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11.
Maria Pihl Krzysztof Kolman Antiope Lotsari Marie Ivarsson Erich Schüster Niklas Lorén 《Journal of Dispersion Science and Technology》2019,40(4):555-562
Development of multi-purpose probes for mass transport measurements is of importance to gain knowledge in diffusional behaviour in heterogeneous structures such as food, hygiene or pharamceuticals. By combining different techniques, such as Fluorescence Recovery After Photobleaching (FRAP) and Nuclear Magnetic Resonance Diffusometry (NMR-d), information of both local and global diffusion can be collected and used to gain insights on for example material heterogeneities and probe-material interactions. To obtain a FRAP-responsive probe, fluorescent silica particles were produced using fluorescent preconjugates added in a modified Stöber process. A NMR-d responsive moiety was introduced by derivatizing the fluorescent silica particles with polyethylene glycol. The particle size distributions were determined by dynamic light scattering and transmission electron microscopy and these measurements were compared to value extrapolated from diffusion measurements using FRAP and NMR-d. The good agreement between the FRAP and NMR-d measurements demonstrates the potential of multi-purpose probes for future applications concerning mass transport at local and global scale simultaneously. 相似文献
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Maus M De R Lor M Weil T Mitra S Wiesler UM Herrmann A Hofkens J Vosch T Müllen K De Schryver FC 《Journal of the American Chemical Society》2001,123(31):7668-7676
Intramolecular F?rster-type excitation energy transfer (FRET) processes in a series of first-generation polyphenylene dendrimers substituted with spatially well-separated peryleneimide chromophores and a terryleneimide energy-trapping chromophore at the rim were investigated by steady-state and time-resolved fluorescence spectroscopy. Energy-hopping processes among the peryleneimide chromophores are revealed by anisotropy decay times of 50--80 ps consistent with a FRET rate constant of k(hopp) = 4.6 ns(-1). If a terryleneimide chromophore is present at the rim of the dendrimer together with three peryleneimide chromophores, more than 95% of the energy harvested by the peryleneimide chromophores is transferred and trapped in the terryleneimide. The two decay times (tau(1) = 52 ps and tau(2) = 175 ps) found for the peryleneimide emission band are recovered as rise times at the terryleneimide emission band proving that the energy trapping of peryleneimide excitation energy by the terryleneimide acceptor occurs via two different, efficient pathways. Molecular- modeling-based structures tentatively indicate that the rotation of the terryleneimide acceptor group can lead to a much smaller distance to a single donor chromophore, which could explain the occurrence of two energy-trapping rate constants. All energy-transfer processes are quantitatively describable with F?rster energy transfer theory, and the influence of the dipole orientation factor in the F?rster equation is discussed. 相似文献
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Chemoselective,Substrate‐directed Fluorination of Functionalized Cyclopentane β‐Amino Acids
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Dr. Loránd Kiss Dr. Melinda Nonn Prof. Reijo Sillanpää Prof. Matti Haukka Prof. Santos Fustero Prof. Ferenc Fülöp 《化学:亚洲杂志》2016,11(23):3376-3381
This work describes a substrate‐directed fluorination of some highly functionalized cyclopentane derivatives. The cyclic products incorporating CH2F or CHF2 moieties in their structure have been synthesized from diexo‐ or diendo‐norbornene β‐amino acids following a stereocontrolled strategy. The synthetic study was based on an oxidative transformation of the ring carbon–carbon double bond of the norbornene β‐amino acids, followed by transformation of the resulted ?all cis“ and ?trans“ diformyl intermediates by fluorination with ?chemodifferentiation“. 相似文献
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Eliasson C Lorén A Engelbrektsson J Josefson M Abrahamsson J Abrahamsson K 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(4):755-760
This paper is aimed to show the possibility to determine individual organic compounds introduced into single living cells with surface-enhanced Raman spectroscopy (SERS). Surface enhancement was achieved with gold colloids that were allowed to diffuse into lymphocytes. An introduced analyte, rhodamine 6G, could be imaged together with for example nucleotides and amino acids of the cell. Multivariate evaluation of surface-enhanced Raman images proved to be a powerful tool for the separation of spectral information of various intracellular components. The principal component analysis (PCA) enabled identification of spectra containing different chemical information and separation of the spectral contribution of rhodamine 6G from the complex cellular matrix. 相似文献
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Constanza Ruiz Prof. Dr. Ángeles Monge Prof. Dr. Enrique Gutiérrez‐Puebla Prof. Dr. Ibon Alkorta Prof. Dr. José Elguero Prof. Juan T. López Navarrete Dr. M. Carmen Ruiz Delgado Dr. Berta Gómez‐Lor 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(30):10651-10660
We present a joint theoretical and experimental study of a series of cyclic indole tetramers aimed at understanding the fundamental electronic properties of this 3D platform and evaluating its potential in the construction of new semiconductors. To this end, we combined absorption and Raman spectroscopy, cyclic voltammetry, and spectroelectrochemistry with DFT calculations. Our results suggest that this platform can be easily and reversibly oxidized. Additionally, it has a HOMO that matches very well with the workfunction of gold, therefore charge injection from a gold electrode is expected to occur without significant barriers. Interestingly, the cyclic tetraindoles allow for good electron delocalization in spite of their saddle‐shaped structures. The steric constraints introduced by N‐substitution significantly inhibits ring inversion of the central cyclooctatetraene unit, whereas it only barely affects the optical and electrochemical properties (a slightly higher oxidation potential and a blueshifted absorption upon alkylation are observed). 相似文献
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Eliasson C Lorén A Murty KV Josefson M Käll M Abrahamsson J Abrahamsson K 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2001,57(9):1907-1915
Multivariate evaluation of surface-enhanced Raman spectra of doxorubicin in plasma was performed. In a principal component analysis (PCA) all spectral features were modelled into three principal components. The major variation of the data was shown to be the variation of doxorubicin Raman signal together with the doxorubicin fluorescence, whereas the variation due to plasma was of minor importance. It was also shown that the surface-enhanced Raman scattering (SERS) measurements were independent on such factors as measurement occasion and silver colloids. The presented results show that with some improvements, quantification of doxorubicin directly in plasma could be possible. 相似文献
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The synthesis of three-dimensional cyclopentane amino acid derivatives with multiple stereocenters and with high regiochemical and diastereochemical diversity has been achieved starting from cyclopentadiene-derived β-aminocyclopentenecarboxylic acid. The small-molecular design was based on stereo- and regiocontrolled functionalization of the starting cyclopentene β-amino acid through stereoselective oxirane formation/regioselective oxirane opening and resulted in regio- and diastereoisomers of novel orthogonally protected aminocyclopentanecarboxylates. 相似文献
20.
Kiss L Mangelinckx S Sillanpää R Fülöp F De Kimpe N 《The Journal of organic chemistry》2007,72(19):7199-7206
Mannich-type addition of benzophenone imine glycinates across newly synthesized N-(p-toluenesulfonyl) alpha-chloroaldimines afforded gamma-chloro-alpha,beta-diamino ester derivatives with moderate diastereoselectivity as separable mixtures of anti and syn diastereomers. The gamma-chloro-alpha,beta-diamino esters were efficiently cyclized under basic conditions to the corresponding beta,gamma-aziridino alpha-amino ester derivatives, representing a new class of conformationally constrained heterocyclic alpha,beta-diamino acid derivatives. The relative configuration of the aziridines was determined via X-ray diffraction analysis. Mechanisms and intermediate transition states to explain the stereochemical outcome of the Mannich reaction with different substrates or under different conditions are proposed. The synthetic importance of the beta,gamma-aziridino alpha-amino ester derivatives is demonstrated by their conversion into the corresponding Boc-protected derivatives and ring opening reactions to alpha,beta-diamino esters and a gamma-amino alpha,beta-unsaturated amino ester. 相似文献