Disk Noise Measurement System for Optical Disks

We developed a system to measure disk noise as a function of both radial and angular position. In order to obtain an accurate disk noise measurement, crosstalk and intersymbol interference were avoided by recording regularly repeating pit patterns and the influence of electronic and laser noise was removed by averaging techniques. We found the system’s mapping ability and its high sensitivity to be very useful in investigating disk noise phenomena in the mastering process. We used the system to assess the accuracy and reproducibility of the photopolymerization replication and Al vapor deposition processes. Also, we investigated the choice of photoresist and found that photoresists with the combination of the narrowest molecular weight distribution and the highest photo-active compound content resulted in the lowest disk noise levels. Our system can, in principle, be adapted to evaluate magneto-optical and phase change disks.     

Proton NMR studies of reduced porphyrin compounds

Detailed ¹H NMR studies of ms tetraphenylchlorins (H₂TPC), new amino- and hydroxypyrroline substituted ms tetraphenylchlorins and ms tetraphenylisobacteriochlorins (H₂TPisoB) are presented and discussed. The results obtained are consistent with the general aspects of the ring current models as applied to the parent porphyrins. According to proton chemical shifts a gradual reduction in the magnitude of the ring current is observed in the order ms tetraphenylporphyrin (H₂TPP) > H₂TPC> ms tetraphenylbacteriochlorin (H₂TPB) > H₂TPisoB. The ¹H NMR spectra show chemical non-equivalence of the pyrroline ring protons due to adjacent substituents, and effects of steric constraints on the aminoalkyl substituents due to the close vicinity to the meso phenyl rings. The non-equivalence of the methylene protons of the pyrroline ring produces geminal coupling between the two methylene protons and vicinal coupling with the adjacent pyrroline proton, more pronounced in H₂TPC? OH and in . Restricted configuration of the methylene groups in the ethyl groups of H₂TPC? C(H)(CH₃)N(CH₂CH₃)₂ produces observable geminal coupling between the methylene protons. ¹H NMR reveals the difference between two types of meso phenyls in the chlorins, and three types of meso phenyls in isobacteriochlorins, as reflected in the chemical shifts of the o-phenyl protons.     

Lipid vesicles in capillary electrophoretic techniques: characterization of structural properties and associated membrane-molecule interactions

This paper reviews the use of lipid vesicles as model membranes in capillary electrophoresis (CE). The history and utility of CE in the characterization of microparticles is summarized, focusing on the application of colloidal electromigration theories to lipid vesicles. For instance, CE experiments have been used to characterize the size, surface properties, enclosed volumes, and electrophoretic mobilities of lipid vesicles and of lipoprotein particles. Several techniques involving small molecules or macromolecules separated in the presence of lipid vesicles are discussed. Interactions between the analytes and the lipid vesicles - acting as a pseudostationary phase or coated stationary phase in electrokinetic chromatography (EKC) - can be used to obtain additional information on the characteristics of the vesicles and analytes, and to study the biophysical properties of membrane-molecule interactions in lipid vesicles and lipoproteins. Different methods of determining binding constants by EKC are reviewed, along with the relevant binding constant calculations and a discussion of the application and limitations of these techniques as they apply to lipid vesicle systems.     

Extended Picard complexes for algebraic groups and homogeneous spaces

For a smooth geometrically integral algebraic variety X over a field k of characteristic 0, we define the extended Picard complex $\mathrm{UPic}(\overline{X})$. It is a complex of length 2 which combines the Picard group $\mathrm{Pic}(\overline{X})$ and the group $U(\overline{X}):=\overline{k}{[\overline{X}]}^{\times }/{\overline{k}}^{\times }$, where $\overline{k}$ is a fixed algebraic closure of k and $\overline{X}=X{\times }_k\overline{k}$. For a connected linear k-group G we compute the complex $\mathrm{UPic}(\overline{G})$ (up to a quasi-isomorphism) in terms of the algebraic fundamental group ${\pi }_1(\overline{G})$. We obtain similar results for a homogeneous space X of a connected k-group G. To cite this article: M. Borovoi, J. van Hamel, C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Factors affecting masking release for speech in modulated noise for normal-hearing and hearing-impaired listeners

The Speech Reception Threshold for sentences in stationary noise and in several amplitude-modulated noises was measured for 8 normal-hearing listeners, 29 sensorineural hearing-impaired listeners, and 16 normal-hearing listeners with simulated hearing loss. This approach makes it possible to determine whether the reduced benefit from masker modulations, as often observed for hearing-impaired listeners, is due to a loss of signal audibility, or due to suprathreshold deficits, such as reduced spectral and temporal resolution, which were measured in four separate psychophysical tasks. Results show that the reduced masking release can only partly be accounted for by reduced audibility, and that, when considering suprathreshold deficits, the normal effects associated with a raised presentation level should be taken into account. In this perspective, reduced spectral resolution does not appear to qualify as an actual suprathreshold deficit, while reduced temporal resolution does. Temporal resolution and age are shown to be the main factors governing masking release for speech in modulated noise, accounting for more than half of the intersubject variance. Their influence appears to be related to the processing of mainly the higher stimulus frequencies. Results based on calculations of the Speech Intelligibility Index in modulated noise confirm these conclusions.     

Bidentate ligands by supramolecular chemistry--the future for catalysis?

In this Frontier Article we give our view on recent developments in transition-metal catalyst development that evolve from a combination of supramolecular strategies and traditional ligand design and development.     

Synthesis of carbosilane dendritic wedges and their use for the construction of dendritic receptors

A divergent route for the synthesis of carbosilane wedges that contain either a bromine or amine as focal point has been developed. These new building blocks enable the construction of various core-functionalized carbosilane dendrimers. As a typical example carbosilane dendrimers up to the third generation containing a N,N',N'-1,3,5-benzenetricarboxamide core (G1-G3) have been synthesized. This new class of molecules has been studied as host molecules and they have been found to bind protected amino acids as guest molecules via hydrogen bonding interactions. A decrease in the association constants was observed for the higher generation dendritic hosts, which is attributed to the increased steric hindrance around the core where the binding site is located. The binding properties of the dendritic host molecules can be tuned by modifying the binding motif at the core of the carbosilane dendrimers. A higher association constant for N-CBZ-protected glutamic acid 1-methyl ester (5) was observed when the third generation N,N',N'-1,3,5-tris(L-alaninyl)benzenetricarboxamide core-functionalized carbosilane dendrimer (G3') was used as the host molecule compared to G3. Different association constants for the formation of the diastereomeric G3'.L-5(K=295 M(-1)) and G3'.(D-5)(2) (K=236 M(-1)) host-guest complexes were observed, pointing to a small enantioselective recognition effect. The difference between the association constants for the formation of the G3'.(L-5)(2) and G3'.(D-5)(2) host-guest complexes was much more pronounced, K=37 M(-1)versus K=10 M(-1), respectively.