Impurity Atoms on Small Transition Metal Clusters. Insights from Density Functional Model Studies

We review our computational studies at the DFT level on small isolated metal clusters of late transition metals that contain atomic (H, C, O) or diatomic (CO, N₂) ligands. These investigations were initiated by the clarification of the structure of iridium and rhodium clusters, as characterized by EXAFS, and then were extended to clusters of other transition metals (Ni, Ru, Pd, Os, Pt). The results suggest that a single H atom hardly changes the structure of a small metal cluster, while the presence of O and C impurity atoms causes large variations in the metal?Cmetal distances. The adsorption of single atoms results in a partial oxidation of the metal moiety, yet addition of an atomic impurity only moderately modifies the electronic properties of small clusters, whereas stronger modifications of the properties are caused when the charge of the metal cluster is varied. The dissociative adsorption of larger amounts of hydrogen, up to 6 H₂ molecules, on metal tetramers causes an elongation of the (average) inter-metallic distances, bringing them close to the experimental values. This body of computational results can be helpful for elucidating the structures of experimentally observed species and for rationalizing their electronic and catalytic properties.     

Gradient polymer-disposed liquid crystal single layer of large nematic droplets for modulation of laser light

The light modulating ability of gradient polymer-disposed liquid crystal (PDLC) single layer of large droplets formed by nematic E7 in UV-cured polymer NOA65 is studied. Operating at relatively low voltages, such PDLC film with a of thickness 10-25?μm and droplet size up to 50?μm exhibits a good contrast ratio and is capable of producing a large phase shift for the propagating coherent light. For a linearly polarized He-Ne laser (λ=633?nm), an electrically commanded phase shift as large as π/2 can be obtained by the large-droplet region of the film. The electrically produced phase shift and its spatial profile controlled by the thickness of the gradient PDLC single layers of large nematic droplets can be useful for tunable spatial light modulators and other devices for active control of laser light.     

A FREQUENCY DOMAIN APPROACH FOR THE ESTIMATION OF PARAMETERS OF SPATIO‐TEMPORAL STATIONARY RANDOM PROCESSES

A frequency domain methodology is proposed for estimating parameters of covariance functions of stationary spatio‐temporal processes. Finite Fourier transforms of the processes are defined at each location. Based on the joint distribution of these complex valued random variables, an approximate likelihood function is constructed. The sampling properties of the estimators are investigated. It is observed that the expectation of these transforms can be considered to be a frequency domain analogue of the classical variogram. We call this measure frequency variogram. The method is applied to simulated data and also to Pacific wind speed data considered earlier by Cressie and Huang (1999). The proposed method does not depend on the distributional assumptions about the process.     

Visualizing the local optical response of semiconducting carbon nanotubes to DNA-wrapping

We studied the local optical response of semiconducting single-walled carbon nanotubes to wrapping by DNA segments using high resolution tip-enhanced near-field microscopy. Photoluminescence (PL) near-field images of single nanotubes reveal large DNA-wrapping-induced red shifts of the exciton energy that are two times higher than indicated by spatially averaging confocal microscopy. Near-field PL spectra taken along nanotubes feature two distinct PL bands resulting from DNA-wrapped and unwrapped nanotube segments. The transition between the two energy levels occurs on a length scale smaller than our spatial resolution of about 15 nm.     

Morphometric and Nanomechanical Features of Platelets from Women with Early Pregnancy Loss Provide New Evidence of the Impact of Inherited Thrombophilia

Pregnancy is associated with hypercoagulation states and increased thrombotic risk, especially in women with thrombophilia. We combine atomic force microscopy (AFM) and flow cytometry to examine the morphology and nanomechanics of platelets derived from women with early pregnancy loss (EPL) and control pregnant (CP) and non-pregnant (CNP) women. Both control groups exhibit similar morphometric parameters (height and surface roughness) and membrane stiffness of platelets. EPL patients’ platelets, on the other hand, are more activated than the control groups, with prominent cytoskeletal rearrangement. In particular, reduced membrane roughness (22.9 ± 6 nm vs. 39.1 ± 8 nm) (p < 0.05) and height (692 ± 128 nm vs. 1090 ± 131 nm) (p < 0.05), strong alteration in the membrane Young modulus, increased production of platelets’ microparticles, and higher expression of procoagulant surface markers, as well as increased occurrence of thrombophilia (FVL, FII20210A, PLA1/A2, MTHFR C677T or 4G/5G PAI-1) polymorphisms were found. We suggest that the carriage of thrombophilic mutations triggers structural and nanomechanical abnormalities in platelets, resulting in their increased activation. The activation state of platelets can be well characterized by AFM, and the morphometric and nanomechanical characteristics might serve as a new criterion for evaluation of the cause of miscarriage and offer the prospect of an innovative approach serving for diagnostic purposes.     

Sorption-induced effects of humic substances on mass transfer of organic pollutants through aqueous diffusion boundary layers: the example of water/air exchange

This study examines the effect of dissolved humic substances (DHS) on the rate of water-gas exchange of organic compounds under conditions where diffusion through the aqueous boundary layer is rate-determining. A synthetic surfactant was applied for comparison. Mass-transfer coefficients were determined from the rate of depletion of the model compounds by means of an apparatus containing a stirred aqueous solution with continuous purging of the headspace above the solution. In addition, experiments with continuous passive dosing of analytes into the water phase were conducted to simulate a system where thermodynamic activity of the chemical in the aqueous phase is identical in the presence and absence of DHS. The experimental results show that DHS and surfactants can affect water-gas exchange rates by the superposition of two mechanisms: (1) hydrodynamic effects due to surface film formation ("surface smoothing"), and (2) sorption-induced effects. Whether sorption accelerates or retards mass transfer depends on its effect on the thermodynamic activity of the pollutant in the aqueous phase. Mass transfer will be retarded if the activity (or freely dissolved concentration) of the pollutant is decreased due to sorption. If it remains unchanged (e.g., due to fast equilibration with a sediment acting as a large source phase), then DHS and surfactant micelles can act as an additional shuttle for the pollutants, enhancing the flux through the boundary layer.     

Fe-Zeolite as on-Site Regenerable Adsorber for Chlorohydrocarbons in Groundwater – from Laboratory to Pilot Test

This study describes the design and upscaling of an on-site regenerable adsorbent fixed bed of Fe-loaded MFI zeolite for removal of chlorinated hydrocarbons (CHCs) from contaminated groundwater from laboratory studies to pilot scale. The zeolite has an excellent adsorption performance for the hydrophilic CHCs and can be regenerated on-site by flushing with H₂O₂ to degrade adsorbed contaminants by a catalytic Fenton-like reaction. In the pilot test, the Fe-zeolite (30 kg) maintained its performance over treatment of 1470 m³ of groundwater in 12 adsorption/regeneration cycles.