全文获取类型
收费全文 | 228篇 |
免费 | 2篇 |
国内免费 | 1篇 |
专业分类
化学 | 196篇 |
数学 | 27篇 |
物理学 | 8篇 |
出版年
2022年 | 4篇 |
2021年 | 15篇 |
2020年 | 2篇 |
2019年 | 4篇 |
2018年 | 4篇 |
2016年 | 4篇 |
2015年 | 6篇 |
2014年 | 7篇 |
2013年 | 9篇 |
2012年 | 5篇 |
2011年 | 6篇 |
2010年 | 12篇 |
2009年 | 7篇 |
2008年 | 14篇 |
2007年 | 16篇 |
2006年 | 13篇 |
2005年 | 7篇 |
2004年 | 14篇 |
2003年 | 8篇 |
2002年 | 7篇 |
2001年 | 7篇 |
2000年 | 4篇 |
1999年 | 9篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1976年 | 1篇 |
1929年 | 1篇 |
1928年 | 1篇 |
1926年 | 1篇 |
1925年 | 2篇 |
1924年 | 1篇 |
1923年 | 2篇 |
1920年 | 1篇 |
1919年 | 1篇 |
1875年 | 1篇 |
1868年 | 1篇 |
排序方式: 共有231条查询结果,搜索用时 15 毫秒
51.
Pacifico J Endo K Morgan S Mulvaney P 《Langmuir : the ACS journal of surfaces and colloids》2006,22(26):11072-11076
The contact angle of water has been measured on a series of self-assembled monolayers (SAM) on thermally evaporated and sputter coated silver surfaces. It is found that micropatterning the surface using nanosphere lithography leads to large increases in the contact angle and generates superhydrophobic surfaces with contact angles >150 degrees. The type of functional groups on the SAMs, the metal island size, and the metal island thickness all contribute to the measured contact angle. The maximum contact angle found was 161 degrees for a fluorinated alkanethiol on 80 nm thick silver islands. 相似文献
52.
53.
S Piccinonna N Margiotta C Pacifico A Lopalco N Denora S Fedi M Corsini G Natile 《Dalton transactions (Cambridge, England : 2003)》2012,41(32):9689-9699
Geminal bisphosphonates (BPs), used in the clinic for the treatment of hypercalcaemia and skeletal metastases, have been also exploited for promoting the specific accumulation of platinum antitumor drugs in bone tissue. In this work, the platinum dinuclear complex [{Pt(en)}(2)(μ-AHBP-H(2))](+) (1) (the carbon atom bridging the two phosphorous atoms carrying a 2-ammonioethyl and a hydroxyl group, AHBP-H(2)) has been used as scaffold for the synthesis of a Pt(II) trinuclear complex, [{Pt(en)}(3)(μ-AHBP)](+) (2), and a Pt(IV) adamantane-shaped dinuclear complex featuring an oxo-bridge, [{Pt(IV)(en)Cl}(2)(μ-O)(μ-AHBP-H(2))](+) (3) (X-ray structure). Compound 2 undergoes a reversible, pH dependent, rearrangement with a neat switch point around pH = 5.4. Compound 3 undergoes a one-step electrochemical reduction at E(pc) = -0.84 V affording compound 1. Such a potential is far lower than that of glutathione (-0.24 V), nevertheless compound 3 can undergo chemical reduction to 1 by GSH, most probably through a different (inner-sphere) mechanism. In vitro cytotoxicity of the new compounds, tested against murine glioma (C6) and human cervix (HeLa) and hepatoma (HepG2) cell lines, has shown that, while the Pt(IV) dimer 3 is inactive up to a concentration of 50 μM, the two Pt(II) polynuclear compounds 1 and 2 have a cytotoxicity comparable to that of cisplatin with the trinuclear complex 2 generally more active than the dinuclear complex 1. 相似文献
54.
Clemente Bretti Concetta De Stefano Claudia Foti Silvio Sammartano Giuseppina Vianelli 《The Journal of chemical thermodynamics》2012,44(1):154-162
The acid–base properties of four aminophenol derivatives, namely m-aminophenol (L1), 4-amino-2-hydroxytoluene (L2), 2-amino-5-ethylphenol (L3) and 5-amino-4-chloro-o-cresol (L4), are studied by potentiometric and titration calorimetric measurements in NaCl(aq) (0 ? I ? 3 mol · kg?1) at T = 298.15 K. The dependence of the protonation constants on ionic strength is modelled by the Debye–Hückel, SIT (Specific ion Interaction Theory) and Pitzer equations. Therefore, the values of protonation constants at infinite dilution and the relative interaction coefficients are calculated. The dependence of protonation enthalpies on ionic strength is also determined. Distribution (2-methyl-1-propanol/aqueous solution) measurements allowed us to determine the Setschenow coefficients and the activity coefficients of neutral species. Experimental results show that these compounds behave in a very similar way, and common class parameters are reported, in particular for the dependence on ionic strength of both protonation constants and protonation enthalpies. 相似文献
55.
Concetta Fazio 《Physik in unserer Zeit》2007,38(5):216-217
56.
Kavosh Majlesi Clemente Bretti Rosalia Maria Cigala Concetta De Stefano Kimia Majlesi Silvio Sammartano 《Journal of solution chemistry》2018,47(3):528-543
A potentiometric method has been used for the determination of the protonation constants of N-(2-hydroxyethyl)iminodiacetic acid (HEIDA or L) at various temperatures 283.15?≤?T/K?≤?383.15 and different ionic strengths of NaCl(aq), 0.12?≤?I/mol·kg?1?≤?4.84. Ionic strength dependence parameters were calculated using a Debye–Hückel type equation, Specific Ion Interaction Theory and Pitzer equations. Protonation constants at infinite dilution calculated by the SIT model are \( \log_{10} \left( {{}^{T}K_{1}^{\text{H}} } \right) = 8.998 \pm 0.008 \) (amino group), \( \log_{10} \left( {{}^{T}K_{2}^{\text{H}} } \right) = 2.515 \pm 0.009 \) and \( \log_{10} \left( {{}^{T}K_{3}^{\text{H}} } \right) = 1.06 \pm 0.002 \) (carboxylic groups). The formation constants of HEIDA complexes with sodium, calcium and magnesium were determined. In the first case, the formation of a weak complex species, NaL, was found and the stability constant value at infinite dilution is log10KNaL?=?0.78?±?0.23. For Ca2+ and Mg2+, the CaL, CaHL, CaL2 and MgL species were found, respectively. The calculated stability constants for the calcium complexes at T?=?298.15 K and I?=?0.150 mol·dm?3 are: log10βCaL?=?4.92?±?0.01, log10βCaHL?=?11.11?±?0.02 and \( \log_{10} \beta_{\text{Ca{L}}_{2}} \)?=?7.84?±?0.03, while for the magnesium complex (at I?=?0.176 mol·dm?3): log10βMgL?=?2.928?±?0.006. Protonation thermodynamic functions have also been calculated and interpreted. 相似文献
57.
Accurate static dipole polarizabilities and hyperpolarizabilities are calculated for the ground states of the Al, Si, P, S, Cl, and Ar atoms. The finite-field computations use energies obtained with various ab initio methods including Moller-Plesset perturbation theory and the coupled cluster approach. Excellent agreement with experiment is found for argon. The experimental alpha for Al is likely to be in error. Only limited comparisons are possible for the other atoms because hyperpolarizabilities have not been reported previously for most of these atoms. Our recommended values of the mean dipole polarizability (in the order Al-Ar) are alpha/e(2)a(0) (2)E(h) (-1)=57.74, 37.17, 24.93, 19.37, 14.57, and 11.085 with an error estimate of +/-0.5%. The recommended values of the mean second dipole hyperpolarizability (in the order Al-Ar) are gamma/e(4)a(0) (4)E(h) (-3)=2.02 x 10(5), 4.31 x 10(4), 1.14 x 10(4), 6.51 x 10(3), 2.73 x 10(3), and 1.18 x 10(3) with an error estimate of +/-2%. Our recommended polarizability anisotropy values are Deltaalpha/e(2)a(0) (2)E(h) (-1)=-25.60, 8.41, -3.63, and 1.71 for Al, Si, S, and Cl respectively, with an error estimate of +/-1%. The recommended hyperpolarizability anisotropies are Deltagamma/e(4)a(0) (4)E(h) (-3)=-3.88 x 10(5), 4.16 x 10(4), -7.00 x 10(3), and 1.65 x 10(3) for Al, Si, S, and Cl, respectively, with an error estimate of +/-4%. 相似文献
58.
Leopoldo Ceraulo Maria Concetta Natoli Pasquale Agozzino Mirella Ferrugia Liliana Lamrtina 《Journal of mass spectrometry : JMS》1991,26(10):857-861
The 75 eV electron impact mass spectra of 1,1-bis(dimethoxyphenyl)methanes bearing o-methoxy groups are dominated by intense peaks corresponding, at least formally, to benzyl ions [(CH3O)2C6H3CH2]+ (b). They arise from ions [((CH3O)2C6H3)2CH]+ (a), which are in turn formed from molecular ions by loss of an alkyl radical through benzylic cleavage. The analysis of compounds labelled with 2H or 13C at methoxy groups led to the determination of the mechanism. Hydrogen migration, as hydride, followed by electrophilic substitution by the methylene carbon of the phenyl methylene ether cation through a six-centred transition state is responsible for the formation of benzylic ions b. 相似文献
59.
The transition temperatures of forty mesomorphic homologous benzylidene-aniline-p,p′-dialkoxy derivatives are reported.
The transition diagrams show different paths for heating and cooling for most of the compounds. Moreover, some compounds with higher length-breadth ratios, show very complicated thermal cycles with some monotropic phases. In any case, the clearing temperatures (Tc) alternate within every series.
The experimental data are discussed briefly and some general considerations on the structure and mesomorphic behaviour are suggested. 相似文献
60.
The formation of open chain polyammonium cation-fluoride and -carbonate complexes was studied by potentiometric and calorimetric techniques at t=25 °C. Several species of HiAL (A=amine; L=F−, CO32−) are formed in both systems with a mean stability (ζ=|zanion×zcation|) and for fluoride and carbonate, respectively. The comparison with analogous systems (chloride and acetate for fluoride and hydrogenphosphate, sulfate and malonate for carbonate) showed that fluoride and carbonate form the most stable species with open chain polyammonium cations, among low molecular weight anions. The N-alkyl substitution does not play negligible role in the stability of these complexes, the species formed by substituted amines being more stable. 相似文献