全文获取类型
收费全文 | 121篇 |
免费 | 4篇 |
专业分类
化学 | 112篇 |
数学 | 4篇 |
物理学 | 9篇 |
出版年
2022年 | 2篇 |
2021年 | 1篇 |
2020年 | 2篇 |
2019年 | 2篇 |
2017年 | 2篇 |
2016年 | 3篇 |
2015年 | 4篇 |
2014年 | 2篇 |
2013年 | 1篇 |
2012年 | 4篇 |
2011年 | 5篇 |
2010年 | 4篇 |
2009年 | 3篇 |
2008年 | 2篇 |
2007年 | 3篇 |
2006年 | 5篇 |
2005年 | 9篇 |
2004年 | 6篇 |
2003年 | 7篇 |
2002年 | 5篇 |
2001年 | 5篇 |
2000年 | 6篇 |
1998年 | 2篇 |
1997年 | 6篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1994年 | 2篇 |
1993年 | 7篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1939年 | 1篇 |
1936年 | 2篇 |
1934年 | 3篇 |
1930年 | 1篇 |
1929年 | 1篇 |
1915年 | 2篇 |
1914年 | 1篇 |
1910年 | 1篇 |
排序方式: 共有125条查询结果,搜索用时 15 毫秒
1.
2.
A quasipotential operator for a system of two scalar particles, and also an integral equation and a normalization condition for the wave function of the connected state, are obtained by the method of two-time Green's functions in an explicitly covariant form. The cases are considered of scalar and electromagnetic interactions of particles of the system.Frantsiska Skoriny Gomel' State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 112–118, June, 1993. 相似文献
3.
The thermal decomposition of four commercial powders and of differently stored single crystals of sodium hydrogen carbonate is studied by power compensation DSC and by optical and FT-IR microscopy. Independently of manufacturer, specified purity and price, the thermal curves of all the commercial powders show a more or less pronounced low temperature peak preceding the one due to the main decomposition. Such small peak is not observed when samples of laboratory recrystallized material are used. However the thermal behaviour of the latter preparation differs remarkably depending on storage conditions: the material kept in closed glass containers decomposes at temperatures higher than those of the material stored in a dessiccator in the presence of concentrated H2SO4. The observation by optical microscopy of the behaviour of the surfaces of single crystals coming from different storage conditions when the temperature is raised in a Kofler heater helps the interpretation of the data collected. The mechanism of the decomposition is discussed and the relevant kinetic parameters reported. 相似文献
4.
Claiser N Souhassou M Lecomte C Gillon B Carbonera C Caneschi A Dei A Gatteschi D Bencini A Pontillon Y Lelièvre-Berna E 《The journal of physical chemistry. B》2005,109(7):2723-2732
High-resolution X-ray diffraction and polarized neutron diffraction experiments have been performed on the Y-semiquinonate complex, Y(HBPz3)2(DTBSQ), in order to determine the charge and spin densities in the paramagnetic ground state, S = (1/2). The aim of these combined studies is to bring new insights to the antiferromagnetic coupling mechanism between the semiquinonate radical and the rare earth ion in the isomorphous Gd(HBPz3)2(DTBSQ) complex. The experimental charge density at 106 K yields detailed information about the bonding between the Y3+ ion and the semiquinonate ligand; the topological charge of the yttrium atom indicates a transfer of about 1.5 electrons from the radical toward the Y3+ ion in the complex, in agreement with DFT calculations. The electron density deformation map reveals well-resolved oxygen lone pairs with one lobe polarized toward the yttrium atom. The determination of the induced spin density at 1.9 K under an applied magnetic field of 9.5 T permits the visualization of the delocalized magnetic orbital of the radical throughout the entire molecule. The spin is mainly distributed on the oxygen atoms [O1 (0.12(1) mu B), O2(0.11(1) mu B)] and the carbon atoms [C21 (0.24(1) mu B), C22(0.20(1) mu B), C24(0.16(1) mu B), C25(0.12(1) mu B)] of the carbonyl ring. A significant spin delocalization on the yttrium site of 0.08(2) mu B is observed, proving that a direct overlap with the radical magnetic orbital can occur at the rare earth site and lead to antiferromagnetic coupling. The DFT calculations are in good quantitative agreement with the experimental charge density results, but they underestimate the spin delocalization of the oxygen toward the yttrium and the carbon atoms of the carbonyl ring. 相似文献
5.
Kassab K Fabris C Defilippis MP Dei D Fantetti L Roncucci G Reddi E Jori G 《Journal of photochemistry and photobiology. B, Biology》2000,55(2-3):128-137
A Zn-phthalocyanine derivative bearing four 4-oxy-N-methyl-piperidinyl peripheral substituents has been formulated in an azone-containing gel for topical administration and its potential as a photodynamic therapy agent has been investigated. The phthalocyanine displays an intense absorbance in the 680 nm range and shows a high photosensitizing activity toward a model biological substrate (N-acetyl-L-tryptophanamide). Upon administration of 20 microg cm(-2) onto the dorsal skin of Balb/c mice, maximal phthalocyanine concentrations (ca. 64.2 ng mg(-1) of skin) are reached at 1 h after the deposition. The photosensitizer appears to be localized in the epidermal layers, since (a) no detectable amounts of phthalocyanine are recovered from the mouse blood and liver; and (b) upon photoactivation with a diode laser at 675 nm, only the epidermis is heavily damaged, as shown by histological and ultrastructural analysis. The photodamage is largely of inflammatory nature and an essentially complete healing of the damaged skin is observed at 72 h after the end of the phototreatment. The minimal phototoxic dose for 20 microg cm(-2) photosensitizer and 675 nm irradiation is found to be (150 mW cm(-2)-120 J cm(-2)) or (180 mW cm(-2)-100 J cm(-2)). 相似文献
6.
Caneschi A Dei A Fabrizi de Biani F Gütlich P Ksenofontov V Levchenko G Hoefer A Renz F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(18):3926-3930
An electronic switch at the molecular level has been realized by using a class of ionic compounds of the formula [Co(L)(diox)]Y (L = tetraazamacrocyclic ligand, Y = mononegative anion). Such compounds undergo temperature- and pressure-induced intramolecular one-electron transfer equilibria. The transition temperature of interconversion varies with the nature of the counterions Y (Y = PF6, BPh4, I). Surprisingly the effect of the anion on the transition temperature is not only governed by its volume but also by its coulombic interaction. 相似文献
7.
Francesca Giuntini Daniele NistriGiacomo Chiti Lia FantettiGiulio Jori Gabrio Roncucci 《Tetrahedron letters》2003,44(3):515-517
The base-catalyzed cyclotetramerization of 3-, 4- and 4,5-dimethylaminophenylthio phthalonitriles with zinc(II)acetate afforded 1(4),8(11),15(18),22(25)- and 2(3),9(10),16(17),23(24)-tetrasubstituted and 2,3,9,10,16,17,23,24-octasubstituted Zn(II)phthalocyanines, respectively. The statistical mixed condensation of the same phthalonitriles with 1,2-dicyanobenzene gave the corresponding mono- and disubstituted derivatives. Methylation of such products afforded a series of cationic Zn(II)phthalocyanines with different pattern of substitution, with potential use as photodynamic agents in microbial infections. 相似文献
8.
The compound bis(di-micro-ethoxo-bis(3,5-di-tert-butylsemiquinonato)dicopper(II)) has been synthesized and its structure was determined by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group C2/c, with a = 37.736(8) A, b = 9.173(2) A, c = 23.270(5) A, beta = 122.24(3) degrees. The structure can be described as a Lewis adduct between two dinuclear [Cu(DBSQ)(C(2)H(5)O)](2) units (DBSQ = 3,5-di-tert-butyl-semiquinonato). The temperature dependence of the magnetic susceptibility was efficiently analyzed by a combined DFT/experimental approach, showing that a rather strong ferromagnetic interaction exists between the DBSQ(-) and the copper(II) ions modulated by an antiferromagnetic interaction between the two copper(II) ions of the dinuclear units. Weak antiferromagnetism between the two units in the unit cell was measured. 相似文献
9.
Takehito Dei Kazuhide Morino Atsushi Sudo Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2012,50(13):2619-2625
Novel copolymers composed of a styrene (St) derivative bearing a vicinal tricarbonyl moiety and various vinyl monomers such as St, methyl methacrylate (MMA), and N‐vinylpyrrolidone (NVP) were synthesized by (1) radical copolymerization of a St derivative with a 1,3‐diketone structure with St, MMA, and NVP and (2) successive oxidation of the resulting copolymers with N‐bromosuccinimide in DMSO to convert their 1,3‐diketone moieties in the side chains into the corresponding vicinal tricarbonyl moieties. Their tricarbonyl moieties were readily hydrated in water‐containing acetone to generate the corresponding copolymers bearing geminal diol structures in the side chains. On the other hand, heating the resulting copolymers bearing the geminal diol structures in vacuo‐enabled successful recovery of the vicinal tricarbonyl moieties to demonstrate the reversible nature of this system. The hydration behavior in powdery state under air atmosphere saturated by water was also investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
10.
Mariangela Potenza Giuseppina Sabatino Francesca Giambi Luca Rosi Anna Maria Papini Luigi Dei 《Analytical and bioanalytical chemistry》2013,405(2-3):691-701
The chemical analysis of egg-based wall paintings—the mezzo fresco technique—is an interesting topic in the characterisation of organic binders. A revised procedure for a dot-enzyme-linked immunosorbent assay (dot-ELISA) able to detect protein components of egg-based wall paintings is reported. In the new dot-ELISA procedure we succeeded in maximizing the staining colour by adjusting the temperature during the staining reaction. Quantification of the colour intensity by visible reflectance spectroscopy resulted in a straight line plot of protein concentration against reflectance in the wavelength range 380–780 nm. The modified dot-ELISA procedure is proposed as a semi-quantitative analytical method for characterisation of protein binders in egg-based paintings. To evaluate its performance, the method was first applied to standard samples (ovalbumin, whole egg, egg white), then to model specimens, and finally to real samples (Giotto’s wall paintings). Moreover, amino acid analysis performed by innovative ultra-performance liquid chromatography was applied both to standards and to model samples and the results were compared with those from the dot-ELISA tests. In particular, after protein hydrolysis (24 h, 114 °C, 6 mol L?1 HCl) of the samples, amino acid derivatization by use of 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate enabled reproducible analysis of amino acids. This UPLC amino acid analysis was rapid and reproducible and was applied for the first time to egg-based paintings. Because the painting technique involved the use of egg-based tempera on fresh lime-based mortar, the study enabled investigation of the effect of the alkaline environment on egg-protein detection by both methods. Figure
Model wall paintings specimens and typical dot-ELISA stains for egg proteins. 相似文献