全文获取类型
收费全文 | 1480篇 |
免费 | 61篇 |
国内免费 | 5篇 |
专业分类
化学 | 1165篇 |
晶体学 | 7篇 |
力学 | 16篇 |
数学 | 166篇 |
物理学 | 192篇 |
出版年
2024年 | 2篇 |
2023年 | 18篇 |
2022年 | 39篇 |
2021年 | 42篇 |
2020年 | 49篇 |
2019年 | 34篇 |
2018年 | 18篇 |
2017年 | 26篇 |
2016年 | 53篇 |
2015年 | 54篇 |
2014年 | 46篇 |
2013年 | 74篇 |
2012年 | 93篇 |
2011年 | 121篇 |
2010年 | 58篇 |
2009年 | 49篇 |
2008年 | 97篇 |
2007年 | 108篇 |
2006年 | 85篇 |
2005年 | 90篇 |
2004年 | 60篇 |
2003年 | 66篇 |
2002年 | 68篇 |
2001年 | 13篇 |
2000年 | 13篇 |
1999年 | 5篇 |
1998年 | 10篇 |
1997年 | 7篇 |
1996年 | 34篇 |
1995年 | 22篇 |
1994年 | 17篇 |
1993年 | 11篇 |
1992年 | 16篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 5篇 |
1986年 | 2篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
排序方式: 共有1546条查询结果,搜索用时 15 毫秒
111.
Francesca Speroni Lisa Elviri Maria Careri Alessandro Mangia 《Analytical and bioanalytical chemistry》2010,397(7):3035-3042
An innovative enzyme-linked immunosorbent assay (ELISA) format based on antibody-coated magnetic micro-particles (MPs) for
the sensitive detection of Ara h3/4 allergen in food is described. The immunosupport is suspended in the incubation solutions
and the MPs with the captured allergen can be easily harvested on a magnet, separated from the solutions, and washed using
an easy-to-use, fast and selective approach that allows its detection and quantification. Two differently coated MPs, ProteinA-Pn-b
and MP-NH2-PAMAM G 1.5 -Pn-b immunosupports, were tested. The functionalization of the MPs with PAMAM-sodium carboxylate dendrimers
elicits a major stability on the immunoglobulin activity resulting in a threefold enhancement of the analytical sensitivity
for the assay with respect to a ProteinA immobilization. Validation was carried out on two different matrices: corn flakes
and biscuits. In the case of MP-NH2-PAMAM G 1.5 -Pn-b immunosupport, limit of detection was found to be 0.2 mg peanuts/kg matrix in both matrices; the linear
response range was demonstrated from 2.5 to 15 mg peanuts/kg matrix by performing statistical tests (homoscedasticity and
Mandel fitting tests). Good accuracy and recovery (>80 ± 2%) were obtained. Different food samples were tested and the results
were compared with those obtained with a commercially available ELISA kit. The results obtained in this work demonstrated
the applicability of the immunomagnetic ELISA methods on real samples and the possibility to perform the assay with significantly
reduced reagent and sample consumption. 相似文献
112.
Melting gels are a class of organically modified silica gels that are rigid at room temperature, flow at temperature T1 and consolidate at temperature T2 (T2 > T1), when crosslinking is complete. The process of (a) softening, (b) becoming rigid and (c) re-softening can be repeated many times. Mixtures of mono-substituted alkoxysilanes and di-substituted alkoxysilanes have been studied in a systematic way to identify suitable melting gel compositions. The mixtures and the resulting melting gels have been characterized for their softening temperatures and consolidation temperatures. With an interest in using these materials for sealing microelectronics, their physical properties have been measured. 相似文献
113.
Zhang S Majewski PW Keskar G Pfefferle LD Osuji CO 《Langmuir : the ACS journal of surfaces and colloids》2011,27(18):11616-11621
Lyotropic nanowire dispersions are attractive precursors for semiconductor device fabrication because they permit the alignment control of active nanomaterials. The reliable production of nanowire-based mesophases, however, is very challenging in practice. We show that appropriately functionalized high-aspect-ratio nanowires of single-crystal ZnO spontaneously form nematic phases in organic and aqueous media. These systems show isotropic, biphasic, and nematic phases on increasing concentration, in reasonable agreement with Onsager's theory for rigid rods interacting via excluded volume. Suspensions were readily processed to produce films with large-area monodomains of aligned nanowires. Imprints of the director field in quiescently dried films display a propensity for bend deformation in the organic mesophase versus splay deformation in the aqueous case, suggesting that system elasticity may be tuned via surface functionalization. These results provide critical insight for the utilization of semiconductor nanowires as novel mesogens and further enable the use of solution-based routes for fabricating optoelectronic devices. 相似文献
114.
Bortolus M Parisio G Maniero AL Ferrarini A 《Langmuir : the ACS journal of surfaces and colloids》2011,27(20):12560-12568
We report a combined theoretical and experimental study on the single-molecule interaction of fullerenes with phospholipid membranes. We studied pristine C(60) (1) and two N-substituted fulleropyrrolidines (2 and 3), one of which (3) bore a paramagnetic nitroxide group. Theoretical predictions of fullerene distribution and permeability across lipid bilayers were combined with electron paramagnetic resonance (EPR) experiments in aligned DMPC/DHPC bicelles containing the paramagnetic fulleropyrrolidine 3 or either one of the diamagnetic fullerenes together with spin-labeled lipids. We found that, at low concentrations, fullerenes are present in the bilayer as single molecules. Their preferred location in the membrane is only slightly influenced by the derivatization: all derivatives were confined just below the hydrophilic/hydrophobic interface, because of the key role played by dispersion interactions between the highly polarizable fullerene cage and the hydrocarbon chains, which are especially tight within this region. However, the deviation from spherical shape is sufficient to induce a preferential orientation of 2 and 3 in the membrane. We predict that monomeric fullerenes spontaneously penetrate the bilayer, in agreement with the results of molecular dynamics simulations, but we point out the limits of the currently used permeability model when applied to hydrophobic solutes. 相似文献
115.
Franco M. Rabagliati Mónica A. Pérez Francisco J. Rodríguez Rodrigo A. Cancino Nocolas Crispel Gabriela A. Mardones Héctor E. Muñoz Marcela A. Saavedra Manuel Vidal Lisa A. Muñoz 《Macromolecular Symposia》2011,304(1):33-39
Summary: Binary metallocene-MAO and ternary diphenylzinc-metallocene-MAO initiator systems have been tested as initiators in the homopolymerization of styrene and also in its copolymerization with several diverse comonomers including substituted styrenes, styrene derivatives, α-olefins and dienes. Various titanocenes and zirconocenes and some exploratory experiment with hafnocene were carried out. The results indicate that titanocenes were more effective than zirconocenes in the homopolymerization of styrene while zirconocenes did better in α-olefin polymerization. It was found that titanocenes generated mainly syndiotactic polystyrene, s-PS, while zirconocenes yielded atactic polystyrene or, depending on the zirconocene, a low percentage of s-PS. For these types of initiators the polymerization process depends largely on the inductive effect of the substituents linked to the benzene ring of styrene and on its position (ortho, meta or para). Substituent multiplicity reduced markedly the effectiveness of these initiator systems. Styrene/isoprene polymerization was also studied using binary zirconocene-MAO initiator systems that yielded low conversions and also low molecular weight polymers. 相似文献
116.
We investigate the decomposition of ammonia on bimetallic surfaces prepared by the deposition of a monolayer of Fe, Co, or Cu on a Pt(111) surface computationally and experimentally. We explore the correlation between predicted activities based on the nitrogen binding energies with experimental decomposition activity on these bimetallic and corresponding monometallic surfaces. Through density functional theory calculations and microkinetic modeling, it is predicted that the Fe-Pt-Pt(111) and Co-Pt-Pt(111) surfaces, with a monolayer of Fe or Co on top of Pt(111), are active toward decomposing ammonia. In contrast, the corresponding subsurface configurations, Pt-Fe-Pt(111) and Pt-Co-Pt(111) are inactive. These predictions were confirmed experimentally through temperature programmed desorption experiments. Decomposition was seen at temperatures below 350 K for the Fe-Pt-Pt(111) and Co-Pt-Pt(111) surfaces. For the Cu∕Pt(111) system, the surface, subsurface and parent metals were each predicted to be inactive, consistent with experiments, further validating the model predictions. The stability of these bimetallic surfaces in the presence of adsorbed nitrogen is also discussed. 相似文献
117.
Hansson PM Skedung L Claesson PM Swerin A Schoelkopf J Gane PA Rutland MW Thormann E 《Langmuir : the ACS journal of surfaces and colloids》2011,27(13):8153-8159
A range of surfaces coated with spherical silica particles, covering the size range from nanometer to micrometer, have been produced using Langmuir-Blodgett (LB) deposition. The particles were characterized both in suspension and in the Langmuir trough to optimize the surface preparation procedure. By limiting the particle aggregation and surface layer failures during the preparation steps, well-defined monolayers with a close-packed structure have been obtained for all particle sizes. Thus, this procedure led to structured surfaces with a characteristic variation in the amplitude and spatial roughness parameters. In order to obtain robust surfaces, a sintering protocol and an AFM-based wear test to determine the stability of the deposited surface layer were employed. Hydrophobization of the LB films followed by water contact angle measurements showed, for all tested particle sizes, the same increase in contact angle compared to the contact angle of a flat hydrophobic surface. This indicates nearly hexagonal packing and gives evidence for nearly complete surface wetting of the surface features. 相似文献
118.
Choonara YE Pillay V Ndesendo VM du Toit LC Kumar P Khan RA Murphy CS Jarvis DL 《Colloids and surfaces. B, Biointerfaces》2011,87(2):243-254
This study focused on evaluating four emulsion-based processing strategies for polymeric nanoparticle synthesis to explicate the mechanisms of nanoparticle formation and the influence on achieving sustained-release of two anti-tuberculosis drugs, isoniazid and rifampicin. Poly(lactic-co-glycolic acid) (PLGA) nanoparticles were formulated with and without sorbitan mono-oleate as a stabilizer using emulsion-solvent-surfactant-evaporation (ESSE) and emulsion-solvent-evaporation (ESE) approaches. An alginate solution gelled by ionic crosslinking with calcium chloride was employed to prepare alginate hydrogel nanoparticles via reverse-emulsion-cationic-gelification (RECG) and reverse-emulsion-surfactant-cationic-gelification (RESCG) approaches. In vitro drug release analysis was performed. The size, zeta potential and morphology of the nanoparticles were analyzed. Molecular mechanics energy relationships (MMER) were employed to explore the spatial disposition of alginate and PLGA with respect to the emulsifying profile of sorbitan monooleate and to corroborate the experimental findings. Results revealed that particle size of the PLGA nanoparticles was influenced by the stabilizer concentration. Nanoparticles synthesized by the ESSE approach had smaller sizes of 240±8.7 nm and 195.5±5.4 nm for rifampicin- and isoniazid-loaded nanoparticles, respectively. This was a substantial size reduction from nanoparticles generated by the ESE approach (>1000 nm). The RESCG approach produced stable and higher nanoparticle yields with desirable size (277±1.0 nm; 289±1.2 nm), a low polydispersity index (27.1±0.3 mV; 28.5±0.5 mV) and drug entrapment efficiency of 73% and 75% for isoniazid and rifampicin, respectively. Drug release from the ESSE and RESCG synthesized nanoparticles displayed desirable release of the two anti-TB drugs with sustained zero-order kinetics over a period of 8h. MMER supported the mechanisms of nanoparticle formation with a sphericalized interlaced network configuration. 相似文献
119.
A set of N-substituted benzoperylene monoimide (BPI) fluorophores was synthesized and characterized structurally and photophysically. Condensation of benzo[ghi]perylene-1,2-dicarboxylic anhydride in the presence of "swallow tail" alkyl amines produced fluorophores that are soluble in a range of organic solvents, highly absorbing in the near-UV (ε(334) = 79,000 M(-1) cm(-1)), and fluorescent in the visible range. Photophysical behavior of the compounds was studied with steady-state and time-correlated single photon counting. The synthesized BPIs exhibit positive solvachromatic emission (λ(em) (hexane) = 469 nm; λ(em) (ethanol) = 550 nm) as a function of solvent polarity with little change in their excited-state lifetime (9.6-6.5 ns) and fluorescence quantum yield (0.27-0.44) over the polarity range studied. Solvachromatic shifts were analyzed using the Lippert-Mataga approach. In nonpolar hydrocarbon solvents evidence of dual emission from closely spaced (562 cm(-1)) S(1) and S(2) excited states is observed. Preliminary peak assignments for the anomalous S(2) emission are made. 相似文献
120.
The M(CO)(4) fragment can be assigned to be isolobal with both CH(3)(+) and CH(2). In order to investigate this ambiguous isolobal assignment, we report calculations on compounds of the type M(CO)(4)L(n), where M is Fe (n = 0), Mn (n = -1), and Co (n = +1) and L is an η(2) ligand with a π bond, generally an alkene. The L's are varied in electron-withdrawing ability, and patterns in computed structural parameters are investigated. We report that the equatorial OC-M-CO angle is sensitive to the electron-withdrawing ability of the alkene just as the isolobal prediction suggests. Other structural parameters that vary monotonically with electron-withdrawing ability of the alkene are the "bending back" of the alkene, the metal-ligand bond distances, and carbon-oxygen bond distances. Changing the metal from neutral Fe to a negatively charged Mn or positively charged Co has the result of increasing and decreasing, respectively, the OC-M-CO angle. Several compounds of Ni(CO)(3)L are also investigated as a further example of the ability of the isolobal concept to yield chemically useful information. 相似文献