全文获取类型
收费全文 | 1568篇 |
免费 | 174篇 |
国内免费 | 328篇 |
专业分类
化学 | 1922篇 |
晶体学 | 18篇 |
力学 | 4篇 |
综合类 | 22篇 |
物理学 | 104篇 |
出版年
2024年 | 6篇 |
2023年 | 14篇 |
2022年 | 36篇 |
2021年 | 47篇 |
2020年 | 96篇 |
2019年 | 62篇 |
2018年 | 53篇 |
2017年 | 49篇 |
2016年 | 85篇 |
2015年 | 77篇 |
2014年 | 76篇 |
2013年 | 147篇 |
2012年 | 92篇 |
2011年 | 98篇 |
2010年 | 78篇 |
2009年 | 94篇 |
2008年 | 103篇 |
2007年 | 103篇 |
2006年 | 83篇 |
2005年 | 75篇 |
2004年 | 79篇 |
2003年 | 60篇 |
2002年 | 51篇 |
2001年 | 41篇 |
2000年 | 36篇 |
1999年 | 39篇 |
1998年 | 48篇 |
1997年 | 35篇 |
1996年 | 38篇 |
1995年 | 32篇 |
1994年 | 24篇 |
1993年 | 21篇 |
1992年 | 15篇 |
1991年 | 21篇 |
1990年 | 11篇 |
1989年 | 10篇 |
1988年 | 4篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1981年 | 2篇 |
1979年 | 1篇 |
1978年 | 4篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1968年 | 1篇 |
排序方式: 共有2070条查询结果,搜索用时 31 毫秒
181.
In DMF-d7 tetrabenzimidazole cavitands 2 exist as monomeric species and vase-like conformers. Several possible arrangements of the four benzimidazole NHs are indicated by 1H NMR spectroscopy. The cavitands form 1:1 inclusion complexes with tetraethyl ammonium and phosphonium cations only when strong hydrogen bonding anions like chloride or acetate are present. These complexes are stable on the NMR time scale at 295 K feature a C2V-symmetrical arrangement of benzimidazole functions. The stability of the C2V-symmetrical tetramethylammonium acetate complex is independent of the temperature. In contrast, tetramethylammonium and phosphonium chloride complexes exist at 233 K as several isomers. This complicated behavior is, in part, attributed to the hydrogen bonding interactions between the anions and the NH groups of benzimidazole functions. 相似文献
182.
Najwa Sbei Belen Batanero Fructuoso Barba Beya Haouas Mohamed Lamine Benkhoud Isidoro Barba 《Tetrahedron》2018,74(16):2068-2072
A new series of 3,4-disubstituted quinazolin-2-ones, with potential T-type calcium channel antagonist activity, and new 4-methylene-quinazolin-2-ones, promising catalysts as N-heterocyclic olefins, have been prepared in good yield by a simple reaction between 2-aminobenzophenone, or 2-aminoacetophenone, and cyanomethyl anion electrogenerated by acetonitrile reduction at a graphite electrode, followed by the addition of different organic isocyanates and subsequent heterocyclization. 相似文献
183.
By AM1 method, the interactions between 1, 3-N, N′-Bis-4-(4′-nitro benzenediazo) phenyl squaraine (BNBPS) and several oxoacid anions have been studied on the basis of the proposed model. The mechanism of the color reactions is suggested and the answers to the question of whether or not BNBPS colorates with HCO_3~-, CO_3~(2-), NO_2~(-), NO_3~-, etc. are given. It is theoretically predicted that BNBPS might be used as the color reagent for SO_4~(2-). 相似文献
184.
Jeong‐Heui Choi Hae‐Jung Yoon Jung‐Ah Do Yong‐Chun Park Jae Hun Kim Dongmi Choi 《Biomedical chromatography : BMC》2011,25(4):493-497
A residual determination method as a regulatory residue method was developed using HPLC‐UVD for prohexadione residues in Chinese cabbage (Brassica pekinensis) and apple (Malus domestica). The developed method consisted of solid–liquid extraction with acidic acetonitrile and ion‐suppression liquid–liquid partitioning, followed by anion exchange cartridge cleanup. The limits of detection and quantitation for the method were 0.005 and 0.02 mg/kg, respectively. The method gave good linearity in the range of 0.02–2.5 mg/kg. Accuracy and precision ranged from 84.1 to 94.1% and from 2.4 to 6.9%, respectively. Additionally, the confirmative conditions of LC‐MS/MS for prohexadione were set in negative electrospray ionization mode with transitions of m/z 211.4 → 167.5 and m/z 211.4 → 123.5 in the selected reaction monitoring mode. The applicability of the method was demonstrated by analyzing real samples collected from local markets in Seoul, Republic of Korea. This developed method fully deserves consideration in accordance with its sensitivity, accuracy and precision required for residue analysis of prohexadione in Chinese cabbages and apples. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
185.
A new one-dimensional dicyanamide bridged zinc(II) complex containing nitronyl nitroxide radicals Zn(NO3)(NIT-1'-MeBzIm)(dca)n·(H2O)n(NIT-1'-MeBzIm = 2-{2'-(l'-me-thyl)benzimidazolyl}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, dca = dicyanamide anion) has been prepared and structurally characterized by single-crystal X-ray diffraction.The complex crystallizes in triclinic, space group P1, with a = 7.428(3), b = 9.839(3), c = 16.708(6), α = 93.270(4), β = 101.642(4), γ = 100.632(4)°, C17.5H21N8O5.5Zn, Mr = 496.79, V = 1169.7(7) 3, Dc = 1.411 g/cm3, μ(MoKα) = 1.096 mm-1, Z = 2, F(000) = 512, R = 0.0583 and wR = 0.1663 for 4295 observed reflections with I > 2σ(I).X-ray analysis reveals that the zinc(II) ion is six-coordinated with a distorted octahedral geometry.These units develop as 1D species where dicyanamide ligands bridge zinc(II) ions.In addition, molecules are linked by π-π piling interactions to form 1-D double-chains.Magnetic investigation indicates that the weak intramolecular interactions are antiferromagnetic with J =-0.27 cm?1, where the spin Hamitonian is defined as H =-2∑i,jJi,jSiS within the complex. 相似文献
186.
G. Patermarakis J. Chandrinos K. Moussoutzanis 《Journal of Electroanalytical Chemistry》2001,510(1-2)
Aluminium was anodised in H2SO4, LiHSO4, NaHSO4, KHSO4, Mg(HSO4)2 and Al(HSO4)3 electrolytes. The kinetics of growth of porous anodic alumina films and of the pore wall oxide dissolution during anodisation was studied. Based on the derived kinetic parameters, suitable physicochemical processes in the barrier layer electrolyte interface controlling the anion incorporation in the barrier layer were suggested and relevant models were formulated. According to these processes Al3+ and H+ ions are rejected from the pore base surface in the attached double layer, where Al3+ ions are solvated, and are transferred to the pore filling solution. The strongly different mobilities of Al3+ and H+ and the necessary space negative charge density distribution in the double layer result in similar concentration distributions of Al3+ and anions inside it, which differ strongly from that of H+. These Al3+ and anion concentrations increase with decreasing mobility of the main cations in the solution which depends on their hydration enthalpy and transport mechanism. The concentration of incorporated anions inside both a thin surface layer of the barrier layer and the double layer vary similarly. For identical surface density and base diameter of pores the decrease of the above mobility reinforces anion incorporation. 相似文献
187.
N‐sulfonylimines (1) were induced by samarium(II) iodide to produce radical anion intermediates (2) in situ, which were trapped by aliphatic ketones (4) to afford heterocoupling products β‐sulfonamido alcohols (5) in moderate to good yields under mild and neutral conditions. 相似文献
188.
189.
The reactions of 4-chloromethyl-1,3,2-dioxathiolane 2-oxides with PhONa in EtOH are accompanied by ring opening under the
action of the ethoxide ion rather than leading to a rearrangement of the starting molecule as has been assumed previously.
Under conditions precluding competition with other nucleophiles, the phenoxide anion smoothly replaces the chlorine atom in
chloromethyl-substituted cyclic sulfites.
Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1774–1777, October, 2000. 相似文献
190.
We have developed a novel alkaline anion exchange membrane derived from poly(ether‐imide) for improved ionic conductivity. The effects of several important parameters on the chloromethylation of the membrane were investigated. These parameters included reaction temperature, reaction time, concentration of chloromethylation agent, concentration of polymer, and the amount of catalyst. The quaternization of the synthesized chloromethylated polymer was studied as well. The results show that all the studied parameters exhibited significant impacts on chloromethylation. Among them, the concentration of the chloromethylation agent played a key role in increasing the chloromethyl functional group attachment onto the polymer. It was found that the gelation could be avoided if these reaction parameters were controlled. It was also found that using an appropriate quaternization approach could significantly improve the ionic conductivity and optimize the conductivity of the membrane even though the functional chloromethyl groups attached to the polymer are limited. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献