全文获取类型
收费全文 | 477篇 |
免费 | 17篇 |
国内免费 | 1篇 |
专业分类
化学 | 331篇 |
晶体学 | 12篇 |
力学 | 11篇 |
数学 | 22篇 |
物理学 | 119篇 |
出版年
2024年 | 1篇 |
2023年 | 9篇 |
2022年 | 11篇 |
2021年 | 23篇 |
2020年 | 18篇 |
2019年 | 13篇 |
2018年 | 9篇 |
2017年 | 2篇 |
2016年 | 15篇 |
2015年 | 15篇 |
2014年 | 9篇 |
2013年 | 27篇 |
2012年 | 44篇 |
2011年 | 57篇 |
2010年 | 17篇 |
2009年 | 22篇 |
2008年 | 40篇 |
2007年 | 31篇 |
2006年 | 23篇 |
2005年 | 22篇 |
2004年 | 16篇 |
2003年 | 5篇 |
2002年 | 6篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 8篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 4篇 |
1991年 | 1篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1980年 | 1篇 |
1979年 | 4篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1974年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有495条查询结果,搜索用时 15 毫秒
1.
H. Kaczmarek J. Kowalonek Z. Klusek S. Pierzgalski S. Datta 《Journal of Polymer Science.Polymer Physics》2004,42(4):585-602
The photooxidative degradation of blends (in a full range of compositions) of amorphous poly(vinyl chloride) (PVC) with semicrystalline poly(ethylene oxide) (PEO) in the form of thin films is investigated using absorption spectroscopy (UV–visible and Fourier transform infrared) and atomic force microscopy (AFM). The amount of insoluble gel formed as a result of photocrosslinking is estimated gravimetrically. It is found that the PVC/PEO blendsí susceptibility to photooxidative degradation differs from that pure of the components and depends on the blend composition and morphology. Photoreactions such as degradation and oxidation are accelerated whereas dehydrochlorination is retarded in blends. The photocrosslinking efficiency in PVC/PEO blends is higher than in PVC; moreover, PEO is also involved in this process. AFM images showing the lamellar structure of semicrystalline PEO in the blend lead to the conclusion that the presence of PVC does not disturb the crystallization process of PEO. The changes induced by UV irradiation allow the observation of more of the distinct PEO crystallites. This is probably caused by recrystallization of short, more mobile chains in degraded PEO or by partial removal of the less stable amorphous phase from the film surface. These results confirm previous information on the miscibility of PVC with PEO. The mechanism of the interactions between the components and the blend photodegradation are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 585–602, 2004 相似文献
2.
Kaczmarek K Walczak B de Jong S Vandeginste BG 《Journal of chemical information and computer sciences》2002,42(6):1431-1442
Automatic alignment (matching) of two-dimensional gel electrophoresis images is of primary interest in the evolving field of proteomics. In the present study, feature-based matching techniques, in their classical and robust versions, are described, and an automatic method of fuzzy alignment (FA) is introduced. This method allows automatic matching of two gel images with different numbers of features with unknown correspondence. Performance of FA is tested on simulated and real data sets. 相似文献
3.
Lukasz Kraszkiewicz 《Tetrahedron》2004,60(41):9113-9119
Two ‘model’ deactivated arenes, benzoic acid and nitrobenzene, were effectively monoiodinated within 1 h at 25-30 °C, with strongly electrophilic I+ reagents, prior prepared from diiodine and various oxidants (CrO3, KMnO4, active MnO2, HIO3, NaIO3, or NaIO4) in 90% (v/v) concd sulfuric acid (ca. 75 mol% H2SO4). Next, an I2/NaIO3/90% (v/v) concd H2SO4 exemplary system was used to effectively mono- or diiodinate a number of deactivated arenes. All former papers dealing with the direct iodination of deactivated arenes are briefly reviewed. 相似文献
4.
Szmytkowski C Piotrowicz M Domaracka A Kłosowski L Ptasińska-Denga E Kasperski G 《The Journal of chemical physics》2004,121(4):1790-1795
Absolute total cross sections (TCSs) for electron scattering from boron trifluoride (BF(3)) and phosphorus trifluoride (PF(3)) molecules have been measured using a linear transmission method. The electron energy ranges from 0.6 to 370 eV for BF(3) and from 0.5 to 370 eV for PF(3). The TCS energy dependence for BF(3) exhibits two very pronounced enhancements: resonantlike narrow feature located near 3.6 eV with the maximum value of 19.2 x 10(-20) m(2), and intermediate energy very broad enhancement with two humps, one centered around 21 eV (18.8 x 10(-20) m(2) in the maximum) and the other near 45 eV (19.5 x 10(-20) m(2)). For PF(3) the TCS has quite different low-energy dependence: at 0.5 eV it has a high value of 70 x 10(-20) m(2) and decreases steeply towards higher energies. Beyond the minimum near 5.5 eV, the TCS reveals two distinct humps: the resonant one centered near 11 eV with the peak value of 32.9 x 10(-20) m(2) and the second one much broader around 35 eV (27.9 x 10(-20) m(2)). The present TCSs for trifluorides are compared to each other as well as to previous TCS data for selected perfluorides and to results for their perhydrided counterparts. The differences and similarities in the shape and magnitude of TCSs are pointed out. 相似文献
5.
Magdalena Barwiolek Dominika Jankowska Anna Kaczmarek-Kdziera Slawomir Wojtulewski Lukasz Skowroski Tomasz Rerek Pawe Popielarski Tadeusz M. Muziol 《Molecules (Basel, Switzerland)》2022,27(21)
Two macrocyclic Schiff bases derived from o-phenylenediamine and 2-hydroxy-5-methylisophthalaldehyde L1 or 2-hydroxy-5-tert-butyl-1,3-benzenedicarboxaldehyde L2, respectively, were obtained and characterized by X-ray crystallography and spectroscopy (UV-vis, fluorescence and IR). X-ray crystal structure determination and DFT calculations for compounds confirmed their geometry in solution and in the solid phase. Moreover, intermolecular interactions in the crystal structure of L1 and L2 were analyzed using 3D Hirshfeld surfaces and the related 2D fingerprint plots. The 3D Hirschfeld analyses show that the most numerous interactions were found between hydrogen atoms. A considerable number of such interactions are justified by the presence of bulk tert-butyl groups in L2. The luminescence of L1 and L2 in various solvents and in the solid state was studied. In general, the quantum efficiency between 0.14 and 0.70 was noted. The increase in the quantum efficiency with the solvent polarity in the case of L1 was observed (λex = 350 nm). For L2, this trend is similar, except for the chloroform. In the solid state, emission was registered at 552 nm and 561 nm (λex = 350 nm) for L1 and L2, respectively. Thin layers of the studied compounds were deposited on Si(111) by the spin coating method or by thermal vapor deposition and studied by scanning electron microscopy (SEM/EDS), atomic force microscopy (AFM), spectroscopic ellipsometry and fluorescence spectroscopy. The ellipsometric analysis of thin materials obtained by thermal vapor deposition showed that the band-gap energy was 3.45 ± 0.02 eV (359 ± 2 nm) and 3.29 ± 0.02 eV (377 ± 2 nm) for L1/Si and L2/Si samples, respectively. Furthermore, the materials of the L1/Si and L2/Si exhibited broad emission. This feature can allow for using these compounds in LED diodes. 相似文献
6.
Valery A. Isidorov Jolanta Maslowiecka Lukasz Szoka Naldo Pellizzer Dora Miranda Ewa Olchowik-Grabarek Monika Zambrzycka Izabela Swiecicka 《Molecules (Basel, Switzerland)》2022,27(22)
The chemical composition of propolis of four species of stingless bees (SLBs) from Argentina was determined, and its antibacterial and anticancer activity was evaluated on selected types of microbes and cancer cell lines. Volatile secretions of all propolis samples are formed by 174 C2–C15 organic compounds, mainly mono- and sesquiterpenes and their derivatives. The chromatograms of ether extracts showed 287 peaks, of which 210 were identified. The most representative groups in the extracts of various propolis samples were diterpenoids (mainly resin acids), triterpenoids and phenolic compounds: long-chain alkenyl phenols, resorcinols and salicylates. The composition of both volatile and extractive compounds turned out to be species-specific; however, in both cases, the pairwise similarity of the propolis of Scaptotrigona postica and Tetragonisca fiebrigi versus that of Tetragona clavipes and Melipona quadrifasciata quadrifasciata was observed, which indicated the similarity of the preferences of the respective species when choosing plant sources of resin. The composition of the studied extracts completely lacked flavonoids and phenolcarboxylic acids, which are usually associated with the biological activity and medicinal properties of propolis. However, tests on selected microbial species and cancer cell lines showed such activity. All propolis samples tested against Paenibacillus larvae, two species of Bacillus and E. coli showed biofilm inhibition unrelated to the inhibition of bacterial growth, leading to a decrease in their pathogenicity. Testing the anticancer activity of ether extracts using five types of cell cultures showed that all four types of propolis studied inhibit the growth of cancer cells in a dose- and time-dependent manner. Propolis harvested by T. clavipes demonstrated the highest cytotoxicity on all tested cell lines. 相似文献
7.
Chip-based optical frequency combs address the demand for compact, bright, coherent light sources of equidistant phase-locked lines. Traditionally, the Fourier Transform Spectroscopy (FTS) technique is considered a suboptimal choice for resolving comb lines in chip-based sensing applications due to the requirement of long optical delays, and spectral distortion from the instrumental line shape. Here, a sub-nominal resolution FTS technique is developed that extracts the comb's offset frequency in any spectral region directly from the measured interferogram without resorting to nonlinear -to- interferometry. This in turn enables 10's of MHz resolution spectrometry with millimeter optical retardations currently limited by the emission linewidth and phase noise of the used lasers. Low-pressure Doppler-broadened absorption lines probed by widely-tunable chip-scale mid-infrared optical frequen with electrical pumping are fully resolved over a span of tens of nanometers. This versatile technique paves the way for compact, electrostatically-actuated, or even all-on-chip high-fidelity FTS, and can be readily applied to boost the resolution of existing commercial instruments with compact interferometers several hundred times. 相似文献
8.
Water-soluble Co (III) and Co (II) complexes with P- or N-coordinated PTA or PTA oxide ligands, respectively, have been prepared and fully characterized, constituting the first examples of cobalt compounds bearing PTA or any ligand with a cage-like PTA core, the latter complex providing also the first PTA oxide coordination to a metal center. 相似文献
9.
Aramburo LR Karwacki L Cubillas P Asahina S de Winter DA Drury MR Buurmans IL Stavitski E Mores D Daturi M Bazin P Dumas P Thibault-Starzyk F Post JA Anderson MW Terasaki O Weckhuysen BM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(49):13773-13781
A combination of atomic force microscopy (AFM), high‐resolution scanning electron microscopy (HR‐SEM), focused‐ion‐beam scanning electron microscopy (FIB‐SEM), X‐ray photoelectron spectroscopy (XPS), confocal fluorescence microscopy (CFM), and UV/Vis and synchrotron‐based IR microspectroscopy was used to investigate the dealumination processes of zeolite ZSM‐5 at the individual crystal level. It was shown that steaming has a significant impact on the porosity, acidity, and reactivity of the zeolite materials. The catalytic performance, tested by the styrene oligomerization and methanol‐to‐olefin reactions, led to the conclusion that mild steaming conditions resulted in greatly enhanced acidity and reactivity of dealuminated zeolite ZSM‐5. Interestingly, only residual surface mesoporosity was generated in the mildly steamed ZSM‐5 zeolite, leading to rapid crystal coloration and coking upon catalytic testing and indicating an enhanced deactivation of the zeolites. In contrast, harsh steaming conditions generated 5–50 nm mesopores, extensively improving the accessibility of the zeolites. However, severe dealumination decreased the strength of the Brønsted acid sites, causing a depletion of the overall acidity, which resulted in a major drop in catalytic activity. 相似文献
10.
Supermolecular interaction energies are analyzed in terms of the symmetry-adapted perturbation theory and operators defining the inaccuracy of the monomer wave functions. The basis set truncation effects are shown to be of first order in the monomer inaccuracy operators. On the contrary, the usual counterpoise correction schemes are of second order in these operators. Recognition of this difference is used to suggest an approach to corrections for basis-set truncation effects. Also earlier claims--that dimer-centered basis sets may lead to interaction energies free of basis-set superposition effects--are shown to be misleading. According to the present study the basis-set truncation contributions, evaluated by means of the symmetry-adapted perturbation theory with monomer-centered basis sets, provide physically and mathematically justified corrections to supermolecular results for interaction energies. 相似文献