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81.
The crystallization of monodisperse linear polyethylene confined in nanoporous alumina is investigated with the calorimetric measurements. We observe a drastic change in crystallization behavior, specifically nucleation, with a decrease in the pore diameter. Crystallization in relatively larger pores with the diameters of 62 and 110 nm occurs at lower temperatures within a very narrow range, whereas crystallization in smaller pores with diameters of 15-48 nm occurs at a higher and broad range of temperatures. Nucleation and crystallization kinetics in nanopores is discussed based on classical nucleation theory as well as the Avrami theory. 相似文献
82.
Piasecki SK Taylor CA Detelich JF Liu J Zheng J Komsoukaniants A Siegel DR Keatinge-Clay AT 《Chemistry & biology》2011,18(10):1331-1340
Chiral building blocks are valuable intermediates in the syntheses of natural products and pharmaceuticals. A scalable chemoenzymatic route to chiral diketides has been developed that includes the general synthesis of α-substituted, β-ketoacyl N-acetylcysteamine thioesters followed by a biocatalytic cycle in which a glucose-fueled NADPH-regeneration system drives reductions catalyzed by isolated modular polyketide synthase (PKS) ketoreductases (KRs). To identify KRs that operate as active, stereospecific biocatalysts, 11 isolated KRs were incubated with 5 diketides and their products were analyzed by chiral chromatography. KRs that naturally reduce small polyketide intermediates were the most active and stereospecific toward the panel of diketides. Several biocatalytic reactions were scaled up to yield more than 100?mg of product. These syntheses demonstrate the ability of PKS enzymes to economically and greenly generate diverse chiral building blocks on a preparative scale. 相似文献
83.
Giyoung Song Suk Man Cho Hee Joon Jung Richard Hahnkee Kim Insung Bae Hyungju Ahn Dr. Du Yeol Ryu Dr. June Huh Dr. Cheolmin Park 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(49):15662-15668
Supramolecular assembly through complementary interaction between molecular subgroups belonging to phase‐separating polymer species offers a great opportunity, not only for constructing nanoscale soft templates reminiscent of conventional block copolymer morphologies, but also for tailoring surface properties by facile removal of one of the structure components by cleaving complementary interactions. Herein we report the fabrication of a novel, organic, nanoporous film through supramolecular assembly of two complementarily, end‐interacting, mono‐end‐functionalized polymers under solvent annealing. The film of end‐functionalized polymer blends under solvent annealing yielded phase‐separated nanodomains that resemble nanoscopically ordered structures of block copolymers, but that are more advantageous due to easily cleavable and exchangeable links between the phase‐separated domains. The removal of one of the components of the precursor structure formed from the end‐functionalized polymers through cleavage of complementary interactions allowed us to fabricate mono‐ or multilayered nanoporous structures in which the chemically useful end‐functionalities of the remnant polymers are rich on the surface of the pores. The resultant, organic, nanoporous films with tailored surface functionality offer a useful platform for various chemical and biological applications. 相似文献
84.
S-nitrosylation (also referred to as nitrosation), a reversible post translational modification (PTM) of cysteine, plays an important role in cellular functions and cell signalling pathways. Nitrosylated proteins are considered as biomarkers of aging and Alzheimer's disease (AD). Microfluidics has been widely used for development of novel tools for separation of protein mixtures. Here we demonstrate two-dimensional micro-electrophoresis (2D μ-CE) separations of nitrosylated proteins from the human colon epithelial adenocarcinoma cells (HT-29) and AD transgenic mice brain tissues. Sodium dodecyl sulphate micro-capillary gel electrophoresis (SDS μ-CGE) and microemulsion electrokinetic chromatography (MEEKC) were used for the first and second dimensional separations, respectively. The effective separation lengths for both dimensions were 10 mm, and electrokinetic injection was used with field strength at 200 V cm(-1). After 80 s separation in the first CGE dimension, fractions were successfully transferred to a second MEEKC dimension for a short 10 s separation. We first demonstrate this 2D μ-CE separation by resolving five standard proteins with molecular weight (MW) ranging from 20 to 64 kDa. We also present a high peak capacity 3D landscape image of nitrosylated proteins from HT-29 cells before and following menadione (MQ) treatment to induce oxidative stress. Additionally, to illustrate the potential of the 2D μ-CE separation method for rapid profiling of oxidative stress-induced biomarkers implicated in AD disease, the nitrosylated protein fingerprints from 11-month-old AD transgenic mice brain and their age matched controls were also generated. To our knowledge, this is the first report on 2D profiling of nitrosylated proteins in biological samples on a microchip. The characteristics of this biomarker profiling will potentially serve as the screening for early detection of AD. 相似文献
85.
We report a proof of principle study for the use of oxalyldihydrazide as a crosslinker for enrichment of carbonylated proteins within a microfluidic chip. Surface modification steps are characterized and analyzed using analytical techniques. We use oxidized cytochrome c as our model protein and demonstrate the chip's ability to capture carbonylated targets. After 100 min of continuous loading, the chip is capable of capturing 7.5 μg of carbonylated protein. All the proteins captured are eluted out of the chip using the elution protocol. Finally, we demonstrate the chip's specificity for oxidized targets by mixing oxidized cytochrome c and TRITC-BSA, with cytochrome c in low abundance. The results show that the chip is efficient at finding its target when unoxidized proteins are present. This is the first report to suggest the use of immobilized oxalyldihydrazide on a microchip as an enrichment methodology for low abundance proteins in a sample. 相似文献
86.
以LiNTf2为催化剂,在无溶剂条件下,醛或酮与三甲基氰硅烷(TMSCN)室温发生加成反应,得到相应的α-氰基硅醚.该法操作简便、反应条件温和、收率高、催化剂易回收和可以重复使用. 相似文献
87.
A commonly used semiparametric model is considered. We adopt two difference based estimators of the linear component of the model and propose corresponding thresholding estimators that can be used for variable selection. For each thresholding estimator, variable selection in the linear component is developed and consistency of the variable selection procedure is shown. We evaluate our method in a simulation study and implement it on a real data set. 相似文献
88.
We perform density functional calculations to investigate structural and dynamical properties of crystalline polyvinylidene difluoride (PVDF) associated with the transition from α to β phase. We examine the change of the conformational energy and the corresponding structure of each phase depending on the lattice parameters of the orthorhombic crystalline structure. From this information, we construct the path that connects the point where the α phase is most stable to the point where the β phase is most stable, and identify the sub‐ region in the lattice parameter space where α and β phases have the same energy. In this sub‐region, we locate the point which gives the lowest conformation energy for both α and β phases, and examine the behaviour of the lowest energy profile and corresponding change of intermediate structures as the conformation of the PVDF chain transforms from α phase to β phase. Finally we perform ab‐initio molecular dynamics simulations and analyse the characteristic dynamics associated with transition from α to β phase. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
89.
Synchronized bursts are a very common feature in biological neural networks, and they play an important role in various brain functions and neurological diseases. This Letter investigates "recurrent synchronized bursts" induced by a single pulse stimulation in cultured networks of rat cortical neurons. We look at how the precision in their arrival times can be modified by a noble time-delayed stimulation protocol, which we term as "Δt training." The emergence of recurrent bursts and the change of the precision in their arrival times can be explained by the stochastic resonance of a damped, subthreshold, neural oscillation. 相似文献
90.
The angular intensity distribution of thermal energy He beam scattered from highly oriented pyrolytic graphite (HOPG) surface has been measured by means of supersonic molecular beam scattering technique in the wide surface temperature range. To separate the elastic and inelastic scattering components, simple analysis method has been developed by applying the classical binary collision theory of the hard cube model (HCM). From the extracted elastic scattering component in the scattering distribution, the Debye temperature of the HOPG surface has been derived as 590 ± 30 K. On the basis of the HCM analysis for the extracted inelastic scattering components of He beam, the effective mass for the HOPG surface has been found to be 72 u (six carbon atoms). 相似文献