pH Rate profiles of FnY356-R2s (n = 2, 3, 4) in Escherichia coli ribonucleotide reductase: evidence that Y356 is a redox-active amino acid along the radical propagation pathway

The Escherichia coli ribonucleotide reductase (RNR), composed of two subunits (R1 and R2), catalyzes the conversion of nucleotides to deoxynucleotides. Substrate reduction requires that a tyrosyl radical (Y(122)*) in R2 generate a transient cysteinyl radical (C(439)*) in R1 through a pathway thought to involve amino acid radical intermediates [Y(122)* --> W(48) --> Y(356) within R2 to Y(731) --> Y(730) --> C(439) within R1]. To study this radical propagation process, we have synthesized R2 semisynthetically using intein technology and replaced Y(356) with a variety of fluorinated tyrosine analogues (2,3-F(2)Y, 3,5-F(2)Y, 2,3,5-F(3)Y, 2,3,6-F(3)Y, and F(4)Y) that have been described and characterized in the accompanying paper. These fluorinated tyrosine derivatives have potentials that vary from -50 to +270 mV relative to tyrosine over the accessible pH range for RNR and pK(a)s that range from 5.6 to 7.8. The pH rate profiles of deoxynucleotide production by these F(n)()Y(356)-R2s are reported. The results suggest that the rate-determining step can be changed from a physical step to the radical propagation step by altering the reduction potential of Y(356)* using these analogues. As the difference in potential of the F(n)()Y* relative to Y* becomes >80 mV, the activity of RNR becomes inhibited, and by 200 mV, RNR activity is no longer detectable. These studies support the model that Y(356) is a redox-active amino acid on the radical-propagation pathway. On the basis of our previous studies with 3-NO(2)Y(356)-R2, we assume that 2,3,5-F(3)Y(356), 2,3,6-F(3)Y(356), and F(4)Y(356)-R2s are all deprotonated at pH > 7.5. We show that they all efficiently initiate nucleotide reduction. If this assumption is correct, then a hydrogen-bonding pathway between W(48) and Y(356) of R2 and Y(731) of R1 does not play a central role in triggering radical initiation nor is hydrogen-atom transfer between these residues obligatory for radical propagation.     

Oxygen reduction to water mediated by a dirhodium hydrido-chloride complex

The two-electron mixed-valence dirhodium complex Rh(2)(0,II)(tfepma)(2)(CN(t)Bu)(2)Cl(2) (tfepma = CH(3)N[P(OCH(2)CF(3))(2)](2)) reacts with HCl to furnish two isomeric dirhodium hydrido-chloride complexes, Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(3)H. In the presence of HCl, the hydride complex effects the reduction of 0.5 equiv of O(2) to 1 equiv of H(2)O, generating Rh(2)(II,II)(tfepma)(2)(CN(t)Bu)(2)Cl(4), which can be prepared independently by chlorine oxidation of the Rh(2)(0,II) precursor. The starting Rh(2)(0,II) complex is regenerated photochemically to close an oxygen-to-water reduction photocycle.     

Frequency and amplitude alterations of sound modes in a space-dependent random mass density field

We investigate the effect of a space-dependent random mass density field on small amplitude acoustic modes that are settled in a semi-infinite medium of a temperature growing linearly with depth. Using a perturbation method, the dispersion relation is derived in the form of Hill's determinant. Numerical solutions of this equation lead to the following conclusions: (a) a weak random field (with σ_eff = 0.05) essentially affects long waves which experience attenuation and a frequency reduction; (b) for a stronger random field (with σ_eff = 0.1), high-order sound modes behave as sound waves as they are attenuated and their frequencies are increased; (c) for a sufficiently strong random field (with σ_eff = 0.2), mode coupling occurs, as a result of which the dispersive curves cross each other, the sound modes loose their identities, and some modes are amplified. Here σ_eff denotes the effective strength of a random field.     

Electronic design criteria for O-O bond formation via metal-oxo complexes

Metal-oxos are critical intermediates for the management of oxygen and its activation. The reactivity of the metal-oxo is central to the formation of O-O bonds, which is the essential step for oxygen generation. Two basic strategies for the formation of O-O bonds at metal-oxo active sites are presented. The acid-base (AB) strategy involves the attack of a nucleophilic oxygen species (e.g., hydroxide) on an electrophilic metal-oxo. Here, active-site designs must incorporate the assembly of a hydroxide (or water) proximate to a high-valent metal-oxo of even d electron count. For the radical coupling (RC) strategy, two high-valent metal-oxos of an odd d electron count are needed to drive O-O coupling. This Forum Article focuses on the different electronic structures of terminal metal-oxos that support AB and RC strategies and the design of ligand scaffolds that engender these electronic structures.     

Photocatalytic hydrogen production

The efficient storage of solar energy in chemical fuels, such as hydrogen, is essential for the large-scale utilisation of solar energy systems. Recent advances in the photocatalytic production of H(2) are highlighted. Two general approaches for the photocatalytic hydrogen generation by homogeneous catalysts are considered: HX (X = Cl, Br) splitting involving both proton reduction and halide oxidation via an inner-sphere mechanism with a single-component catalyst; and sensitized H(2) production, employing sacrificial electron donors to regenerate the active catalyst. Future directions and challenges in photocatalytic H(2) generation are enumerated.     

Structurally homologous beta- and meso-alkynyl amidinium porphyrins

Alkynylamidinium groups have been introduced at the beta and meso positions of a nickel(II) porphyrin (PNi(II)) framework. The modification permits the distance between the amidinium-amidine acid-base group and porphyrin to be increased while effectively maintaining pi conjugation between the porphyrin macrocycle and the acid-base functionality. Use of an ethynyl spacer as a linker (i) extends the amidinium functionality away from the sterically bulky mesityl groups of the porphyrin, allowing it to be nearly planar with respect to the porphyrin ring, and (ii) draws the pi-orbital character of the porphyrin out toward the amidinium functionality, thereby engendering sensitivity of the electronic properties of the porphyrin macrocycle to the protonation state of the amidinium. The barrier for rotation of the amidinium group, as calculated by time-dependent density functional theory (TDDFT), is approximately 8.5 kT (5 kcal/mol) for both porphyrins. Analysis of UV-visible absorption profiles for the beta- and meso-alkynylamidinium PNi(II) upon deprotonation enables accurate determination of the amidinium acidity constants for the ground state (pK(a)(beta) = 7.03 +/- 0.1, pK(a)(meso) = 7.74 +/- 0.1 in CH(3)CN) and excited state (pK(a)*(beta) = 6.89 +/- 0.1, pK(a)*(meso) = 8.37 +/- 0.1 in CH(3)CN) porphyrins. Whereas pK(a)* < pK(a) for the beta-alkynylamidinium porphyrin, pK(a)* > pK(a) for the meso-alkynylamidinium porphyrin, indicating that beta-alkynylamidinium PNi(II) is a photoacid and meso-alkynylamidinium PNi(II) is a photobase. These divergent behaviors are supported by analysis of the frontier molecular orbitals of the homologous pair with TDDFT.