0000000001306808
AUTHOR
Philip Heier
Atmospheric pressure plasma polymerisation of metalloporphyrins containing mesoporous membranes for gas sensing applications
Abstract Metalloporphyrins are embedded in an organosilicon matrix by an easily up-scalable atmospheric pressure dielectric barrier discharge method. The integrity of the metalloporphyrins, followed by UV–visible spectroscopy, is successfully preserved and their aggregation prevented. The single molecule properties, rather than the bulk ones, are thus enhanced. Exposure to triethylamine, which reaches the metalloporphyrins through the pores of the organosilicon membrane, led to a shift in the absorption spectrum and confirms the gas sensing potential of such coatings.
A new class of ZnIIand CrIIIporphyrins incorporated into porous polymer matrices via an atmospheric pressure plasma enhanced CVD to form gas sensing layers
Designed ZnII and CrIII porphyrins (ZnIIP, CrIIIP(Cl)(H2O)) and conventional ZnIITPP and CrIIITPP(Cl)(H2O) are immobilized into porous polysiloxane films via chemical vapor deposition enhanced by an atmospheric pressure dielectric barrier discharge. UV/vis spectroscopy and mass spectrometry prove the integrity of the chromophores after the plasma treatment. The optical amine sensing capabilities of the films are investigated spectroscopically on exposure to triethylamine vapors. A series of coatings with different porphyrin loadings indicate influences of the deposition conditions on the growth of the sensing films and hence the device performance. Additionally, the synthesis and characteri…
Plasma Polymer Membranes for Immobilising Metalloporphyrins
Atmospheric pressure dielectric barrier discharge formation of organosilicon thin films loaded with zinc 5,10,15,20-tetraphenylporphyrin (Zn(TPP)) was investigated for different deposition conditions. UV–visible spectroscopy and scanning electron microscopy revealed the effects of the metalloporpyhrins injection parameters and the plasma polymerisation conditions can affect the dispersion of the metalloporphyrins and the morphology of the coatings. The stability of the embedded Zn(TPP) molecules was investigated by orbitrap mass spectrometry.
αα- and αβ-Zinc-meso-A2B2-tetraarylporphyrins with large optical responses to triethylamine
Synthesis and separation of αα- and αβ-meso-A(2)B(2)-zinc(II) tetraarylporphyrin atropisomers with A = mesityl and B = ortho-phenylethynyl-phenyl are reported. Both isomers exhibit large optical responses upon axial NEt(3) coordination which are visible to the human eye and could therefore be beneficial for the design of smart amine sensing materials. The larger spectral changes as compared to Zn(TPP) are attributed to pronounced distortions of the porphyrin π-system due to steric interactions of the coordinating amine with the porphyrin periphery. This effect as well as the coordination site of NEt(3) at the αα-isomer have been studied by NMR experiments and were rationalized by DFT calcul…
Dual application of (aqua)(chlorido)(porphyrinato)chromium(III) as hypersensitive amine-triggered ON switch and for dioxygen activation.
Although synthesis and substitution reactions of chlorido chromium(III) porphyrins Cr(III)(TPP)(Cl)(L) (H2TPP = 5,10,15,20-tetraphenyl porphyrin, L = pyridine, H2O, ROH, etc.), have been well-established in coordination chemistry for decades, an unexpected dichotomous reactivity of Cr(III)(TPP)(Cl)(H2O) (1) toward amines is disclosed here. This reactivity leads to the application of 1 as highly sensitive substoichiometric and irreversible ON switch for amine detection by an autocatalytic pathway. The concomitant activation of O2 by the 1/amine system is furthermore exploited in an electrochemically driven epoxidation of norbonene using O2 as initial oxidant.
Optical sensing responses of CrIIICl(TPP)(H2O)-based coatings obtained by an atmospheric pressure plasma method – Application to the detection of volatile amines
Food spoilage processes are a considerable concern for both the food industry and the consumer, due to financial, food quality and food safety aspects. A primary issue is the prevention/monitoring of the formation of biogenic and volatile amines, such as occurring in fish and in other microbiologically unstable food items rich in proteins, produced by e.g. oxidative decarboxylation of amino acids. One strategy for their monitoring is the development of films with colorimetric sensing properties that are able to indicate food spoilage. The aim of this investigation was the development of a novel metalloporphyrin-based coating allowing the sensitive detection of typical volatile amines, such …
CCDC 895382: Experimental Crystal Structure Determination
Related Article: Philip Heier, Christoph Förster, Dieter Schollmeyer, Nicolas Boscher, Patrick Choquet, Katja Heinze|2013|Dalton Trans.|42|906|doi:10.1039/C2DT31943H
CCDC 895383: Experimental Crystal Structure Determination
Related Article: Philip Heier, Christoph Förster, Dieter Schollmeyer, Nicolas Boscher, Patrick Choquet, Katja Heinze|2013|Dalton Trans.|42|906|doi:10.1039/C2DT31943H