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41.
    
The design of photoswitchable transition metal complexes with tailored properties is one of the most important challenges in chemistry. Studies explaining the underlying mechanisms are, however, scarce. Herein, the early relaxation dynamics towards NO photoisomerization in trans-[RuCl(NO)(py)4]2+ is elucidated by means of non-adiabatic dynamics, which provided time-resolved information and branching ratios. Three deactivation mechanisms (I, II, III) in the ratio 3:2:4 were identified. Pathways I and III involve ultrafast intersystem crossing and internal conversion, whereas pathway II involves only internal conversion.  相似文献   
42.
    
As part of our ongoing study of the toxicity of compounds derived from 1,1-bis(4-hydroxyphenyl)-2-ferrocenylbut-1-ene, we have recently shown that closely analogous [3]ferrocenophane complexes have an in vitro toxicity level substantially higher than that of their ferrocene counterparts, particularly in the case of mono- and diphenol complexes. In this study we have examined whether the presence of a dimethylamino chain, analogous to the chain in hydroxytamoxifen, is capable of producing in the ferrocenophane series the same antiestrogenic effect observed for OH-Tam and Fc-OH-Tam. To this end, we have synthesized and characterized new complexes bearing various side-chains [O(CH2)3NMe2, O(CH2)3piperidine, O(CH2)3pyrrolidine, NHCO(CH2)2NMe2] and studied the biochemical properties of those complexes possessing appropriate solubility. The results revealed that the new complexes of [3]ferrocenophane have very strong antiproliferative effects; one of the compounds bearing an NHCO(CH2)2NMe2 chain has an IC50 value of 0.05 ± 0.02 µm for MDA-MB-231 breast cancer cells. All the complexes showed affinity for the estradiol receptor. At the low (nanomolar range) concentrations at which the estrogenic/antiestrogenic effect is expressed in these molecules, the presence of an amino-substituted side-chain does not induce in the [3]ferrocenophane series the antiestrogenic effect observed with OH-Tam and Fc-OH-Tam. However, this effect has been found for the complex with a slightly longer chain [O(CH2)4NMe2].  相似文献   
43.
  总被引:1,自引:0,他引:1  
Since GHB (gamma-hydroxybutyric acid) is naturally produced in the human body, clinical and forensic toxicologists must be able to discriminate between endogenous levels and a concentration resulting from exposure. To suggest an alternative to the use of interpretative concentration cut-offs, the detection of exogenous GHB in urine specimens was investigated by means of gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). GHB was isolated from urinary matrix by successive purification on Oasis MCX and Bond Elute SAX solid-phase extraction (SPE) cartridges prior to high-performance liquid chromatography (HPLC) fractioning using an Atlantis dC18 column eluted with a mixture of formic acid and methanol. Subsequent intramolecular esterification of GHB leading to the formation of gamma-butyrolactone (GBL) was carried out to avoid introduction of additional carbon atoms for carbon isotopic ratio analysis. A precision of 0.3 per thousand was determined using this IRMS method for samples at GHB concentrations of 10 mg/L. The (13)C/(12)C ratios of GHB in samples of subjects exposed to the drug ranged from -32.1 to -42.1 per thousand, whereas the results obtained for samples containing GHB of endogenous origin at concentration levels less than 10 mg/L were in the range -23.5 to -27.0 per thousand. Therefore, these preliminary results show that a possible discrimination between endogenous and exogenous GHB can be made using carbon isotopic ratio analyses.  相似文献   
44.
    
Relative stabilities of methanolic solutions of dyes that are potentially important for labeling of biological macromolecules with a visible‐red or near‐infrared fluorophore were evaluated in the presence of molecular oxygen under dark and light conditions.  相似文献   
45.
    
Three methods were used to synthesize a series of the title compounds. The ketones absorb in the visible region, and upon protonation (pH<6) they are converted to hydroxy‐substituted heptamethine cyanines that show an intense absorption in the near‐infrared region (>700 nm). The conversion is reversible and depends solely on pH conditions.  相似文献   
46.
    
Immediate‐release solid dispersions of a slowly dissolving active pharmaceutical ingredient, spironolactone, were prepared by supercritical‐CO2‐assisted melt extrusion (a solvent‐free and continuous manufacturing technology) using Eudragit E as matrix. Through optimizing process parameters (i.e. temperature, melt throughput, pressure and CO2 flow), stable foams with high porosity, homogeneous structure and thin (even submicronic) walls could be prepared, as revealed by scanning electron microscopy. The samples were found to be rigid enough to mill, enabling further processing, as is necessary to formulate tablets. The influence of extrusion temperature and melt throughput on residual drug crystallinity was measured using non‐invasive confocal Raman mapping coupled with chemometric analysis, while the influence on the degree of drug degradation was determined using high performance liquid chromatography. The plasticizing effect of supercritical CO2 was shown to reasonably improve the purity of the prepared solid dispersions by enabling high‐yield production at lower temperature ranges. At the same time, shorter residence time and lower temperature slightly increased residual drug crystallinity. The obtained foamy structures ensured immediate drug dissolution in an acidic medium. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   
47.
The electrochemical oxidation of hexa-N-pyrrolylbenzene in organic media leads, via intramolecular coupling of the pyrrole residues, to the deposition of a molecular semiconductor film on an electrode surface. In situ electron spin resonance–electrochemical experiments reveal that the semiconductor is endowed with both properties of conducting polymers (i.e., reversible oxidation) and polyaromatic molecular materials (i.e., highly paramagnetic). The material, which is easy to process as soft homogeneous thin film, shows a tunable 0 to 1 spin concentration per molecule at room temperature by controlling the electrochemical potential. Contribution to the Fall Meeting of the European Materials Research Society, Symposium D: 9th International Symposium on the Electrochemical–Chemical Reactivity of Metastable Materials, Warsaw, 17th–21st September, 2007. An erratum to this article can be found at  相似文献   
48.
    
Ligand‐based 19F NMR screening represents an efficient approach for performing binding assays. The high sensitivity of the methodology to receptor binding allows the detection of weak affinity ligands. The observable NMR parameters that are typically used are the 19F transverse relaxation rate and isotropic chemical shift. However, there are few cases where the 19F longitudinal relaxation rate should also be used. A theoretical and experimental analysis of the 19F NMR transverse and longitudinal relaxation rates at different magnetic fields is presented along with proposed methods for improving the sensitivity and dynamic range of these experiments applied to fragment‐based screening. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   
49.
Mari JM  Cachard C 《Ultrasonics》2011,51(5):632-638
The acoustical behaviour of straight micro tools (SMT), such as sub-millimetre needles or electrodes, is delicate and their automated maintaining in the image plane displayed to the practitioner must handle the extremely varying signal they backscatter. Because of the complex nature of the scattering by a narrow rod target, the localization process has to face two main tasks before being able to conduct 3D location: the reduction of the apparent diameter when this latter is visible, and the detection of the instrument and its real depth of penetration. In this paper, a methodology based on these steps is proposed, along with preliminary implementations of each of the steps. This methodology exploit the acoustic duality of those SMT and treat different acoustic aspects separately: first the apparent diameter is reduced through a deconvolution process, associating the backscattering to a purely linear acoustic process without attenuation; second, the imaging is treated as a pure attenuation process, and the signal is summed post-ROI to achieve the detection. Finally, the complete localisation is achieved by combining the two first steps with a previously tested global 3D straight line location technique: the Parallel Integral Projection. Experiments are conducted in vitro with 700 μm graphite rods and 150 μm in diameter tungsten electrode crossing gelatine and cryogel phantoms, and ex vivo on a porcine liver to assess the efficiency of the proposed implementations and of the whole methodology. The volumes were acquired with a Kretztechnic 530D scanner customized so as to provide the raw RF data. Results show that the combination of the different step-methods reduces progressively the apparent diameter, and that the detection step is essential to the proper localization of the micro tool. The final resolution improvement is at least of 3 and estimated to be typically of 12, for a final estimated apparent diameter reaching the average 400 μm resolution cell in the porcine liver.  相似文献   
50.
We demonstrated that Yb:YAG single crystal fibers have a strong potential for the amplification of femtosecond pulses. Seeded by 230?fs pulses with an average power of 400?mW at 30?MHz delivered by a passively mode-locked Yb:KYW oscillator, the system produced 330?fs pulses with an average power of 12?W. This is the shortest pulse duration ever produced by an Yb:YAG amplifier. The gain in the single crystal fiber reached a value as high as 30 in a simple double-pass configuration.  相似文献   
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