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81.
Since hollow-fiber flow field-flow fractionation (HF FIFFF) utilizes a cylindrical channel made of a hollow-fiber membrane, which is inexpensive and simple in channel assembly and thus disposable, interests are increasing as a potential separation device in cells, proteins, and macromolecules. In this study, performance of HF FIFFF of proteins is described by examining the influence of flow rate conditions and length of fiber (polyacrylonitrile or PAN in this work) on sample recovery as well as experimental plate heights. The interfiber reproducibility in terms of separation time and recovery was also studied. Experiments showed that sample recovery was consistent regardless of the length of fiber when the effective field strength (equivalent to the mean flow velocity at the fiber wall) and the channel void time were adjusted to be equivalent for channels of various fiber lengths. This supported that the majority of sample loss in HF FIFFF separation of apoferritin and their aggregates may occur before the migration process. It is finally demonstrated that HF FIFFF can be applied for characterizing the reduction in Stokes' size of low density lipoproteins from blood plasma samples obtained from patients having coronary artery disease and from healthy donors.  相似文献   
82.
    
Micro-thermal field-flow fractionation was used to characterize the particle size distribution of nanometer-sized diamond nanoparticles. Although the experimental conditions were chosen to perform high-speed separation, and, consequently, the resolution achieved experimentally was not very high, the application of the original correction method for the zone spreading allowed for obtaining of very good calculated particle size distribution or, explicitly, a true polydispersity index of the diamond nanoparticle sample. The future use of several samples of diamond nanoparticles of different average sizes and different surface chemistries should allow deeper insight into the effect of these particulate characteristics on the retention in micro-thermal field-flow fractionation.  相似文献   
83.
    
A universal technique has been proposed to sort two‐dimensional (2D) sub‐nanometer thin crystals (manganese dioxide MnO2 and molybdenum disulfide MoS2) according to their lateral dimensions. This technique is based on tuning the zeta potential of their aqueous dispersions which induces the selective sedimentation of large‐sized 2D crystals and leaves the small‐sized counterparts in suspension. The electrocatalytic properties of as‐obtained 2D ultrathin crystals are strongly dependent on their lateral size. As a proof‐of‐concept study, the small‐sized MnO2 nanocrystals were tested as the electrocatalysts for the urea‐oxidation reaction (UOR), which showed outstanding performance in both half reaction and full electrolytic cell. A mechanism study reveals the enhanced performance is associated with the remarkable structural properties of MnO2 including ultrathin (ca. 0.95 nm), laterally small‐sized (50–200 nm), and highly exposed active centers.  相似文献   
84.
    
We investigated theoretically the effects of the cross‐stream migration and the local average orientation of rodlike particles on the shape‐based separation using field‐flow fractionation. The separation behavior was analyzed by comparing the retention ratios of spheres and rods. The retention ratio of a rod was evaluated through the derivation of its cross‐sectional concentration profile by considering the rod migration and the local average orientation. Our study in various flow conditions showed that the rod migration, caused by the hydrodynamic interaction with a wall, can affect the separation behavior as a lift‐hyperlayer mode. We also demonstrated that the local average orientation, which is a function of a local shear rate and a rotational diffusivity, results in the transverse diffusivity that is different from its perpendicular diffusivity. These results suggest that the experimental separation behaviors of rods in field‐flow fractionation may not be fully explained by the current theory based on the normal mode and the steric mode. We also characterized each condition where one of the normal mode, the steric mode of spheres, and the lift‐hyperlayer mode of rods is dominant.  相似文献   
85.
    
Summary: Crystallization analysis fractionation (Crystaf) is a polymer characterization technique based on differences in chain crystallizabilities in a dilute solution during non-isothermal crystallization. Crystaf profiles, a weight distribution function of chains crystallized at each temperature, can be used to infer the chemical composition distribution (CCD) of copolymers when a Crystaf calibration curve, a relationship between peak crystallization temperature and average comonomer content, is known. In this investigation, the effect of the number average molecular weight, comonomer type, and cooling rate on Crystaf calibration curves were experimentally investigated. It was found that the cooling rate and comonomer type may strongly affect Crystaf calibration curves, while the influence of molecular weight is relatively subtle.  相似文献   
86.
    
Summary: Temperature rising elution fractionation (TREF) and crystallization analysis fractionation (CRYSTAF) fractionate semicrystalline polymers according to their crystallizabilities from dilute solution and have been widely used to measure the CCD of LLDPE. A new fractionation technique, known as crystallization elution fractionation (CEF), has been developed recently. The main difference between CEF and TREF and CRYSTAF is that the crystallization cycle in CEF is performed dynamically under solvent flow in a long column that contains an inert support material. In this paper, several metallocene-LLDPE resins have been analyzed by CEF to investigate the effect of cooling cycle parameters, comonomer fraction, polymer molecular weight, and blend cocrystallization on the fractionation. This new technique can be used to obtain CCDs with better resolution and in shorter times than TREF and CRYSTAF.  相似文献   
87.
    
In this study, a series of linear poly(triazole)s (PTAs) were successfully synthesized by the metal‐ and solvent‐free, thermal click polymerization of diazide and dialkyne (A2 + B2) monomers. All click polymerizations proceeded smoothly at 80 °C in an open atmosphere without protection from oxygen and moisture. After being polymerized for 36 h, the crude polymer was further fractionated into three fractions using a multistep precipitation method. By selectively choosing precipitating agents, this process produced poly(triazole) fractions with low polydispersity index (<1.30). The resulting PTAs are soluble in common organic solvents and stable at a temperature up to 320 °C. Furthermore, the methyl benzoate moieties in the main chain can serve as useful building blocks for further postpolymerization functionalization, yielding 1,2,4‐triazole derivatives. This functionalization strategy offers potential for the development of novel triazole‐based materials. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012  相似文献   
88.
    
Summary: An artificial neural network (ANN) with a 4-3-3-1 architecture was developed to estimate average comonomer content of ethylene/1-olefin copolymers from crystallization analysis fractionation (Crystaf) results. The ANN was trained with a back propagation algorithm. It was found that average comonomer contents predicted from ANN agree well with experimental results for both training and testing data sets. The developed ANN was also used to systematically investigate the effects of chain microstructures and Crystaf operating conditions on Crystaf calibration curves.  相似文献   
89.
    
Heterogeneous Ziegler-Natta catalysts produce polyolefins that have broad distributions of molecular weight (MWD) and chemical composition (CCD). For such broad distributions, mathematical models are useful to quantify the information provided by polyolefin analytical techniques such as high-temperature gel permeation chromatography (GPC), temperature rising elution fractionation (TREF), and crystallization analysis fractionation (CRYSTAF). In this paper, we developed a mathematical model to deconvolute the MWD and CCD of polyolefins simultaneously, using Flory's most probable distribution and the cumulative CCD component of Stockmayer's distribution. We have applied this procedure to “model” polyolefin resins and to one industrial linear low-density polyethylene (LLDPE) resin. The proposed methodology is able to deconvolute theoretical distributions even when random noise is added to the MWDs and CCDs, and it can be used to calculate the minimum number of active site types on heterogeneous Ziegler-Natta catalysts.  相似文献   
90.
    
The applicability of different concentration detection methods for online quantification of liposomes upon asymmetric flow field‐flow fractionation was investigated. Filter‐extruded egg phosphatidylcholine liposomes of different size were used. Online quantification using a differential refractive index (dRI) detector was found feasible for relatively high sample loads in the magnitude of 100 μg lipid (under the chosen fractionation conditions). UV–Vis detection of the turbidity of liposomes was ruled out as online detection method because turbidity increases with particle size and the signal is not only concentration but also particle‐size dependent. Staining of liposomes by Rhodamine phosphatidylethanolamine or Sudan Red and subsequent online UV–Vis detection at the absorption maximum of the dye enabled quantification with much higher sensitivity than dRI detection. Furthermore analyte loss and carry‐over phenomena upon repeated injection of varying liposome sample loads were studied using regenerated cellulose (RC) membranes as accumulation wall. It could be shown that RC membranes are prone to adsorption in case of very small sample loads (0.5 μg). This effect may be overcome by pre‐saturation of the membrane with sample loads of at least 2 μg. For higher sample loads adsorptive losses play a minor role. Recovery from pre‐saturated membranes reached approximately 100% and carry‐over was found negligible.  相似文献   
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