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51.
van Breemen AJ Herwig PT Chlon CH Sweelssen J Schoo HF Setayesh S Hardeman WM Martin CA de Leeuw DM Valeton JJ Bastiaansen CW Broer DJ Popa-Merticaru AR Meskers SC 《Journal of the American Chemical Society》2006,128(7):2336-2345
Butyl, hexyl, and decyl derivatives of the liquid-crystalline organic semiconductor 5,5' '-bis(5-alkyl-2-thienylethynyl)-2,2':5',2' '-terthiophene were synthesized and studied with respect to their structural, optical, and electrical properties. By means of an optimized thermal annealing scheme the hexyl and decyl compounds could be processed into self-assembled monodomain films of up to 150 mm in diameter. These were investigated with X-ray diffractometry, which revealed a clearly single-crystalline monoclinic morphology with lamellae parallel to the substrate. Within the lamellae the molecules were found to arrange with a tilt of about 50 degrees with the rubbing direction of the polyimide alignment layer. The resulting, close side-to-side packing was confirmed by measurements of the UV/vis absorption, which showed a dichroic ratio of 19 and indicated H-aggregation. AFM analyses revealed self-affinity in the surface roughness of the monodomain. The compounds showed bipolar charge transport in TOF measurements, with hole mobilities reaching up to 0.02 cm(2)/Vs and maximum electron mobilities around 0.002 cm(2)/Vs. The hexyl derivative was processed into large-area monodomain top-gate field-effect transistors, which were stable for months and showed anisotropic hole mobilities of up to 0.02 cm(2)/Vs. Compared to multidomain bottom-gate transistors the monodomain formation allowed for a mobility increase by 1 order of magnitude. 相似文献
52.
A new CE detection method was developed for the chiral drug bupropion (a second-generation antidepressant), based on phosphorescence both in the direct and in the sensitized mode using pulsed laser excitation at 266 nm. Electrokinetic chromatography using 5 mM sulfated-α-CD as chiral selector in 25 mM phosphate buffer at pH 3 allowed the separation of bupropion enantiomers with a high chiral resolution (Rs>3). In the sensitized phosphorescence detection mode, excitation energy is transferred from the analyte to an acceptor (1-bromo-4-napthhalenesulfonic acid or biacetyl) followed by time-resolved phosphorescence detection under deoxygenated buffer conditions. Using 2 × 10(-4) M biacetyl as the acceptor an LOD of 2 × 10(-7) M was obtained for each enantiomer, about 40 times better than in the direct mode. Under these separation conditions, no significantly different phosphorescence lifetimes (measured on-line) were obtained for the two bupropion enantiomers. The suitability of the method was demonstrated with the quantification of bupropion in a pharmaceutical formulation and its determination in a spiked urine sample. 相似文献
53.
Four types of working electrodes are compared with respect to sensitivity, resolution, peak width and suitability for copper speciation studies by differential-pulse anodic stripping voltammetry. The hanging mercury drop electrode, two rotating mercury film electrodes with in-situ and pre-formed films and a stationary mercury film electrode with a vibrationally induced jet-stream are examined. The last electrode appears to be the most useful system with the highest sensitivity. Conditions for mercury film formation must be optimized for each individual electrochemical system in order to avoid erroneous conclusions from standard addition procedures and apparent complexation capacity measurements. 相似文献
54.
Experimental requirements for room-temperature phosphorescence measurements in liquids (RTPL) are discussed. Phosphorescence quantum yields and triplet lifetimes of some brominated naphthalenes and halogenated biphenyls at 77 K in 2-methyltetrahydrofuran and at room temperature in hexane are reported and compared. Surprisingly the naphthalenes show only little loss in quantum yields in going from 77 K to room temperature. Sensitized phosphorescence is discussed as a means of expanding the analytical potential of RTPL. Results with a model system of benzophenone as a donor (analyte) and 1,4-dibromonaphthalene as an acceptor are presented. 相似文献
55.
Dijkstra RJ Slooten CJ Stortelder A Buijs JB Ariese F Brinkman UA Gooijer C 《Journal of chromatography. A》2001,918(1):25-36
The on-line coupling of liquid chromatography (LC) and Raman spectroscopy (RS) via an entirely plastic liquid-core waveguide (LCW) was optimized in terms of excitation wavelength of the laser, especially in relation to the fluorescence background, and the length of the LCW. Excitation at 632.8 nm (He-Ne laser) was found to be a good compromise between a wavelength long enough to strongly reduce the fluorescence background and, on the other hand, short enough to avoid (re)-absorption of laser light and Raman signals by H2O in LCWs of considerable length. This conclusion is supported by a theoretical discussion on the optimization of LCW lengths as function of the excitation wavelength for H2O and 2H2O. When using the He-Ne laser the optimum length is approximately 50 cm for H2O; this corresponds to a detection cell volume of 19 microl for an LCW of 220 microm I.D., which is fully compatible with conventional-size LC. The influence of an organic modifier, usually necessary for reversed-phase LC, on the free spectral window was evaluated. The potential applicability of LC-LCW-RS was shown for a mixture of adenosine 5'-monophosphate (AMP), guanosine 5'-monophosphate (GMP) and uridine 5'-monophosphate (UMP), utilizing an aqueous eluent without the addition of a modifier. Improved detectability was achieved by using the stopped-flow mode and applying a large-volume-injection procedure (injection volume: 200 microl). Under these conditions, the limit of identification for AMP, GMP and UMP was in the 0.1-0.5-mg/ml range. 相似文献
56.
G. W. Somsen L. P. P. van Stee C. Gooijer U. A. Th. Brinkman N. H. Velthrost
T. Visser
《Analytica chimica acta》1994,290(3):269-276Liquid chromatography (LC) was coupled semi on-line to Fourier transform infrared spectrometry (FT-IR) using a spray-jet assembly interface to eliminate the LC eluent prior to IR detection. The usefulness of the LC-FT-IR system in the identification of closely related compounds in complex mixtures is demonstrated by the analysis of a chlorinated pyrene sample which contains a number of chloropyrene isomers and congeners. Characteristic FT-IR transmission spectra of all constituents could be recorded. Since most of these compounds have not been analysed by IR before, spectral assignment was mainly based on the empirical Hansen—Berg rules for substituted pyrenes. The identification limits for the chloropyrenes typically were 5–10 ng injected. 相似文献
57.
Several analytes, such as bromide, iodide, sulphite, nitrite, substituted anilines and organosulphur compounds cause quenching of peroxyoxalate chemiluminescence. This phenomenon, quenched peroxyoxalate chemiluminescence, can be used as a method of detection for liquid chromatography. The potential of quenched chemiluminescence is discussed, with special attention give to its compatibility with aqueous separation systems. An immobilized fluorophore, 3-aminofluoranthene on controlled pore glass, is packed in the detector cell. Liquid-state studies show that the influence of both the nature and concentration of the fluorophore is small, which indicates a more complicated mechanism of the chemiluminescence reaction than previously assumed. It is shown that bis(2-nitrophenyl)oxalat is a more suitable oxalate for quenched chemiluminescence detection than bis(2,4,6-trichlorophenyl) oxalate. This is demostrated for ion-chromatography of bromide and iodide and the aqueous reversed-phase separation of organosulphur compounds. Detection limits in the low nanogram and sub-nanogram region are reported for the above compounds. When an electronic inverter was used, calibration curves were linear over a concentration range of 2–3 decades. The method is quite selective and can be applied to relatively complex matrices without sample pretreatment. 相似文献
58.
A homogeneous continuous-flow assay using fluorescence resonance energy transfer (FRET) for detection was developed to measure the hydrolysis of HIV Protease Substrate 1 (to which two choromophores, EDANS and DABCYL are covalently attached) by a protease (e.g. Subtilisin Carlsberg) and the influence of inhibitors. In the continuous-flow assay, an inhibitor solution and an enzyme solution were first eluted into the system and allowed to react with each other in a reaction coil. Subsequently, the substrate solution was added to an enzyme-inhibitor mixture in a second reaction coil and incubated for 1 min. Finally, the fluorescence intensity was monitored.The system was also utilized to measure the inhibition of the protease by two weak acidity inhibitors which are 4-(2-aminoethyl)benzenesulfonyl fluoride hydrochloride (AEBSF) and ethylenediaminetetraacetic acid (EDTA). Using the obtained optimum conditions for AEBSF, a detection limit of 0.3 mmol/l was achieved and the relative standard deviation was below 3.7% in the 2.5-7.5 mmol/l range. For EDTA, which required a 20 times higher substrate concentration than AEBSF, a detection limit of 0.2 mmol/l was obtained and the relative standard deviation was below 9.6% in the 0.5-7.5 mmol/l range.The optimization of pH, substrate concentration, enzyme concentration, reaction time and temperature are described. Organic modifier effects were also investigated. Methanol, acetonitrile and DMSO could be tolerated up to 30%. 相似文献
59.
Application of an integrated optics (IO) microcavity (MC) for evanescent excitation of two-photon excited fluorescence (TPF) is demonstrated. The MC provides a high local intensity, which is required for the TPF, because of resonant enhancement of the intracavity power and a strong two-dimensional confinement of the guided mode. Numerical estimations show a large increase, by more than a factor of 104 of the TPF intensity at the MC compared to a conventional straight waveguide. This will lead to a significant improvement of the detection limits of UV-absorbing chromophores (down to 10−8 M) when using the MC as a biosensor. Feasibility of TPF excitation using an IO MC is confirmed experimentally for the first time. 相似文献