Near infrared photochemistry of pyruvic acid in aqueous solution

Recent experimental and theoretical results have suggested that organic acids such as pyruvic acid, can be photolyzed in the ground electronic state by the excitation of the OH stretch vibrational overtone. These overtones absorb in the near-infrared and visible regions of the spectrum where the solar photons are plentiful and could provide a reaction pathway for the organic acids and alcohols that are abundant in the earth's atmosphere. In this paper the overtone initiated photochemistry of aqueous pyruvic acid is investigated by monitoring the evolution of carbon dioxide. In these experiments CO(2) is being produced by excitation in the near-infrared, between 850 nm and ～1150 nm (11,765-8696 cm(-1)), where the second OH vibrational overtone (Δν = 3) of pyruvic acid is expected to absorb. These findings show not only that the overtone initiated photochemical decarboxylation reaction occurs but also that in the aqueous phase it occurs at a lower energy than was predicted for the overtone initiated reaction of pyruvic acid in the gas phase (13,380 cm(-1)). A quantum yield of (3.5 ± 1.0) × 10(-4) is estimated, suggesting that although this process does occur, it does so with a very low efficiency.     

Visible-light photochemistry of 6-formyl-7,8-dihydropterin in aqueous solution

Pterins are a family of heterocyclic compounds present in a wide range of living systems and are involved in different photobiological processes. 6-Formyl-7,8-dihydropterin (H₂Fop), is a product of oxidation of several natural occurring pterin derivatives, and its absorption spectrum presents as special feature an intense band in the visible region. Studies of the photochemistry of H₂Fop in aqueous solutions under visible radiation and room temperature were performed. The photochemical reactions were followed by UV–vis spectrophotometry, electrochemical measurement of dissolved O₂, enzymatic methods for H₂O₂ determination and HPLC. When H₂Fop in air-equilibrated solution was exposed to light, O₂ was consumed, the reactant was oxidized to 6-formylpterin (Fop), and H₂O₂ released. When the photolysis took place in the absence of O₂, a red compound was generated. This product was rapidly oxidized to Fop on admission of O₂. The quantum yields of H₂Fop disappearance and of photoproducts formation are reported and the effect of pH is analyzed. The potential biological implications of the results obtained are also discussed.     

Picosecond kinetics and transient spectra of pseudoisocyanine monomers and J-aggregates in aqueous solution

Bleaching of monomer and J-aggregate bands of pseudoisocyanine was observed using tunable excitation wavelengths. Both bleached bands decrease with (15 ± 3) ps. A residual J-band bleaching exists up to 1 ns. A new transient absorption in superposition with the J-band was round to consist of two bands with different time behaviour.     

UV radiation effects on flavocytochrome b2 in dilute aqueous solution

A dilute aqueous solution of flavocytochrome b2 when exposed to inactivating doses of UV radiation at 280 nm underwent reversible loss in activity both under aerated and deaerated conditions. The active site as well as the substrate binding sites were found to be modified in the irradiated enzyme. Irradiation of the enzyme in the UV-C range resulted in partial unfolding of the polypeptide framework. Destruction and/or modification of both tryptophan and tyrosine residues as well as heme moieties took place. Preliminary laser flash photolysis studies suggest that the initial photo-ionization takes place with tryptophan and tyrosine residues with the formation of excited states and radicals, and then rapid transfer of electrons takes place to histidyl and cystinyl sites which might have eventually been altered in the process.     

UV and H2O2/UV degradation of a pharmaceutical intermediate in aqueous solution

The degradation of 5-methyl-1,3,4-thiadiazole-2-thiol (MMTD), a pharmaceutical intermediate found in some aquifers of Northern Italy, has been investigated by means of UV and UV/H2O2 treatments. The study has been carried out with a 17 W low pressure mercury lamp at room temperature, using a (100)/(1) (H2O2)/(MMTD) molar ratio. The results have demonstrated that: (i) with an initial MMTD concentration of 1 mg/l, 90% MMTD removal can be achieved within 1 hour or less than 5 minutes by UV or UV/H2O2 respectively; (ii) the sole UV irradiation does not cause any MMTD mineralization; (iii) with an initial MMTD concentration of 50 mg/l, 4 hours of UV/H2O2 treatment lead to an almost complete mineralization of the MMTD organic sulfur and to a partial mineralization of carbon (59%) and nitrogen (14%). The identification of degradation by-products, performed by HPLC-UV-MS analysis, revealed that the sole UV irradiation gives rise to the MMTD transformation into a single by-product that continuously accumulates in the solution. Conversely, the UV/H2O2 treatment forms seven intermediates that undergo further degradation through the breakdown of the thiadiazole ring. On the basis of the obtained results a degradation pathway has been proposed.     

Radiationless transition rates of thymine and uracil in neutral aqueous solution at 300°K

Recent experiments in low-intensity fluorescence spectrometry, flash photolysis and continuous photolysis at 300°K in an aqueous medium have provided data for uracil and thymine from which all the pertinent phenomenological characteristics (Φ_fl^0′, Φ_isc^0′, Φ′_chem) of the 0′ level can be evaluated. It is necessary to postulate considerable internal conversion ¹S → ⁰S with τ_ic ≈ 1–2 × 10⁻¹² sec, this process correlating with the dielectric relaxation time of water.     

Stable conformations of tripeptides in aqueous solution studied by UV circular dichroism spectroscopy

Determination of the precise solution structure of peptides is of utmost importance to the understanding of protein folding and peptide drugs. Herein, we have measured the UV circular dichroism (UVCD) spectra of tri-alanine dissolved in D(2)O, H(2)O, and glycerol. The results clearly show the coexistence of a polyproline II or 3(1)-helix and a somewhat disordered flat beta-strand conformation, in complete agreement with recent predictions from spectroscopic data (Eker et al. J. Am. Chem. Soc. 2002, 124, 14 330-14 341). A thermodynamic analysis revealed that enthalpic contributions of about 11 and 17 kJ/mol stabilize polyproline II in D(2)O and H(2)O, respectively, but at room temperature they are counterbalanced by entropic contributions, which clearly favor the more disordered beta-strand conformation. It is hypothesized that this delicate balance is the reason for the variety of structural propensities of amino acid residues in the absence of nonlocal interactions. The isotope effect yielding a higher occupation of polyproline II in H(2)O with respect to D(2)O strongly suggests that a hydrogen-bonding network involving the peptide and water molecules in the hydration shell plays a major role in stabilizing this conformation. The equilibrium between polyproline II and beta-strand is practically maintained in glycerol, which suggests that glycerol can substitute water as stabilizing solvent for the polyproline II conformation. We also measured the UVCD spectra of tri-valine and tri-lysine (both at acidic pD) in D(2)O and found them to adopt a flat beta-strand and left-handed turn structure, respectively, in accordance with recent analyses of vibrational spectroscopy data. Generally, the present study adds substantial evidence to the notion that the so-called random coil state of peptides is much more structured than generally assumed.     

The solution photochemistry of substituted cycloheptatrienes

The solution photochemistry of several ethoxycarbonyl- and ethoxycarbonyl-methoxy-substituted cycloheptatrienes has been investigated. The results have been used to analyse the directional specificity of ring-closure and 1,7-hydrogen migration reactions. This specificity is interpreted in terms of polarisation within the S₁ state which undergoes either (a) allowed photochemical reactions to give the observed products directly or (b) isomerisation to a trans, cis, cis-cyclohepatriene which then reacts via allowed ground-state processes. In at least two instances the directional specificity of the ring-closure reaction is wavelength dependent and this is attributed to the differing reactivities of the S₁ and S₂ states.     

Condensed phase photochemistry of acetic acid in the vacuum UV

The vacuum ultraviolet (VUV) photolysis of acetic acid (HAC) in Ar, N₂, CO and CO-doped argon matrices was performed at 10 K by systematically exciting into specific absorption bands with various VUV resonance line sources. The major overall processes which occur as a reuslt of photoexcitation are (1) CH₃COOH + hν → CH₄ + CO₂, (2) and (3) CH₃COOH + hν → CH₃ + CO₂ + H and (4) CH₃COOH + hν → CH₃OH + CO. All three of these overall processes occur to varying extents as a result of excitation into the four VUV bands of HAC. The results of experiments performed in CO and N₂ matrices suggest that reactions (2) and/or (3) dissociate from triplet states corresponding to n′ → π^* and n → σ^* (3s) transitions. Isotopic CD₃COOH experiments were performed and assisted in confirming previously proposed gas phase mechanisms.     

Nonlinear UV laser photochemistry of oxygen-deficient centers in silica glass

The paper presents the results of studies into the effect of high-power UV laser radiation on silica glass with a high concentration of oxygen-deficient centers (ODC's) the type of SiGe and SiSi. Irradiation has been demonstrated to cause the destruction of ODC's and formation of E′ and H(II) paramagnetic defect centers as a result of a two-photon absorption process. The discussion covers the mechanisms of laser-induced and thermal post-irradiation reactions involved.     

The photochemistry of thymidylyl-(3'-5')-5-methyl-2'-deoxycytidine in aqueous solution

The photochemistry of the dinucleoside monophosphate thymidylyl-(3'-5')-5-methyl-2'-deoxycytidine (Tpm5dC) has been studied in aqueous solution using both 254 nm and UV-B radiation. A variety of dinucleotide photoproducts containing 5-methylcytosine (m5C) have been isolated and characterized. These include two cyclobutane dimers (CBD) (the cis-syn [c,s]and trans-syn forms), a (6-4) adduct and its related Dewar isomer, and two isomers of a product in which the m5C moiety was converted into an acrylamidine. Small amounts of thymidylyl-(3'-5')-thymidine (TpT) were also formed, presumably as a secondary photoreaction product. In addition, a photoproduct was characterized in which the m5C moiety was lost, thus generating 3'-thymidylic acid esterified with 2'-deoxyribose at the 5-hydroxyl on the sugar moiety. The c,s CBD of Tpm5dC readily undergoes deamination to form the corresponding CBD of TpT. The kinetics of this deamination process has been studied; the corresponding enthalpy and entropy of activation for the reaction have been evaluated at pH 7.4 as being, respectively, 73.4 kJ/mol and -103.5 J/K mol. Deamination was not observed for the other characterized photoproducts of Tpm5dC.     

Kinetics of tartrazine photodegradation by UV/H2O2 in aqueous solution

In the present work, kinetics of tartrazine decay by UV irradiation and H₂O₂ photolysis, and the removal of total organic carbon (TOC) under specific experimental conditions was explored. Irradiation experiments were carried out using a photoreactor of original design with a low-pressure Hg vapour lamp. The photodegradation rate of tartrazine was optimised with respect to the H₂O₂ concentration and temperature for the constant dye concentration of 1.035 × 10^?5 M. Tartrazine degradation and the removal of TOC followed the pseudo-first-order kinetics. The much higher k _obs value for tartrazine degradation (7.91 × 10^?4 s^?1) as compared with the TOC removal (2.3 × 10^?4 s^?1) confirmed the presence of reaction intermediates in the solution.     

Picosecond time-resolved spectroscopic studies of a monomer—dimer system of 3,3′-diethyl thiacarbocyanne iodide in aqueous solution

Transient absorption in the blue and near-infrared and bleaching of 3,3'-diethyl thiacarbocyanine iodide monomers and dimers weres studied. The monomer excited-state lifetime is 145 ± 10 ps, the recovery time of the dimers is 460 ± 50 ps. An intermediate state with a rise time of 80 ps and decay time of 500 ps has been detected between 670 and 730 nm.     

The solution photochemistry of αβ-unsaturated sulphones

1-Phenyl-2-(benzenesulphonyl)-ethylene and 1-phenyl-2-(benzenesulphonyl)-prop-1-ene have been shown to undergo $\text{Z}$,$\text{E}$-photoisomerisation, whereas 2-benzenesulphonylindene readily forms [_π2 + _π2] photoadducts with 2,3-dimethylbut-2-ene, cyclopentene, and cyclohexene.     

Quinone sensitized electron transfer photooxidation of nucleic acids: chemistry of thymine and thymidine radical cations in aqueous solution

The 2-methyl-1,4-naphthoquinone (MQ) sensitized photooxidation of nucleic acid derivatives has been studied by laser flash photolysis and steady state methods. Thymine and thymidine, as well as other DNA model compounds, quench triplet MQ by electron transfer to give MQ radical anions and pyrimidine or purine radical cations. Although the pyrimidine radical cations cannot be directly observed by flash photolysis, the addition of N,N,N',N'-tetramethyl-1,4-phenylenediamine (TMPD) results in the formation of the TMPD radical cation via scavenging of the pyrimidine radical cation. The photooxidation products for thymine and thymidine are shown to result from subsequent chemical reactions of the radical cations in oxygenated aqueous solution. The quantum yield for substrate loss at limiting substrate concentrations is 0.38 for thymine and 0.66 for thymidine. The chemistry of the radical cations involves hydration by water leading to C(6)-OH adduct radicals of the pyrimidine and deprotonation from the N(1) position in thymine and the C(5) methyl group for thymidine. Superoxide ions produced via quenching of the quinone radical anion with oxygen appear to be involved in the formation of thymine and thymidine hydroperoxides and in the reaction with N(1)-thyminyl radicals to regenerate thymine. The effects of pH were examined in the range pH 5-8 in both the presence and absence of superoxide dismutase. Initial C(6)-OH thymine adducts are suggested to dehydrate to give N(1)-thyminyl radicals.     

Femtosecond pump-probe studies of nitrosyl chloride photochemistry in solution

We present a femtosecond pump-probe study of the primary events of nitrosyl chloride (ClNO) photochemistry in solution. Following 266 nm photolysis, the resulting evolution in optical density is measured for ClNO dissolved in acetonitrile, chloroform, and dichloromethane. The results demonstrate that photolysis results in the production of a photoproduct that has an absorption band maximum at 295 nm in acetonitrile and 330 nm in chloroform and dichloromethane. To determine the extent of Cl production, comparative photochemical studies of methyl hypochlorite (MeOCl) and ClNO are performed. Photolysis of MeOCl in solution results in the production of the Cl:solvent charge-transfer complex; therefore, a comparison of the spectral evolution observed following MeOCl and ClNO photolysis under identical photolysis conditions is performed to determine the extent of Cl production following ClNO photolysis. We find that similar to the gas-phase photochemistry, Cl and NO formation is the dominant photochemical channel in acetonitrile. However, the photochemistry in chloroform and dichloromethane is more complex, with a second product formed in addition to Cl and NO. It is proposed that in these solvents photoisomerization also occurs, resulting in the production of ClON. The results presented here represent the first detailed examination of the solution phase photochemistry of ClNO.