Unusual photophysical properties of a new tricyclic derivative of thiopurines in terms of potential applications.

The thio analogues of purine bases have been found to possess notable biological and pharmacological capabilities and have an important role to play as anticancer and immunosuppressive drugs. In this work a new tricyclic analogue of guanosine containing sulfur was synthesized, in particular, DTEG (2',3',5'-tri-O-acetyl-6,9-dithioethanoguanosine). Although there is promise for thiopurine derivatives for biomedical applications, there are some liabilities in regard to their exposure to light. As a preliminary survey for such difficulties with DTEG, this work looks into spectral and photophysical processes of DTEG using time-resolved and steady-state optical excitation. In contrast to other thiopurines, which have long-lived triplets, DTEG is shown to have a short-lived triplet making it less dangerous for singlet-oxygen sensitization. Even in anaerobic solutions, its photoreactivity is negligible. These various unusual photochemical properties of DTEG are consistent with DTEG being very promising as an alternative drug to the currently used 6-thiopurines. DTEG also has some interesting photophysical behavior that is distinct from other thioketones. Although thioketones have an unusual fluorescence violating Kasha's Rule and emitting from the second excited singlet state, DTEG does this also, but, in addition, it shows dual fluorescence by emitting from its first excited singlet as well. The assignments of the nature of these excited states are supported by DFT results. This theory and associated kinetic analysis show quantitatively that the dual fluorescence is, in part, tied to the relatively fast S2 to S1 internal conversion compared to other S2 decays and, in part, tied to the relatively slow nonradiative decay of S1 itself.

Evaluation of Hydroxyl Radical Reactivity by Thioether Group Proximity in Model Peptide Backbone: Methionine versus S-Methyl-Cysteine.

Hydroxyl radicals (HO•) have long been regarded as a major source of cellular damage. The reaction of HO• with methionine residues (Met) in peptides and proteins is a complex multistep process. Although the reaction mechanism has been intensively studied, some essential parts remain unsolved. In the present study we examined the reaction of HO• generated by ionizing radiation in aqueous solutions under anoxic conditions with two compounds representing the simplest model peptide backbone CH3C(O)NHCHXC(O)NHCH3, where X = CH2CH2SCH3 or CH2SCH3, i.e., the Met derivative in comparison with the cysteine-methylated derivative. We performed the identification and quantification of transient species by pulse radiolysis and final products by LC-MS and high-resolution MS/MS after γ-radiolysis. The results allowed us to draw for each compound a mechanistic scheme. The fate of the initial one-electron oxidation at the sulfur atom depends on its distance from the peptide backbone and involves transient species of five-membered and/or six-membered ring formations with different heteroatoms present in the backbone as well as quite different rates of deprotonation in forming α-(alkylthio)alkyl radicals.

N-Terminal Decarboxylation as a Probe for Intramolecular Contact Formation in γ-Glu-(Pro)n-Met Peptides.

The kinetics of intramolecular-contact formation between remote functional groups in peptides with restricted conformational flexibility were examined using designed peptides with variable-length proline bridges. As probes for this motion, free radicals were produced using the •OH-induced oxidation at the C-terminal methionine residue of γ-Glu-(Pro)n-Met peptides (n = 0-3). The progress of the radicals' motion along the proline bridges was monitored as the radicals underwent reactions along the peptides' backbones. Of particular interest was the reaction between the sulfur atom located in the side chain of the oxidized Met residue and the unprotonated amino group of the glutamic acid moiety. Interactions between them were probed by the radiation-chemical yields (expressed as G values) of the formation of C-centered, α-aminoalkyl radicals (αN) on the Glu residue. These radicals were monitored directly or via their reaction with p-nitroacetophenone (PNAP) to generate the optically detected PNAP•- radical anions. The yields of these αN radicals were found to be linearly dependent on the number of Pro residues. A constant decrease by 0.09 µM J-1 per spacing Pro residue of the radiation-chemical yields of G(αN) was observed. Previous reports support the conclusion that the αN radicals in these cases would have to result from (S∴N)+-bonded cyclic radical cations that arose as a result from direct contact between the ends of the peptides. Furthermore, by analogy with the rate constants for the formation of intramolecularly (S∴S)+-bonded radical cations in Met-(Pro)n-Met peptides ( J. Phys. Chem. B 2016, 120, 9732), the rate constants for the formation of intramolecularly (S∴N)+-bonded radical cations are activated to the same extent for all of the γ-Glu-(Pro)n-Met peptides. Thus, the continuous decrease of G(αN) with the number of Pro residues (from 0 to 3) suggests that the formation of a contact between the S-atom in the C-terminal Met residue and the N-atom of a deprotonated N-terminal amino group of Glu is controlled in peptides with 0 to 3 Pro residues by the relative diffusion of the S•+ and unoxidized N-atom. The overall rate constants of cyclization to form the (S∴N)-bonded radical cations were estimated to be 3.8 × 106, 1.8 × 106, and 8.1 × 105 s-1 for peptides with n = 0, 1, and 2 Pro residues, respectively. If activation is the same for all of the peptides, then these rate constants are a direct indication for the end-to-end dynamics along the chain.

Water-Triggered Photoinduced Electron Transfer in Acetonitrile-Water Binary Solvent. Solvent Microstructure-Tuned Reactivity of Hydrophobic Solutes.

The solvent-composition dependence of quenching triplet states of benzophenone (3BP) by anisole in acetonitrile-water (ACN-H2O) mixtures was investigated by laser flash photolysis over the water mole fraction (xw) increasing from 0 to 0.92. Single exponential decay of 3BP was observed over the whole composition range. The quenching rate constant consistently increased with the water content but increased far more rapidly with xw > 0.7. The water-triggered electron-transfer (ET) mechanism was confirmed by a steeply growing quantum yield of the benzophenone ketyl radical anion, escaping back-ET when the partial water volume exceeded the acetonitrile one. The water-content influence on the 3BP quenching rate was described by a kinetic model accounting for the microheterogeneous structure of the ACN-H2O mixtures and the very different solubility of the reactants in the solvent components. According to the model, the ET mechanism occurs at a rate constant of 1.46 × 109 M-1 s-1 and is presumably assisted by the ACN-H2O hydrogen-bonding interaction.

Why does the presence of silicon atoms improve the emission properties of biphenyl derivatives? - Verification of various hypotheses by experiment and theory.

In the course of studying silicon modifications to improve emission properties of commonly used organic compounds, biphenyl with dimethylsilylvinyl groups in the para position (3-Si) was investigated. A comparative study was performed on the exact C-analogue (3-C) and expanded to biphenyl and dimethylbiphenyl to emphasize the general trend observed. Compound 3-Si displayed emission properties clearly different than all of the investigated hydrocarbon compounds, i.e. twice stronger fluorescence (Φf = 0.6) and a 3-times larger radiative rate constant as compared to 3-C in acetonitrile. Searching for the source of the unique emission of 3-Si, singlet and triplet processes were investigated for all of the compounds using steady-state and time-resolved methods, and their principal photophysical parameters are reported. Experimental work was supported by the theoretical predictions obtained using the EOM-CCSD method. The results led to the conclusion that the strong emission of 3-Si must be due to silicon's presence that enhanced intensity borrowing from the strongly allowed S0 → S2 transition and the larger S1 → S0 transition moment.

New Insights into the Reaction Paths of 4-Carboxybenzophenone Triplet with Oligopeptides Containing N- and C-Terminal Methionine Residues.

The oxidation processes of l-Met-(Pro)n-l-Met peptides that contain two Met residues located on the N and C termini and separated by a defined number (n = 0-4) of proline residues were investigated in aqueous solutions using laser flash photolysis. The use of such peptides allowed for distance control between the sulfur atoms located in the side chains of the Met residues. Interactions between side chains of the Met residues were probed by the observation of transients with σ*-type 2c-3e (S∴S)+, (S∴N)+, and (S∴O)+ bonds as well as of α-(alkylthio)alkyl radicals (αS). This approach enabled the monitoring, in real time, of the efficiency and kinetics of interactions between amino acid chains. Such knowledge is important, inter alia, for long-distance electron-transfer (ET) processes because amino acid side chains can serve as relay stations. The yields of these transients (measured as quantum yields (Φ)) were found to be dependent on the number of Pro residues, however, not dependent in a simple way on the average distance between sulfur atoms in Met residues. A decrease in the yield of the (S∴S)+ species with the number of Pro residues occurred at the expense of an increase in the yields of intramolecular three electron-bonded (S∴O)+/(S∴N)+ radical cations and αS radicals. These observations were rationalized by the fact that the time required for adequate overlap of the bonding orbitals is a key factor effecting the yield of the (S∴S)+ species. The time, however, can be controlled not only by the average distance but also by the specific geometrical and conformational properties of the peptide molecules.

Electron transfer in silicon-bridged adjacent chromophores: the source for blue-green emission.

Si-Bridged chromophores have been proposed as sources for blue-green emission in several technological applications. The origin of this dual emission is to be found in an internal charge transfer reaction. The current work is an attempt to describe the details of these processes in these kinds of substances, and to design a molecular architecture to improve their performance. Nuclear motions essential for intramolecular charge transfer (ICT) can involve processes from twisted internal moieties to dielectric relaxation of the solvent. To address these issues, we studied ICT between adjacent chromophores in a molecular compound containing N-isopropylcarbazole (CBL) and 1,4-divinylbenzene (DVB) linked by a dimethylsilylene bridge. In nonpolar solvents emission arises from the local excited state (LE) of carbazole whereas in solvents of higher polarity dual emission was detected (LE + ICT). The CT character of the additional emission band was concluded from the linear dependence of the fluorescence maxima on solvent polarity. Electron transfer from CBL to DVB resulted in a large excited-state dipole moment (37.3 D) as determined from a solvatochromic plot and DFT calculations. Steady-state and picosecond time-resolved fluorescence experiments in butyronitrile (293-173 K) showed that the ICT excited state arises from the LE state of carbazole. These results were analyzed and found to be in accordance with an adiabatic version of Marcus theory including solvent relaxation.

Fluorescent H-aggregates of an asymmetrically substituted mono-amino Zn(ii) phthalocyanine.

The photophysical properties of a newly synthesized unsymmetrically substituted zinc phthalocyanine derivative (1) bearing in its peripheral positions six n-hexylsulfanyl substituents and one amino-terminated n-hexylsulfanyl substituent were investigated. This mono-amino phthalocyanine exhibited a high tendency to form H-type aggregates in all of the investigated solvents: dichloromethane (DCM), tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO). Several species of H-aggregates were present together in relatively broad concentration ranges in THF and DCM, whereas in DMSO they were observed separately depending on the concentration used. Despite the widely accepted non-emissive character of H-type dimers, the H-type aggregates of phthalocyanine 1 were highly emissive in all solvents: the fluorescence quantum yield in DMSO for the n-aggregate is equal to 0.05, whereas for the (n + 1)-aggregate it is 0.11. Upon (n + 1)-aggregation, the fluorescence lifetime of the n-aggregate increased from ca. 2.5 ns to 3.3 ns. Based on these results, the radiative lifetimes of both species were computed: 48 ns for the n-aggregate and 29 ns for the (n + 1)-aggregate. The determined oscillator strengths for the n-aggregate and the (n + 1)-aggregate in DMSO were 0.04 and 0.12, respectively. The observed emission of the H-type (n + 1)-aggregate was assigned to the radiative transition from the upper exciton state to the ground state, which could be rationalized by a constant thermal repopulation of the upper exciton state. The experimental findings were supported by theoretical calculations.

Formation of a Three-Electron Sulfur-Sulfur Bond as a Probe for Interaction between Side Chains of Methionine Residues.

The mechanism of oxidation processes of l-Met-(Pro)n-l-Met peptides that contain two Met residues located on the N- and C-terminal and separated by a defined number (n = 0-4) of proline residues was investigated in aqueous solutions using pulse radiolysis. The use of such peptides allowed for distance control between the sulfur atoms located in the side chains of the Met residues. The formation of a contact between the side chains of the Met residues was probed by the observation of transients with σ*-type 2c-3e S∴S and S∴O bonds as well as of α-(alkylthio)alkyl radicals (αS). This approach enabled the monitoring, in real time, of the efficiency and kinetics of interactions between methionine side chains. Such knowledge is important, inter alia, for long-distance electron transfer processes because methionine side chains can serve as relay stations and also for many aspects of protein folding when the formation of a contact between two amino acid residues in an unfolded polypeptide chain plays a central role in protein-folding mechanisms. The yields of these transients (measured as G-values) were found to be dependent on the number of Pro residues; however, they were not dependent in a simple way on the average distance ⟨rS-S⟩ between the sulfur atoms in Met residues. A decrease in the yield of the (S∴S)(+) species with an increase in the number of Pro residues in the bridge occurred at the expense of an increase in the yields of the intramolecular three-electron-bonded (S∴O)(+) radical cations and αS radicals. A detailed understanding of these trends in the chemical yields was developed by modeling the underlying chemical kinetics with Langevin dynamical simulations of the various oligoproline peptide chains and combining them with a simple statistical mechanical theory on the end-to-end contact rates for polymer chains. This analysis showed that the formation of a contact between terminal Met residues in the peptides with 0-2 Pro residues was controlled by the activated formation of (S∴S)(+) whereas in the peptides with 3 and 4 Pro residues, by the relative diffusion of the sulfur radical cation and unoxidized sulfur atom. In this picture, the dynamics of the other radical products can be seen to be only indirectly dependent on the length of the proline bridges because their formation is in competition with (S∴S)(+) formation.

Intramolecular charge transfer photoemission of a silicon-based copolymer containing carbazole and divinylbenzene chromophores. Electron transfer across silicon bridges.

A new copolymer consisting of N-isopropylcarbazole/dimethylsilylene bridge/divinylbenzene units was synthesized and characterized. Dual fluorescence was observed in this copolymer in polar solvents. The absence of the second band at the lower transition energy of the two emission maxima in nonpolar solvents and the quantitative correlation of the lower-energy emission band maxima with solvent polarity indicate that the lower-energy emission band arises from an intramolecular charge transfer (ICT) state. A series of model compounds was synthesized to investigate the source of the charge transfer. It was found that the Si-bridged dyad with a single N-isopropylcarbazole and a single divinylbenzene was the minimum structure necessary to observe dual luminescence. The lack of dual luminescence in low-temperature glasses indicates that the ICT requires a conformation change in the copolymer. Analogous behavior in the Si-bridged dyad suggests that the ICT in the copolymer is across the silicon bridge. Results from time-resolved luminescence measurements with picosecond and subnanosecond excitation were used to support the thesis that twisted charge-transfer states are the likely source of the observed dual luminescence.

Sensitized photooxidation of s-methylglutathione in aqueous solution: intramolecular (S∴O) and (S∴N) bonded species.

Nanosecond laser flash photolysis was used to generate sulfur radical cations of the thioether, S-methylglutathione (S-Me-Glu), via the one-electron oxidation of this thioether by triplet 4-carboxybenzophenone. The purpose of this investigation was to follow the neighboring group effects resulting from the interactions between the sulfur radical cationic sites and nearby lone-pair electrons on heteroatoms within the radical cation, especially the electron lone-pairs on heteroatoms in the peptide bonds. The tripeptide, S-Me-Glu, offers several possible competing neighboring group effects that are characterized in this work. Quantum yields of the various radicals and three-electron bonded (both intramolecular and intermolecular) species were determined. The pH dependence of photoinduced decarboxylation yields was used as evidence for the identification of a nine-membered ring, sulfur-nitrogen, three-electron bonded species. The mechanisms of the secondary reactions of the radicals and radical cations were characterized by resolving their overlapping transient-absorption spectra and following their kinetic behavior. In particular, sulfur-oxygen and sulfur-nitrogen three-electron bonded species were identified where the oxygen and nitrogen atoms were in the peptide bonds.

Photoinduced CC-coupling reactions of rigid diastereomeric benzophenone-methionine dyads.

The reactions of ketone/methionine systems are widely used as efficient and selective sources of biorelevant radical species. In this study, we address intramolecular variants of this couple with respect to its photosynthetic utility and as a mechanistic model of underlying elementary reaction steps of biological importance, especially with respect to the study of photoinitiated electron transport in complex peptides. The outcomes of this study are two-fold: (1) steady-state irradiation of sterically constrained benzophenone/methionine dyads afforded stable photocyclization products with high yield and product selectivity. (2) Mechanistic insights into the triplet-triggered product formation were obtained from an analysis of the flash photolysis results and the molecular structure of the stable product formed upon irradiation. Time-resolved experiments identified (net) hydrogen-atom transfer from the methionine as the mechanism of the triplet quenching and the resulting biradicals as the major precursor of the isolated stable product. Both the analyses of triplet quenching and stable-product formation in the diastereomeric pairs point to effects of chiral center configuration, i.e., significant stereoselectivity is observed for all elementary steps. The underlying stereochemical restraints were quantitatively addressed by means of molecular dynamics simulations.

Evidence for a slow and oxygen-insensitive intra-molecular long range electron transfer from tyrosine residues to the semi-oxidized tryptophan 214 in human serum albumin: its inhibition by bound copper (II).

A slow, long range electron transfer (SLRET) in human serum albumin (HSA) is observed from an intact tyrosine (Tyr) residue to the neutral tryptophan (Trp) radical (Trp·) generated in pulse radiolysis. This radical is formed, at neutral pH, through oxidation with Br (2) (·-) radical anions of the single Trp 214 present. The SLRET rate constant of ~0.2 s(-1) determined is independent of HSA concentration and radiation dose, consistent with an intra-molecular process. This is the slowest rate constant so far reported for an intra-molecular LRET. In sharp contrast with the LRET reported for other proteins, the SLRET observed here is insensitive to oxygen, suggesting that the oxidized Trp is inaccessible to-or do not react with radiolytically generated O (2) (·-) . In N(2)O-saturated solutions, the SLRET is inhibited by Cu(2+) ions bound to the His 3 residue of the N-terminal group of HSA but it is partially restored in O(2)-saturated solutions.

Efficient photochemical oxidation of anisole in protic solvents: electron transfer driven by specific solvent-solute interactions.

The dynamics of the bimolecular quenching of triplet excited benzophenone by anisole was studied by nanosecond flash photolysis. We carried out a detailed study of the solvent dependence of the reaction rates and efficiencies in a number of protic and non-protic solvents. These studies were augmented by theoretical modelling and experimental investigation of solute/solvent interactions in the triplet excited and the ground state, respectively. The triplet quenching that follows Stern-Volmer kinetics in all cases is profoundly dependent on the nature of the solvent, with the highest reactivity being consistently found in protic solvents. The results in non-protic solvents are compatible with unproductive quenching via a charge-transfer state, whereas the generally fast quenching in protic solvents is accompanied by efficient formation of free-radical products. Analysis of the solvent dependence in terms of Marcus theory reveals the impact of specific solvation of benzophenone by protic solvents on the ET driving force and kinetics. Specific solvation is found to support efficient free radical ion formation in media of moderate and low polarity as well.

Efficient alpha-(alkylthio)alkyl-type radical formation in (*)OH-induced oxidation of alpha-(methylthio)acetamide.

Pulse radiolysis with UV-vis/ESR detection and steady-state gamma-radiolysis, combined with chromatographic techniques, were used to investigate the detailed mechanism of the (*)OH-induced oxidation of alpha-(methylthio)acetamide (alpha-MTA) in aqueous solution. The main pathway involves the formation of hydroxysulfuranyl radicals alpha-MTA-(>S(*)-OH) and alpha-(alkylthio)alkyl radicals H(3)C-S-(*)CH-C( horizontal lineO)-NH(2) (lambda(max) S(*)-OH) radicals undergo efficient conversion to intermolecularly three-electron-bonded dimeric radical cations of alpha-MTA-(>S thereforeS<)(+) (lambda(max) = 480 nm), especially for high alpha-MTA concentrations. In contrast, at low proton concentrations, alpha-MTA-(>S(*)-OH) radicals decompose via the elimination of water, formed through intramolecular hydrogen (attached to the nitrogen atom) transfer to the hydroxysulfuranyl moiety within a six-membered structure. This process leads to the formation of the imine radical H(3)C-S-CH(2)-C( horizontal lineO)(*)NH, which subsequently decays in three independent channels. The first decay channel begins with a beta-scission followed by hydrolysis and a subsequent Hofmann rearrangement. One of the end products of this first decay channel is CO(2), which was detected. The second decay channel involves an intramolecular hydrogen transfer from the deltaC carbon atom to the radical imine site producing the alpha-(alkylthio)alkyl radical H(2)C(*)-S-CH(2)-C( horizontal lineO)-NH(2). In the third decay channel there is a 1,3-hydrogen shift in the imine radical which forms the radical H(3)C-S-(*)CH-C( horizontal lineO)-NH(2). The presence of the amide group induces more complex radical chemistry that leads unexpectedly to the degradation of the CH(3)SCH(2)CONH(2) molecule into gaseous products, CO(2) and NH(3). These features of the mechanism of the (*)OH-induced oxidation of alpha-MTA are quite different from those seen in other organic sulfides in neutral solutions.

Kinetics of reversible photoisomerization: determination of the primary quantum yields for the E-Z photoisomerization of silylenephenylenevinylene derivatives.

The kinetics scheme for directly excited, photoreversible reactions is solved exactly under the assumptions of no irreversible side reactions and constant excitation intensity for the duration of the reaction. The advantages of the methodology over the extrapolation-to-zero-time and the back-reaction correction methods are (i) that the quantum yields of both the forward and reverse photoreactions can be obtained starting from either pure reactant or pure product and (ii) the conversion percentage is not limited to a narrow domain in the neighborhood of small conversions. Examples of E-Z photoisomerizations are given to illustrate the fitting procedures required. The results from these examples are compared to the photoisomerization method of extrapolating the empirical quantum yields to zero time and the back-reaction correction. The exact equations are used to justify the extrapolation-to-zero-time method and to establish criteria on extrapolation ranges for the conversion percentage of starting material.

Photocycloaddition of the T1 excited state of thioinosine to uridine and adenosine.

Novel photoadducts were obtained by irradiation of thioinosine (6-thiopurine riboside, TI) in deaerated aqueous solution without and in the presence of uridine and adenosine. Excitation (lambda > 300 nm) of TI to its excited S2 state yields a single bimolecular photoproduct. It is a purine-pyrimidine diriboside in which the purine ring is attached to the amide nitrogen of 6-amino-4-thioxo-5-formamidopyrimidine. When TI was irradiated in the presence of an excess of adenosine, two photoproducts were isolated: diribosides of N-(4,6-diaminopirymidin-5-yl)-N-formyl-6-aminopurine and N-(4-amino-6-formylamino-pyrimidin-5-yl)-6-aminopurine, both containing a purine and a formylaminopyrimidine (Fapy) fragment. The photoreaction of TI with uridine gave two regioisomeric photoproducts identified as diribosides containing either 5- or 6-(purin-6-yl)uracil as aglycones. A multistep mechanism leading to the stable photoproducts is proposed. In the first step of the mechanism, the C=S group of the excited TI undergoes a [2 + 2] cycloaddition regioselectively to the N(7)=C(8) bond of the purine ring or adds in a non-regioselective manner to the C(5)=C(6) bond of uracil. The unstable photoproducts thus formed undergo a series of dark reactions at room temperature. The photocycloaddition reactions originate from the excited T1 state of TI. This conclusion is supported by a combination of evidence from reaction quenching studies using both steady-state quantum yield determinations and kinetics results from nanosecond laser flash photolysis. The T1 state of TI is quenched by other TI molecules in their S0 state (self-quenching) and also by uridine and adenosine, all with large rate constants (0.8-5) x 10(9) M(-1) s(-1). The quantum yields of the reactions are in general very low (phi(R) < or = 8 x 10(-3)). The sources of the inefficiency in the photocycloaddition of TI to uridine and adenosine are discussed. The photoproducts containing the Fapy residue undergo deformylation and isomerization of the ribosyl moiety (anomerization, furanose/pyranose transformation) upon heating in aqueous solution. Products of the transformations were identified.

Neighboring amide participation in thioether oxidation: relevance to biological oxidation.

To investigate neighboring amide participation in thioether oxidation, which may be relevant to brain oxidative stress accompanying beta-amyloid peptide aggregation, conformationally constrained methylthionorbornyl derivatives with amido moieties were synthesized and characterized, including an X-ray crystallographic study of one of them. Electrochemical oxidation of these compounds, studied by cyclic voltammetry, revealed that their oxidation peak potentials were less positive for those compounds in which neighboring group participation was geometrically possible. Pulse radiolysis studies provided evidence for bond formation between the amide moiety and sulfur on one-electron oxidation in cases where the moieties are juxtaposed. Furthermore, molecular constraints in spiro analogues revealed that S-O bonds are formed on one-electron oxidation. DFT calculations suggest that isomeric sigma*(SO) radicals are formed in these systems.

Stereoselectivity of the hydrogen-atom transfer in benzophenone-tyrosine dyads: an intramolecular kinetic solvent effect.

To be or not to be solvated is the decisive parameter that controls the photoinduced hydrogen-atom transfer in diastereomeric ketone/phenol dyads. A kinetic solvent effect that refers to hydrogen bonding between the phenol and the solvent is suggested to be the main source of the stereoselective discrimination in the hydrogen transfer (see figure).

One-electron reduction of superoxide radical-anions by 3-alkylpolyhydroxyflavones in micelles. Effect of antioxidant alkyl chain length on micellar structure and reactivity.

In micellar solutions, one-electron reduction of *O2(-) radical-anions by 3-alkylpolyhydroxyflavones (FnH) with alkyl chains of n = 1, 4, 6, 10 carbons produces phenoxyl radicals ( (*Fn) identical to those obtained by one-electron oxidation by *Br2(-) radical-anions or by repair of tryptophan radicals. In cetyltrimethylammonium bromide (CTAB), F1H localizes in the Stern layer, and alkyl chains of other FnH solubilize in the hydrophobic interior, interacting with cetyl tails. This interaction produces more compact micelles with lower intramicellar fluidity, as suggested by the increase in the pseudo-first-order rate constant of *Fn formation ( k 1) from approximately 390 s (-1) for n = 1 to 610 s (-1) for n = 10, leading to an intramicellar bimolecular rate constant of 1 x 10 (5) M (-1) s (-1). Additionally, *F1 and *F4 decay by intermicellar bimolecular reaction (2 k = 20 and 2 x 10 (5) M (-1) s (-1), respectively) whereas other *Fn radicals are stable over seconds due to increased localization with regards to the Stern layer. In contrast, the thick uncharged hydrophilic palisade layer and the compact hydrophobic core of Triton X100 micelles are responsible for a much higher microviscosity resulting in a decrease in k 1 from approximately 15.6 s (-1) for n = 1 to 9.6 s (-1) for n = 10.