Theoretical investigations of the electronic states of porphyrins. II. Normal and hyper phosphorus porphyrins

Ab initio methods have been used to calculate the ground and excited states of “normal” and “hyper” porphyrins. Perturbation theory and CI methods were used to determine differential ground and excited-state correlation effects for [P^v(P)F₂]⁺ and [P^III(P)]⁺. A comparison is made to the INDO /S /CI predicted wavefunctions and spectra and to the experimental spectra of closely related molecules. The “hyper” [P^III(P)]⁺ calculations show some very low energy electronic transitions which provide an explanation for an anomalous “red” band in the spectrum and for the lack of fluorescence. Ab initio calculations also predict that (1) the lowest energy ¹A₁ state is a two-configuration wavefunction which can be described as a diradical, (2) the two lowest-energy singlet excited states are double excitations from the closed shell SCF configuration, and (3) a ³B₂ state is very close in energy to the lowest ¹A₁ state.     

Chemistry of pteridine N-oxides (review)

Reactions involving the direct oxidation of pteridine derivatives to their N-oxides are examined. The relationship between the structures of the N-oxides and their physicochemical properties (UV spectra and pK_a values) is discussed.     

Synthesis and characterization of Eu-doped hydroxyapatite through a microwave assisted microemulsion process

Europium doped hydroxyapatite (Eu:HAp) nanosized particles with multiform morphologies have been successfully prepared via a simple microemulsion-mediated process assisted with microwave heating. The physicochemical properties of the samples were well characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), photoluminescence (PL) spectra, and the kinetic decays, respectively. The results reveal that the obtained Eu:HAp particles are well assigned to the hexagonal lattice structure of the hydroxyapatite phase. Additionally, it is found that samples exhibit uniform morphologies which can be controlled by altering the pH values. Furthermore, the samples show the characteristic ⁵D₀–⁷F_1–4 emission lines of Eu³⁺ excited by UV radiation.     

Structure analysis of naturally occurring alkyl porphyrins by hydrogen chemical ionisation mass spectrometry

Chemical ionisation (CI) mass spectrometry with H₂ as reagent gas has been used to obtain spectra of a number of demetallated alkyl porphyrins from an oil shale and a bitumen. The spectra give more structural informa- tion than the electron impact spectra, by way of odd electron dipyrrolic fragment ions. Thus, the structural possibilities for a novel /c30 aetio porphyrin have been narrowed to two, although¹HNMR only reduced the possibilities to six. The spectra of four types of components containing a five, six, seven or methyl-substituted six membered exocyclic ring show, for example, that three out of four C₃₂ isomers can be distinguished. The technique offers promise as a tool in structural elucidation of other novel naturally occurring porphyrins.     

Porphyrins. 24. Identification of isomeric monoesters of natural porphyrins by PMR spectroscopy

The monomethyl esters of mono(dimethylamides) and the bisdimethylamides of mesoporphyrin-IX, mesoporphyrin-III, and mesoporphyrin-XIII have been obtained, together with their zinc complexes. A relationship has been found between the chemical shifts of the signals for CONMe₂ in the PMR spectra and the positions of the substituents in the porphyrin ring, enabling a correct assignment to be made for the first time of these signals to the groups in positions 13² and 17² of the porphyrin ring, to establish the structures of the isomeric monomethyl esters of mesoporphyrin-IX, and to develop a method of identifying monoesters of natural porphyrins by converting them into the monoesters of the mono(dimethylamides) of mesoporphyrin-IX, followed by examination of their PMR spectra.For Communication 23, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 780–786, June 1988.     

Halogenation of the components of nucleic acids

Summary Preparative methods have been worked out for the bromination of unprotected deoxy-AMP, deoxy-GMP, and deoxy-CMP and methods have been devised for the isolation and purification of the bromine derivatives.Some physicochemical characteristics (UV spectra, R_f values on thin-layer and paper chromatography, coefficients of millimolar extinction) of the bromine derivatives of the DNA components obtained have been determined.Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 524–527, July–August, 1976.     

Some novel manganese(III) porphyrins with catalytic properties

Abstract

A series of manganese(III) porphyrins with 4-methylimidazole have been prepared. These are high-spin complexes having general formula [Mn^III(THMPP)X(4-MeIm)], where THMP?=?5,10,15,20-tetra(4-hydroxy-3-methoxyphenyl)porphine ligand, X?=?Cl^?, Br^?, NCS^?, or N₃^? and 4-MeIm?=?4-methylimidazole. All the complexes have been characterized by UV-visible, FT-IR, ESI-MS spectra, elemental analyses and magnetic susceptibility measurements. These manganese(III) porphyrins oxidize aromatic alcohols to aldehydes. The oxidation reactions have been carried out at room temperature in the presence of oxidants such as NaIO₄, H₂O₂, and NaOCl. The comparative studies proved that NaIO₄ behaves as the most efficient oxidant in these oxidative transformation reactions.     

Studies on halogen derivatives of phenylazochromotropic acid: I. The acid-base properties

The acid-base properties of six halogen derivatives of phenylazochromotropic acid have been studied in an attempt to apply them as metallochromic or chromophoric indicators. The absorption spectra are studied in buffer solutions of varying pH values. The variation of spectra with pH indicates the presence of two equilibria between H₂D^2?, HD^3? and D^4? species. The pK values of the naphthlenic OH groups are determined spectrophotometrically and are discussed in relation to molecular structure while those of the sulfonic acid groups are determined potentiometrically.     

Effect of Oxyethylete Units on Adsorption and Micellization Properties of Novel Benzene Sulfonate Surfactants

The surface tension and fluorescence spectra of sodium octyl-[ω-octyloxy-poly(oxyethylene)]-yl-benzene sulfonates (APE_nBS) aqueous solutions have been investigated by Wilhelmy plate method and intrinsic probe methods, respectively to study the effect of EO units on their properties. It was discovered that the surface performance of these surfactants was greatly outstanding: the values of critical micelle concentration (CMC) reached to be of the order of magnitude of 10^?5 mol/L, the values of surface tension at CMC, γ_CMC, were between 25.79 to 31.02 mN/m, and the effectiveness and efficiency of surface tension reduction were excellent. The introduction of oxyethylene units to the surfactant molecule evidently improved the solubility of APE_nBS. With the increase in EO units, the CMC slightly changed after the first decreased. On the other hand, the surface excess concentration at saturation, Γ _max, decreased after the first increased and γ_CMC increased after the first decreased accordingly. The CMC determined by fluorescence spectra of intrinsic probe method were accorded with the CMC measured by surface tension method. The aggregation number N, characterized by quenching the fluorescence spectra with methyl viologen (MV²⁺) as the extrinsic quencher, gradually decreased first (from 0 to1) and then slightly changed (from 1 to 4) with increasing EO chain length. So we concluded that the appropriate number of EO units was the key factor to get the best physicochemical properties of APE_nBS.     

Copolymerisation of 2-hydroxyethyl methacrylate with siloxanyl monomers

Acryloxymethylpentamethyldisiloxane (AMS) and methacryloxymethylpentamethyldisiloxane (MMS) have been prepared and purified chromatographically. Some physicochemical properties have been measured for these monomers as well as for highly purified 2-hydroxyethyl methacrylate (HEMA). Hydroxyl group analysis on copolymers of AMS with HEMA and of MMS with HEMA, obtained by free radical copolymerisation to low conversion, enabled monomer reactivity ratios to be determined by several procedures. The average values were r_HEMA = 0.86, r_AMS = 0.55 and r_HEMA = 0.97, r_MMS = 0.33. These values have been invoked in computing integral curves for the instantaneous copolymer composition throughout the whole range of conversion.     

The formation of charge-transfer complexes from N-vinylindole and chlorine,bromine, and iodine

The reaction of vinylindole with bromine, chlorine, and iodine in CCl₄ solution in the cold leads to the formation of charge-transfer complexes (CTC). The formation of CTC has been confirmed by a study of the physicochemical properties and the IR and UV spectra of the reaction products.     

Spectrophotometric and potentiometric study of the acid—base equilibria of indophenols in aqueous media

Six indophenols, with redox and acid—base indicator properties, have been examined by spectrophotometric and potentiometric methods. By analysing the absorption spectra obtained at different pH values, three independent values were obtained for their K_Ox dissociation constants, which are closely related to their properties as acid—base indicators. Three of the indophenols have also been examined by acid—base and redox potentiometric titrations. All K_Ox and E° values agree well with polarographic values. The use of these substances as visual acid—base and redox indicators is discussed.     

Synthetic inorganic ion exchanger. IX. Thorium antimonate. Synthesis,properties and ion exchange separations

Summary Thorium antimonate has been synthesised by mixing 0.1 M Th(NO₃)₄ solution in 0.1 N HNO₃ and 0.05 M potassium pyroantimonate and by mixing 0.1 M Th(NO₃)₄ solution in 0.1 N HNO₃ with 0.1 M SbCl₅ in 4N HCl at controlled pH. The preparative procedure, composition, I.R. spectra, chemical and thermal stability, physico-chemical properties and distribution coefficients of metal ions on thorium antimonate have been determined at pH 5.5–6.5. On the basis of distribution co-efficient values separations of Cu(II) from Mg(II), Ni(II), Mn(II), Mg(II), from Zn(II) and Cd(II) and Zn(II) from Cd(II) have been achieved. Part VIII: Reference [1]     

4-Dimethylaminocinnamaldehyde As a Photometric Reagent for Primary Aromatic Amines

The interaction of primary aromatic amines (PAAs) with 4-dimethylaminocinnamaldehyde (DMACA) is studied in various media by UV, IR, and ¹H NMR spectroscopy. The optimum conditions for these reactions have been found, and the reasons for better analytical effects in the condensation reaction of PAAs with this reagent have been revealed. The physicochemical properties of the analytical form are studied using the aniline–DMACA model system as an example. A correlation has been found between the pH_opt of the reactions under study and the pK _a values of arylamines.     

Absorption UV spectroscopy and electronic structure of ionic and tautomeric forms of hydroxy and methoxy derivatives of cytosine and adenine,and of some 5-substituted analogs of pyrimidines

The individual absorption spectra of various ionic and tautomeric species of some derivatives of nucleic-acid components have been determined by computer handling of the summary spectra of these compounds measured at different pH values. These individual spectra have been decomposed into separate bands represented by log-normal curves and corresponding to different electronic transitions. Using the parameter system calculated earlier for the molecules of the vitamin B₆ family, the calculation of the electronic spectra and electronic structure of various ionic and tautomeric species of the molecules studied have been carried out in the π-electron approximation. These properties have also been calculated by the all-valence electronic method CNDOS . The calculated results correlate well with both approximations and with our experimental spectral data. The localization of the molecular electronic excitation studied on the transition to the S₁ and T₁ states is considered in connection with the reactivity in these states.     

Physical,structural and luminescence investigation of Eu3+-doped lithium-gadolinium bismuth-borate glasses for LEDs

The aim of the current report is to fabricate Eu³⁺-doped glasses with the chemical composition of 50Li₂O-15Gd₂O₃-5Bi₂O₃-(30-x)B₂O₃-xEu₂O₃ (where x = 0.5, 1.0, 1.5, 2.0 and 2.5 mol%), with the help of conventional melt quenching technique. The fabricated glasses have been studied with help of physical, structural and luminescence properties for application of LEDs. The structural properties were investigated by XRD and FTIR spectra. Physical properties have been measured. Direct and indirect optical energy band gap (E_g) have been calculated and found to be increasing with Eu₂O₃ concentration. Luminescence spectra have been observed from photo and radioluminescence spectra and found in good agreement with each other, however the concentration quenching was not determined for the samples. The high-covalence and asymmetric nature was confirmed from Photoluminescence emission and RL emission transition as well as from the higher values of luminescence intensity ratio. The JO parameters have been found for the better performance of lasing materials. The lifetime's data have been found to be decreasing from 1.64 to 1.50 ms, which is the confirmation of energy transfer in Eu³⁺ ions through cross relaxations. From the calculated properties it has been suggested that the present glass samples might be good for red-light emitting devices.     

NMR evidence for planar chirality in natural porphyrins

The ¹H NMR spectra of several six-coordinate cobalt(III) porphyrins of general formula L₂Co(DPDME)CI, where DPDME=deuteroporphyrin dimethyl ester and L is an optically active ligand, have been measured at 250 or 400 MHz. In a few cases, two signals of equal intensity are observed for the L ligand protons. This magnetic non-equivalence, which never exceeds 0.04 ppm, is thought to arise from the planar chirality of the porphyrin ring, which makes a proton in the ligand L above the porphyrin ring and the corresponding proton below this ring diastereotopic.     

Singlet molecular oxygen quantum yield measurements of some porphyrins and metalloporphyrins

Hematoporphyrin IX dimethyl ester (HPDME), tetraphenylporphyrin (TPP), tetra(4-methoxyphenyl)porphyrin (TMPP), tetra(3,4-dimethoxyphenyl)porphyrin (TDMPP), tetra(3,4,5-trimethoxyphenyl)porphyrin (TTMPP), tetraanthrylporphyrin (TAP) and tetraacridylporphyrin (TACP), and their Zn²⁺, SnX ₂ ²⁺ , Pd²⁺ and Pt²⁺ complexes have been prepared and characterized. The singlet molecular oxygen quantum yield (ϕ_Δ) values of the above porphyrins and their metal derivatives in N,N-dimethyl formamide (DMF) have been measured in the presence of 1,3-diphenylisobenzofuran (DPBF) as¹O₂ acceptor using steady state technique after correcting for the intensity of light absorbed by the photosensitizers. The ϕ_Δ values for the free base porphyrins are usually around 0.60. Hematoporphyrin IX dimethyl ester and its metal derivatives follow the order: HPDME (ϕ_Δ = 0.60) > Zn HPDME (0.40) > PdHPDME (0.34) > Sn(OH)₂ HPDME (0.28) > PtHPDME (0.24). Zinc(II) complexes of tetraarylporphyrins show about 65% efficiency in ϕ_Δ values are compared to the ϕ_Δ values of their corresponding free base porphyrins. These results can be explained on the basis of catalyzed intersystem crossing to the ground state. The ϕ_λ values of the above free base porphyrins and their metal complexes in DMF in presence of DPBF using single-pulsed laser excitation technique follow similar trends.     

Adsorption of oxygen-containing aromatics used in petrochemical,pharmaceutical and food industries by means of lignin based active carbons

The adsorption processes of three aromatic chemicals onto activated carbons (ACs) from aqueous solutions have been studied. Eucalyptus kraft lignin obtained from cellulose industry as a residual biomass has been used to prepare activated carbons by physical activation with CO₂. The influences of the activation time on the surface areas and pore volumes of the ACs were analyzed. The physicochemical properties and the surface chemical structure of the adsorbents have been studied by means of N₂ and CO₂ adsorption, ultimate analysis, XPS, TPD and SEM. XPS and TPD spectra of the ACs have suggested the presence of aromatic rings and carbon-oxygen functional groups in the solid surfaces. The potential use of the ACs for the removal of acetaminophen (paracetamol), salicylic acid and benzoic acid has been investigated at different pH, temperature and contact time. The adsorption equilibrium data have been correlated to Langmuir isotherm model. The thermodynamic study has been developed, the values of ΔH, ΔG, and ΔS have been calculated and they indicated that the processes are endothermic for acetaminophen and exothermic for salicylic and benzoic acids. The analysis of the kinetic experiments showed that the effective diffusivities are low; 10⁻¹² to 10⁻¹¹ cm²/s, and they are the corresponding to intraparticle mass transfer, which appears as the controlling step for the net adsorption processes.     

Schwingungsverhalten des syn- und anti-acetaldoxims: 2. Mitt. normalkoordinatenbehandlung

Normal coordinate calculations on CH₃CHNOH, CH₃CHNOD, CH₃CDNOD and CD₃CDNOD have been carried out applying the general harmonic valence force field. The calculated frequencies of the normal vibrations considered agree satisfactorily with the corresponding values obtained from the spectra. The potential energy distributions have also been calculated; they were used to interpret the behaviour of characteristic vibrations.