Complete absorption spectra, free from interference due to an unbound acceptor and donor, of several charge-transfer complexes have been examined. These spectra serve as a significant test to the applicability of the Mulliken two-state model for this series of complexes. the appearance of multiple new absorption bands and the trend in the observed oscillator strength of the CT transitions and the localized excitation within the complex spectrum require significant expansions of Mulliken's simple two-state model. Multiple new CT absorption bands are frequently encountered and their appearance has been explained in terms of multiple ion-pair states participating in CT interactions. the relative positions of these bands are predicted based on the gas-phase ionization potentials of the donors and the electron affinity of the acceptor in excellent agreement with the observed spectra achieved. the integrated absorption intensities of the localized bands within each CT complex spectrum have been measured and used as an indicator of the extent on intensity borrowing by the CT transition. These measurements show that for the better donors used in this study, i.e. hexamethylbenzene and pentamethylbenzene, intensity borrowing is not significant. However, for the poorer donors used, an increasing contribution of the LE within the CT absorption bands is observed. a multi-state model, which includes the localized excited state of the acceptors well as additional ion-pair states, is the minimum required to describe these complexes. 相似文献
It's not easy being green : Real‐time visualization of labeled ribosomes and de novo synthesized green fluorescent protein molecules using single‐molecule‐sensitive fluorescence microscopy demonstrates that the mutant GFPem is produced with a characteristic time of five minutes. Fluorescence of the fastest GFP molecules appears within one minute (see picture).
A rapid immunoassay for sensitive detection of microcystin-LR using a portable chemiluminescence multichannel immunosensor (CL-MADAG) was developed. The sensor device is based on a capillary ELISA technique in combination with a miniaturized fluidics system and uses chemiluminescence as the detection principle. Minimum concentrations of at least 0.2 μg L−1 microcystin-LR could be unambiguously measured in a spiked buffer system as well as in spiked real water samples. A single sample analysis for detection of microcystin-LR could be accomplished in just 13 min on the CL-MADAG. Besides providing a highly reproducible, fast and easy to perform test format, one major advantage of the newly established capillary immunoassay is represented by the feasibility of an internal retrospective quality control mechanism. Finally, simultaneous CL-MADAG measurements employing our inhibition immunoassay and a sandwich ELISA could be successfully demonstrated. 相似文献
Abstract— The evaluation of the equilibrium constants for charge-transfer complex formation has been of interest for five decades. During this time, absorption spectroscopy using Benesi-Hildebrand, or related methods, has been used to obtain the equilibrium constants. These methods require relatively high concentrations of donor or acceptor to be present in solution when weakly bound complexes are studied, conditions that lead to the formation of higher order complexes and inconsistent determinations of these constants. A new method is presented that allows weakly bound charge-transfer complexes to be studied under low concentration conditions and the equilibrium constants to be determined accurately for the first time. Using this method, the equilibrium constant for the formation of 1, 2, 4, 5-tetracyanobenzene/pentamethylbenzene charge-transfer complex was found to be K CT= 6.8 ± 0.3 M −1 with an extinction coefficient at 400 nm of εCT= 150 ± 30cm−1M−1. 相似文献
Liquid chromatography negative ion electrospray ionisation tandem mass spectrometry has been used for characterisation of naturally occurring prenylated fungal metabolites and synthetic derivatives. The fragmentation studies allow an elucidation of the decomposition pathways for these compounds. It could be shown, that the prenyl side chain is degraded by successive radical losses of C5 units. Both the benzoquinones and the phenolic derivatives display significant key ions comprising the aromatic ring. In some cases, the formation of significant oxygen-free key ions could be evidenced by high-resolution MS/MS measurements. Furthermore, the different types of basic skeletons, benzoquinones and phenol type as well as cyclic prenylated compounds, can be differentiated by their MS/MS behaviour.
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Fruiting bodies of Suillus bovinus, the structure of boviquinone-4 and its negative ion MS2 spectrum 相似文献
We report on the incoherent beam combination of the four narrow-linewidth fiber amplifier chains running at different wavelengths. Each main amplifier stage consists of a large-mode-area photonic crystal fiber delivering more than 2 kW of optical power. The four output beams are spectrally combined to a single beam with an output power of 8.2 kW using a polarization-independent dielectric reflective diffraction grating mainly preserving the beam quality of the individual fiber amplifiers. 相似文献
In this work, composite microelectrodes from poly(3,4‐ethylenedioxythiophene) (PEDOT) and carbon nanotubes (CNT) are characterized as electrochemical sensing material for neurotransmitters. Dopamine can be detected using square wave voltammetry at these microelectrodes. The CNTs improve the sensitivity by a factor of two. In addition, the selectivity towards dopamine in the presence of ascorbic acid and uric acid was examined. While both electrodes, PEDOT and PEDOT‐CNT are able to detect all measured concentrations of dopamine in the presence of uric acid, small concentrations of dopamine and ascorbic acid are only distinguishable at PEDOT‐CNT electrodes. Changing the pH has a strong influence on the selectivity. Moreover, it is possible to detect concentrations as low as 1 µM dopamine in complex cell culture medium. Finally, other catecholamines like serotonin, epinephrine, norepinephrine and L ‐dopa are also electrochemically detectable at PEDOT‐CNT microelectrodes. 相似文献