Activation of alkenes and H2 by [Fe]-H2ase model complexes

The established ability of the Fe(II) bridging hydride species (micro-H)(micro-pdt)[Fe(CO)2(PMe3)]2+, 1-H+, to take-up and heterolytically activate dihydrogen, resulting in H/D scrambling of H2/D2 and H2/D2O mixtures (Zhao et al. Inorg. Chem. 2002, 41, 3917) has prompted a study of simultaneous alkene/H2 activation by such [Fe]H2ase model complexes. That the required photolysis produced an open site was substantiated by substitution of CO in 1-H+ by CH3CN with formation of structurally characterized [(micro-H)(micro-pdt)[Fe(CO)2(PMe3)][Fe(CO)(CH3CN)(PMe3)]]+[PF6]-. Under similar photolytic conditions, H/D exchange reactions between D2 and terminal alkenes (ethylene, propene and 1-butene), but not bulkier alkenes such as 2-butene or cyclohexene, were catalyzed by 1-H+ and the edt (SCH2CH2S) analogue, 2-H+. Substantial regioselectivity for H/D exchange at the internal vinylic hydrogen was observed. The extent to which the olefins were deuterium enriched vs deuterated was catalyst dependent. The stabilizing effect of the binuclear chelating ligands, SCH2CH2CH2S, pdt, and SCH2CH2S, edt, is required for the activity of binuclear catalysts, as the mono-dentate micro-SEt analogue decomposed to inactive products under the photolytic conditions of the catalysis. Reactions of 1 and 2 with EtOSO2CF3 yielded the S-alkylated products, [(micro-SCH2CH2CH2SEt)[Fe(CO)2(PMe3)]2]+[SO3CF3]- (1-Et+), and 2-Et+, rather than micro-C2H5 analogues to the micro-H of 1-H+. The stability and lack of reactivity toward H2 of 1-Et+ and 2-Et+, indicates they are not on the reaction path of the olefin/D2 H/D exchange process. A mechanism with olefin binding to an open site created by CO loss and formation of an Fe-(CH2CHDR) intermediate is indicated. A likely role of a binuclear chelate effect is implicated for the unique S-XXX-S cofactor in the active site of [Fe]H2ase.     

Computational study of the halogen atom-benzene complexes

The structures of halogen atom-benzene complexes were investigated by modern DFT and ab initio computational methods. The spectroscopic properties of the complexes are also predicted and are in good agreement with experiment where such data have been reported. The fluorine atom-benzene complex is predicted to be a sigma complex due to the strength of a C-F bond. The chlorine atom-benzene complex is predicted to have an eta(1) pi complex structure, which is only slightly more favorable (1.1 kcal/mol with the BH&HLYP/6-311++G method including the ZPE correction) than a sigma complex but is significantly more stable (4.4 kcal/mol with the BH&HLYP/6-311++G method including the ZPE correction) than the eta(6) pi complex. The bromine and iodine benzene complexes are also predicted to prefer an eta(1) pi complex structure.     

Total synthesis of lucilactaene, a cell cycle inhibitor active in p53-inactive cells

Hetero-bis-metalated 1,3-butadiene is employed in the lynchpin coupling of synthetic fragments of the side chain of the antitumor agent, lucilactaene. Sequential Stille and Suzuki-Miyaura couplings interpolate this unique boron/tin diene into the pentaene chain. The total synthesis of lucilactaene was accomplished efficiently, in just eight linear steps.     

Iron(III) p-toluenesulfonate catalyzed synthesis of homoallyl ethers from acetals and aldehydes

Iron(III) p-toluenesulfonate, Fe(OTs)₃·6H₂O, is an inexpensive, versatile and commercially available catalyst for the allylation of acetals using allyltrimethylsilane to yield homoallyl ethers in moderate to good yields. The one-pot conversion of aldehydes to homoallyl ethers using alkoxysilanes has also been accomplished using Fe(OTs)₃·6H₂O as a catalyst. The use of mild reaction conditions and a relatively non-corrosive catalyst make this method an attractive option for the synthesis of a range of homoallyl ethers.     

Gold nanoparticles as a colorimetric sensor for protein conformational changes

Spherical gold nanoparticles and flat gold films are prepared in which yeast iso-1-cytochrome c (Cyt c) is covalently bound to the gold surface by a thiol group in the cystein 102 residue. Upon exposure to solutions of different pH, bound Cyt c unfolds at low pH and refolds at high pH. This conformational change causes measurable shifts in the color of the coated nanoparticle solutions detected by UV-VIS absorption spectroscopy and in the refractive index (RI) of the flat gold films detected by surface plasmon resonance (SPR) spectroscopy. Both experiments demonstrate the same trend with pH, suggesting the use of protein-covered gold nanoparticles as a simple colorimetric sensor for conformational change.     

Ti(III)-Mediated reductions of N-hydroxy imidazoles to 1-protio-2,4(5)-disubstituted derivatives

N-hydroxy imidazoles are converted $\text{via}$ TiCl₃ in MeOH/H₂O to N-protio derivatives, useful precursors of chiral amino acids.     

Dendritic nanowire ultraviolet laser array

Self-organized dendritic crystal growth is explored to assemble uniform semiconductor nanowires into highly ordered one-dimensional microscale arrays that resemble comb structures. The individual ZnO nanowires have uniform diameters ranging from 10 to 300 nm. They are evenly spaced on a stem with a regular periodicity of 0.1-2 micrometer. Under optical excitation, each individual ZnO nanowire serves as a Fabry-Perot optical cavity, and together they form a highly ordered nanowire ultraviolet laser array.     

Field-portable, high-speed GC/TOFMS

This work is focused on developing a fast gas chromatograph, time-of-flight mass spectrometer (GC/TOFMS) for man-portable field use. The goal is to achieve a total system solution for meeting performance, size, weight, power, cost, and ruggedness requirements for a laboratory in the field. The core technology will also be adaptable to specific applications including real-time point detection for hazardous chemical releases (e.g., chemical weapons), for biological agent signature identification, and for mobile monitoring platforms (e.g., air, ship, truck). Previously we presented results of a feasibility demonstration for a 30-lb field-portable TOFMS system. In this work we present recent progress in integrating a low-power, high-speed GC and show the capability for accurately recording fast GC transients for targeted compound detection using a quadrupole ion trap, time-of-flight instrument (QitTof).     

Eu(III) macrocyclic complexes promote cleavage of and bind to models for the 5'-cap of mRNA. Effect of pendent group and a second metal ion

The interaction of three Eu(III) macrocyclic complexes Eu(THED)3+, Eu(ATHC)3+, and Eu(ATHC)3+, and Eu(S-THP)3+ with two 5'-cap model compounds, GpppG and m7GpppG is studied (THED = 1,4,7,10-tetrakis(2-hydroxyethyl)-1,4,7,-10-tetraazacyclododecane, ATHC = 1-(carbamoylmethyl)-4,7,10-tris(2-hydroxyethyl)-1,4,7,10- tetraazacyclododecane, S-THP = 1S,4S,7S,10S-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane). Laser-induced excitation luminescence spectroscopy is used to study the binding of Eu(S-THP)3+ to GpppG (K = 5.9 x 10(4) M-1) and to characterize the Eu(S-THP)-GpppG complex. Both Eu(THED)3+ and Eu(S-THP)3+ bind to m7GpppG as monitored by use of fluorescence spectroscopy with binding constants of 5.9 x 10(3) and 4.4 x 10(4) M-1, respectively. The kinetics of cleavage of GpppG by two macrocyclic complexes is studied. Cleavage of GpppG by Eu(THED)3+ is accelerated by 15-fold in the presence of an equivalent of Zn(NO3)2 at pH 7.3, 37 degrees C, suggesting that two metal ions accelerate the cap cleavage reaction. Eu(ATHC)3+ promotes cleavage of GpppG with a pseudo-first-order rate constant of 2.6 x 10(-5) s-1 at pH 7.3, 37 degrees C, and 0.30 mM complex.     

Enhanced fluorescence from arrays of nanoholes in a gold film

Arrays of sub-wavelength holes (nanoholes) in gold films were used as a substrate for enhanced fluorescence spectroscopy. Seven arrays of nanoholes with distinct periodicities (distances between the holes) were fabricated. The arrays were then spin-coated with polystyrene films containing different concentrations of the fluorescent dye oxazine 720. The dye was excited via resonant extraordinary transmission of the laser source through the nanoholes. Enhanced fluorescence was observed when the geometric characteristics of the arrays allowed for an enhancement in the transmitted excitation. This enhancement occurred via surface plasmon excitation by the laser and a consequential increase in the local electromagnetic field in a sub-wavelength region at the metal-film interface. It was demonstrated that the sensitivity of the fluorescence measurement (change in signal vs change in dye concentration in the polymer film) is significantly larger at the surface plasmon resonance conditions than that obtained from equivalent films on glass substrates. Enhancement factors for the fluorescence emission were calculated for each array, with a maximum enhancement of close to 2 orders of magnitude as compared to the emission of films on glass. The results presented here indicate that arrays of nanoholes are interesting substrates for the development of fluorescence sensors based on surface plasmon resonance, as they provide a platform that allows both spatial confinement and enhancement of excitation light. Moreover, the collinear characteristics of the present optical setup, due to the resonant extraordinary transmission through the nanohole arrays, are more conducive to miniaturization and chip integration than more traditional experimental geometries.