Reductive nitrosylation of tetraoxometallates. Part VIII1. A virtually single step synthesis of azido-nitrosyl derivatives of chromium(I) directly from chromate in aqueous-aerobic media.

Azido-nitrosyl complexes and their derivatives of the types [Cr(NO)(N₃)₅]^3? and [Cr(NO)(N₃)₂(L-L)] [L-L = 2,2′bipyridine (bipy) and 1,10 phenanthroline (phen)] were synthesised directly from chromate ion using hydroxylamine hydrochloride, azide ion and hydroxyl ion and other appropriate ligands virtually in a single step process in an aqueous aerobic medium. The compounds are characterised by IR, molecular weight, molar conductance, magnetic susceptibility, esr and electronic spectral data.     

Estimation of the Sea Level Muon Spectra at Different Zenith Angles below 10 TeV Energy

The moderate energy primary cosmic ray nucleon spectrum has been calculated from the direct measurements of Webber et al., Seo et al., and Menn et al. along with the other results surveyed by Swordy. Using these directly measured primary mass composition results all particle primary nucleon energy spectrum has been constructed using superposition model to estimate the energy spectra of muons from the decay of the cosmic ray non-prompt and prompt mesons in the atmosphere. The Z-factors have been estimated from the CERN LEBC-EHS on the Lorentz invariant cross section results on pp ^±X and pp K^±X inclusive reactions and FNAL data on ^±p ^±X reactions, and duly corrected for A--A collisions. Using these Z-factors the meson energy spectra in the atmosphere have been calculated. The sea level muon energy spectra at zenith angles 0°, 45°, 72°, and 75° have been derived from the decay of non-prompt mesons by adopting standard diffusion equation of hadronic cascades. The contribution of charmed mesons to muon spectrum has also been accounted by adapting the conventional procedure. The derived differential sea level muon energy spectra for energies 10 TeV have been found to follow the power law fits of the form N (E) const. E ^-. Our estimated muon energy spectra at zenith angles 75° have been found comparable with the global spectrograph muon flux results of MARS, DEIS, and MSU groups.     

Implementing EPR Dosimetry for Life-Threatening Incidents: Factors Beyond Technical Performance

Starting with the assumption that a device to detect unplanned radiation exposures is technically superior to current technology, we examine the additional stakeholders and processes that must be considered to move the device from the lab into use. The use is to provide reliable information to triage people for early treatment of exposure to ionizing radiation that could lead to the Acute Radiation Syndrome. The scenario is a major accident or terrorist event that leaves a large number of people potentially exposed, with the resulting need to identify those to treat promptly or not. In vivo EPR dosimetry is the exemplar of such a technique.Three major areas are reviewed: policy considerations, regulatory clearance, and production of the device. Our analysis of policy-making indicates that the current system is very complex, with multiple significant decision-makers who may have conflicting agendas. Adoption of new technologies by policy-makers is further complicated because many sources of expert input already have made public stances or have reasons to prefer current solutions, e.g., some may have conflicts of interest in approving new devices because they are involved with the development or adoption of competing techniques. Regulatory clearance is complicated by not being able to collect evidence via clinical trials of its intended use, but pathways for approval for emergency use are under development by the FDA. The production of the new device could be problematical if the perceived market is too limited, particularly for private manufacturers; for in vivo EPR dosimetry the potential for other uses may be a mitigating factor.Overall we conclude that technical superiority of a technique does not in itself assure its rapid and effective adoption, even where the need is great and the alternatives are not satisfactory for large populations. Many important steps remain to achieve the goals of approval and adoption for use.     

Combined quantum mechanical and molecular mechanical simulations of one- and two-electron reduction potentials of flavin cofactor in water, medium-chain acyl-CoA dehydrogenase, and cholesterol oxidase

Flavin adenine dinucleotide (FAD) is a common cofactor in redox proteins, and its reduction potentials are controlled by the protein environment. This regulation is mainly responsible for the versatile catalytic functions of flavoenzymes. In this article, we report computations of the reduction potentials of FAD in medium-chain acyl-CoA dehydrogenase (MCAD) and cholesterol oxidase (CHOX). In addition, the reduction potentials of lumiflavin in aqueous solution have also been computed. Using molecular dynamics and free-energy perturbation techniques, we obtained the free-energy changes for two-electron/two-proton as well as one-electron/one-proton addition steps. We employed a combined quantum mechanical and molecular mechanical (QM/MM) potential, in which the flavin ring was represented by the self-consistent-charge density functional tight-binding (SCC-DFTB) method, while the rest of the enzyme-solvent system was treated by classical force fields. The computed two-electron/two-proton reduction potentials for lumiflavin and the two enzyme-bound FADs are in reasonable agreement with experimental data. The calculations also yielded the pKa values for the one-electron reduced semiquinone (FH*) and the fully reduced hydroquinone (FH2) forms. The pKa of the FAD semiquinone in CHOX was found to be around 4, which is 4 units lower than that in the enzyme-free state and 2 units lower than that in MCAD; this supports the notion that oxidases have a greater ability than dehydrogenases to stabilize anionic semiquinones. In MCAD, the flavin ring interacts with four hydrophobic residues and has a significantly bent structure, even in the oxidized state. The present study shows that this bending of the flavin imparts a significant destabilization (approximately 5 kcal/mol) to the oxidized state. The reduction potential of lumiflavin was also computed using DFT (M06-L and B3LYP functionals with 6-31+G(d,p) basis set) with the SM6 continuum solvation model, and the results are in good agreement with results from explicit free-energy simulations, which supports the conclusion that the SCC-DFTB/MM computation is reasonably accurate for both 1e(-)/1H+ and 2e(-)/2H+ reduction processes. These results suggest that the first coupled electron-proton addition is stepwise for both the free and the two enzyme-bound flavins. In contrast, the second coupled electron-proton addition is also stepwise for the free flavin but is likely to be concerted when the flavin is bound to either the dehydrogenase or the oxidase enzyme.     

Ultrafast photoinduced electron transfer from dimethylaniline to coumarin dyes in sodium dodecyl sulfate and triton X-100 micelles

The primary steps of photoinduced electron transfer (PET) from N,N-dimethylaniline (DMA) to five coumarin dyes are studied in an anionic micelle [sodium dodecyl sulfate (SDS)] and a neutral micelle [triton X-100 (TX-100)] using femtosecond upconversion. The rate of PET in micelle is found to be highly nonexponential. In both the micelles, PET displays components much faster (approximately 10 ps) than the slow components (180-2900 ps) of solvation dynamics. The ultrafast components of electron transfer exhibit a bell-shaped dependence on the free energy change. This is similar to Marcus inversion. The rates of PET in TX-100 and SDS micelle are, in general, faster than those in cetyltrimethylammonium bromide (CTAB) micelle. In the SDS and TX-100 micelle, the Marcus inversion occurs at -DeltaG0 approximately 0.7 eV which is lower than that (approximately 1.2 eV) in CTAB micelle. Possible causes of variation of PET in different micelles are discussed.     

Excitation wavelength dependence of solvation dynamics in a supramolecular assembly: PEO-PPO-PEO triblock copolymer and SDS

The triblock copolymer (PEO)20-(PPO)70-(PEO)20 (P123) forms a supramolecular aggregate with sodium dodecyl sulfate (SDS). The solvation dynamics and anisotropy decay of coumarin 480 (C480) in different regions of a P123-SDS aggregate are studied through variation of the excitation wavelength (lambdaex) using femtosecond upconversion. In a P123 micelle, because of the drastic differences in polarity between the hydrophilic corona region (PEO block) and the hydrophobic PPO core, C480 exhibits a pronounced red edge excitation shift (REES) of emission maximum by 24 nm. In the P123-SDS aggregate, SDS penetrates the core of the P123 micelle. This increases the polarity of the core and reduces the difference in the polarity between the core and the corona region. In a P123-SDS aggregate, the REES is much smaller (5 nm) which suggests a reduced difference between the core and the corona. Solvation dynamics in a P123 micelle displays a bulklike ultrafast component (<0.3 and 1 ps) in the PEO corona region, a 200 ps component arising from dynamics of polymer segments, and a very long component (5000 or 3000 ps) due to the highly restricted PPO core. In a P123-SDS aggregate, at lambdaex = 375 and 405 nm, the solvation dynamics is found to be faster than that in P123 micelle. In this case, the component (3000 ps) arising from the core region is faster than that (5000 ps) in P123 micelle. In both P123 micelle and P123-SDS aggregate, the relative contribution of the core region decreases and that of the corona region increases with an increase in lambdaex. At lambdaex = 435 nm, which probes the hydrophilic corona, the solvation dynamics for both P123 micelle and P123-SDS aggregate are almost similar.     

Mechanical and chemical analysis of plasma and ultraviolet-ozone surface treatments for thermal bonding of polymeric microfluidic devices

Here we have demonstrated that radio frequency plasma and ultraviolet-ozone (UVO) surface modifications are effective treatments for enabling the thermal bonding of polymeric microfluidic chips at temperatures below the T(g) (glass transition temperature) of the polymer. The effects of UVO and plasma treatments on the surface properties of a cyclic polyolefin and polystyrene were examined with X-ray photoelectron spectroscopy (XPS), contact angle measurements, atomic force microscopy (AFM) surface roughness measurements and surface adhesion measurements with AFM force-distance data. Three-point bending tests using a dynamic mechanical analyzer (DMA) were used to characterize the bond strength of thermally sealed polymer parts and the cross-sections of the bonded microchannels were evaluated with scanning electron microscopy (SEM). The experimental results demonstrated that plasma and UVO surface treatments cause changes in the chemical and physical characteristics of the polymer surfaces, resulting in a decrease in T(g) at the surface, and thus allowing the microfluidic chips to be effectively bonded at temperatures lower than the T(g) of the bulk polymer without losing the intended channel geometry.     

Impact of membrane immobilization on particle formation and trichloroethylene dechlorination for bimetallic Fe/Ni nanoparticles in cellulose acetate membranes

The use of membrane immobilization to carry out the batch dechlorination of trichloroethylene (TCE) using bimetallic Fe/Ni (4:1, Fe to Ni) nanoparticles in cellulose acetate membranes is examined using modeling of transport phenomenon based on experimental results. Membranes are synthesized using both gelation and solvent evaporation techniques for phase inversion. The reduction of metal ions within cellulose acetate phase-inversion membranes was accomplished using sodium borohydride reduction to obtain up to 2 wt % total metals. Characterization of the mixed-matrix structure reveals a bimodal particle distribution ranging between 18 and 80 nm within the membrane cross section. The distribution is the result of changes in the morphology of the cellulose acetate support. The diffusivity and linear partitioning coefficient for the chlorinated organic were measured and are 2.0 x 10(-8) cm2.s-1 and 3.5 x 10(-2) L.g-1, respectively. An unsteady-state model for diffusion through a membrane with reaction was developed to predict experimental results with an error of only 7.2%. The error can be attributed to the lack of the model to account for loss of reactivity through pH effects, alloy effects (bimetallic ratio), and oxidation of nanoparticles. Simulations were run to vary the major transport variables, partitioning and diffusivity, and determine their impact on reaction kinetics. Of the two, diffusivity was less significant because it really only influences the time required for maximum TCE partitioning to the membrane to be achieved and has no effect on the limiting capacity of the membrane for TCE. Therefore, selection of an appropriate support material is crucial for development of highly reactive mixed-matrix membrane systems.     

Binding of Organic Dyes with Human Serum Albumin: A Single‐Molecule Study

Kinetics of binding of dyes at different sites of human serum albumin (HSA) has been studied by single‐molecule spectroscopy. The protein was immobilized on a glass surface. To probe different binding sites (hydrophobic and hydrophilic) two dyes, coumarin 153 ( C153 , neutral) and rhodamine 6G ( R6G , cationic) were chosen. For both the dyes, a major (ca. 96‐98 %) and minor (ca. 3 %) binding site were detected. Rate constants of association and dissociation were simultaneously determined from directly measuring fluctuations in fluorescence intensity (τ_off and τ_on) and from this the equilibrium (binding) constants were calculated. Fluorescence lifetimes at individual sites were obtained from burst‐integrated lifetime analysis. Distributions of lifetime histograms for both the probes ( C153 and R6G ) exhibit two maxima, which indicates the presence of two binding domains in the protein. Unfolding of the protein has been studied by adding guanidinium hydrochloride (GdnHCl) to the solution. It is observed that addition of GdnHCl affects the dissociation and association kinetics and hence, binding equilibrium of the association of C153 . However, the effect of binding of R6G is not affected much. It is proposed that GdnHCl affects the hydrophobic binding sites more than the hydrophilic site.     

Metallic radionuclides in the development of diagnostic and therapeutic radiopharmaceuticals

Metallic radionuclides are the mainstay of both diagnostic and therapeutic radiopharmaceuticals. Therapeutic nuclear medicine is less advanced but has tremendous potential if the radionuclide is accurately targeted. Great interest exists in the field of inorganic chemistry for developing target specific radiopharmaceuticals based on radiometals for non-invasive disease detection and cancer radiotherapy. This perspective will focus on the nuclear properties of a few important radiometals and their recent applications to developing radiopharmaceuticals for imaging and therapy. Other topics for discussion will include imaging techniques, radiotherapy, analytical techniques, and radiation safety. The ultimate goal of this perspective is to introduce inorganic chemists to the field of nuclear medicine and radiopharmaceutical development, where many applications of fundamental inorganic chemistry can be found.