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861.
Cylindrical block copolymer micelles with a crystalline poly(ferrocenyldimethylsilane) (PFDMS) core and a long corona-forming block are known to elongate through an epitaxial growth mechanism on addition of further PFDMS block copolymer unimers. We now report that addition of the semicrystalline homopolymer PFDMS(28) to monodisperse short (ca. 200 nm), cylindrical seed micelles of PFDMS block copolymers results in the formation of aggregated structures by end-to-end coupling to form micelle networks. The resulting aggregates were characterized by dynamic light scattering (DLS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). In some cases, a core-thickening effect was also observed where the added homopolymer appeared to deposit and crystallize at the core-corona interface, which resulted in an increase of the width of the micelles within the networks. No evidence for aggregation was detected when the amorphous homopolymer poly(ferrocenylethylmethylsilane) (PFEMS(25)) was added to the cylindrical seed micelles whereas similar behavior to PFDMS(28) was noted for semicrystalline polyferrocenyldimethylgermane (PFDMG(30)). This suggested that the crystallinity of the added homopolymer is critical for subsequent end-to-end coupling and network formation to occur. We also explored the tendency of the cylindrical seed micelles to form aggregates by the addition of PI-b-PFDMS (PI = polyisoprene) block copolymers (block ratios 6:1, 3.8:1, 2:1, or 1:1), and striking differences were noted. The results ranged from typical micelle elongation, as reported in previous work, at high corona to core-forming block ratios (PI-b-PFDMS; 6:1) to predominantly end-to-end coupling at lower ratios (PI-b-PFDMS; 2:1, 1:1) to form long, essentially linear structures. The latter process, especially for the 2:1 block copolymer, led to much more controlled aggregate formation compared with that observed on addition of homopolymers.  相似文献   
862.
Open- and closed-loop control of vortex shedding in two-dimensional flow over a flat plate at high angle of attack is numerically investigated at a Reynolds number of 300. Unsteady actuation is modeled as a body force near the leading or trailing edge and is directed either upstream or downstream. For moderate angles of attack, sinusoidal forcing at the natural shedding frequency results in phase locking, with a periodic variation of lift at the same frequency, leading to higher unsteady lift than the natural shedding. However, at sufficiently high angles of attack, a subharmonic of the forcing frequency is also excited and the average lift over the forcing period varies from cycle-to-cycle in a complex manner. It is observed that the periods with the highest averaged lift are associated with particular phase differences between the forcing and the lift, but that this highest-lift shedding cycle is not always stably maintained with open-loop forcing. We design a feedback algorithm to lock the forcing with the phase shift associated with the highest period-averaged lift. It is shown that the compensator results in a stable phase-locked limit cycle for a broader range of forcing frequencies than the open-loop control, and that it is able to stabilize otherwise unstable high-lift limit cycles that cannot be obtained with open-loop control. For example, at an angle of attack of 40°, the feedback controller can increase the averaged magnitude of force on the plate by 76% and increase the averaged lift coefficient from 1.33 to 2.43.  相似文献   
863.
Films and monoliths containing the spin crossover complex [Fe(Htrz)(2)(trz)](BF(4)) (trz = 1,2,4-triazole) as nanoparticles have been obtained. The dispersion and consecutive inclusion of the Fe complex in a silica matrix prepared from tetramethoxysilane or tetraethoxysilane afford monoliths or films with a violet colour at room temperature, which turns white above 380 K. This change of colour is reversible. This thermochromic behaviour has been characterized by measuring the magnetic properties together with thermogravimetric studies and Raman spectroscopy, the result of which all demonstrate that both films and monoliths undergo a spin crossover. Microscopy studies confirm the occurrence of the Fe complex as nanoparticles, in both the monoliths and the films. The facile synthesis of these materials as nanoparticles in transparent films should open the possibility of the synthesis of high quality films.  相似文献   
864.
N-Ts and N-Boc derivatives of 1,2-diamines and 1,2-amino alcohols are shown to undergo efficient Pd(II)-catalyzed aza-Wacker reactions with a large range of electron-deficient alkenes. The resulting enamine intermediate generally undergoes cyclization with the second heteroatom to form 1,3-heterocycles. The sequence facilitates the rapid synthesis of saturated oxazolidines, imidazolidines, and their derivatives. Use of N-L-valinol derivatives results in highly diastereoselective reactions, where the net stereochemical outcome diverges between N-Ts and N-Boc.  相似文献   
865.
In this paper several characteristic features of time-of-flight mass spectrometry in coupling with gas chromatography are demonstrated and the parameters are compared to quadrupole mass analyzer. In the second part, the comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry was applied in human metabolomic field, particularly in the determination of pathological markers of Inherited Metabolic Disorders (IMDs).  相似文献   
866.
The direct gas phase catalytic oligomerization of methane at temperatures ≤673 K has been demonstrated using AlBr(3)-HBr superacid. The reaction produces C(2)+ hydrocarbons and hydrogen in a single step at 1 atm in a continuous flow reactor at a nominal residence time of 60 s. The essentially complete conversion of methane appears to be due to protolytic activation of methane in the presence of H(+)AlBr(4)(-).  相似文献   
867.
The Fourier-transform Raman and infrared spectra of 2-amino-5-fluoro benzoic acid has been recorded and analyzed. The optimized geometry of the other halogen substitution (Cl, Br) have been computed with the help of density functional theory. The detailed interpretation of vibrational spectra of 2-amino-5-fluoro benzoic acid have performed in terms of potential energy distribution analysis. Natural bond orbital analysis on 2-amino-5-fluoro benzoic acid, 2-amino-5-chloro benzoic acid and 2-amino-5-bromo benzoic acid has been carried out for various intramolecular interactions that are responsible for the stabilization of the molecule. The pKa values of 2-amino-5-fluoro benzoic acid, 2-amino-5-chloro benzoic acid and 2-amino-5-bromo benzoic acid are computed using MOPAC and it is related with HOMO-LUMO energy difference obtained from Gaussian 03 software. The biological activity of 2-amino-5-fluoro benzoic acid has been predicted based on these values. The inhibition activity of 2-amino-5-bromo benzoic acid with the protein tyrosine kinase 3LQ8 is simulated by using Autodock software.  相似文献   
868.
The near-infrared Fourier transform (NIR-FT) Raman and Fourier transform infrared (FT-IR) spectral analyses of 2,6-bis(benzylidene)cyclohexanone (BBC) molecule, a potential drugs for the treatment of P388 leukemia cells, were carried out along with density functional computations. The optimized geometry of BBC using density functional theory shows that the energetically favored chair conformation is not observed for central cyclohexanone ring and is found to possess a nearly ‘half chair’ conformation and shows less expansion of the angles and more rotation about the bonds. The existence of intramolecular C–H?O improper, blue-shifted hydrogen bond was investigated by means of the NBO analysis. The lowering of carbonyl stretching vibration can be attributed to the mesomeric effect and the π-orbital conjugation induced by the unsaturation in the α-carbon atoms and co-planarity of the (–CHC–(CO)–CCH–) group.  相似文献   
869.
The health care sector is one of the fastest growing sectors in the United States. Researchers are interested in conducting studies in the area of health economics in order to propose solutions to curb the rapid increase in health care spending and to improve the efficiency of the health care system in the United States. Specifically, hospital efficiency is one important research area in health economics. In this paper, data envelopment analysis (DEA) is used to assess hospital efficiency. An additive super-efficiency model is presented and applied to a sample of general acute care hospitals in Pennsylvania. In addition to the conventional choice of input and output variables, we include the survival rate as a quality measure of health outcome in the set of output variables. Thus our model takes both the quantity and the quality of the output into account. With the results obtained from our proposed DEA model, inefficiencies can be identified for hospitals to address without sacrificing the quality of care.  相似文献   
870.
Minimizing coupling between coil elements is technically challenging in designing large-sized, volume-type phased-array coils for human head imaging at ultrahigh fields, e.g., 7 T. As a widely used decoupling method, the capacitive decoupling method has shown excellent performance for loop array. However, building a multi-channel loop array with capacitive decoupling method is laborious that tuning frequency and matching of one coil element will affect adjacent elements and even next adjacent elements. In this study, we made an 8-channel loop-array transmit/receive radio-frequency coil on a 7 T magnetic resonance imaging system with the guidance of frequency domain three-dimensional electromagnetic and radio-frequency circuit co-simulation. The position of decoupling capacitors was investigated and values of all capacitors were predicted from co-simulation. The co-simulation approach cost about 2 days and the error of the predicted and practical capacitance was <5 %. To demonstrate the accuracy of simulation, we evaluated the simulated and measured S-parameter matrixes and B 1 + profiles in a birdcage-like excitation mode on a cylindrical water phantom. In addition, B 1 + maps and images of human head were shown with the fabricated coil. To demonstrate the parallel imaging performance of this coil array, GRE images using GRAPPA acceleration with the reduction factor R of 1, 2, 3, and 4 were acquired.  相似文献   
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