Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy.

Complexes with weakly coordinating ligands are often formed in chemical reactions and can play key roles in determining the reactivity, particularly in catalytic reactions. Using time-resolved X-ray absorption fine structure (XAFS) spectroscopy in combination with time-resolved IR (TRIR) spectroscopy and tungsten hexacarbonyl, W(CO)6, we are able to structurally characterize the formation of an organometallic alkane complex, determine the W-C distances, and monitor the reactivity with silane to form an organometallic silane complex. Experiments in perfluorosolvents doped with xenon afford initially the corresponding solvated complex, which is sufficiently reactive in the presence of Xe that we can then observe the coordination of Xe to the metal center, providing a unique insight into the metal-xenon bonding. These results offer a step toward elucidating the structure, bonding, and chemical reactivity of transient species by X-ray absorption spectroscopy, which has sensitivity to small structural changes. The XAFS results indicate that the bond lengths of metal-alkane (W-H-C) bond in W(CO)5(heptane) as 3.07 (±0.06) Å, which is longer than the calculated W-C (2.86 Å) for binding of the primary C-H, but shorter than the calculated W-C (3.12 Å) for the secondary C-H. A statistical average of the calculated W-C alkane bond lengths is 3.02 Å, and comparison of this value indicates that the value derived from the XAFS measurements is averaged over coordination of all C-H bonds consistent with alkane chain walking. Photolysis of W(CO)6 in the presence of HSiBu3 allows the conversion of W(CO)5(heptane) to W(CO)5(HSiBu3) with an estimated W-Si distance of 3.20 (±0.03) Å. Time-resolved TRIR and XAFS experiments following photolysis of W(CO)6 in perfluoromethylcyclohexane (PFMCH) allows the characterization of W(CO)5(PFMCH) with a W-F distance of 2.65 (±0.06) Å, and doping PFMCH with Xe allows the characterization of W(CO)5Xe with a W-Xe bond length of 3.10 (±0.02) Å.

Synthesis and Photophysical Study of a [NiFe] Hydrogenase Biomimetic Compound Covalently Linked to a Re-diimine Photosensitizer.

The synthesis, photophysics, and photochemistry of a linked dyad ([Re]-[NiFe2]) containing an analogue ([NiFe2]) of the active site of [NiFe] hydrogenase, covalently bound to a Re-diimine photosensitizer ([Re]), are described. Following excitation, the mechanisms of electron transfer involving the [Re] and [NiFe2] centers and the resulting decomposition were investigated. Excitation of the [Re] center results in the population of a diimine-based metal-to-ligand charge transfer excited state. Reductive quenching by NEt3 produces the radically reduced form of [Re], [Re](-) (kq = 1.4 ± 0.1 × 10(7) M(-1) s(-1)). Once formed, [Re](-) reduces the [NiFe2] center to [NiFe2](-), and this reduction was followed using time-resolved infrared spectroscopy. The concentration dependence of the electron transfer rate constants suggests that both inter- and intramolecular electron transfer pathways are involved, and the rate constants for these processes have been estimated (kinter = 5.9 ± 0.7 × 10(8) M(-1) s(-1), kintra = 1.5 ± 0.1 × 10(5) s(-1)). For the analogous bimolecular system, only intermolecular electron transfer could be observed (kinter = 3.8 ± 0.5 × 10(9) M(-1) s(-1)). Fourier transform infrared spectroscopic studies confirms that decomposition of the dyad occurs upon prolonged photolysis, and this appears to be a major factor for the low activity of the system toward H2 production in acidic conditions.

Dynamic structure elucidation of chemical reactivity by laser pulses and X-ray probes.

Visualising chemical reactions by X-ray methods is a tantalising prospect. New light sources provide the prospect for studying atomic, electronic and energy transfers accompanying chemical change by X-ray spectroscopy and inelastic scattering. Here we assess how this adventure can illuminate inorganic and catalytic chemistry. In particular X-ray inelastic scattering provides a means of exploiting X-ray free electron lasers, as a parallel to laser Raman spectroscopy.

Steady-state and pseudo-steady-state photocrystallographic studies on linkage isomers of [Ni(Et4dien)(η2-O,ON)(η1-NO2)]: identification of a new linkage isomer.

At temperatures below 150 K, the photoactivated metastable endo-nitrito linkage isomer [Ni(Et4 dien)(η(2)-O,ON)(η(1)-ONO)] (Et4 dien=N,N,N',N'-tetraethyldiethylenetriamine) can be generated with 100 % conversion from the ground state nitro-(η(1)-NO2) isomer on irradiation with 500 nm light, in the single crystal by steady-state photocrystallographic techniques. Kinetic studies show the system is no longer metastable above 150 K, decaying back to the ground state nitro-(η(1)-NO2) arrangement over several hours at 150 K. Variable-temperature kinetic measurements in the range of 150-160 K show that the rate of endo-nitrito decay is highly dependent on temperature, and an activation energy of Eact =+48.6(4) kJ mol(-1) is calculated for the decay process. Pseudo-steady-state experiments, where the crystal is continually pumped by the light source for the duration of the X-ray experiment, show the production of a previously unobserved, exo-nitrito-(η(1)-ONO) linkage isomer only at temperatures close to the metastable limit (ca. 140-190 K). This exo isomer is considered to be a transient excited-state species, as it is only observed in data collected by pseudo-steady-state methods.

Dynamic structural science: recent developments in time-resolved spectroscopy and X-ray crystallography.

To understand the mechanism of biological processes, time-resolved methodologies are required to investigate how functionality is linked to changes in molecular structure. A number of spectroscopic techniques are available that probe local structural rearrangements with high temporal resolution. However, for macromolecules, these techniques do not yield an overall high-resolution description of the structure. Time-resolved X-ray crystallographic methods exist, but, due to both instrument availability and stringent sample requirements, they have not been widely applied to macromolecular systems, especially for time resolutions below 1 s. Recently, there has been a resurgent interest in time-resolved structural science, fuelled by the recognition that both chemical and life scientists face many of the same challenges. In the present article, we review the current state-of-the-art in dynamic structural science, highlighting applications to enzymes. We also look to the future and discuss current method developments with the potential to widen access to time-resolved studies across discipline boundaries.

Energy dispersive XAFS: characterization of electronically excited states of copper(I) complexes.

Energy dispersive X-ray absorption spectroscopy (ED-XAS), in which the whole XAS spectrum is acquired simultaneously, has been applied to reduce the real-time for acquisition of spectra of photoinduced excited states by using a germanium microstrip detector gated around one X-ray bunch of the ESRF (100 ps). Cu K-edge XAS was used to investigate the MLCT states of [Cu(dmp)2](+) (dmp =2,9-dimethyl-1,10-phenanthroline) and [Cu(dbtmp)2](+) (dbtmp =2,9-di-n-butyl-3,4,7,8-tetramethyl-1,10-phenanthroline) with the excited states created by excitation at 450 nm (10 Hz). The decay of the longer lived complex with bulky ligands, was monitored for up to 100 ns. DFT calculations of the longer lived MLCT excited state of [Cu(dbp)2](+) (dbp =2,9-di-n-butyl-1,10-phenanthroline) with the bulkier diimine ligands, indicated that the excited state behaves as a Jahn-Teller distorted Cu(II) site, with the interligand dihedral angle changing from 83 to 60° as the tetrahedral coordination geometry flattens and a reduction in the Cu-N distance of 0.03 Å.

Laser-based absorption spectroscopy as a technique for rapid in-line analysis of respired gas concentrations of O2 and CO2.

The use of sidestream analyzers for respired gas analysis is almost universal. However, they are not ideal for measurements of respiratory gas exchange because the analyses are both temporally dissociated from measurements of respiratory flow and also not generally conducted under the same physical conditions. This study explores the possibility of constructing an all optical, fast response, in-line breath analyzer for oxygen and carbon dioxide. Using direct absorption spectroscopy with a diode laser operating at a wavelength near 2 µm, measurements of expired carbon dioxide concentrations were obtained with an absolute limit of detection of 0.04% at a time resolution of 10 ms. Simultaneously, cavity enhanced absorption spectroscopy at a wavelength near 760 nm was employed to obtain measurements of expired oxygen concentrations with an absolute limit of detection of 0.26% at a time resolution of 10 ms. We conclude that laser-based absorption spectroscopy is a promising technology for in-line analysis of respired carbon dioxide and oxygen concentrations.

Fiber-optic infrared reflection absorption spectroscopy for trace analysis on surfaces of varying roughness. Part II: Acetaminophen on stainless steel.

Investigations of the effects of surface roughness on the utility of grazing-angle Fourier transform infrared reflection absorption spectroscopy (IRRAS) as a method for quantifying trace contamination of metal surfaces have been extended to acetaminophen, a model active pharmaceutical agent, on 316 stainless steel. The effects are more complicated than for the surfactant sodium dodecyl sulfate (SDS) on stainless steel; they include a strong surface-finish dependence of sensitivity and nonlinear behavior at surface loadings above approximately 1-2 microg cm(-2). Using data from samples in the loading range 0-0.5 microg cm(-2), unbiased partial least squared calibrations can be readily achieved for individual surface finishes with detection limits of L(D) approximately 0.15 microg cm(-2). However, as found for SDS on stainless steel, models built using data from samples of mixed surface roughness are more problematic.

Grazing-angle fiber-optic fourier transform infrared reflection-absorption spectroscopy for the in situ detection and quantification of two active pharmaceutical ingredients on glass.

Fourier transform infrared reflection-absorption spectroscopy has been used with a fiber-optic grazing-angle reflectance probe as a rapid, in situ method for trace surface analysis of acetaminophen and aspirin at loadings of approximately 0-2 microg cm(-2) on glass. Partial least-squares multivariate regression permits the loadings to be quantified, simultaneously, with root-mean-squared errors of prediction of RMSEP approximately 0.1 microg cm(-2) for both compounds. The detection limits are estimated to be LD approximately 0.2 microg cm(-2).

Fiber-optic infrared reflection absorption spectroscopy for trace analysis on surfaces of varying roughness: Sodium dodecyl sulfate on stainless steel.

The effect of surface roughness on the analytical performance of a fiber-optic grazing-angle infrared reflection absorption spectroscopy (IRRAS) system has been investigated. The instrument was used to develop calibrations to quantify trace surface loadings for sodium dodecyl sulfate (SDS) on 316 stainless steel with three different surface finishes. Partial least squares (PLS) calibrations were developed for both individual finishes and combinations of finishes. For SDS on individual surface finishes, the root mean square (rms) error of cross-validation (RMSECV) varied between 0.08 and 0.12 microg cm(-2) with values of R2 between 0.89 and 0.96. A combined model for SDS on all surfaces gave an RMSECV of 0.18 microg cm(-2) with an R2 of 0.85.

Oxidative damage to DNA and aging.

Oxidative damage to DNA increases with age in several tissues and animal models, and mitochondrial DNA has a higher level of oxidative damage than nuclear DNA. Dietary restriction extends lifespan and is associated with reduced levels of damage to mitochondrial and nuclear DNA. The effect of exercise on DNA damage appears to be related to the intensity of the exercise.