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101.
In this study, we combined a cell-penetrating γ-peptide, PEG-1, with antimicrobial undecapeptides in order to provide compounds with anticancer properties against MDA-MB-231 human breast cancer cells. We demonstrated that the conjugates were more cytotoxic than Ac-PEG-1 and the parent undecapeptides. We also evaluated the toxicity of the conjugates against non-malignant cells. The peptide conjugate with the best biological profile was BP77-PEG-1, which, at 10 μM, showed a 71% growth inhibition in MDA-MB-231 cells and only a 17% inhibition in non-malignant cells. Therefore, this study suggests that PEG-1 mediated the undecapeptide delivery into cancer cells and that these conjugates are the proof-of-concept of this strategy to generate improved anticancer drugs based on peptides.  相似文献   
102.
    
Pd and Ni dimers supported by PSiP ligands in which two hypervalent five‐coordinate Si atoms bridge the two metal centers are reported. Crystallographic characterization revealed a rare square‐pyramidal geometry at Si and an unusual asymmetric M2Si2 core (M=Pd or Ni). DFT calculations showed that the unusual structure of the core is also found in a model in which the phosphine and Si centers are not part of a pincer group, thus indicating that the observed geometry is not imposed by the PSiP ligand. NBO analysis showed that an asymmetric four‐center two‐electron (4c‐2e) bond stabilizes the hypervalent Si atoms in the M2Si2 core.  相似文献   
103.
Well‐defined copper(I) complexes of composition [Tpm*,BrCu(NCMe)]BF4 (Tpm*,Br=tris(3,5‐dimethyl‐4‐bromo‐pyrazolyl)methane) or [Tpa*Cu]PF6 (Tpa*=tris(3,5‐dimethyl‐pyrazolylmethyl)amine) catalyze the formation of 2,5‐disubstituted oxazoles from carbonyl azides and terminal alkynes in a direct manner. This process represents a novel procedure for the synthesis of this valuable heterocycle from readily available starting materials, leading exclusively to the 2,5‐isomer, attesting to a completely regioselective transformation. Experimental evidence and computational studies have allowed the proposal of a reaction mechanism based on the initial formation of a copper–acyl nitrene species, in contrast to the well‐known mechanism for the copper‐catalyzed alkyne and azide cycloaddition reactions (CuAAC) that is triggered by the formation of a copper–acetylide complex.  相似文献   
104.
    
The surface modification of electrodes attracts great interest in electrocatalysis. It has often been observed that deposition of foreign adatoms on the surface of an electrode can originate a significant enhancement in the catalytic activity. For example, it has been reported that nickel deposits on Pt surfaces improve the rate of the hydrogen evolution reaction (HER, Nature Energy 2017, 2, 17031). During the deposition process of such metal adlayers, the pH and the nature of the ions in the electrolyte play an important role. Phosphate species are typically used to prepare buffer solutions in a wide range of pH. Therefore, electrolytes containing phosphate species are used in a large number of applications. However, the effect of phosphate on platinum surface modification with nickel deposits has not been studied yet. In this work, new data about the interaction of phosphate with nickel adatoms deposited on Pt(111) at pH 5 is investigated using cyclic voltammetry and infrared spectroscopy. The results show that, when nickel is in solution, the phosphate ions are adsorbed at lower potentials than in the absence of nickel. In addition, Laser-Induced Temperature Jump Technique demonstrates that nickel facilitates the adsorption of phosphate because of a shift of the potential of zero charge (pzc) toward negative potentials. This increases the magnitude of the positive electric field on the electrode surface, at a given potential E>pzc, facilitating the adsorption of anions. CO displacement technique has been also employed to obtain additional information about co-adsorbed phosphate on nickel adlayers. Finally, the HER has been studied at pH 5 in the presence of nickel, with and without phosphate in the bulk solution.  相似文献   
105.
    
Despite the known nucleophilic nature of [M(CF3)2] (M=Cu, Ag, Au) complexes, their participation in trifluoromethylation reactions of aryl halides remains unexplored. Here, for the first time, selective access to a [Cu(CF3)2] species is reported, which is ubiquitous in Cu-mediated trifluoromethylations, and we rationalize its complex mechanistic scenario as well as its behavior compared to its silver and gold congeners through a combination of experimental and computational approaches.  相似文献   
106.
    
A general protocol for the enantioselective synthesis of 3-heterosubstituted-2-amino-1-ols was developed based on metal- free intramolecular regio- and stereoselective diene aziridination and regioselective opening. Kinetic resolution of the resulting (1′-NR1R2 and 1′-SR)-4-oxazolidinones was performed using ABCs organocatalysts, expanding the application of this methodology.  相似文献   
107.
    
In situ electrochemical infrared spectroscopy and Raman spectroscopy are powerful tools for probing potential-dependent adstructures at solid/liquid electrochemical interfaces. However, it is very difficult to quantitatively interpret the observed spectral features including potential-dependent vibrational frequency and spectral intensity, even from model systems such as single-crystal electrode/liquid interfaces. The clear understanding of electrochemical vibrational spectra has remained as a fundamental issue for four decades. Here, we have developed a method to combine computational vibrational spectroscopy tools with interfacial electrochemical models to accurately calculate the infrared and Raman spectra. We found that the solvation model and high precision level in the self-consistent-field convergence are critical elements to realize quantitative spectral predictions. This method''s predictive power is verified by analysis of a classic spectroelectrochemical system, saturated CO molecules electro-adsorbed on a Pt(111) electrode. We expect that this method will pave the way to precisely reveal the physicochemical mechanism in some electrochemical processes such as electrocatalytic reactions.

An integrated approach for quantitatively predicting the electrochemical-infrared and electrochemical-Raman spectra and STM images of Pt(111)(2 × 2)-3CO adstructures has been developed.  相似文献   
108.
    
Mechanochemistry is an emerging field with many potential applications in sustainable chemistry. But despite the growing interest in the field, its underlying mechanistic foundations are not fully understood yet. This work presents the application of computational tools, such as DFT calculations in continuum and microkinetic modeling, to the analysis of mechanically activated procedures. Two reactions reported in previous experimental publications were studied: (i) a series of Diels-Alder reactions and (ii) the synthesis of sulfonylguanidines. Calculations succeed in reproducing experimentally reported reaction times. The procedures were mostly standard, coupled with some sensitive choices in terms of starting concentrations and dielectric constant. This means that these particular reactions accelerated by ball milling followed the same mechanism as the equivalent reactions in solution. The implications of this result on the general picture of mechanochemical processes are discussed.  相似文献   
109.
The oxidation of ammonia on platinum surfaces is a structure sensitive reaction that takes place almost exclusively on Pt(100) sites. This report shows how dependent the activity is on different arrangements of (100) sites of platinum. The effect of two-dimensional domains has been addressed by using stepped surfaces having terraces with (100) geometry, either with (111) and (110) steps. The results were compared with those obtained from stepped surfaces having terraces with (111) or (110) symmetry and monatomic (100) steps, thus representing monodimensional (100) domains. The observed behavior confirms the extreme sensitivity of the reaction to the different arrangement of this type of square sites.  相似文献   
110.
The Romans used a vast array of colors in their mural paints. The applied pigment mixtures containing Egyptian blue resulting in green, ochre, brown, gray, and white hues were studied. The chromatic characterization of wall paintings by electronic spectroscopy provided an easy and reliable procedure for the grouping of the samples to be studied (see Table). Subsequent use of other spectroscopic techniques such as Fourier‐transform (FT) IR and energy‐dispersive X‐ray spectroscopy (EDS), combined with X‐ray diffraction (XRD), led to convenient identification of the pictorial layer components that define and differentiate each chromatic group. Colors impossible to produce with only one pigment can be obtained by mixing Egyptian blue with other pigments. The dominant wavelength is displaced in such way that the artist obtains new tonalities.  相似文献   
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