Synthesis and characterization of emulsifier-free quaternarized vinylbenzylchloride latexes

Polycationic polymers have been obtained through a two-step procedure. First, poly-vinylbenzylchloride [P(VBC)] latexes were prepared under emulsifier-free conditions using a cationic initiator: 2,2-azobis(2-amidinopropane) hydrochloride; then the resulting latexes were reacted with trimethylamine. Particular attention was paid to side reactions occurring during the hydrolysis of the chloromethyl groups and the crosslinking reaction due to a transfer reaction onto polymer. The influence of various parameters on the particle size and structure of latexes as well as secondary reactions were investigated through a careful characterization.     

Settling of paraffin crystals in cooled middle distillate fuels

The mechanism of action of additives that control the sedimentation of paraffin crystals after their crystallization in model diesel oil has been studied by means of a new experimental approach. The chemical analysis of the crystals and detailed measurements of the sedimentation phenomenon give new insights into this complex process. Thus, the wax antisettling additives used for preventing wax crystal sedimentation adsorb at the surfaces of wax particles and provide them with enhanced colloidal stability. The settling rate is not related to the size of the crystals or the viscosity of the liquid medium, but to the ability of the additives to prevent the aggregation of wax crystals. The reported methodology makes it possible to investigate the fundamental mechanisms, but also to evaluate structure-activity relationships of the various additives used in the petroleum industry.     

Unusual hysteresis in the magnetic susceptibility of cubic hexaboride KB6

Electrical resistivity, magnetic susceptibility, and electron paramagnetic resonance measurements were carried out for cubic hexaboride KB(6), which is one electron short of completely filling its conduction band. It is found that KB(6) is not metallic and has localized spins. KB(6) exhibits a highly unusual hysteresis in the magnetic susceptibility below 100 K, which suggests that it undergoes a slow relaxation process.     

Syntheses of d-Glucosaminyl Bolaamphiphiles1

Abstract

Twelve N-acetyl or NH2-free D-glucosaminyl bolaamphiphiles have been synthesized by the intermediate of N-allyloxycarbonyl-d-glucosaminyl precursors. Thus, glycosylation of α,ω-diols with 1,3,4,6-tetra-O-acetyl-2-allyloxycarbonylamino-2-deoxy-β-d-glucopyranose (1) gave the bis(glycosides) 2a-h in good yields and without column chromatography. Alkaline treatment of these derivatives followed by acetylation gave the peracetylated N-acetyl compounds 3a-h which were further deprotected by the Zemplén deacetylation procedure to the N-acetyl-d-glucosaminyl bolaamphiphiles 4a-h. The bis(glycosides) 2c,d,g were also transformed into the O-acetylated amino-free derivatives 5c,d,g by chemospecific deprotection of the N-allyloxycarbonyl groups with palladium (0). Further deprotection of the ester functions led to the completely deprotected bolaamphiphiles 7c,d,g with high yields. Fully deprotected compounds 7a,d,g,h were also obtained from 2a,d,g,h by alkaline treatment and purification by column chromatography. Surface tension measurements were realized for aqueous solutions containing the soluble bolaamphiphiles.     

Bioconjugatable Azo‐Based Dark‐Quencher Dyes: Synthesis and Application to Protease‐Activatable Far‐Red Fluorescent Probes

We describe the efficient synthesis and one‐step derivatization of novel, nonfluorescent azo dyes based on the Black Hole Quencher‐3 (BHQ‐3) scaffold. These dyes were equipped with various reactive and/or bioconjugatable groups (azido, α‐iodoacetyl, ketone, terminal alkyne, vicinal diol). The azido derivative was found to be highly reactive in the context of copper‐catalyzed azide–alkyne cycloaddition (CuAAC) reactions and allowed easy synthetic access to the first water‐soluble (sulfonated derivative) and aldehyde‐modified BHQ‐3 dyes, the direct preparation of which failed by means of conventional azo‐coupling reactions. The aldehyde‐ and α‐iodoacetyl‐containing fluorescence quenchers were readily conjugated to aminooxy‐ and cysteine‐containing peptides by the formation of a stable oxime or thioether linkage, respectively. Further fluorescent labeling of the resultant peptide conjugates with red‐ or far‐red‐emitting rhodamine or cyanine dyes through sequential and/or one‐pot bioconjugations, led to novel Förster resonance energy transfer (FRET) based probes suitable for the in vivo detection and imaging of urokinase plasminogen activator, a key protease in cancer invasion and metastasis.     

Investigation of block depth distribution in PS‐b‐PMMA block copolymer using ultra‐low‐energy cesium sputtering in ToF‐SIMS

Directed self‐assembly of block copolymers (BCPs) is a promising candidate for next generation nanolithography. In order to validate a given pattern, the lateral and in‐depth distributions of the blocks should be well characterized; for the latter, time‐of‐flight (ToF) SIMS is a particularly well‐adapted technique. Here, we use an ION‐TOF ToF‐SIMS V in negative mode to provide qualitative information on the in‐depth organization of polystyrene‐b‐polymethylmethacrylate (PS‐b‐PMMA) BCP thin films. Using low‐energy Cs⁺ sputtering and Bi₃⁺ as the analysis ions, PS and PMMA homopolymer films are first analyzed in order to identify the characteristic secondary ions for each block. PS‐b‐PMMA BCPs are then characterized showing that self‐assembled nanodomains are clearly observed after annealing. We also demonstrate that the ToF‐SIMS technique is able to distinguish between the different morphologies of BCP investigated in this work (lamellae, spheres or cylinders). ToF‐SIMS characterization on BCP is in good agreement with XPS analysis performed on the same samples. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation and structure of alkali metal intercalation compounds

The preparation methods of intercalation compounds fall into four main groups: use of alkali metal solutions in liquid ammonia, organometallic reagents, electrochemical methods, and solid state processes. Each of these will be briefly described and a general comparison of the advantages and disadvantages will be made. Structural problems concern the positions occupied by the guest ions and their mobility from one site to one another in the host structure. The resulting ionic conductivity of the intercalation compounds depends on factors such as the ratio between available and occupied sites in the van der Waals gap, the ionicity of the bonds in the host structure, the site geometry, and the nature of the alkali metal.     

Renormalisation du produit, Jacobiens et transformations de Riesz

The “correction algorithm”, applied in probability theory to the pointwise product of two martingales, has a natural analogue in the real-variable setting. It turns out that the corresponding bilinear operators obtained in this way provide us with a new “renormalization algorithm”, in the sense of Coifman, Dobyinski and Meyer. We give a few examples of applications, regarding multidimensional Hardy spaces and various nonlinear quantities.     

Aerosol formation in an isothermal stagnation flow

An experiment has been performed in a laminar stagnation point flow in which two non-premixed reactants produced an aerosol of sub-micron particles. The reactants were NH₃ and HCl. The rate of mixing of the reactants was determined by the velocity gradient or strain rate of the flow; the response of the aerosol dynamics to the flow field was measured with a laser light scattering technique. Laser Doppler Spectroscopy was used to measure the particle size. It was found that the particle size was independent of the strain rate of the flow. On the other hand, the particle number density decreased as the strain rate increased. It is argued that the intensity of light scattered from the aerosol is, therefore, a measure of the amount of product of the relatively slow NH₃-HCl reaction.     

Probability masses fitting in the analysis of manufacturing flow lines

The analysis of manufacturing systems with finite capacity and with general service time distributions is made of two steps: the distributions have first to be transformed into tractable phase-type distributions, and then the modified system can be analytically modelled. In this paper, we propose a new alternative in order to build tractable phase-type distributions, and study its effects on the global modelling process. Called “probability masses fitting” (PMF), the approach is quite simple: the probability masses on regular intervals are computed and aggregated on a single value in the corresponding interval, leading to a discrete distribution. PMF shows some interesting properties: it is bounding, monotonic, refinable, it approximates distributions with finite support and it conserves the shape of the distribution. With the resulting discrete distributions, the evolution of the system is then exactly modelled by a Markov chain. Here, we focus on flow lines and show that the method allows us to compute upper and lower bounds on the throughput as well as good approximations of the cycle time distributions. Finally, the global modelling method is shown, by numerical experiments, to compute accurate estimations of the throughput and of various performance measures, reaching accuracy levels of a few tenths of a percent.