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131.
Crosslinking is a feasible way to prepare biodegradable polymers with potential in biomedical applications such as controlled release of active agents and tissue engineering. A synthesis route in which functional telechelic aliphatic polyester oligomers are used as precursors for the preparation of crosslinked polyesters and poly(ester anhydride)s is described. Mechanical properties, degradation characteristics and rate, and bioactivity can be modified widely by controlling the chemical composition and architecture of the crosslinkable oligomers. In tissue engineering, photocrosslinking allows to use crosslinkable oligomers in advanced manufacturing techniques like micromolding in capillaries, stereolithography and two-photon polymerization. 相似文献
132.
Ruuska H Arola E Kortelainen T Rantala TT Kannus K Valkealahti S 《The Journal of chemical physics》2011,134(13):134904
Influence of acrylic acid grafting of isotactic polypropylene on the dielectric properties of the polymer is investigated using density functional theory (DFT) calculations, both in the molecular modeling and three-dimensional (3D) bulk periodic system frameworks. In our molecular modeling calculations, polarizability volume, and polarizability volume per mass which reflects the permittivity of the polymer, as well as the HOMO-LUMO gap, one of the important measures indicating the electrical breakdown voltage strength, were examined for oligomers with various chain lengths and carboxyl mixture ratios. When a polypropylene oligomer is grafted with carboxyl groups (cf. acrylic acid), our calculations show that the increase of the polarizability volume α' of the oligomer is proportional to the increase of its mass m, while the ratio α'/m decreases from the value of a pure polymer when increasing the mixture ratio. The decreasing ratio of α'/m under carboxyl grafting indicates that the material permittivity might also decrease if the mass density of the material remains constant. Furthermore, our calculations show that the HOMO-LUMO gap energy decreases by only about 15% in grafting, but this decrease seems to be independent on the mixture ratio of carboxyl. This indicates that by doping polymers with additives better dielectric properties can be tailored. Finally, using the first-principles molecular DFT results for polarizability volume per mass in connection with the classical Clausius-Mossotti relation, we have estimated static permittivity for acrylic acid grafted polypropylene, assuming the structural density keeping constant under grafting. The computed permittivity values are in a qualitative agreement with the recent experiments, showing increasing tendency of the permittivity as a function of the grafting composition. In order to validate our molecular DFT based approach, we have also carried out extensive three-dimensional bulk periodic first-principles total-energy calculations in the frameworks of the density functional theory and density functional perturbation theory (DFPT) for crystalline acrylic acid grafted polypropylene. Interestingly, the computed electronic and dielectric properties behave very similarly between the simplified molecular DFT modeling and the more realistic 3D bulk periodic DFPT method. In particular, the static permittivity values [ε(r)(0)] from the molecular DFT-Clausius-Mossotti modeling are in excellent agreement with the high-frequency dielectric constant values (ε(∞)) from the DFPT method. This obviously implies that the chain-to-chain interaction to dielectric and electronic properties of acrylic acid polypropylene, to a first approximation, can be neglected, therefore justifying the usage of molecular DFT modeling in our calculations. 相似文献
133.
A series of coordination polymers with anionic, cationic, and neutral metal-carboxylate frameworks have been synthesized by using a flexible tetrapodal ligand tetrakis[4-(carboxyphenyl)oxamethyl] methane acid (H(4)X). The reactions between divalent transition-metal ions and H(4)X ligands gave [M(3)X(2)]·[NH(2)(CH(3))(2)](2)·8DMA (M = Co (1), Mn (2), Cd(3)) which have anionic metal-carboxylate frameworks with NH(2)(CH(3))(2)(+) cations filled in channels. The reactions of trivalent metal ions Y(III), Dy(III), and In(III) with H(4)X ligands afforded cationic metal-carboxylate frameworks [M(3)X(2)·(NO(3))·(DMA)(2)·(H(2)O)]·5DMA·2H(2)O (M = Y(4), Dy(5)) and [In(2)X·(OH)(2)]·3DMA·6H(2)O (6) with the NO(3)(-) and OH(-) serving as counterions, respectively. Moreover, a neutral metal-carboxylate framework [Pb(2)X·(DMA)(2)]·2DMA (7) can also be isolated from reaction of Pb(II) and H(4)X ligands. The charged metal-carboxylate frameworks 1-5 have selectivity for specific counterions in the reaction system, and compounds 1 and 2 display ion-exchange behavior. Moreover, magnetic property measurements on compounds 1, 2, and 5 indicate that there exists weak antiferromagnetic interactions between magnetic centers in the three compounds. 相似文献
134.
Pirilä M Martikainen M Ainassaari K Kuokkanen T Keiski RL 《Journal of colloid and interface science》2011,353(1):257-262
Dissolved arsenic in drinking water is a global concern as it causes serious health problems. The purpose of this research was to study the applicability of an industrial intermediate product, a mixture of titanium hydroxide and titanium dioxide for removing aqueous arsenic. The material is common, inexpensive, and non-toxic, making it an attractive choice for drinking water purification. The kinetics and equilibrium of removing both primary inorganic arsenic forms, As(III) and As(V), were studied by separate batch experiments. The tested material functioned well in removing both of these arsenic forms. The apparent values for Langmuir monolayer sorption capacities were 31.8 mg/g for As(III) and 33.4 mg/g for As(V) at pH 4. The studied TiO(2) performed the best in acidic conditions, but also reasonably well in other pH conditions. 相似文献
135.
Markus Lindqvist Dr. Kirill Axenov Dr. Martin Nieger Dr. Minna Räisänen Prof. Markku Leskelä Prof. Timo Repo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(31):10412-10418
Dimethylamino‐(+)‐camphorenamine reacted with an equimolar amount of Piers’ borane, HB(C6F5)2, to give the corresponding iminium–hydroborate zwitterionic salt. Being in equilibrium with the parent enamine–HB(C6F5)2 N–B pair, this salt was able to split hydrogen heterolytically, hydrogenating the iminium group in the molecule. Detailed studies revealed that the hydrogen splitting in this reaction proceeded through an intermolecular pathway leading to a bornylamine–HB(C6F5)2 adduct. When the starting enamine is present in excess over HB(C6F5)2, the produced bornylamine–HB(C6F5)2 adduct breaks up, eliminating free bornylamine and forming the initial camphorenamine– HB(C6F5)2 pair. This results in hydrogenation of the camphorenamine framework in a catalytic fashion. 相似文献
136.
Kallio M Jussila M Raimi P Hyötyläinen T 《Analytical and bioanalytical chemistry》2008,391(6):2357-2363
A previously constructed semi-rotating cryogenic modulator was modified for comprehensive two-dimensional gas chromatography
(GC×GC). The retention time repeatability was improved by replacing the modulator control program unit with a new system.
Peak widths obtained with the modified modulator were comparable with those obtained with the previous modulator and other
modulator types. The modulator was easy to construct and it can be installed in any commercial GC system. The constructed
GC×GC–FID system and data obtained by gas chromatography–mass spectrometry (GC–MS) were used for identification of unknowns
in forest aerosol samples.
Figure A semi-rotating cryogenic modulator in which modulation is based on two-step cryogenic trapping with continuously flowing
carbon dioxide has been developed for comprehensive two-dimensional gas chromatography 相似文献
137.
Aminlashgari N Hakkarainen M 《Journal of the American Society for Mass Spectrometry》2012,23(6):1071-1076
Novel surface assisted laser desorption ionization-mass spectrometry (SALDI-MS) method was developed for rapid analysis of
low molecular mass polyesters and their degradation products by laser desorption ionization-mass spectrometry. Three polycaprolactone
materials were analyzed by the developed method before and after hydrolytic degradation. The signal-to-noise values obtained
by SALDI-MS were 20–100 times higher compared with the ones obtained by using traditional MALDI-MS matrices. A clean background
at low mass range and higher resolution was obtained by SALDI-MS. Different nanoparticle, cationizing agent, and solvent combinations
were evaluated. Halloysite nanoclay and magnesium hydroxide showed the best potential as SALDI surfaces. The SALDI-MS spectrum
of the polyester hydrolysis products was verified by ESI-MS. The developed SALDI-MS method possesses several advantages over
existing methods for similar analyses. 相似文献
138.
Single-drop microextraction (SDME), an emerging miniaturised extraction technique, was for the first time combined with multiple headspace extraction (MHE) to enable the quantitative determination of volatiles in solid matrixes by SDME technique. The concept of multiple headspace single-drop microextraction (MHS-SDME) was then applied for quantitative determination of styrene in polystyrene (PS) samples. Good linearity for the multiple headspace extraction was obtained when the migration of styrene was facilitated by grinding the samples and incubating them for 1 h at 150 degrees C prior the first extraction. Two microlitres of butyl acetate was used as the single-drop microextraction solvent and the extraction time was 5 min per cycle. The relative standard deviation (RSD) for single-drop microextraction of styrene standard at n=6 was 7.6%. Linearity was shown for styrene concentrations between 0.005 and 0.75 microg/ml (R2=0.999). This corresponds to total amount of styrene between 0.1 and 15 microg. The limit of quantitation for styrene standard at S/N 10 was 0.005 microg/ml. The developed method was validated against and showed good agreement with an earlier reported dissolution-precipitation method. 相似文献
139.
J Hakala J Dobaczewski D Gorelov T Eronen A Jokinen A Kankainen VS Kolhinen M Kortelainen ID Moore H Penttilä S Rinta-Antila J Rissanen A Saastamoinen V Sonnenschein J Aystö 《Physical review letters》2012,109(3):032501
Atomic masses of the neutron-rich isotopes ^{121-128}Cd, ^{129,131}In, ^{130-135}Sn, ^{131-136}Sb, and ^{132-140}Te have been measured with high precision (10?ppb) using the Penning-trap mass spectrometer JYFLTRAP. Among these, the masses of four r-process nuclei ^{135}Sn, ^{136}Sb, and ^{139,140}Te were measured for the first time. An empirical neutron pairing gap expressed as the odd-even staggering of isotopic masses shows a strong quenching across N=82 for Sn, with a Z dependence that is unexplainable by the current theoretical models. 相似文献
140.