Correlations between structure and far-infrared active modes in polythiophenes

We have investigated the experimental X-ray and far-infrared responses of three polythiophenes synthesized from a thiophene, alpha-bithiophene, and alpha-quaterthiophene monomer. The X-ray data show that the crystallinity of the different polythiophene samples depends on the synthesis conditions. An excellent correlation between the crystallinity of polythiophenes and their far-infrared signatures is demonstrated. In addition, the assignment of the far-infrared phonon modes in polythiophenes is given by using both an experimental filiation procedure and first-principles calculations. In particular, the ring libration inside the polymeric chain, directly involved in the electron-phonon coupling, is assigned.     

Electrophoresis PDMS/glass chips with continuous on-chip derivatization and analysis of amino acids using naphthalene-2,3-dicarboxaldehyde as fluorogenic agent

In this work, we developed a PDMS electrophoresis device able to carry out on-chip derivatization and quantification of amino acids (AAs) using naphthalene-2,3-dicarboxaldehyde (NDA) as a fluorogenic agent. A chemical modification of the PDMS surface was found compulsory to achieve the derivatization of AAs with NDA and a limit of detection (LOD) of 40 nM was reached for glycine. Finally, we suggested the applicability of this microdevice for the analysis of real biological samples such as a rat hippocampus microdialysate.     

A feasible approach to all-electronic digital labeling and readout for cell identification

We present two critical innovations that enable a unique, purely electronic approach to microfluidic whole-cell analysis, focusing on the problem of cell identification and sorting. We used fully-scalable lithographic techniques to microfabricate digital barcodes, providing a means for low-cost, large volume production. We have demonstrated molecular functionalization of the barcodes, using biotin-streptavidin, as well as human CD4 antibody, and we have successfully linked the barcodes to polystyrene beads using the biotin-streptavidin complex. This functionalization allows unique barcodes to be attached to specific cell types, based on phenotype. We have also implemented an electronic barcode readout scheme, using a radio frequency microsensor integrated in an elastomeric microfluidic channel, that can read individual barcodes at rates in excess of 1000 labels s(-1). The barcodes are biologically compatible, and coupled with the electronic sensing technology, provide a route to compact, inexpensive, disposable cell identification, sorting and purification.     

Strain state in bcc Fe films grown on Si(1 1 1)

The strain state of Fe films grown on Si(1 1 1) has been investigated by X-ray diffraction (XRD) in the thickness range between 11 and 304 monolayers. Fe grows tetragonally distorted with the orientation relationship Fe(1 1 1) // Si(1 1 1) . At low coverage, the films grow pseudomorphic. Above 15 monolayers the films are characterized by the coexistence of a pseudomorphic phase with another one which relaxes with the Fe thickness. This relaxation proceeds rapidly in the earlier stages then slowly with the film thickness. The XRD characterization allows one to obtain quantitative information on the in-plane and out-of-plane strains.     

High power all-fibered femtosecond master oscillator power amplifier at 1.56 μm

Direct amplification of output from chirped pulse oscillator (CPO) to 3.3?W of average power (pulse energy of 118?nJ in 20?ps pulse duration before compression) was achieved in a properly designed cladding pumped large mode area Er-doped fiber. Various configurations of CPO cavity with different FWHM of output spectrum and pulse duration were investigated. Fourier limit compression with 480?fs pulse duration and 32?kW peak power has been obtained for pulses with 14.8?nm FWHM spectrum. Subsequent nonlinear compression in a standard SMF-28 fiber yielded pulses as short as 145?fs.     

Modeling of micro-perforated panels in a complex vibro-acoustic environment using patch transfer function approach

A micro-perforated panel (MPP) with a backing cavity is a well known device for efficient noise absorption. This configuration has been thoroughly studied in the experimental conditions of an acoustic tube (Kundt tube), in which the MPP is excited by a normal incident plane wave in one dimension. In a more practical situation, the efficiency of MPP may be influenced by the vibro-acoustic behavior of the surrounding systems as well as excitation. To deal with this problem, a vibro-acoustic formulation based on the patch transfer functions (PTF) approach is proposed to model the behavior of a micro-perforated structure in a complex vibro-acoustic environment. PTF is a substructuring approach, which allows assembling different vibro-acoustic subsystems through coupled surfaces. Upon casting micro-perforations and the flexibility of the MPP under transfer function framework, the proposed PTF formulation provides explicit representation of the coupling between subsystems and facilitates physical interpretation. As an illustration example, application to a MPP with a backing cavity located in an infinite baffle is demonstrated. The proposed PTF formulation is finally validated through comparison with experimental measurements available in the literature.     

Injection and flow control system for microchannels

In spite of considerable efforts, flow control in micro-channels remains a challenge owing to the very small ratio of channel/supply-system volumes, as well as the induction of spurious flows by extremely small pressure or geometry changes. We present here an inexpensive and robust system for flow control in a microchannel system, based on a dynamic control of reservoir pressures at the end of each channel. This system allows flow equilibration with a time constant smaller than one second, and is also able to maintain stable flux from stopped flow to many microl min(-1) range over several hours. It is robust to changes in ambient pressure and temperature. This system further includes a feature for sub-microliter sample injection during the experiment. We quantify flow control in elastomer and thermoplastic channels, and demonstrate the impact on one application of the system, namely the reproducible, automated separation of large DNA by electrophoresis in a self-organized magnetic bead matrix in a microchannel.     

Spectroscopic characterization of microscopic hydrogen-bonding disparities in supercritical water

The local hydrogen-bonding environment in supercritical water (380 degrees C, 300 bars, density 0.54 gcm3) was studied by x-ray Raman scattering at the oxygen K edge. The spectra are compared to those of the gas phase, liquid surface, bulk liquid, and bulk ice, as well as to calculated spectra. The experimental model systems are used to assign spectral features and to quantify specific local hydrogen-bonding situations in supercritical water. The first coordination shell of the molecules is characterized in more detail with the aid of the calculations. Our analysis suggests that approximately 65% of the molecules in supercritical water are hydrogen bonded in configurations that are distinctly different from those in liquid water and ice. In contrast to liquid water the bonded molecules in supercritical water have four intact hydrogen bonds and in contrast to ice large variations of bond angles and distances are observed. The remaining approximately 35% of the molecules exhibit two free O-H bonds and are thus either not involved in hydrogen bonding at all or have one or two hydrogen bonds on the oxygen side. We determine an average O-O distance of 3.1+/-0.1 A in supercritical water for the H bonded molecules at the conditions studied here. This and the corresponding hydrogen bond lengths are shown to agree with neutron- and x-ray-diffraction data at similar conditions. Our results on the local hydrogen-bonding environment with mainly two disparate hydrogen-bonding configurations are consistent with an extended structural model of supercritical water as a heterogeneous system with small patches of bonded molecules in various tetrahedral configurations and surrounding nonbonded gas-phase-like molecules.     

Sur la ribosylation de divers mercapto-2 benzoazoles

A comparative study of the ribosylation reaction of various 2-mercaptobenzazoles using the three more usual techniques was performed: acid-catalyzed fusion, reaction of the silylated aglycones with 1-acetoxy and 1-halogeno sugars, respectively. For all the various 2-mercaptobenzazoles the N-nucleosides were obtained and fully characterized. The reactivity of 2-mercapto-benzimidazole is quite particular as we have noticed the formation of the corresponding N₁, N₃-diriboside and of an unusual 2-2-anhydro nueleoside.     

Reactions of acyl anions generated from acid chlorides and diiodosamarium

Acid chlorides react with SmI₂ to give α-diketones. Various experiments show that the initially formed acyl radical is rapidly transformed into an acyl anion which is thus generated by quite an unusual route.This species acylates acid chlorides, aldehydes and ketones in situ to give α-diketones and α-ketols. There are some limitations to this acyl anion chemistry but the reactions are realized with a good efficiency at room temperature in THF solution.