Synthesis and molecular structure of [Au3Ru4(μ3-H)(CO)12(PPh3)3]

The title compound can be prepared in good yield by heating either [Ru₄(μ-H)₄(CO)₁₂] or [Au₂Ru₄(μ₃-H)₂(CO)₁₂(PPh₃)₂] with [AuMe(PPh₃)] in toluene. The related compound [Au₃Ru₄(μ₃-H)(μ-dppm)(CO)₁₂(PPh₃)] has also been prepared. Both trigoldtetraruthenium clusters undergo dynamic behaviour in solution, involving intramolecular rearrangement of the metal core, as revealed by variable temperature NMR studies. The crystal structure of [Au₃Ru₄(μ₃-H)(CO)₁₂(PPh₃)₃] has been established by an X-ray diffraction study. The metal atom core comprises a trigonal bipyramidal AuRu₄ unit with two AuRu₂ faces capped by gold atoms.     

ULTRAVIOLET RADIATION INHIBITS BOTH ACCESSORY CELL AND RESPONDER T CELL FUNCTION IN THE PROLIFERATIVE RESPONSE TO HAPTENATED-SELF

Abstract— Photoprotection i. e. the increased resistance of the cells preilluminated with near ultraviolet light (300–380 nm) to the lethal action of 254 nm radiations is observed in wild-type Escherichia coli B cells (which exhibits the Fil phenotype) but requires either an integrated prophage or a rec A mutation to be detected in E. coli K12 strains. Here we have demonstrated that significant photoprotection occurs in an E. coli K12 rec A⁺ cell containing the Ion allele which is responsible for filamentous growth (Fil phenotype) after 254 nm irradiation. The Fil phenotype can be suppressed by the sfi A of sfi B suppressor genes. Since the E. coli K12 rec A⁺ Ion sfi B strain exhibits no more photoprotection, these data support the conclusion that in Ion strains photoprotection is due to the abolition of the 254 nm induced filamentation by the near ultraviolet treatment. In addition, we show here that near ultraviolet illumination of the cells leads to a severe restriction of the bulk protein synthesis, as well as of the inducibility of β-galactosidase and tryptophanase. These effects are observed only in nuv ⁺ cells that contains 4-thiouridine the chromophore responsible for photoprotection. We propose that in Ion (lysogenic) strains, photoprotection is due to prevention of the SOS response. During the growth lag, the low residual level of protein synthesis does not allow the induction of the SOS response and accordingly prevents filamentation (the lytic cycle). Concomitantly the SOS triggering signals are eliminated via DNA repair.     

Investigating Inner-Sphere Reorganization via Secondary Kinetic Isotope Effects in the C-H Cleavage Reaction Catalyzed by Soybean Lipoxygenase: Tunneling in the Substrate Backbone as Well as the Transferred Hydrogen

This work describes the application of NMR to the measurement of secondary deuterium (2° (2)H) and carbon-13 ((13)C) kinetic isotope effects (KIEs) at positions 9-13 within the substrate linoleic acid (LA) of soybean lipoxygenase-1. The KIEs have been measured using LA labeled with either protium (11,11-h2-LA) or deuterium (11,11-d2-LA) at the reactive C11 position, which has been previously shown to yield a primary deuterium isotope effect of ca. 80. The conditions of measurement yield the intrinsic 2° (2)H and (13)C KIEs on k(cat)/K(m) directly for 11,11-d2-LA, whereas the values for the 2° (2)H KIEs for 11,11-h2-LA are obtained after correction for a kinetic commitment. The pattern of the resulting 2° (2)H and (13)C isotope effects reveals values that lie far above those predicted from changes in local force constants. Additionally, many of the experimental values cannot be modeled by electronic effects, torsional strain, or the simple inclusion of a tunneling correction to the rate. Although previous studies have shown the importance of extensive tunneling for cleavage of the primary hydrogen at C11 of LA, the present findings can only be interpreted by extending the conclusion of nonclassical behavior to the secondary hydrogens and carbons that flank the position undergoing C-H bond cleavage. A quantum mechanical method introduced by Buhks et al. [J. Phys. Chem. 1981, 85, 3763] to model the inner-sphere reorganization that accompanies electron transfer has been shown to be able to reproduce the scale of the 2° (2)H KIEs.     

Enzymatic methyl transfer: role of an active site residue in generating active site compaction that correlates with catalytic efficiency

Human catechol-O-methyltransferase (COMT) catalyzes a methyl transfer from S-adenosylmethionine (AdoMet) to dopamine. Site-specific mutants at three positions (Tyr68, Trp38, and Val108) have been characterized with regard to product distribution, catalytic efficiency, and secondary kinetic isotope effects. The series of mutations at Tyr68 within wild-type protein and the common polymorphic variant (Val108Met) yields a linear correlation between the catalytic efficiency and the size of the secondary kinetic isotope effect. We conclude that active site compaction in COMT is modulated by a proximal side chain residing behind the sulfur-bearing methyl group of AdoMet. These findings are discussed in the context of the active site compression that has been postulated to accompany enzyme-supported hydrogen tunneling.     

The fragmentation-recombination mechanism of the enzyme glutamate mutase studied by QM/MM simulations

The radical mechanism of the conversion of glutamate to methylaspartate catalyzed by glutamate mutase is studied with quantum mechanical/molecular mechanical (QM/MM) simulations based on density functional theory (DFT/MM). The hydrogen transfer between the substrate and the cofactor is found to be rate limiting with a barrier of 101.1 kJ mol(-1). A careful comparison to the uncatalyzed reaction in water is performed. The protein influences the reaction predominantly electrostatically and to a lesser degree sterically. Our calculations shed light on the atomistic details of the reaction mechanism. The well-known arginine claw and Glu 171 ( Clostridium cochlearium notation) are found to have the strongest influence on the reaction. However, a catalytic role of Glu 214, Lys 322, Gln 147, Glu 330, Lys 326, and Met 294 is found as well. The arginine claw keeps the intermediates in place and is probably responsible for the enantioselectivity. Glu 171 temporarily accepts a proton from the glutamyl radical intermediate and donates it back at the end of the reaction. We relate our results to experimental data when available. Our simulations lead to further understanding of how glutamate mutase catalyzes the carbon skeleton rearrangement of glutamate.     

Photocatalytic degradation of phenolic syntan using TiO2 impregnated activated carbon

Investigations were carried out to study the photocatalytic degradation of phenolic syntan (PS), a widely used environmentally polluting chemical in the leather tanning industry. Photocatalytic inactive commercial TiO(2) was used as the precursor for the preparation of TiO(2) impregnated activated carbon (Ti-AC) photocatalyst. Experiments were conducted by varying the concentrations of PS solution (50-1000 mg/l), pH (2.5-10) and time intervals to optimize the working parameters. A 254 nm UV light was used throughout the study. The effect of PS degradation using Ti-AC was also compared with direct UV photolysis. The Ti-AC was characterized using X-ray Diffraction (XRD), Diffuse Reflectance Spectroscopy (DRS), Scanning Electron Microscopy (SEM) and energy dispersive X-ray analysis (EDX) to determine the structural, optical, surface morphology and elemental analysis respectively. X-ray studies revealed the formation of catalytically active anatase phase in Ti-AC. Photodegradation of PS was examined by chemical oxygen demand (COD) method. PS degradation occurred at both the extreme end of acidic and alkaline pH conditions. However, the percentage degradation was comparatively higher at pH 2.5. The photodegradation followed pseudo first order kinetics. UV-Visible studies substantiated the occurrence of bathochromic and hyperchromic effects as a result of ring opening in the PS molecule.     

Effect of intraligand π-delocalization on the photophysical properties of two new Ru(II) complexes

Two new Ru(II) complexes, [Ru(bpy)₂(1-COO-iqu)]⁺ (2; bpy = 2,2′-bipyridine, 1-COO-iqu^? = isoquinoline-1-carboxylate) and [Ru(bpy)₂(3-COO-iqu)]⁺ (3; 3-COO-iqu^? = isoquinoline-3-carboxylate), were prepared and their crystal structures solved. The ground and excited state properties of 2 and 3 were characterized and compared to those of [Ru(bpy)₃]²⁺ (1). The presence of the oxygen atom in the Ru(II) coordination sphere makes 2 and 3 easier to oxidize than 1. The Ru → bpy MLCT absorption and emission of 2 and 3 are red-shifted relative to that of 1 in CH₂Cl₂, and the E₀₀ energies were estimated to be 1.89 eV and 1.95 eV from the low temperature emission of 2 and 3, resulting in excited state oxidation potentials of ?1.03 V and ?1.10 V vs SCE, respectively. In addition to the short-lived emissive ³MLCT state, a long-lived species is observed in the transient absorption of 3 in DMSO (τ = 49 μs) and pyridine (τ = 44 μs), assigned to a solvent-coordinated complex. This intermediate is not observed for 3 in non-polar solvents or for 2. The absence of the solvent coordinated intermediate in 2 is explained by the stronger Ru–O bond afforded by the lower conjugation in that extends onto the carboxylic acid in the 1-COO-iquo^?ligand, compared to that in the 3-COO-iqu^?ligand in 3. Transient absorption experiments also show that the ³MLCT excited state of 3 is able to reduce methyl viologen.     

The relationship among voice onset, voice quality, and fundamental frequency: a dynamical perspective

In dynamical motor theory, skill acquisition occurs as a modification of preexisting coordination patterns or attractor states. The purpose of this study was to assess how different levels of voice onset, voice quality, and fundamental frequency (F₀) combine to form the attractor states common to voice motor control. Three levels of voice onset (glottal, simultaneous, and breathy), voice quality (modal speech, mixed, and falsetto), and fundamental frequency (low, mid, and high) were manipulated by vocally untrained, female subjects. Percent correct of acquisition trials and self-report of effort were used as measures of stable phonations indicative of an attractor state. Using intensity as a covariate, the results provided support for two of the three predicted triads representing attractor states in female speakers: (1) glottal onset/modal speech quality/low F₀; and (2) breathy onset/falsetto quality/high F₀. The results of this study suggest that certain parameters of voice motor control, such as onset, quality, and F₀, exist as part of a dynamical system that can be identified and manipulated in voice motor acquisition and learning.     

Luminescent iridium(III) complexes with N^C^N-coordinated terdentate ligands: dual tuning of the emission energy and application to organic light-emitting devices

A family of complexes (1a-3a and 1b-3b) was prepared, having the structure Ir(N^C^N)(N^C)Cl. Here, N^C(∧)N represents a terdentate, cyclometallating ligand derived from 1,3-di(2-pyridyl)benzene incorporating CH(3) (1a,b), F (2a,b), or CF(3) (3a,b) substituents at the 4 and 6 positions of the benzene ring, and N^C is 2-phenylpyridine (series a) or 2-(2,4-difluorophenyl)pyridine (series b). The complexes are formed using a stepwise procedure that relies on the initial introduction of the terdentate ligand to form a dichloro-bridged iridium dimer, followed by cleavage with the N^C ligand. (1)H NMR spectroscopy reveals that the isomer that is exclusively formed in each case is that in which the pyridyl ring of the N^C ligand is trans to the cyclometallating aryl ring of the N^C^N ligand. This conclusion is unequivocally confirmed by X-ray diffraction analysis for two of the complexes (1b and 3a). All of the complexes are highly luminescent in degassed solution at room temperature, emitting in the green (1a,b), blue-green (2a,b), and orange-red (3a,b) regions. The bidentate ligand offers independent fine-tuning of the emission energy: for each pair, the "b" complex is blue-shifted relative to the analogous "a" complex. These trends in the excited-state energies are rationalized in terms of the relative magnitudes of the effects of the substituents on the highest occupied and lowest unoccupied orbitals, convincingly supported by time-dependent density functional theory (TD-DFT) calculations. Luminescence quantum yields are high, up to 0.7 in solution and close to unity in a PMMA matrix for the green-emitting complexes. Organic light emitting devices (OLEDs) employing this family of complexes as phosphorescent emitters have been prepared. They display high efficiencies, at least comparable, and in some cases superior, to similar devices using the well-known tris-bidentate complexes such as fac-Ir(ppy)(3). The combination of terdentate and bidentate ligands is seen to offer a versatile approach to tuning of the photophysical properties of iridium-based emitters for such applications.