The Interaction of Glymes with Surfactant Micelles

The critical micelle concentrations (CMC) values and counterion dissociation (α values) have been determined for a number of mixed micellar systems consisting of two typical ionic surfactants and glycol ethers (glymes) as cosurfactants, namely diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Conductance experiments were used to determine the CMC and α values of the mixed micelles as a function of glyme concentration in the aqueous mixed solvent. Favorable interactions between sodium dodecyl sulfate micelles and glyme cosurfactants were deduced from the decreases in the CMC values and the large increase in the α values of these systems as a function of increasing glyme concentration in the mixed solvents. In contrast to the anionic surfactant/glyme systems, in general, there appeared to be little favorable interactions between the surfactant and glymes when micelles of the cationic surfactant dodecyltrimethylammonium bromide were formed in water/glyme solvent systems containing an increasing amount of the glymes. The interaction of glymes with the surfactant micelles was examined closely via ¹³C nuclear magnetic resonance (NMR) chemical shifts for both surfactant and glyme carbons; these chemical shifts changes were interpreted in terms of the distribution and the localization of the glymes in the aggregates. Finally, partition constants, determined from two-dimensional diffusion-oriented spectroscopy (2D-DOSY) experiments, were used to calculate thermodynamic quantities of transfer of the glymes between the bulk phase and the self-assembled aggregates. All these results are interpreted in terms of the key contributions that both the glyme ethoxylated groups and alkyl endgroups make to the hydrophobic interactions.     

Electrochemistry at capped platinum nanoparticle Langmuir Blodgett films: A study of the influence of platinum amount and of number of LB layers

Platinum nanoparticles (n-Pt), over-grafted with 2-thiophenecarbonyl chloride are assembled on gold electrodes, by the Langmuir Blodgett (LB) technique using behenic acid (BHA) as promoting agent. These layers are electrochemically active without any preliminary activation. The [Fe(CN)₆]^3−/4− redox couple was used as electrochemical probe. This paper reports on the influence of the number of deposited LB layers, and the n-Pt density on the electrochemical response. n-Pt density was modified by the change of the “BHA/n-Pt” ratio. Cyclic voltammograms of “[Fe(CN)₆]^3−/4−” were observed whatever the coating conditions. As soon as the first layer was deposited the electrochemical response was associated to the n-Pt coverage, its response slightly increased up to a steady state for five or seven layers. As expected, the increase of the Pt density favored the increase of the current density. XPS analysis performed before and after electrochemical cycling showed that 4-mercaptoaniline capped platinum nanoparticles, and their over grafting were chemically and electrochemically stable. Analysis of influence of the number or the n-Pt density of the layers showed that the electrochemically active part of LB electrodes was provided by the last layer plus a part of the underlying one.     

Electronic transfer through Langmuir-Blodgett layers of capped platinum nanoparticles: An electrochemical approach

Amine functionalized platinum nanoparticles have been modified by over-grafting two different molecules, 2-thiophenecarbonyl chloride (Pt-1) and 1-hexyl-4-(4-isothiocyanatophenyl)-bicyclo (2, 2, 2) octane (Pt-2). Cyclic voltammetry was performed at gold electrodes coated with Langmuir-Blodgett (LB) mixed films of Pt-1 and Pt-2 nanoparticles, and behenic acid. From five layers the electrochemical response was essentially provided by the last LB component. The electrochemical responses towards the [Fe(CN)₆]^3−/4− couple were strongly influenced by the nature of the over-grafted molecules: films of Pt-2 presented an almost complete blocking effect, while films of Pt-1 allowed the redox reaction to occur on Pt nanoparticles. In order to understand the reasons for such different behaviors we built up hetero-nanostructures by superposing Pt-1 and Pt-2 LB layers in different ways, yielding different kinds of “sandwich” structures. The electrochemical response depended on the electrode ending. When Pt-1 nanoparticles were in the outer layer, in contact with the electrolyte solution, the electrode was electroactive toward the redox probe, while when Pt-2 layers were in the outer layer no electroactivity was detected. For sandwiches made of Pt-1, with a variable thickness of an intercalated film of Pt-2, the electrode response to [Fe(CN)₆]^3−/4− was modulated by the thickness of the inter-layer: the thicker the layer, the lower the response.     

Destabilizing interactions between the partners of a bifunctional fusion protein

Hybrid MalE–GVP is a bifunctional protein in vitro sinceit binds maltose as protein MalE of Escherichia coli and sinceit is dimeric and specifically binds single-stranded DNA asprotein GVP of phage M13. The oxidation rate of a unique cysteineresidue was used to compare the stabilities of GVP in its freeand hybrid forms, under conditions where MalE was either foldedor unfolded by a denaturing agent. The results showed that boththe covalent link and tertiary non-covalent interactions betweenMalE and GVP destabilized GVP in MalE–GVP. To test whetherGVP had identical structures in its free and hybrid forms, mutationswere used as local conformational probes. The effects of thesemutations on the capabilities of MalE–GVP to dimerizeand to bind single-stranded DNA were assayed in vitro. Theywere compatible with the effects of the same mutations on theglobal activity of free GVP in vivo and with the effects thatcould be predicted from the known data on free GVP, in particularits crystal structure. Thus, one partner of a hybrid proteincan be destabilized by the other partner while maintaining itsstructural and functional characteristics.     

INFLUENCE OF MATERIAL REMOVAL ON THE DYNAMIC BEHAVIOR OF THIN-WALLED STRUCTURES IN PERIPHERAL MILLING

Machining is a material removal process that alters the dynamic properties during machining operations. The peripheral milling of a thin-walled structure generates vibration of the workpiece and this influences the quality of the machined surface. A reduction of tool life and spindle life can also be experienced when machining is subjected to vibration. In this paper, the linearized stability lobes theory allows us to determine critical and optimal cutting conditions for which vibration is not apparent in the milling of thin-walled workpieces. The evolution of the mechanical parameters of the cutting tool, machine tool and workpiece during the milling operation are not taken into account. The critical and optimal cutting conditions depend on dynamic properties of the workpiece. It is illustrated how the stability lobes theory is used to evaluate the variation of the dynamic properties of the thin-walled workpiece. We use both modal measurement and finite element method to establish a 3D representation of stability lobes. The 3D representation allows us to identify spindle speed values at which the variation of spindle speed is initiated to improve the surface finish of the workpiece.     

A (Triphenylphosphine)Silver (I) Complex as a New Performance Additive in Free‐Radical Photopolymerization under Air

Unusual photochemical properties of an Ag(I)‐derived complex, i.e., bis[(µ‐chloro)bis(triphenylphosphine)silver (I)] ([Ag](PPh₃)) are demonstrated when used in free‐radical photopolymerization reactions: i) [Ag](PPh₃) can act as an innovative photoinitiating system when associated with a commercial type I photoinitiator 2,2‐dimethoxy‐2‐phenylacetophenone to overcome the oxygen inhibition effect during the free‐radical photopolymerization of acrylate monomers, thus accelerating the kinetics of polymerization under air; ii) silver‐based nanoparticles can be in situ generated under air, thus leading to new antibacterial coatings which prevent the growth of Escherichia coli and Staphylococcus aureus after few hours of incubation.     

Improving accuracy in detecting acoustic onsets.

In current cognitive psychology, naming latencies are commonly measured by electronic voice keys that detect when sound exceeds a certain amplitude threshold. However, recent research (e.g., K. Rastle & M. H. Davis, 2002) has shown that these devices are particularly inaccurate in precisely detecting acoustic onsets. In this article, the authors discuss the various problems and solutions that have been put forward with respect to this issue and show that classical voice keys may trigger several tens of milliseconds later than acoustic onset. The authors argue that a solution to this problem may come from voice keys that use a combination of analogue and digital noise (nonspeech sound) detection. It is shown that the acoustic onsets detected by such a device are only a few milliseconds delayed and correlate highly (up to .99) with reaction time values obtained by visual waveform inspection. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Chicken fat dry fractionation: Effects of temperature and time on crystallization,filtration and fraction properties

A surface response experimental design was used to quantify the effects of the final cooling temperature and the residence time at this temperature on the filtration characteristics of the crystal suspension and the quality of the fractions during chicken fat dry fractionation. The crystal morphology was monitored to gain insight into the observed effects. Temperature affected crystallization and the characteristics of the olein and stearin fractions. The crystals became fragmented as the residence time increased, thus leading to a decrease in the filterability of the crystal suspension and an increase in the proportion of the entrained liquid phase. The residence time only affected the quality of the stearin fraction. This time effect was noted at high cooling temperatures in the investigated experimental domain. At low temperatures, increasing the residence time enhanced crystal growth and increased the extent of unsaturation of both fractions without modifying the filtration features.     

An Effective Power-Aware At-Speed Test Methodology for IP Qualification and Characterization

Advanced nanometer technologies have led to a drastic increase in operational frequencies resulting in the performance of circuits becoming increasingly vulnerable to timing variations. The increasing process spread in advanced nanometer nodes poses considerable challenges in predicting post-fabrication silicon performance from timing models. Thus, there is a great need to qualify basic building structures on silicon in terms of critical parameters before they could be integrated within a complex System-on-Chip (SoC). The work of this paper presents a configurable circuit and an associated power-aware at-speed test methodology for the purpose of qualifying basic standard cells and complex IP structures to detect the presence of timing faults. Our design has been embedded within test-chips used for the development of the 28 nm Fully Depleted Silicon On Insulator (FD-SOI) technology node. The relevant silicon results and analysis validate the proposed power-aware test methodology for qualification and characterization of IPs and provide deeper insights for process improvements.