Metalloprotein association,self-association,and dynamics governed by hydrophobic interactions: simultaneous occurrence of gated and true electron-transfer reactions between cytochrome f and cytochrome c(6) from Chlamydomonas reinhardtii

Noninvasive reconstitution of the heme in cytochrome c(6) with zinc(II) ions allowed us to study the photoinduced electron-transfer reaction (3)Zncyt c(6) + cyt f(III) --> Zncyt c(6)(+) + cyt f(II) between physiological partners cytochrome c(6) and cytochrome f, both from Chlamydomonas reinhardtii. The reaction kinetics was analyzed in terms of protein docking and electron transfer. In contrast to various protein pairs studied before, both the unimolecular and the bimolecular reactions of this oxidative quenching take place at all ionic strengths from 2.5 through 700 mM. The respective intracomplex rate constants are k(uni) (1.2 +/- 0.1) x 10(4) s(-1) for persistent and k(bi) (9 +/- 4) x 10(2) s(-1) for the transient protein complex. The former reaction seems to be true electron transfer, and the latter seems to be electron transfer gated by a structural rearrangement. Remarkably, these reactions occur simultaneously, and both rate constants are invariant with ionic strength. The association constant K(a) for zinc cytochrome c(6) and cytochrome f(III) remains (5 +/- 3) x 10(5) M(-1) in the ionic strength range from 700 to 10 mM and then rises slightly to (7 +/- 2) x 10(6) M(-1), as ionic strength is lowered to 2.5 mM. Evidently, docking of these proteins from C. reinhardtii is due to hydrophobic interaction, slightly augmented by weak electrostatic attraction. Kinetics, chromatography, and cross-linking consistently show that cytochrome f self-dimerizes at ionic strengths of 200 mM and higher. Cytochrome f(III) quenches triplet state (3)Zncyt c(6), but its dimer does not. Formation of this unreactive dimer is an important step in the mechanism of electron transfer. Not only association between the reacting proteins, but also their self-association, should be considered when analyzing reaction mechanisms.     

Active-site structure and electron-transfer reactivity of plastocyanins

The active-site structures of Cu(II) plastocyanins (PCu's) from a higher plant (parsley), a seedless vascular plant (fern, Dryopteris crassirhizoma), a green alga (Ulva pertusa), and cyanobacteria (Anabaena variabilis and Synechococcus) have been investigated by paramagnetic (1)H NMR spectroscopy. In all cases the spectra are similar, indicating that the structures of the cupric sites, and the spin density distributions onto the ligands, do not differ greatly between the proteins. The active-site structure of PCu has remained unaltered during the evolutionary process. The electron transfer (et) reactivity of these PCu's is compared utilizing the electron self-exchange (ESE) reaction. At moderate ionic strength (0.10 M) the ESE rate constant is dictated by the distribution of charged amino acid residues on the surface of the PCu's. Most higher plant and the seedless vascular plant PCu's, which have a large number of acidic residues close to the hydrophobic patch surrounding the exposed His87 ligand (the proposed recognition patch for the self-exchange process), have ESE rate constants of approximately 10(3) M(-)(1) s(-)(1). Removal of some of these acidic residues, as in the parsley and green algal PCu's, results in more favorable protein-protein association and an ESE rate constant of approximately 10(4) M(-)(1) s(-)(1). Complete removal of the acidic patch, as in the cyanobacterial PCu's, leads to ESE rate constants of approximately 10(5)-10(6) M(-)(1) s(-)(1). The ESE rate constants of the PCu's with an acidic patch also tend toward approximately 10(5)-10(6) M(-)(1) s(-)(1) at higher ionic strength, thus indicating that once the influence of charged residues has been minimized the et capabilities of the PCu's are comparable. The cytochromes and Fe-S proteins, two other classes of redox metalloproteins, also possess ESE rate constants of approximately 10(5)-10(6) M(-)(1) s(-)(1) at high ionic strength. The effect of the protonation of the His87 ligand in PCu(I) on the ESE reactivity has been investigated. When the influence of the acidic patch is minimized, the ESE rate constant decreases at high [H(+)].     

Electronic energy self-exchange with macrocyclic chromium(III) complexes

The luminescence lifetimes of N-deuterated Cr(III) complexes of macrocyclic tetraamine ligands, trans-CrN(4)X(2)(n)()(+), are substantially longer than those of their undeuterated counterparts in room temperature solution. Thus, excited-state emission quenching of the longer lived species by the shorter lived species may be studied by analyzing the decay profile following pulsed excitation. Flash photolysis experiments were carried out for three deuterated/undeuterated pairs of trans-CrN(4)X(2)(n)()(+) complexes (where X = CN-, NH(3), and F-). For the trans-Cr(cyclam)(CN)(2)(+) system in H(2)O, it was determined that energy transfer was occurring between the deuterated and undeuterated species. Although the rate constant of energy transfer was too fast to measure explicitly, it could be bracketed as k(et) >7 x 10(6) M(-1) s(-1). For this reaction it was possible to measure an equilibrium constant which was very near 1.0. For trans-Cr(cyclam)(NH(3))(2)(3+) in DMSO, it was also established that energy transfer was occurring and rate constants of 2.4 x 10(6) M(-1) s(-1) (mu = 0.1) and 9.7 x 10(6) M(-1) s(-1) (mu = 1.0) were determined by a Stern-Volmer analysis. For trans-Cr(tet a)F(2+) in H(2)O, no energy transfer was observed, which implies that the rate constant is <3 x 10(5) M(-1) s(-1). Because these energy-transfer reactions represent self-exchange energy transfer and are thus thermoneutral, we are able to analyze the results using Marcus theory and draw some conclusions about the relative importance of nuclear reorganization and electronic factors in the overall rate.     

Electron transfer reactions of tris(polypyridine)cobalt(III) complexes, [Co(N-N)3]3+, with verdazyl radicals in acetonitrile solution

The kinetics and mechanisms of the reactions of 3-(4-X)-phenyl-1,5-diphenyl-verdazyl radicals where X = Cl, H, CH3 and CH3O with [Co(N-N)3]3+, N-N = 2,2'-bipyridyl (bpy), 1,10-phenanthroline (phen) and 4,7-dimethyl-1,10-phenanthroline (4,7-Me2phen), have been investigated in acetonitrile at 25 degrees C and ionic strength 0.05 mol dm(-3)(nC4H9)4NPF6 using stopped flow spectrophotometry. In all cases, transfer of one electron from the radical takes place resulting in the production of a Co(II) species and a verdazylium cation. The electron transfer occurs by an outer-sphere mechanism and the reactions appear to be consistent with Marcus theory. The self-exchange rate constants for the verdazyl-verdazylium cation have been estimated and are of the order of 3.4(+/-1.9) x 10(7) dm(3) mol(-1) s(-1). This rate constant is consistent with the fact that the reactions of [Ru(bpy)3]3+ with verdazyl radicals are too rapid to be investigated by stopped flow spectrophotometry.     

Electron transfer in uranyl(VI)-uranyl(V) complexes in solution

The rates and mechanisms of the electron self-exchange between U(V) and U(VI) in solution have been studied with quantum chemical methods. Both outer-sphere and inner-sphere mechanisms have been investigated; the former for the aqua ions, the latter for binuclear complexes containing hydroxide, fluoride, and carbonate as bridging ligand. The calculated rate constant for the self-exchange reaction UO(2)(+)(aq) + UO(2)(2+)(aq) <=>UO(2)(2+)(aq) + UO(2)(+)(aq), at 25 degrees C, is k = 26 M(-1) s(-1). The lower limit of the rate of electron transfer in the inner-sphere complexes is estimated to be in the range 2 x 10(4) to 4 x 10(6) M(-1) s(-1), indicating that the rate for the overall exchange reaction may be determined by the rate of formation and dissociation of the binuclear complex. The activation energy for the outer-sphere model calculated from the Marcus model is nearly the same as that obtained by a direct calculation of the precursor- and transition-state energy. A simple model with one water ligand is shown to recover 60% of the reorganization energy. This finding is important because it indicates the possibility to carry out theoretical studies of electron-transfer reactions involving M(3+) and M(4+) actinide species that have eight or nine water ligands in the first coordination sphere.     

Electrochemistry and homogeneous self-exchange kinetics of the aqueous 12-tungstoaluminate(5-/6-) couple

The effect of alkali metal (M) chloride or triflate supporting electrolytes (0.1-1.0 mol L(-1)) on the midpoint potential E(m) of the aqueous AlW12O40(5-/6-) couple in cyclic voltammetry, after correction (E(corr)) for liquid junction potentials, can be represented in terms of ionic strength according to the extended Debye-Hückel equation. However, unrealistically short AlW12O40(5-/6-)-cation closest-approach distances are required to accommodate the specific effects of M+, and the infinite-dilution potential E(corr)(0) values are not quite consistent from one M+ to another. The pressure dependence of Em is qualitatively consistent with expectations based on the Born-Drude-Nernst theory. The strong accelerating effects of supporting electrolytes on the standard electrode reaction rate constant k(el) at pH 3 as measured by alternating current voltammetry (ACV), and on the homogeneous self-exchange rate constant k(ex) at pH 3-7 as measured by 27Al line broadening, depend specifically on the identity and concentration of M+ (Li+ < Na+ < K+ < Rb+) rather than on the ionic strength, whereas the effect of the nature of the supporting anion (Cl- or CF3SO3-) is negligible. Extrapolation of k(el) and k(ex) to zero [M+] indicates that the uncatalyzed electron transfer rate is negligibly small relative to the M+ catalyzed rates. The kinetic effects of M+ show no evidence of the saturation expected had they been due primarily to ion pairing with AlW12O40(5-/6-). The catalytic effect of M+ operates primarily through lowering the enthalpy of activation, which is partially offset by a strongly negative entropy of activation and, for the homogeneous exchange catalyzed by K+ or Rb+, becomes mildly negative; thus, the catalytic effect of M(+) is enthalpy-driven but entropy-limited. For the electrode reaction, the volume of activation averages +4.5 +/- 0.2 cm(3) mol(-1) for all M+ and [M+], in contrast to the negative value predicted theoretically for the uncatalyzed reaction. These results are consistent with a reaction mechanism, previously proposed for other anion-anion electron-transfer reactions, in which anion-anion electron transfer is facilitated by partially dehydrated M+.     

Redox reactivity and reorganization energy of zinc cytochrome c cation radical

Little is known about transient intermediates in photoinduced electron-transfer reactions of metalloproteins. Oxidative quenching of the triplet state of zinc cytochrome c, 3Zncyt, is done at 20 degrees C, pH 7.00, and ionic strength of 1.00 M, conditions that suppress the thermal back-reaction and prolong the lifetime of the cation radical, Zncyt+. This species is reduced by [Fe(CN)6]4-, [W(CN)8]4-, [Os(CN)6]4-, [Mo(CN)8]4-, and [Ru(CN)6]4- complexes of similar structures and the same charge. The rate constants and thermodynamic driving forces for these five similar electron-transfer reactions were fitted to Marcus theory. The reorganization energy of Zncyt+ is lambda = 0.38(5) eV, lower than that of native cytochrome c, because the redox orbital of the porphyrin cation radical is delocalized and possibly because Met80 is not an axial ligand to the zinc(II) ion in the reconstituted cytochrome c. The rate constant for electron self-exchange between Zncyt+ and Zncyt, k11 = 1.0(5) x 10(7) M(-1) s(-1), is large owing to the extended electron delocalization and relatively low reorganization energy. These results may be relevant to zinc(II) derivatives of other heme proteins, which are often used in studies of photoinduced electron-transfer reactions.     

Electron and hydrogen-atom self-exchange reactions of iron and cobalt coordination complexes

Reported here are self-exchange reactions between iron 2,2'-bi(tetrahydro)pyrimidine (H(2)bip) complexes and between cobalt 2,2'-biimidazoline (H(2)bim) complexes. The (1)H NMR resonances of [Fe(II)(H(2)bip)(3)](2+) are broadened upon addition of [Fe(III)(H(2)bip)(3)](3+), indicating that electron self-exchange occurs with k(Fe,e)(-) = (1.1 +/- 0.2) x 10(5) M(-1) s(-1) at 298 K in CD(3)CN. Similar studies of [Fe(II)(H(2)bip)(3)](2+) plus [Fe(III)(Hbip)(H(2)bip)(2)](2+) indicate that hydrogen-atom self-exchange (proton-coupled electron transfer) occurs with k(Fe,H.) = (1.1 +/- 0.2) x 10(4) M(-1) s(-1) under the same conditions. Both self-exchange reactions are faster at lower temperatures, showing small negative enthalpies of activation: DeltaH++(e(-)) = -2.1 +/- 0.5 kcal mol(-1) (288-320 K) and DeltaH++(H.) = -1.5 +/- 0.5 kcal mol(-1) (260-300 K). This behavior is concluded to be due to the faster reaction of the low-spin states of the iron complexes, which are depopulated as the temperature is raised. Below about 290 K, rate constants for electron self-exchange show the more normal decrease with temperature. There is a modest kinetic isotope effect on H-atom self-exchange of 1.6 +/- 0.5 at 298 K that is close to that seen previously for the fully high-spin iron biimidazoline complexes.(12) The difference in the measured activation parameters, E(a)(D) - E(a)(H), is -1.2 +/- 0.8 kcal mol(-1), appears to be inconsistent with a semiclassical view of the isotope effect, and suggests extensive tunneling. Reactions of [Co(H(2)bim)(3)](2+)-d(24) with [Co(H(2)bim)(3)](3+) or [Co(Hbim)(H(2)bim)(2)](2+) occur with scrambling of ligands indicating inner-sphere processes. The self-exchange rate constant for outer-sphere electron transfer between [Co(H(2)bim)(3)](2+) and [Co(H(2)bim)(3)](3+) is estimated to be 10(-)(6) M(-1) s(-1) by application of the Marcus cross relation. Similar application of the cross relation to H-atom transfer reactions indicates that self-exchange between [Co(H(2)bim)(3)](2+) and [Co(Hbim)(H(2)bim)(2)](2+) is also slow, < or =10(-3) M(-1) s(-1). The slow self-exchange rates for the cobalt complexes are apparently due to their interconverting high-spin [Co(II)(H(2)bim)(3)](2+) with low-spin Co(III) derivatives.     

Direct oxidation of L-cysteine by [FeIII(bpy)2(CN)2]+ and [FeIII(bpy)(CN)4]-

The oxidation of L-cysteine by the outer-sphere oxidants [Fe(bpy)2(CN)2]+ and [Fe(bpy)(CN)4]- in anaerobic aqueous solution is highly susceptible to catalysis by trace amounts of copper ions. This copper catalysis is effectively inhibited with the addition of 1.0 mM dipicolinic acid for the reduction of [Fe(bpy)2(CN)2]+ and is completely suppressed with the addition of 5.0 mM EDTA (pH<9.00), 10.0 mM EDTA (9.010.0) for the reduction of [Fe(bpy)(CN)4]-. 1H NMR and UV-vis spectra show that the products of the direct (uncatalyzed) reactions are the corresponding Fe(II) complexes and, when no radical scavengers are present, L-cystine, both being formed quantitatively. The two reactions display mild kinetic inhibition by Fe(II), and the inhibition can be suppressed by the free radical scavenger PBN (N-tert-butyl-alpha-phenylnitrone). At 25 degrees C and micro=0.1 M and under conditions where inhibition by Fe(II) is insignificant, the general rate law is -d[Fe(III)]/dt=k[cysteine]tot[Fe(III)], with k={k2Ka1[H+]2+k3Ka1Ka2[H+]+k4Ka1Ka2Ka3{/}[H+]3+Ka1[H+]2+Ka1Ka2[H+]+Ka1Ka2Ka3}, where Ka1, Ka2, and Ka3 are the successive acid dissociation constants of HSCH2CH(NH3+)CO2H. For [Fe(bpy)2(CN)2]+, the kinetics over the pH range of 3-7.9 yields k2=3.4+/-0.6 M(-1) s(-1) and k3=(1.18+/-0.02)x10(6) M(-1) s(-1) (k4 is insignificant in the fitting). For [Fe(bpy)(CN)4]- over the pH range of 6.1-11.9, the rate constants are k3=(2.13+/-0.08)x10(3) M(-1) s(-1) and k4=(1.01+/-0.06)x10(4) M(-1) s(-1) (k2 is insignificant in the fitting). All three terms in the rate law are assigned to rate-limiting electron-transfer reactions in which various thiolate forms of cysteine are reactive. Applying Marcus theory, the self-exchange rate constant of the *SCH2CH(NH2)CO2-/-SCH2CH(NH2)CO2- redox couple was obtained from the oxidation of L-cysteine by [Fe(bpy)(CN)4]-, with k11=4x10(5) M(-1) s(-1). The self-exchange rate constant of the *SCH2CH(NH3+)CO2-/-SCH2CH(NH3+)CO2- redox couple was similarly obtained from the rates with both Fe(III) oxidants, a value of 6x10(6) M(-1) s(-1) for k11 being derived. Both self-exchange rate constants are quite large as is to be expected from the minimal rearrangement that follows conversion of a thiolate to a thiyl radical, and the somewhat lower self-exchange rate constant for the dianionic form of cysteine is ascribed to electrostatic repulsion.     

Slow hydrogen atom self-exchange between Os(IV) anilide and Os(III) aniline complexes: relationships with electron and proton transfer self-exchange

Hydrogen atom, proton and electron transfer self-exchange and cross-reaction rates have been determined for reactions of Os(IV) and Os(III) aniline and anilide complexes. Addition of an H-atom to the Os(IV) anilide TpOs(NHPh)Cl(2) (Os(IV)NHPh) gives the Os(III) aniline complex TpOs(NH(2)Ph)Cl(2) (Os(III)NH(2)Ph) with a new 66 kcal mol(-1) N-H bond. Concerted transfer of H* between Os(IV)NHPh and Os(III)NH(2)Ph is remarkably slow in MeCN-d(3), with k(ex)(H*) = (3 +/- 2) x 10(-3) M(-1) s(-1) at 298 K. This hydrogen atom transfer (HAT) reaction could also be termed proton-coupled electron transfer (PCET). Related to this HAT process are two proton transfer (PT) and two electron transfer (ET) self-exchange reactions, for instance, the ET reactions Os(IV)NHPh + Os(III)NHPh(-) and Os(IV)NH(2)Ph(+) + Os(III)NH(2)Ph. All four of these PT and ET reactions are much faster (k = 10(3)-10(5) M(-1) s(-1)) than HAT self-exchange. This is the first system where all five relevant self-exchange rates related to an HAT or PCET reaction have been measured. The slowness of concerted transfer of H* between Os(IV)NHPh and Os(III)NH(2)Ph is suggested to result not from a large intrinsic barrier but rather from a large work term for formation of the precursor complex to H* transfer and/or from significantly nonadiabatic reaction dynamics. The energetics for precursor complex formation is related to the strength of the hydrogen bond between reactants. To probe this effect further, HAT cross-reactions have been performed with sterically hindered aniline/anilide complexes and nitroxyl radical species. Positioning steric bulk near the active site retards both H* and H(+) transfer. Net H* transfer is catalyzed by trace acids and bases in both self-exchange and cross reactions, by stepwise mechanisms utilizing the fast ET and PT reactions.     

Cation-independent electron transfer between ferricyanide and ferrocyanide ions in aqueous solution

Electron transfer between Fe(CN)(6)(3-) and Fe(CN)(6)(4-) in homogeneous aqueous solution with K(+) as the counterion normally proceeds almost exclusively by a K(+)-catalyzed pathway, but this can be suppressed, and the direct Fe(CN)(6)(3)(-)-Fe(CN)(6)(4-) electron transfer path exposed, by complexing the K(+) with crypt-2.2.2 or 18-crown-6. Fe((13)CN)(6)(4-)-NMR line broadening measurements using either crypt-2.2.2 or (with extrapolation to zero uncomplexed [K(+)]) 18-crown-6 gave consistent values for the rate constant and activation volume (k(0) = (2.4 +/- 0.1) x 10(2) L mol(-1) s(-1) and Delta V(0) = -11.3 +/- 0.3 cm(3) mol(-1), respectively, at 25 degrees C and ionic strength I = 0.2 mol L(-1)) for the uncatalyzed electron transfer path. These values conform well to predictions based on Marcus theory. When [K(+)] was controlled with 18-crown-6, the observed rate constant k(ex) was a linear function of uncomplexed [K(+)], giving k(K) = (4.3 +/- 0.1) x 10(4) L(2) mol(-2) s(-1) at 25 degrees C and I = 0.26 mol L(-1) for the K(+)-catalyzed pathway. When no complexing agent was present, k(ex) was roughly proportional to [K(+)](total), but the corresponding rate constant k(K)' (=k(ex)/[K(+)](total)) was about 60% larger than k(K), evidently because ion pairing by hydrated K(+) lowered the anion-anion repulsions. Ionic strength as such had only a small effect on k(0), k(K), and k(K)'. The rate constants commonly cited in the literature for the Fe(CN)(6)(3-/4-) self-exchange reaction are in fact k(K)'[K(+)](total) values for typical experimental [K(+)](total) levels.     

Kinetics and mechanisms of the oxidation of iodide and bromide in aqueous solutions by a trans-dioxoruthenium(VI) complex

The kinetics and mechanisms of the oxidation of I (-) and Br (-) by trans-[Ru (VI)(N 2O 2)(O) 2] (2+) have been investigated in aqueous solutions. The reactions have the following stoichiometry: trans-[Ru (VI)(N 2O 2)(O) 2] (2+) + 3X (-) + 2H (+) --> trans-[Ru (IV)(N 2O 2)(O)(OH 2)] (2+) + X 3 (-) (X = Br, I). In the oxidation of I (-) the I 3 (-)is produced in two distinct phases. The first phase produces 45% of I 3 (-) with the rate law d[I 3 (-)]/dt = ( k a + k b[H (+)])[Ru (VI)][I (-)]. The remaining I 3 (-) is produced in the second phase which is much slower, and it follows first-order kinetics but the rate constant is independent of [I (-)], [H (+)], and ionic strength. In the proposed mechanism the first phase involves formation of a charge-transfer complex between Ru (VI) and I (-), which then undergoes a parallel acid-catalyzed oxygen atom transfer to produce [Ru (IV)(N 2O 2)(O)(OHI)] (2+), and a one electron transfer to give [Ru (V)(N 2O 2)(O)(OH)] (2+) and I (*). [Ru (V)(N 2O 2)(O)(OH)] (2+) is a stronger oxidant than [Ru (VI)(N 2O 2)(O) 2] (2+) and will rapidly oxidize another I (-) to I (*). In the second phase the [Ru (IV)(N 2O 2)(O)(OHI)] (2+) undergoes rate-limiting aquation to produce HOI which reacts rapidly with I (-) to produce I 2. In the oxidation of Br (-) the rate law is -d[Ru (VI)]/d t = {( k a2 + k b2[H (+)]) + ( k a3 + k b3[H (+)]) [Br (-)]}[Ru (VI)][Br (-)]. At 298.0 K and I = 0.1 M, k a2 = (2.03 +/- 0.03) x 10 (-2) M (-1) s (-1), k b2 = (1.50 +/- 0.07) x 10 (-1) M (-2) s (-1), k a3 = (7.22 +/- 2.19) x 10 (-1) M (-2) s (-1) and k b3 = (4.85 +/- 0.04) x 10 (2) M (-3) s (-1). The proposed mechanism involves initial oxygen atom transfer from trans-[Ru (VI)(N 2O 2)(O) 2] (2+) to Br (-) to give trans-[Ru (IV)(N 2O 2)(O)(OBr)] (+), which then undergoes parallel aquation and oxidation of Br (-), and both reactions are acid-catalyzed.     

Self-exchange reaction of [Ni(mnt)2](1-,2-) in nonaqueous solutions

The rate constant, k, for the homogeneous electron transfer (self-exchange) reaction between the diamagnetic bis(maleonitriledithiolato)nickel dianion, [Ni(mnt) 2] (2-), and the paramagnetic monoanion, [Ni(mnt) 2] (1-), has been determined in acetone and nitromethane (CH 3NO 2) using (13)C NMR line widths at 22 degrees C (mnt = 1,2-S 2C 2(CN) 2). The values of k (2.91 x 10 (6) M (-1) s (-1) in acetone, 5.78 x 10 (6) M (-1) s (-1) in CH 3NO 2) are faster than those for the electron transfer reactions of other Ni(III,II) couples; the structures of [Ni(mnt) 2] (1-) and [Ni(mnt) 2] (2-) allow for a favorable overlap that lowers the free energy of activation. The values of k are consistent with the predictions of Marcus theory. In addition to k, the spin-lattice relaxation time, T 1e, of [Ni(mnt) 2] (1-) is obtained from the NMR line width analysis; the values are consistent with those predicted by spin relaxation theory.     

Reduction of octacyanomolybdate(V) by thioglycolic acid in aqueous media

In aqueous media at 25 degrees C [Mo(CN)(8)](3-) is reduced by thioglycolic acid (HSCH(2)COOH, TGA), and the reaction is strongly accelerated by the presence of trace amounts of copper ions. Dipicolinic acid (dipic) is an effective inhibitor of the copper catalysis. Both with and without dipic the reaction has the stoichiometry 2[Mo(CN)(8)](3-) + 2TGA --> 2[Mo(CN)(8)](4-) + RSSR, where RSSR is the disulfide derived from formal oxidative dimerization of TGA. In the presence of dipic, PBN (N-tert-butyl-alpha-phenyl-nitrone), and with a large excess of TGA the rate law for consumption of [Mo(CN)(8)](3-) is first order in both [TGA] and [Mo(CN)(8)(3-)]. The complex pH dependence is consistent with (-)SCH(2)CO(2)(-) being highly reactive (k = 1.8 x 10(4) M(-1) s(-1)), the monoanion being less reactive, and HSCH(2)CO(2)H being unreactive. A mechanism is proposed in which the dianion undergoes electron transfer to [Mo(CN)(8)](3-), thus generating the thiyl radical. Analysis of the electron-transfer rate constant in terms of Marcus theory yields an effective self-exchange rate constant for the thiolate/thiyl redox couple that is in reasonable agreement with the value derived previously from the reaction of TGA with [IrCl(6)](2-). When copper catalysis is inhibited, the two reactions differ substantially in that the yield of (-)O(3)SCH(2)CO(2)(-) is significant for [IrCl(6)](2-) but undetectable for [Mo(CN)(8)](3-).     

Electron transfer reactions between copper(II) porphyrin complexes and various oxidizing reagents in acetonitrile

Homogeneous electron transfer reactions of the Cu(II) complexes of 5,10,15,20-tetraphenylporphyrin (TPP) and 2,3,7,8,12,13,17,18-octaethylporphyrin (OEP) with various oxidizing reagents were spectrophotometrically investigated in acetonitrile. The reaction products were confirmed to be the pi-cation radicals of the corresponding Cu(II)-porphyrin complexes on the basis of the electronic spectra and the redox potentials of the complexes. The rate of the electron transfer reaction between the Cu(II)-porphyrin complex and solvated Cu(2+) was determined as a function of the water concentration under the pseudo first-order conditions where Cu(2+) is in large excess over the Cu(II)-porphyrin complex. The decrease in the pseudo first-order rate constant with increasing the water concentration was attributed to the stepwise displacement of acetonitrile in [Cu(AN)(6)](2+)(AN = acetonitrile) by water, and it was concluded that only the Cu(2+) species fully solvated by acetonitrile, [Cu(AN)(6)](2+), possesses sufficiently high redox potential for the oxidation of Cu(ii)-OEP and Cu(ii)-TPP. The reactions of the Cu(II)-porphyrin complexes with other oxidizing reagents such as [Ni(tacn)(2)](3+)(tacn = 1,4,7-triazacyclononane) and [Ru(bpy)(3)](3+)(bpy = 2,2'-bipyridine) were too fast to be followed by a conventional stopped-flow technique. Marcus cross relation for the outer-sphere electron transfer reaction was used to estimate the rate constants of the electron self-exchange reaction between Cu(II)-porphyrin and its pi-cation radical: log(k/M(-1) s(-1))= 9.5 +/- 0.5 for TPP and log(k/M(-1) s(-1))= 11.1 +/- 0.5 for OEP at 25.0 degrees C. Such large electron self-exchange rate constants are typical for the porphyrin-centered redox reactions for which very small inner- and outer-sphere reorganization energies are required.     

Direct electrochemical behavior of cytochrome c on DNA-modified glassy carbon electrode and its application to cytochrome c biosensor.

DNA was immobilized on glassy carbon electrodes to fabricate DNA-modified electrodes. The direct electron transfer of horse heart cytochrome c on DNA-modified glassy carbon electrode was achieved. A pair of well-defined redox peaks of cytochrome c appeared at Epc = -0.017 V and Epa = 0.009 V (vs. Ag/AgCl) in 10 mM phosphate buffer solution (pH 7.0) at a scan rate of 50 mV/s. The electron transfer coefficient (alpha) and the standard rate constant of the surface reaction (Ks) of cytochrome c on DNA-modified electrodes could be estimated to be 0.87 and 34.52 s(-1), respectively. The DNA-modified glassy carbon electrode could be applied to detect cytochrome c by means of differential pulse voltammetry (DPV). The cathodic peak current was proportional to the quantity of cytochrome c in the range of 4.0 x 10(-6) M to 1.2 x 10(-5) M. The correlation coefficient is 0.996, and with the detection limit was 1.0 x 10(-6) M (three times the ratio of signal to noise, S/N = 3).     

The effect of ionic strength on the electron-transfer rate of surface immobilized cytochrome C

Horse heart cytochrome c was immobilized on four different self-assembled monolayer (SAM) films. The electron tunneling kinetics were studied in the different assemblies as a function of the ionic strength of the buffer solution using cyclic voltammetry. When cytochrome c is electrostatically immobilized, the standard electron exchange rate constant k0 decreases with the increase of the solution's ionic strength. In contrast, the protein covalently attached or ligated has a rate constant independent of the ionic strength. The inhomogeneity of electrostatically immobilized cytochrome c increases with the increase of the solution's ionic strength whereas that of the covalently attached protein is independent of the ionic strength. A comparison of these different electron-transfer behaviors suggests that the thermodynamically stable geometry of cytochrome c in the electrostatic assemblies is also an electron transfer favorable one. It suggests that the surface charges of cytochrome c are capable of guiding it into geometries in which its front surface faces the electron-transfer partner. The inhomogeneity observed in this study indicates that a distribution of cytochrome c orientations and thus a distribution of electron transfer rate constants exists.     

Physical parameters and electron-transfer kinetics of the copper(II/I) complex with the macrocyclic sexadentate ligand [18]aneS6

The electron-transfer kinetics of the complex formed by copper(II/I) with the sexadentate macrocyclic ligand 1,4,7,10,13,16-hexathiacyclooctadecane ([18]aneS6) have been measured in acetonitrile with a series of three oxidizing agents and three reducing agents. These studies have been supplemented by determinations of the redox potential and the stability constants of the Cu(I)- and Cu(II)([18]aneS6) complexes in both acetonitrile and aqueous solution. The Marcus cross relationship has been applied to the cross-reaction rate constants for the six reactions studied to resolve the electron self-exchange rate constant for the Cu(II/I)([18]aneS6) complex. An average value of k11 = 3 x 10(3) M(-1) s(-1) was obtained at 25 degrees C, mu = 0.10 M in acetonitrile. This value is approximately 2 orders of magnitude smaller than the values reported previously for the corresponding Cu(II/I) complexes with the quadridentate and quinquedentate homoleptic homologues having all ethylene bridges, namely, 1,4,7,10-tetrathiacyclododecane ([12]aneS4) and 1,4,7,10,13-pentathiacyclopentadecane ([15]aneS5). This significant difference in reactivity is attributed to the greater rearrangement in the geometry of the inner-coordination sphere that accompanies electron transfer in the Cu(II/I)([18]aneS6) system, wherein two Cu-S bonds are ruptured upon reduction. In contrast to other Cu(II/I) complexes with macrocyclic polythiaethers that have self-exchange rate constants within the same range, no evidence for conformationally gated electron transfer was observed, even in the case of the most rapid oxidation reaction studied.     

Electron self-exchange in the solid-state: cocrystals of hydroquinone and bipyridyl triazole.

Solid-state voltammetry, spectroscopy, and microscopy studies have been used to probe the proton and electron conductivity within a self-assembled cocrystal, HQBpt. This crystallographically defined material contains 3,5-bis(pyridin-2-yl)-1,2,4-triazole, HBpt, dimers that are pi-stacked and hydrogen bonded to 1,4-hydroquinone, H(2)Q, in a herringbone arrangement. When deposited onto platinum microelectrodes, the cocrystal exhibits a well-defined voltammetric response corresponding to oxidation of H(2)Q to the quinone, Q, across a wide range of voltammetric time scales, electrolyte compositions, and pH values. Scanning electron microscopy reveals that redox cycling in aqueous perchlorate solutions in which the pH is systematically varied from 1 to 7 triggers electrocrystallization and the extensive formation of rodlike crystals. Fast scan rate voltammetry reveals that the homogeneous charge transport diffusion coefficient, D(app), is independent of the perchlorate concentration for 0.1 < [ClO(4)(-)] < 1.0 M (pH 6.6) at 3.14 +/- 0.11 x 10(-)(9) cm(2) s(-)(1). Moreover, D(app) is independent of the perchloric acid concentration for concentrations greater than approximately 2.0 M, maintaining a value of 4.81 +/- 0.07 x 10(-)(8) cm(2) s(-)(1). The observation that D(app) is independent of the supporting electrolyte suggests that the rate-determining step for homogeneous charge transport is not the availability of charge-compensating counterions or protons, but the dynamics of electron self-exchange between H(2)Q and Q. We have used the Dahms-Ruff formalism to determine electron self-exchange rate constants which are 2.84 +/- 0.22 x 10(9) and 9.69 +/- 0.73 x 10(10) M(-)(1) s(-)(1) for pH values greater than approximately 2.0 and less than -0.3, respectively. Significantly, these values are more than 2 orders of magnitude larger that those found for benzoquinone self-exchange reactions in aqueous solution. These results indicate that hydrogen bonds play an important role in supporting rapid electron transfer. The increase in D(app) between pH 1.0 and -0.3 is associated with protonation of the HBpt moieties, which triggers a reversible change in the material's structure.     

Reduction and oxidation of hydroperoxo rhodium(III) complexes by halides and hypobromous acid

Oxygen atom transfer from trans-L(H(2)O)RhOOH(2+) [L = [14]aneN(4) (L(1)), meso-Me(6)[14]aneN(4) (L(2)), and (NH(3))(4)] to iodide takes place according to the rate law -d[L(H(2)O)RhOOH(2+)]/dt = k(I)[L(H(2)O)RhOOH(2+)][I(-)][H(+)]. At 0.10 M ionic strength and 25 degrees C, the rate constant k(I)/M(-)(2) s(-)(1) has values of 8.8 x 10(3) [L = (NH(3))(4)], 536 (L(1)), and 530 (L(2)). The final products are LRh(H(2)O)(2)(3+) and I(2)/I(3)(-). The (NH(3))(4)(H(2)O)RhOOH(2+)/Br(-) reaction also exhibits mixed third-order kinetics with k(Br) approximately 1.8 M(-)(2) s(-)(1) at high concentrations of acid (close to 1 M) and bromide (close to 0.1 M) and an ionic strength of 1.0 M. Under these conditions, Br(2)/Br(3)(-) is produced in stoichiometric amounts. As the concentrations of acid and bromide decrease, the reaction begins to generate O(2) at the expense of Br(2), until the limit at which [H(+)] 2(NH(3))(4)(H(2)O)RhOH(2+) + O(2); i.e., the reaction has turned into the bromide-catalyzed disproportionation of coordinated hydroperoxide. In the proposed mechanism, the hydrolysis of the initially formed Br(2) produces HOBr, the active oxidant for the second equivalent of (NH(3))(4)(H(2)O)RhOOH(2+). The rate constant k(HOBr) for the HOBr/(NH(3))(4)(H(2)O)RhOOH(2+) reaction is 2.9 x 10(8) M(-)(1) s(-)(1).