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111.
    
Carbon dioxide (CO2)‐responsive polymers have been gaining considerable interest because of their reactions with CO2, giving rise to gas‐switchable properties, which can easily be reversed by mild heating or purging with inert gases. Herein, the synthesis of a series of side‐chain amino acids (alanine, leucine, isoleucine, phenylalanine, tryptophan) appending poly(meth)acrylates carrying primary amine (? NH2) groups via reversible addition‐fragmentation chain transfer (RAFT) polymerization method was reported. It was found that alanine, leucine, isoleucine containing polymers displayed solubility–insolubility transition behavior and their associated property changes (solution transmittance, electrical conductivity, pH, zeta potential, and hydrodynamic diameter) in water upon alternate bubbling of CO2/N2 at room temperature. Among the three CO2‐sensitive polymers only leucine based macromolecule was further chain extended with a thermoresponsive motif, di(ethylene glycol) methyl ether methacrylate (DEGMMA), via RAFT polymerization. CO2‐tunable lower critical solution temperature and self‐assembling behavior of the diblock copolymer was carefully examined by UV–vis, 1H NMR spectroscopy, dynamic light scattering (DLS), and field emission‐scanning electron microscopy (FE‐SEM) to establish dual thermo and gas‐tunable flip–flop micellizaion from the as‐synthesized block copolymer. Formation of polyammonium methacrylate bearing bicarbonate as counter anion is responsible for pendant primary amine containing polymer induced CO2‐responsiveness. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2794–2803  相似文献   
112.
    
In this report, we have synthesized organic/inorganic hybrid peptide–poly(?‐caprolactone) (PCL) conjugates via ring opening polymerization (ROP) of ?‐caprolactone (CL) in the presence of two sequence defined peptide initiators, namely POSS‐Leu‐Aib‐Leu‐NH2 (POSS: polyhedral oligomeric silsesquioxane; Leu: Leucine; Aib: α‐aminoisobutyric acid) and OMe‐Leu‐Aib‐Leu‐NH2. Covalent attachment of peptide segments with the PCLs were examined by 1H and 29Si NMR spectroscopy, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOF‐MS) and FTIR spectroscopy. Supramolecular inclusion complexations of synthesized peptide‐PCL conjugates with α‐cyclodextrin (α‐CyD) were studied to understand the effect of POSS/OMe‐peptide moieties at the PCL chain ends. Inclusion complexation of peptide‐PCL conjugates with α‐CyD produced linear polypseudorotaxane, confirmed by 1H NMR, FTIR, powder X‐ray diffraction (PXRD), polarized optical microscopy (POM) and differential scanning calorimetry (DSC). Extent of α‐CyD threading onto the hybrid peptide‐PCL conjugated polymers is less than that of α‐CyD threaded onto the linear PCL. Thus, PCL chains were not fully covered by the host α‐CyD molecules due to the bulky POSS/OMe‐peptide moieties connected with the one edge of the PCL chains. PXRD experiment reveals channel like structures by the synthesized inclusion complexes (ICs). Spherulitic morphologies of POSS/OMe‐peptide‐PCL conjugates were fully destroyed after inclusion complexation with α‐CyD and tiny nanoobjects were produced. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3643–3651.  相似文献   
113.
Storage and separation of small (C1–C3) hydrocarbons are of great significance as these are alternative energy resources and also can be used as raw materials for many industrially important materials. Selective capture of greenhouse gas, CO2 from CH4 is important to improve the quality of natural gas. Among the available porous materials, MOFs with permanent porosity are the most suitable to serve these purposes. Herein, a two‐fold entangled dynamic framework {[Zn2(bdc)2(bpNDI)]?4DMF}n with pore surface carved with polar functional groups and aromatic π clouds is exploited for selective capture of CO2, C2, and C3 hydrocarbons at ambient condition. The framework shows stepwise CO2 and C2H2 uptake at 195 K but type I profiles are observed at 298 K. The IAST selectivity of CO2 over CH4 is the highest (598 at 298 K) among the MOFs without open metal sites reported till date. It also shows high selectivity for C2H2, C2H4, C2H6, and C3H8 over CH4 at 298 K. DFT calculations reveal that aromatic π surface and the polar imide (RNC=O) functional groups are the primary adsorption sites for adsorption. Furthermore, breakthrough column experiments showed CO2/CH4 C2H6/CH4 and CO2/N2 separation capability at ambient condition.  相似文献   
114.
Synthesis of ionic liquids (IL) based on oxygen‐containing spirobipyrrolidinium salts with BF4, BF3C2F5, and NTf2 as counterions was undertaken. Their physical and electrochemical properties were evaluated for suitability for Room Temperature Ionic Liquids (RTIL) application. Reduction in melting point occurred upon exchange of C(2) by an O‐atom of spirobipyrrolidinium, without sacrificing the electrochemical stability; while introduction of alkyl groups between the N‐ and O‐atoms led to incorporation of asymmetry, and hence reduced the melting points, and viscosity.  相似文献   
115.
    
In this letter, considering the metric of a rotating polytropic black hole in the Boyer-Lindquist coordinates, at first, we derive the thermodynamic parameters such as entropy S, Helmholtz free energy F, internal energy U and Gibbs free energy G and study its dependence on the outer horizon by depicting suitable graphs. Then after reconstruction of the metric of the same in the Eddington-Finkelstein coordinates, we establish the interior volume of the black hole. We further analyze the variations of the interior volume with the small change of the advanced time with respect to the radius. Here we show the existence of a certain value of the radius for which this variation becomes maximum. Moreover, we show the dependence of this maximum value of the radius on the mass of the black hole. We derive the differential form of the interior volume for this limit of the radius and hence the maximal interior volume of the said black hole. Finally, we analyze the same thermodynamic parameters inside the black hole and present a comparative study between the parameters in the outer and interior regions of the black hole.https://doi.org/10.1209/0295-5075/acc47e  相似文献   
116.
    
We theoretically demonstrate stacked-dipole-resonators–based (broadside near-field coupling configuration) multilayer metasurfaces separated by a vanadium dioxide film to achieve stronger field confinement in the spacer (VO2) region. Under relatively intense terahertz excitation (20 Vm−1) assisted by larger area electric field confinement,insulator-to-metal transition (IMT) in VO2 spacer is realized resulting in frequency (dipole mode) and amplitude (Fano mode) tunable metasurfaces. Enhancement in probing THz field triggers much stronger field confinement inside the spacer layer leading to increased VO2 conductivity (responsible for IMT) through the Poole-Frankel effect. Such broadside coupled IMT-based terahertz metamaterials can help in realizing active meta devices for THz domain.https://doi.org/10.1209/0295-5075/ac6e82  相似文献   
117.
Interaction of a beta-carboline based biologically active molecule, 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a] quinolizine (AODIQ), with alpha-, beta-, and gamma-cyclodextrins (CDs) in aqueous solution has been studied using steady state and time-resolved fluorescence and steady-state fluorescence anisotropy techniques. Polarity dependent intramolecular charge transfer (ICT) process is responsible for the remarkable sensitivity of this biological fluorophore to the CD environments. Upon encapsulation, the CT fluorescence exhibits hypsochromic shift along with enhancements in the fluorescence yield, fluorescence anisotropy (r), and fluorescence lifetime. The reduction in the nonradiative deactivation rate of the fluorophore within the CD nanocavities leads to an increase in both fluorescence yield and lifetime. Among the three CDs, gamma-CD shows the most spectacular confinement effect. The results establish the formation of 1:1 AODIQ:CD inclusion complexes in alpha- and beta-CDs. In aqueous gamma-CD solutions, however, depending on the concentration of the gamma-CD, formation of both 1:1 and 1:2 complexes have been revealed. Hydrodynamic radii of the 1:1 and 1:2 probe-gamma-CD supramolecular complexes have also been determined.  相似文献   
118.
Palmetto wood is garnering growing interest as a template for creating biologically-inspired polymer composites due to its historical use as an energy absorbing material in protective structures. In this study, quasi-static three-point bend tests have been performed to characterize the mechanical behavior of Palmetto wood. Full-field deformation measurements are obtained using Digital Image Correlation (DIC) to elucidate on the strain fields associated with the mechanical response. By analyzing strain fields at multiple length scales, it is possible to study the more homogeneous mechanical behavior at the macro-scale associated with the global load-deformation response; while at the microscale the mechanical behavior is more inhomogeneous due to microstructural failure mechanisms. Thus, it was possible to determine that, despite the presence of discontinuous macro-fiber reinforcement, at the macro-scale the response is associated with classical bending and progressive failure processes that are adequately described by Weibull statistics proceeding from the tensile side of the specimen. At the microscale, however, the failure mechanisms giving rise to the macroscopic response consist of both shear-dominated debonding between the fiber and matrix, and inter-fiber matrix failure due to pore collapse. These microscale mechanisms are present in both the compressive and tensile regions of the specimen, most likely due to local macro-fiber bending, which is independent of the global bending state. The pore collapse mechanism observed during mechanical loading appears to improve the energy absorption of the matrix material, thereby, transferring less energy and shear strain to the macro-fiber-matrix interface for initiation of debonding. However, the pore collapse mechanism can also accumulate substantial shear strain, which results in matrix shear cracking. Through these complex failure mechanisms, Palmetto wood exhibits a high resistance to catastrophic failure after damage initiation, an observation that can be used as inspiration for creating new polymer composite materials.  相似文献   
119.
120.
Degradation of organic pollutants in wastewater is a common subject of discussion under advanced oxidation process. To detect the degradation of colourless organic pollutants conventional analytical techniques are available but their sophistication makes it difficult to pursue in all form of chemical laboratories. In the present study it was found that during degradation of Dichlorvos using diethylene triamine pent acetic acid (DTPA) stabilized nano zero valent iron (nZVI), COD removal and ac conductivity change has been done simultaneously. In this degradation study the heterogeneous Fenton type oxidation method was employed and an LCR circuit (which contains inductor, capacitor and resistor) was used to measure the ac conductivity. This study aims to find out a correlation between ac conductivity and COD removal using simple response surface methodology (RSM) so that the degradation of colourless pollutants can be estimated easily and also to identify the best processing parameters to optimise Dichlorvos degradation. It was found that COD removal in most of all cases, was more than 60% when the change in final ac conductivity more than 600% with respect to initial value. All of the experimental results were in good accord with the projected outcome.  相似文献   
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