Magnetic Field Effects on the Dynamics of Radical Pairs in Micelles: A New Approach to Understanding the "Cage Effect"

The effect of temperature on the photolysis of dibenzyl ketone and 4-methyldibenzyl ketone in sodium dodecyl sulfate micelles was studied by laser flash photolysis and product distributions derived from steady-state photolysis. At high temperatures, the product distribution and radical decay kinetics are primarily due to random encounters of radicals, and the "cage effect" cannot be rationalized by geminate recombination reactions that occur before the radicals escape from the micelles. A mechanism is proposed in which the enhancement of the crosstermination product derived from random encounters is due to the different partitioning of each radical species between the micelles and the aqueous phase, thereby leading to different rates for the self-termination reactions.     

PHOTOCHEMISTRY IN A CYCLODEXTRIN CAVITY. PRIMARY PROCESSES IN THE PHOTOREDUCTION OF 3- and 4-BENZOYLPYRIDINE STUDIED BY LASER FLASH-PHOTOLYSIS*

The photochemistry of 3- and 4-benzoylpyridine-cyclodextrin inclusion complexes (BPyCDx) was examined by nanosecond laser flash-photolysis and stationary techniques. The lifetimes of the triplet complex and of the triplet radical pair, formed by H-abstraction from a glucose unit of the CDx, have been measured in β-CDx complexes. The reactivity of the heterocyclic ketones with CDx is higher than that of benzophenone, but the lower binding ability of the macrocycle toward these more hydrophylic molecules induces faster separation of the geminate radicals. The quantum yields of the escaped radicals and their decay kinetics have been determined. The β-CDx cage favours geminate recombination reactions, while α- and -γ-CDx tend to release the guest molecule. Cage products have been spectroscopically characterized in the case of the 3-BPy-β-CDx system.     

Triplet energy distribution in photoinitiators containing two dissociable groups

Suitable probe molecules containing the benzophenone chromophore and one dissociable bond [perester 1 or C-X (4, 5)] or two such bonds (2, 3) have been synthesized and studied to examine intramolecular triplet energy dispersion. Triplet energies and phosphorescence quantum yields as well as quantum efficiencies of bond scissions have been studied, and the flow of triplet energy in such molecules is discussed. Upon irradiation at 350 nm in either benzene or methanol, the target peresters undergo dissociation of both cleavable groups, producing a pair of radicals. The presence of a benzylic chloride function has little influence on the efficiency of perester dissociation. However, the presence of a benzylic bromide function was found to decrease the quantum yield of decomposition of the perester function of 3. This can be explained by taking into account the effect of the heavy atom and the rate of cage geminate radical pair recombination. The nature of the heavy atom perturbation, however, was found to be different in 5 as compared with 3.     

Synthesis and photochemistry of a new class of photocleavable protein cross-linking reagents

A new series of photocleavable protein cross-linking reagents based on bis(maleimide) derivatives of diaryl disulfides have been synthesised. They have been functionalised with cysteine and transient absorption spectra for the photolysis reaction have been recorded by using the pump-probe technique with a time resolution of 100 femtoseconds. Photolysis of the disulfide bond yields the corresponding thiyl radicals in less than a picosecond. There is a significant amount of geminate recombination, but some of the radicals escape the solvent cage and the quantum yield for photocleavage is 30 % in water.     

介质环境对辣根国氧化物酶催化荧光反应体系的影响

探讨了缓冲溶液,溶剂和表面活性剂对对羟基苯丙酸-国氧化氢- 辣根国沿化区酶反应体系反应平衡及产物荧光性质的影响,表明二聚体荧光产物中存在酸碱平衡,应荧光滴定法求得其酸离解常数pK~a≈8.3.碱式产物的荧光强于酸式, 碱性环境使酶活性降低,反应平衡时间延长,阳离子胶束溴化十六烷基三甲胺(CTMAB) 和氯化十六烷基三甲铵(CTMAC)对该体系兼有催化和增敏作用,据此提出一种更为灵敏的测定辣根过氧化物酶的方法.     

Measurements of the photodissociation quantum yields of MbNO and MbO(2) and the vibrational relaxation of the six-coordinate heme species

The (t approximately 0) photodissociation quantum yields (Y(0)) of MbNO and MbO(2) are measured to be 50 +/- 5 and 28 +/- 6%, respectively, using MbCO (Y(0) = 100%) as a reference. When photolysis does not take place, we find that a significant portion of the photon energy contributes to heating of the residual six-coordinate heme (MbNO and MbO(2)). The time constant for vibrational relaxation of the six-coordinate ligand-bound heme is found to be close to 1 ps for both samples. The MbO(2) sample also shows a approximately 4-ps optical response that is assigned to a rapid phase (25-30% amplitude) of O(2) geminate rebinding. We observe no additional geminate recombination in the MbO(2) sample out to 120 ps. In contrast, the MbNO sample displays significant geminate recombination over the first 120 ps, which can be adequately fit with two exponentials whose amplitudes and time constants appear to depend weakly on the pump wavelength. This more complex kinetic behavior conceivably arises due to heating of the photodissociated heme and its effect on the geminate recombination as the system cools. Overall, the data are consistent with a hypothesis that distortions along the iron-ligand bending coordinate play a key role in the photodissociation process. The transient formation of an unphotolyzable FeO(2) side-on binding geometry is suggested to be responsible for the lowered quantum yield of MbO(2) relative to MbNO.     

Studies of the photolysis of aromatic esters in solution and in polymer films

Photolysis of 2-naphthylenemethyl-1-naphthylacetate (NMNA) and 9-anthracenemethyl-9-anthrylacetate (AMAA) yields radicals of methylnaphthalene and methylanthracene, respectively. The longevity of these radicals makes them suitable probes for studying primary and secondary cage recombination processes in solution, and in polymeric matrices. 2,2-Di-(4-tert-octylphenyl-1-picrylhydrazyl) (DPPH) is utilized as a radical trap to report on radicals which escape from the solvent cage. Quantum yields for photolysis of NMNA and AMAA were determined in solution and in poly(methyl methacrylate) films. Both unimolecular and bimolecular processes are suppressed as a result of the greater effective viscosity in polymeric media.     

CHLORANIL-PHOTOSENSITIZED MONOMERIZATION OF DIMETHYLTHYMINE CYCLOBUTANE DIMERS and EFFECT OF MAGNESIUM PERCHLORATE

The photosensitized monomerization of the cyclobutane dimers of 1,3-dimethylthymine by p-chloranil was investigated by means of steady-state irradiation and laser-flash photolysis. Quantum yields for the monomerization are 0.34 for the cis,syn dimer, 0.39 for the trans,syn dimer, and much less than 10(-2) for the cis,anti isomer. Formation of the chloranil anion radical associated with quenching of triplet chloranil by the dimers demonstrates that electron transfer from dimers to triplet chloranil occurs to initiate the monomerization. Kinetic analysis suggested that the syn-dimer cation radicals undergo the ring cleavage at greater than or equal to 10(9) s-1 before escaping from the solvent cage, while the reactivity of the anti-dimer cation radical is very low. The different reactivities of the syn and anti dimer cation radicals are discussed in terms of through-bond coupling between the n orbitals of N(1) and N(1') involving the cyclobutane-ring sigma orbitals. In the cases of the syn-dimers, the sensitizer-dimer ion-radical pairs undergo the rapid geminate recombination that works as a major energy dissipating channel responsible for the lower-than-unity quantum yields. It has been found that the presence of Mg(ClO4)2 at 0.1 M enhances approximately 1.5 times either the monomerization of the syn dimers or the formation of the chloranil anion radical. A laser-flash photolysis study shows that Mg2+ forms a complex with either the triplet or the anion radical of chloranil. The net salt effects are attributed to the retardation of the rapid geminate recombination by the participation of Mg2+ in the sensitizer-dimer ion-radical pairs.     

Photoinduced electron transfer and geminate recombination in the group head region of micelles

A pump-probe spectroscopic study of photoinduced forward electron transfer and geminate recombination between donors and acceptors located in the head group regions of micelles is presented. The hole donor is octadecyl-rhodamine B (ODRB) and the hole acceptor is N,N-dimethyl-aniline (DMA). The experiments are conducted as a function of the DMA concentration in the dodecyltrimethylammonium bromide and tetradecyltrimethylammonium bromide micelles. In spite of the fact that the absorptions of both the ODRB radical and ground state bleach spectrally overlap with the ODRB excited state absorption, a procedure that makes it possible to determine the geminate recombination dynamics is presented. These experiments are the first to measure the dynamics of geminate recombination in micelles, and the experiments have two orders of magnitude better time resolution than previous studies of forward transfer. The experimental data are compared to statistical mechanics theoretical calculations of both the forward transfer and the geminate recombination. The theory includes important aspects of the topology of the micelle and the diffusion of the donor-acceptors in the micelle head group region. A semiquantitative but nonquantitative agreement between theory and experiments is achieved.     

水对环己烷-磷酸三丁酯体系γ辐解和脉冲辐解的影响(英文)

为确定辐解体系中烷烃单重态的来源,研究了水对环己烷(C6H12)-磷酸三丁酯(TBP)体系γ辐解和脉冲辐解的影响.水显著地抑制C6H12-TBPγ辐解体系中TBP酸式辐解产物的生成,酸式辐解产物的G值从无水体系的8.2降至水饱和体系的1.9,表明水分子既抑制了TBP自身辐解生成的TBP单重态,又通过阻断单重态C6H12与TBP之间的能量转移,消除了C6H12自身辐解对单重态TBP的酸式辐解产物的敏化作用.但在以二苯酮(Bp)为探针的TBP-Bp和C6H12-TBP-Bp脉冲辐解体系中,水的加入并未抑制辐解产物羰自由基的产额,其机理是,水分子通过与偕离子对反应而抑制C6H12单重态和TBP单重态的产生,但不影响羰自由基的生成.这也许是辐解体系中大部分(G=1.3)单重态C6H12和部分(G=0.8)单重态TBP来源于偕离子对[C6H12·+…e-]和[TBP·+…e-]的复合的直接证据.由于极性较大,水可用作偕离子对的高效捕捉剂.     

The effects of media properties on the horseradish peroxidase-catalyzed fluorogenic reaction

The effects of media properties including buffers, acidity, solvents and surfactant on horseradish peroxidase-catalyzed fluorogenic reaction were investigated. The results showed that the so-called non-fluorescent hydrogen donors were in fact fluorescent. There existed an acid—base equilibrium in the fluorescent dimer product. For p -hydroxyphenylpropionic acid, a pK_a value of 8.0 for the product was obtained from its titration curve. The product fluorescence increased with higher pH, however, a longer time was needed to reach the reaction equilibrium due to the pH mismatch problem. Cationic micelles cetyltrimethylammonium bromide and cetyltrimethylammonium chloride could reduce the pH mismatch and offered a way to further increase the determination sensitivity. Finally, a micelle-enhanced flow-injection analysis of horseradish peroxidase is suggested.     

Apparent Molar Volume and Apparent Molar Adiabatic Compressibility Studies of 2,6-Di-tert-butyl-4-methylphenol and 2-tert-Butyl-4-methoxyphenol in Aqueous Micelle Solutions of Hexadecyltrimethylammonium Chloride as a Function of Surfactant Concentration and Temperature

Ultrasonic velocities and densities of aqueous solutions of cetyltrimethylammonium chloride have been measured at concentrations below 0.35 mol kg^-1 at 25, 35, and 45°C. Apparent molar volume and apparent molar adiabatic compressibility properties of the aqueous surfactant solutions were derived from these data. Apparent molar volumes and apparent molar adiabatic compressibilities of 2,6-di-tert-butyl-4-methylphenol and 2-tert-butyl-4-methoxyphenol dissolved in aqueous micellar solutions of cetyltrimethylammonium chloride were determined as a function of surfactant concentration and temperature. The results obtained for the binary and ternary systems are compared with those previously published for binary aqueous cetyltrimethylammonium bromide systems and for ternary systems of this surfactant containing the same additives. The degree of counterion dissociation from the micelles and the effect this has on the extent of hydration of the head group region of the micelle are shown to have an effect on the solubilization sites of hydrophobic-like additives in these micelles.     

Magnetic Field Effects on the Dynamics of Radical Pairs: The Partition Effect in Vesicles

A combination of product studies and laser flash photolysis (LFP) was used to study the recombination of radical pairs derived from dibenzyl ketone (DBK) and its methyl derivative. Two sizes of vesicles consisting of dioctade-cyldimethylammonium chloride (DODAC) were generated. In the product studies, irradiation of the ketone led to a substantial overall cage effect both above and below the phase-transition temperature. However, LFP results demonstrate that no geminate reactions, that correspond to the reactions of radicals generated from the same precursor molecule are occurring even at room temperature. The results are discussed in terms of the partition effect where the cage effect is determined by the differences in the solubility of the radical inside the vesicle bilayer and in the aqueous phase. In small (30 nm diameter) vesicles, most of the random recombination occurs after re-entry of the radicals into the bilayer, whereas in large (?150 nm) liposomes, a significant proportion of the recombination reactions takes place in the bulk water. This work demonstrates that magnetic fields can efficiently alter the reactivity of radicals involved in nongeminate pathways and further supports the use of the radical pair mechanism to explain possible effects of magnetic fields in biological systems.     

Cetylpyridinium chloride micelles as a selective fluorescence quenching solvent media for discriminating between alternant versus nonalternant polycyclic aromatic hydrocarbons

Fluorescence behavior of 41 polycyclic aromatic hydrocarbons (PAHs) dissolved in aqueous micellar cetyltrimethylammonium chloride (CTAC) solvent media and in five different cetyltrimethylammonium chloride + cetylpyridinium chloride (CPC) surfactant mixtures is reported. Experimental fluorescence measurements reveal that CPC is a selective fluorescence quenching agent for alternant PAHs. The cetylpyridinium ion effectively quenched emission intensities of the 21 alternant PAHs studied. Emission intensities of nonalternant PAHs, with a few noted exceptions, were unaffected by the presence of CPC in the mixed cationic surfactant micelles.     

Dramatic Effect of Magnetite Particles on the Dynamics of Photogenerated Free Radicals

Abstract— Polymeric particles of about 1 u.m in diameter and containing around 40% magnetite have a dramatic influence on the dynamics of triplet radical pair reactions occurring in micelles in their vicinity. The effect has been monitored with laser flash photolysis techniques and results in a decrease of the number of radicals that separate from their geminate partner and an acceleration of radical pair geminate reactions. The effect involves remote interactions because the solution contains ca 10¹¹micelles for each polymeric particle. Magnetite also perturbs the way in which the radicals interact with an external magnetic field.     

Magnetic field control of photoinduced silver nanoparticle formation

The micellar photoreduction of benzophenone in the presence of Ag+ leads to very rapid and efficient formation of silver nanoperticles. External magnetic fields can be used to control the rate of formation and properties of silver nanoparticles generated by reaction of ketyl radicals formed in the photoreduction of benzophenone in surfactant micelles. The effect is attributed to Zeeman splitting of the triplet sublevels of the confined radical pair that causes a reduction in the rate of geminate processes and increases the availability of ketyl radicals (through escape processes) for metal ion reduction.     

The Origin of Magnetic Field Dependent Recombination in Alkylcobalamin Radical Pairs

Magnetic field effect studies of alkylcobalamin photolysis provide evidence for the formation of a reactive radical pair that is born in the singlet spin state. The radical pair recombination process that is responsible for the magnetic field dependence of the continuous-wave (CW) quantum yield is limited to the diffusive radical pair. Although the geminate radical pair of adenosylcob(III)alamin also undergoes magnetic field dependent recombination (A. M. Chagovetz and C. B. Grissom, J. Am. Chem. Soc. 115, 12152–12157, 1993), this process does not account for the magnetic field dependence of the CW quantum yield that is only observed in viscous solvents. Glycerol and ethylene glycol increase the microviscosity of the solution and thereby increase the lifetime of the spin-correlated diffusive radical pair. This enables magnetic field dependent recombination among spin-correlated diffusive radical pairs in the solvent cage. Magnetic field dependent recombination is not observed in the presence of nonviscosigenic alcohols such as isopropanol, thereby indicating the importance of the increased microviscosity of the medium. Paramagnetic radical scavengers that trap alkyl radicals that escape the solvent cage do not diminish the magnetic field effect on the CW quantum yield, thereby ruling out radical pair recombination among randomly diffusing radical pairs, as well as excluding the involvement of solvent-derived radicals. Magnetic field dependent recombination among alkylcobalamin radical pairs has been simulated by a semiclassical model of radical pair dynamics and recombination. These calculations support the existence of a singlet radical pair precursor.     

Production of free radicals and triplets from contact radical pairs and from photochemically generated radical ions

The quantum yields of triplets and free radicals (or radical ions) that escaped recombination in photochemically created primary radical pairs (or radical ion pairs) are calculated. As the products of monomolecular photodissociation, the neutral radicals appear at contact, while the ions are initially distributed over the space due to distant photoionization (bimolecular electron transfer) in the liquid solution. The diffusional dependence of the quantum yields is shown to be different when recombination starts from contact or from separated reactants. The experimental data for recombination of ionized perylene with aromatic amine counterions is well fitted with the noncontact initial distribution provided the recombination is also noncontact and even more distant than ionization.