Compensating for frequency shifts in modulation transfer spectroscopy caused by residual amplitude modulation

Residual amplitude modulation (RAM) distorts saturated absorption signals, limiting the accuracy of optical frequency references based on modulation transfer spectroscopy (MTS). Described here are two independent means by which RAM is produced in these references: (1) by the modulator and (2) when the overlap of the optical fields in the saturable absorber is asymmetric. Methods to vary RAM generated by either mechanism will be outlined and these will be used to show how RAM arising from one effect can be cancelled by the other. A theoretical treatment of MTS signals in references containing RAM is given and used to evaluate the level of signal distortion allowing the conditions for RAM cancellation to be determined. This technique is applied to improve the frequency accuracy of a reference by an order of magnitude.     

Bioinorganic chemistry of Parkinson's disease: structural determinants for the copper-mediated amyloid formation of alpha-synuclein

The aggregation of alpha-synuclein (AS) is a critical step in the etiology of Parkinson's disease (PD). A central, unresolved question in the pathophysiology of PD relates to the role of AS-metal interactions in amyloid fibril formation and neurodegeneration. Our previous works established a hierarchy in alpha-synuclein-metal ion interactions, where Cu(II) binds specifically to the protein and triggers its aggregation under conditions that might be relevant for the development of PD. Two independent, non-interacting copper-binding sites were identified at the N-terminal region of AS, with significant difference in their affinities for the metal ion. In this work we have solved unknown details related to the structural binding specificity and aggregation enhancement mediated by Cu(II). The high-resolution structural characterization of the highest affinity N-terminus AS-Cu(II) complex is reported here. Through the measurement of AS aggregation kinetics we proved conclusively that the copper-enhanced AS amyloid formation is a direct consequence of the formation of the AS-Cu(II) complex at the highest affinity binding site. The kinetic behavior was not influenced by the His residue at position 50, arguing against an active role for this residue in the structural and biological events involved in the mechanism of copper-mediated AS aggregation. These new findings are central to elucidate the mechanism through which the metal ion participates in the fibrillization of AS and represent relevant progress in the understanding of the bioinorganic chemistry of PD.     

Combined time- and space-resolved Raman spectrometer for the non-invasive depth profiling of chemical hazards

A time-resolved inverse spatially offset Raman spectrometer was constructed for depth profiling of Raman-active substances under both the lab and the field environments. The system operating principles and performance are discussed along with its advantages relative to traditional continuous wave spatially offset Raman spectrometer. The developed spectrometer uses a combination of space- and time-resolved detection in order to obtain high-quality Raman spectra from substances hidden behind coloured opaque surface layers, such as plastic and garments, with a single measurement. The time-gated spatially offset Raman spectrometer was successfully used to detect concealed explosives and drug precursors under incandescent and fluorescent background light as well as under daylight. The average screening time was 50 s per measurement. The excitation energy requirements were relatively low (20 mW) which makes the probe safe for screening hazardous substances. The unit has been designed with nanosecond laser excitation and gated detection, making it of lower cost and complexity than previous picosecond-based systems, to provide a functional platform for in-line or in-field sensing of chemical substances.     

The affine equivariant sign covariance matrix: asymptotic behavior and efficiencies

We consider the affine equivariant sign covariance matrix (SCM) introduced by Visuri et al. (J. Statist. Plann. Inference 91 (2000) 557). The population SCM is shown to be proportional to the inverse of the regular covariance matrix. The eigenvectors and standardized eigenvalues of the covariance matrix can thus be derived from the SCM. We also construct an estimate of the covariance and correlation matrix based on the SCM. The influence functions and limiting distributions of the SCM and its eigenvectors and eigenvalues are found. Limiting efficiencies are given in multivariate normal and t-distribution cases. The estimates are highly efficient in the multivariate normal case and perform better than estimates based on the sample covariance matrix for heavy-tailed distributions. Simulations confirmed these findings for finite-sample efficiencies.     

Hausdorff Dimension and Non-degenerate Families of Projections

We study parameterized families of orthogonal projections for which the dimension of the parameter space is strictly less than that of the Grassmann manifold. We answer the natural question of how much the Hausdorff dimension may decrease by verifying the best possible lower bound for the dimension of almost all projections of a finite measure. We also show that a similar result is valid for smooth families of maps from the n-dimensional Euclidean space to the m-dimensional one.     

Aerosol characterization and lung deposition of synthesized TiO2 nanoparticles for murine inhalation studies

This study presents a novel exposure protocol for synthesized nanoparticles (NPs). NPs were synthesized in gas phase by thermal decomposition of metal alkoxide vapors in a laminar flow reactor. The exposure protocol was used to estimate the deposition fraction of titanium dioxide (TiO₂) NPs to mice lung. The experiments were conducted at aerosol mass concentrations of 0.8, 7.2, 10.0, and 28.5 mg m^?3. The means of aerosol geometric mobility diameter and aerodynamic diameter were 80 and 124 nm, and the geometric standard deviations were 1.8 and 1.7, respectively. The effective density of the particles was approximately from 1.5 to 1.7 g cm^?3. Particle concentration varied from 4 × 10⁵ cm^?3 at mass concentrations of 0.8 mg m^?3 to 12 × 10⁶ cm^?3 at 28.5 mg m^?3. Particle phase structures were 74% of anatase and 26% of brookite with respective crystallite sized of 41 and 6 nm. The brookite crystallites were approximately 100 times the size of the anatase crystallites. The TiO₂ particles were porous and highly agglomerated, with a mean primary particle size of 21 nm. The specific surface area of TiO₂ powder was 61 m² g^?1. We defined mice respiratory minute volume (RMV) value during exposure to TiO₂ aerosol. Both TiO₂ particulate matter and gaseous by-products affected respiratory parameters. The RMV values were used to quantify the deposition fraction of TiO₂ matter by using two different methods. According to individual samples, the deposition fraction was 8% on an average, and when defined from aerosol mass concentration series, it was 7%. These results show that the exposure protocol can be used to study toxicological effects of synthesized NPs.     

Illumination with Ultraviolet or Visible Light Induces Chemical Changes in the Water-soluble Manganese Complex, [Mn4O6(bpea)4]Br4

We measured the photosensitivity of an artificial tetranuclear oxo–Mn(IV) complex, [Mn₄O₆(bpea)₄]Br₄, which has an adamantane-shaped {Mn₄O₆}⁴⁺ core. Illumination caused changes in the absorption spectrum of the compound consistent with a one-electron reduction in the compound. Bromide appears to be the most probable electron donor in the reaction system. Chemical modification of the cluster appears to destabilize it, predisposing it to reductive degradation. UV light was more efficient than visible light in causing the changes. The data support the suggestion that the natural oxygen-evolving Mn complex is photosensitive and can oxidize components of the oxygen-evolving complex in its excited state causing photoinhibition, and that photostability is an important issue in designing Mn complexes for artificial photosynthesis. Furthermore, light-induced oxidation of bromide by [Mn₄O₆(bpea)₄]⁴⁺ may suggest that oxidation of chloride is involved in natural water splitting or has been involved during the evolution of the water-splitting enzyme.     

Nano-scale copper oxidation on leadframe surface

Copper oxidation studies were carried out by means of field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) and electron energy loss spectroscopy (EELS) techniques. The growth of copper oxide occurs as a copper surface comes in an oxygen containing environment. The reaction sequence leading to oxidation of the copper surface is generally accepted to be oxygen chemisorption, nucleation and growth of the surface oxide and bulk oxide growth. HRTEM examination of the cross section of the oxidized copper sample revealed the interface region in between the copper and copper oxide. At high oxidation temperature, formation of micro-voids and separations were observed along this interface region. Poor adhesion at this interface region due to micro-voids and separation were found to be the root cause of delamination issue. EELS analysis determined that for regions with intact interface the oxidation system is Cu/CuO/Cu₂O/CuO, however, in regions containing micro-voids or separation it is found to be Cu/Cu₂O/CuO.     

The synthesis of α,α-difluoroaldehydes and ketones via claisen rearrangements

The Claisen rearrangements of reactants containing two fluorine atoms in either the allyl or vinyl fragment are described.     

Synthesis and characterization of a silyl substituted bis(indenyl) zirconium dichloride and comparison of its olefin polymerization behavior to a siloxy substituted analogue

The synthesis and characterization of rac‐[ethylenebis(1‐(tert‐butyldimethylsilyl)‐3‐indenyl)]zirconium dichloride ( 3 ) is reported. The silyl substituted 3 /MAO was compared to its siloxy substituted analogue ( 4 ) in ethylene homo‐ and in ethylene‐1‐hexene copolymerizations to elucidate the effect of the heteroatom on polymerization performance. The influence of monomer and cocatalyst concentration and the polymerization temperature was investigated. The oxygen between the indenyl ligand and the bulky tert‐butyldimethylsilyl group in the siloxy substituted 4 /MAO was found to have a positive influence on polymerization activity and copolymerization performance. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 127–133, 2001