Investigation of Photoinduced Processes in Water-Soluble Cationic Ni-Porphyrin by the Resonance Raman Scattering Method

By the resonance Raman scattering spectroscopy (RRS) method, photoinduced processes involving cationic Ni-5,10,15,20-tetrakis(4-N-methylapyridiniumyl)porphyrin (Ni(TMpy-P4)) in a phosphate water buffer have been investigated. Excitation into different regions of the Soret band at wavelengths of 397, 423, 441.6, and 457.9 nm permitted separate investigation of the behavior of the 4- and 6-coordinated forms of Ni(TMpy-P4). It has been found that Ni(TMpy-P4) is characterized by two photoinduced processes: the deactivation of initially 4-coordinated Ni(TMpy-P4) is followed by the addition to it, as axial ligands, of two water molecules from the environment to form a nonequilibrium 6-coordinated form Ni(TMpy-P4)(H₂O)₂ in the ground state, whereas in the process of deactivation of the excited 6-coordinated complex there occurs a dissociation of the axial water ligands to form a nonequilibrium 4-coordinated complex Ni(TMpy-P4) in the ground state. Some of the 4-coordinated molecules of Ni(TMpy-P4) are deactivated through the excited B _1g ^*-state without undergoing extracoordination. Quantitative analysis of the RRS spectra using the global fitting method has shown that in the course of deactivation 33% of photoexcited 6-coordinated molecules of Ni(TMpy-P4)(H₂O)₂ retain their axial ligands, relaxing through the dark long-lived intermediate state of the 6-coordinated form.     

Inhibition and Promotion of the Oxidation Processes of Water-Soluble Cationic Co(II)-Porphyrin Under Its Interaction with Nucleic Acids

Using the methods of absorption spectroscopy and resonance Raman scattering, we have made a comparative study of water-soluble cationic Co(II)- and Co(III)-5,10,15,20-tetrakis(4-N-methyl-pyridiniumyl)porphyrins(Co^II(TMpy-P4) and Co^III(TMpy-P4) with DNA and synthetic single- and double-stranded polynucleotides. It has been found that Co^II(TMpy-P4), which in aqueous solutions containing no nucleic acids is readily oxidized to Co^III(TMpy-P4) by the molecular oxygen dissolved there, markedly changes its oxidation ability when bound to nucleic acid. Under interaction with guanine-containing polynucleotides, the rate of change in the oxidation state of cobalt from Co(II) to Co(III) increases as compared to such for the solution of porphyrin in a buffer. But in complexes with DNA and adenine- and thymine-containing polynucleotides, CoII(TMpy-P4), on the contrary, becomes stable. The observed effects of inhibition/promotion of Co^II(TMpy-P4) oxidation when it is bound to nucleic acids are assumed to be due to the weakening/strengthening of the electron-donor properties of the extraligand on cobalt, which leads to a change in cobalt affinity to molecular oxygen. The role of immobilized water molecules in the change in the properties of cobalt extraligands has been considered. On the basis of the analysis of the spectral data obtained, modes for incorporating Co^II(TMpy-P4) into DNA and model polynucleotides are proposed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 538–545, July–August 2005.     

Reactions of homobinuclear platinum and palladium complexes with carbon monoxide

The reactivity of homobimetallic complexes of platinum(II) and palladium(II) containing diethyl(diphenylphosphinomethyl)amine (ddpa = (C₆H₅)₂PCH₂N(C₂H₅)₂) as a bridging ligand has been investigated. Carbon monoxide reacts reversibly with these complexes. The species formed are binuclear carbonyl-bridged derivatives, which can isomerize to ionic terminal carbonyl complexes. Reaction of [PtCl₂(CO)]₂[(C₂H₅)₄N]₂ with ddpa in dichloromethane gives the ionic platinum(I) complex [Pt(ddpa)Cl₂]₂[(C₂H₅)₄N]₂, which reacts with carbon monoxide. Still, homobimetallic derivatives of palladium(I) are unstable, and none have been isolated.     

Enhancement in the reducibility of cobalt oxides on a mesoporous silica supported cobalt catalyst

The silylation of SBA-15 enhances the reducibility of cobalt oxides on a SBA-15 supported cobalt catalyst, and consequently increases the catalytic activity for Fischer-Tropsch synthesis of hydrocarbons from syngas and selectivity for longer chain products.     

A PORPHYRIN-DNA EXCIPLEX: RESONANCE RAMAN SPECTRA OF ELECTRONICALLY EXCITED Cu(TMpy-P4) BOUND TO POLY(dA-dT)-POLY(dA-dT)

The resonance Raman spectra of water-soluble porphyrins, Cu(TMpy-P4) and Ni(TMpy-P4), and their mixtures with DNA, Poly(dG-dC).Poly(dG-dC), and Poly(dA-dT).Poly(dA-dT) were measured using 426 nm pulsed laser excitation (and 556 nm for some applications). At high laser power, the solution of Cu(TMpy-P4) mixed with DNA or Poly(dA-dT).Poly(dA-dT) exhibits new bands at 1550 and 1349 cm-1 that are not observed for Cu(TMpy-P4) alone or for Cu(TMpy-P4) mixed with Poly(dG-dC).Poly(dG-dC). These extra bands do not appear when the resonance Raman spectra are measured by a cw laser or by a pulsed laser with low power. Similar mixtures of M(TMpy-P4) (where M = Ni, Zn, Co, Mn, and H2) with these nucleic acids exhibit no such bands even by high power pulsed laser excitation. We attribute the new resonance Raman bands to an electronically excited Cu(TMpy-P4), stabilized by forming an exciplex with the A-T site of the nucleic acid. The minimum lifetime value of such an exciplex was estimated to be on the order of 10 ps.     

Imaging and multiple scattering through media containing optically active particles

This paper examines the behaviour of polarized light scattered by a medium containing small chiral spheroidal particles. We show that for single scattering the observed phenomena of optical activity may be interpreted in terms of an averaged Mueller matrix and describe how the degree of polarization is affected by such a medium. The polarization properties of multiply scattered light by chiral particles are considered through the use of Monte Carlo simulations. It is shown that the effects of chirality under multiple scattering can be interpreted as an order-preserving influence in a disordered system and that this influence can, in principle, be exploited for the purposes of imaging.     

A simple synthesis of catalytically active,high surface area ceria aerogels

A simple synthetic route for preparing high surface area, structurally stable ceria aerogels is presented. Ceria aerogels were doped with 1% palladium: a water-gas shift (WGS) active metal. A reduced Pd/ceria aerogel and an as-prepared Pd/ceria aerogel are compared to determine the effect of pretreatment conditions on WGS activity. The BET surface area of the as-prepared ceria aerogel was 345 m²/g. CO chemisorption data and high-resolution TEM images indicate that the particle size of palladium on the reduced Pd/ceria sample was approximately 15 nm. X-ray photoelectron spectroscopy (XPS) data establish that the fraction of Ce³⁺ from Ce₂O₃ was approximately the same for both reduced and as-prepared samples. XPS data also indicate that approximately 44% of the palladium on the reduced Pd/ceria sample was converted to the metallic form. Each catalyst was tested for WGS activity. The reduced Pd/ceria sample exhibited the greatest WGS activity as compared with the other samples used in this study.     

In Silico Anticipation of Metabolic Pathways Extended to Organic Chemistry Reactions: A Case Study with Caffeine Alkaline Hydrolysis and The Origin of Camellimidazoles

Camellimidazoles A–C were recently reported as natural substances in Keemun black tea. Although a “biosynthetic” route to these intriguing imidazole dimers was proposed from caffeine by the authors in this seminal report, we envisioned that a artefactual scenario, consisting of alkaline hydrolysis of caffeine and spontaneous cascade reactions with a methylene donor such as formaldehyde or methylene chloride, could also have led to their formation. To capture the diversity of molecules obtained under these conditions (i.e. alkaline treatment of caffeine/formaldehyde), an in silico MetWork-based pipeline was implemented, highlighting the sought-after camellimidazoles B and C. A wealth of further compounds were also tagged, notably comprising the herein newly described and unnatural camellimidazoles D –F that were subsequently confirmed as anticipated in silico upon extensive spectroscopic analyses. Likewise, camellimidazoles B and C could also be obtained using methylene chloride as an alternative methylene donor which may also have occurred in the initial phytochemical pipeline that implied this solvent. The current investigation emphasizes the fitness of MetWork tagging to extend the logic of in silico anticipation of metabolic pathways to organic chemistry reactions.     

Columnar Phases from Covalent and Hydrogen-Bonded Liquid-Crystalline Ferrocene Derivatives

The synthesis and liquid-crystalline properties of tetracatenar covalent and H-bonded bis-ferrocene derivatives 1 and 2 , respectively, are reported. Both compounds gave rise to enantiotropic columnar liquid-crystalline behavior with a hexagonal molecular organization. To explore the possibility to obtain also calamitic liquid-crystalline phases from H-bonded ferrocene-containing liquid crystals, a rod-shaped ferrocene mesogen 3 was synthesized, which gave rise to enantiotropic smectic C and smectic A phases. For the first time, a rational synthetic design at the ferrocene level led to ferrocene-based liquid-crystals with columnar behavior and to H-bonded metallomesogens.     

Picosecond dynamics and mechanism of the interaction of a photoexcited Cu(II)-porphyrin with a DNA-modeling polynucleotide

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 62, No. 2, pp. 110–121, March–April, 1995.