Porphyrin matrices

Chen, Y. T., and Ling, Y. C. (2002). Detection of water-soluble vitamins by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry using porphyrin matrices. J. Mass Spectrom. 37 716-730. 

Complexes III and IV have Fe-porphyrin prosthetic groups (hemes), complex IV also contains copper atoms which are involved in electron transport. Complexes I, III, and IV use the energy of electron transport to pump protons out of the matrix so as to maintain a pH gradient and an electrical potential difference across the inner membrane required for ATP synthesis (see below and Appendix 3). It is important to remember that all dehydrogenations of metabolic substrates remove two protons as well as two electrons and that a corresponding number of protons are consumed in the final reduction of dioxygen (Figures 5, 6). 

The processes that govern the formation of ash particles are complex and only partially understood (Figure 7.12). The mineral matter in pulverized coal is distributed in various forms some is essentially carbon-free and is designated as extraneous some occurs as mineral inclusions, typically 2-5 pm in size, dispersed in the coal matrix and some is atomically dispersed in the coal either as cations on carboxylic acid side chains or in porphyrin-type stmctures. The behavior of the mineral matter during combustion depends strongly on the chemical and physical state of the mineral inclusions. 

ORR catalysis by Fe or Co porphyrins in Nation [Shi and Anson, 1990 Anson et al., 1985 Buttry and Anson, 1984], polyp5rrolidone [Wan et al., 1984], a surfactant [Shi et al., 1995] or lipid films [CoUman and Boulatov, 2002] on electrode surfaces has been studied. The major advantages of diluting a metalloporphyrin in an inert film include the abUity to study the catalytic properties of isolated molecules and the potentially higher surface loading of the catalyst without mass transport Umit-ations. StabUity of catalysts may also improve upon incorporating them into a polymer. However, this setup requires that the catalyst have a reasonable mobUity in the matrix, and/or that a mobile electron carrier be incorporated in the film [Andrieux and Saveant, 1992]. The latter limits the accessible electrochemical potentials to that of the electron carrier. 

Proniewicz LM, Paeng IR, Nakamoto K. 1991. Resonance raman spectra of two isomeric dioxygen adducts of iron(II) porphyrins and rr-cation radical and nonradical oxoferryl porphyrins produced in dioxygen matrixes Simultaneous observation of more than seven oxygen isotope sensitive bands J Am Chem Soc 113 3294. 

Tetra(o-aminophenyl)porphyrin, H-Co-Nl TPP, can for the purpose of electrochemical polymerization be simplistically viewed as four aniline molecules with a common porphyrin substituent, and one expects that their oxidation should form a "poly(aniline)" matrix with embedded porphyrin sites. The pattern of cyclic voltammetric oxidative ECP (1) of this functionalized metal complex is shown in Fig. 2A. The growing current-potential envelope represents accumulation of a polymer film that is electroactive and conducts electrons at the potentials needed to continuously oxidize fresh monomer that diffuses in from the bulk solution. If the film were not fully electroactive at this potential, since the film is a dense membrane barrier that prevents monomer from reaching the electrode, film growth would soon cease and the electrode would become passified. This was the case for the phenolically substituted porphyrin in Fig. 1. 

A similar catalytic activity with a monomeric porphyrin of iridium has been observed when adsorbed on a graphite electrode.381-383 It is believed that the active catalyst on the surface is a dimeric species formed by electrochemical oxidation at the beginning of the cathodic scan, since cofacial bisporphyrins of iridium are known to be efficient electrocatalysts for the tetraelectronic reduction of 02. In addition, some polymeric porphyrin coatings on electrode surfaces have been also reported to be active electroactive catalysts for H20 production, especially with adequately thick films or with a polypyrrole matrix.384-387... 

Heavy metal ions detection with porphyrin in sol-gel is possible, too56. The porphyrin, used for detection of heavy metal ions (Hg2+, Pb2+, Cd2+), was 5,10,15,20-tetra(4-N-methylpyridil)porphyrin (TMPyP) preferred to other porphyrins because it was not leaked out of the matrix. The study of metallation of the porphyrin immobilized in sol-gel emphasized the formation of 1 1 complex for each ion with a constant of complexation depending on the nature of the ions. The strongest effects were observed for mercury due to the specific interaction of this metal with the porphyrin. 

The two water-soluble porphyrins, 5,10,15,20-tetra(4-N-methyl-pyridiniumyl) porphyrin (H2TMPyP4+) and 5,10,15,20-tetra(4-sulfonato) porphyrin (H2TPPS4 ), were immobilized in the silica sol-gel matrix and served as the pH sensors as well65. The sol-gels doped with porphyrin were... 

Fig. lOa-c. Higher order splittings in symmetry planes Single crystal nitrogen ENDOR spectrum of Cu(TPP) diluted into (H20)Zn(TPP) with Bo normal to the porphyrin plane B0 = 327.7 mT. a) Observed spectrum. (Adapted from Ref. 66) b) Transition frequencies obtained by numerical diagonalization of the full spin Hamiltonian matrix (Four nitrogen nuclei). (Ref. 68) c) First order frequencies, (Eq. (3.10))... 

Frauenkron, M. Berkessel, A. Gross, J.H. Analysis of Ruthenium Carbonyl-Porphyrin Complexes a Comparison of Matrix-Assisted Laser Desorp-tion/Ionization Time-of-Flight, Fast-Atom Bombardment and Field Desorption Mass Spectrometry. Eur. Mass Spectrom. 1997, 5,427-438. 

The precursor model of FAB applies well to ionic analytes and samples that are easily converted to ionic species within the liquid matrix, e.g., by protonation or deprotonation or due to cationization. Those preformed ions would simply have to be desorbed into the gas phase (Fig. 9.6). The promoting effect of decreasing pH (added acid) on [M+H] ion yield of porphyrins and other analytes supports the precursor ion model. [55,56] The relative intensities of [Mh-H] ions in FAB spectra of aliphatic amine mixtures also do not depend on the partial pressure of the amines in the gas phase, but are sensitive on the acidity of the matrix. [57] Furthermore, incomplete desolvation of preformed ions nicely explains the observation of matrix (Ma) adducts such as [M+Ma+H] ions. The precursor model bears some similarities to ion evaporation in field desorption (Chap. 8.5.1). 

Musselman, B. Watson, J.T. Chang, C.K. Direct Evidence for Preformed Ions of Porphyrins in die Solvent Matrix for FAB-MS. Org. Mass Spectrom. 1986, 27, 215-219. 

Jones, R.M. Lamb, J.H. Lim, C.K. Urinary Porphyrin Profiles by Laser Desorp-tion/Ionization-TOF-MS Without the Use of Classical Matrixes. Rapid Commun. Mass Spectrom. 1995, 9, 921-923. 

In symmetrical porphyrins NH-tautomers do not distinguish in structure and have identical electronic spectra. Correspondingly, in most cases the spectral separation between the individual tautomers (a E) does not exceed 100 cm l and is due to crystalline matrix effect (6,7). Therefore, NH-tautomerism can be effectively detected at 77 K and 4.2 K in the Shpol skii matrix only at selective monochromatic excitation (5-7). In chlorins, the... 

Protein-Conformation Effects on the Metal-Protein Linkage. Since we have been unable to find model Ni-porphyrin complexes whose Raman frequencies come close to those of the Ni-reconstituted proteins, it is clear that the protein matrix has an impressive effect on axial ligation. We might also ask what is the effect of changes in protein conformation on axial ligation. 

General. NMR spectra were obtained on a Bruker WM-250 instrument with tetramethylsilane (TMS) as internal standard. UV-visible spectra were taken on a Varian Cary 219. Fast-atom bombardment (FAB) mass spectrometry (MS) analysis were completed on a Vacuum Generators ZAB-2F double-focusing or a Varian MAT CH5 mass spectrometer equipped with an Ion Tech FAB Gun. Solvents for FAB matrix were made up of thioglycerol, dithiothreitol, and dithioerythretol (2 1 1) addition of 0.1M trifluoroacetic acid to the matrix facilitated the ionization of the porphyrins during FAB analysis.(13)... 

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