption bands of analytes, along with noise and systematic interference, successful calibration models can be generated by employing the method proposed here. We show that the elimination of major interference sources from the aqueous NIR spectra results in a substantial improvement in the precision of prediction, and reduces the required number of PLS components in the model. In addition, the strategy proposed here can be applied to various analytical data for quantitative purposes as well. 相似文献
84.
Yildiray Topcu Omer Andac Veysel T. Yilmaz William T. A. Harrison 《Journal of Molecular Structure》2002,610(1-3):99-103
The synthesis, molecular and crystal structure of bis(triethanolamine)Mn(II) saccharinate, [Mn(tea)2](sac)2 are reported. The configuration of the tea ligands results in an unusual example of coordination number seven for the Mn(II) ion. The two triethanolamine (tea) ligands coordinate to the Mn(II) ion forming a monocapped trigonal prism geometry, in which one of the tea ligands behaves as a tridentate ligand, while the other one acts as a tetradentate donor. The free and coordinated hydroxyl hydrogens of the tea ligands are involved in hydrogen bonding with the amine nitrogen, carbonyl and sulfonyl oxygens of the neighbouring sac ions to form a three-dimensional infinite network. A weak π–π interaction between the phenyl rings of the sac ions also occurs. 相似文献
85.
Two types of directional couplers for transverse electric (TE) modes are described: short and multihole couplers, respectively. They selectively pick one mode out of a mode mixture in an overmoded circular waveguide system. Unwanted modes are either statistically kept at low level or are suppressed by destructive interference in the coupling waveguide. Mode selectivity and directivity in multihole couplers oscillate up and down with an increasing number of holes, finally reaching a minimum of approximately 20 dB, unless there are competing modes with rational fractions of the beat wavelength. A multihole coupler for the TE02 mode (28 GHz, 63.4 mm waveguide diameter, 41 holes) and a length of 1.6 m shows a calculated directivity of 68 dB and suppresses the unwanted modes TE01 with 34 dB (24 dB), TE22 with 37 dB (45 dB), and further modes TEm (<5, m<6) with 17 dB to 34 dB in forward direction (figures in parentheses are for unwanted modes propagating in backward direction).A short directional coupler for the TE01 mode (28 GHz, 63.4 mm waveguide diameter) with 16 holes and a length of 230 mm shows a directivity of 55 to 100 dB between 27.9 and 28.1 GHz, suppressing the TE02 mode with 35 to 80 dB, the TE03 mode with 30 to 65 dB, and the TE22 mode with 30 to 70 dB. 相似文献
86.
Crystal structure of the title compound, Cu(phen)(H2O)2·ClO4(phen=1,10-phenanthroline), was deter-mined by X-ray crystallography. It crystallizes in the monoclinic system, space group C2/c with lattice parameters a=1.49071(4)nm, b=1.38594(4)nm, c=0.70292(1)nm, β=108.509(1)° and Z=4; The Cu(Ⅰ) ion is chelated by a phen ligand and two aqua ligands in cis arrangement and assumes a C2 symmetric square-planar geometry with the CuN2O2 core. Eight Cu(phen)(H2O)2·ClO4 molecules are interconnected by strong hydrogen bonds between coordinated water molecules and uncoordinated perchlorate anions to form a molecular scale cavities along c axis. The bond distances of Cu-N and Cu-O are 0.2003(4)nm and 0.1973(3)nm, respectively. CCDC: 197600. 相似文献
87.
Warrener Ronald N. Malpass John R. Butler Douglas N. Sun Guangxing 《Structural chemistry》2001,12(3-4):291-304
The thermal addition of N-carbobenzyloxyisoindole (N-Z isoindole) 11a, generated by the reaction of 3,6-di(2-pyridyl)-s-tetrazine 9 with N-Z 7-azabenzonorbornadiene 8a, onto dimethyl tricyclo[4.2.1.02.5]nona-3,7-diene-3,4-dicarboxylate 17 occurred site selectively at the cyclobutene -bond to form a stereoisomeric mixture of 1 : 1-adducts 18 and 19, in which the bent-frame isomer 19 was dominant (ratio 5 : 1). In contrast, N-benzyl tetrafluoroisoindole 11c reacted with 17 only under high-pressure conditions (14 kbar, RT, 4 days) to afford 1 : 1-adducts at the cyclobutene site, in which the extended-frame isomer 18c was dominant and the accompanying bent-frame product 19c reverted to starting materials soon after isolation. These same stereoselectivities were used to prepare "windscreen wiper" compound 28c having two mobile N-benzyl substituents attached to a rigid scaffold by the reaction of N-benzyl tetrafluoroisoindole 11c with tetramethyl tetracyclo[4.4.1.0.2,5.07.10]undeca-3,8-diene-3,4,7,8-tetracarboxylate 23. Cavity bis-(cyclobutene-1,2-diester) 6 reacted with N-benzyl tetrafluoroisoindole 11c twice over to produce cavity structure 36 with two O- and two N-benzyl bridges on the inner face, whereas the narrower cavity bis-alkene 32 stopped at the 1 : 1-addition stage. The dynamics of the Z-group in the dual adducts 26a–28a are discussed briefly and key adducts and cavity systems have been structurally evaluated by X-ray crystallography, VT NMR, and molecular modeling. 相似文献
88.
A high-powered, microwave-induced nitrogen–oxygen plasma (N2–O2–MIP) generated by using an Okamoto cavity at atmospheric pressure was investigated when the observation height, the flow rate of carrier gas, and the oxygen content were varied as the experimental parameters. The emission characteristics of the plasma were evaluated with regard to the excitation temperature and the intensity ratio of atomic line to ionic line. The excitation temperature of the N2–O2–MIP was in the range of 5100–5700 K when the oxygen content was varied from 0 to 30% at the observation height of 7 mm and the carrier gas flow rate of 0.6 l/min. The intensity ratio of atomic line to ionic line was elevated with an increase in the oxygen content. 相似文献
89.
Free-energy-perturbation theory from molecular dynamics calculations has been used to obtain the DeltaG of adjoining cavities' formation in water. The DeltaGs for systems with three, five and seven cavities are compared with that of a single cavity of the same volume, and found to be in good agreement. The conditions under which the analytical formulation of the energy of cavity formation proposed by Pierotti holds are discussed. The data for a single cavity have been tabulated and can lend themselves to a simple numerical implementation in standard quantum chemical packages, which can be used when high accuracy for DeltaG(cav) is required. 相似文献
90.
LIU Jin-Song JI Guang-Bin LI Zi-Quan CAO Jie-Ming ZHENG Ming-Bo KE Xing-Fei 《中国化学》2007,25(10):1584-1587
ZnS with hexagonal prism morphology has been synthesized successfully by molten-salt method with ZnS nanoparticles as precursors, and the ZnS nanoparticles were prepared by one-step solid-state reaction of Zn(CH3COO)2·2H2O with Na2S·9H2O at ambient temperature. Crystal structure and morphology of the product were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and HRTEM. Ultraviolet-visible optical absorption spectrum of the ZnS hexagonal prism shows a distinct red shift from that of bulk ZnS crystals and photoluminescence spectrum exhibits strong emissions at 380 and 500 nm, respectively. Further experiments were designed and the formation mechanism of the ZnS hexagonal prism has been also discussed in brief. 相似文献