Synthesis of fluorinated oligomers for supercritical carbon dioxide applications

Syntheses of various fluorine‐based surfactants, namely fluorinated‐segment‐containing block co‐oligomers, were achieved by the radical polymerization of mainly acrylate‐based monomers. These types of surfactants serve as stabilizers for supercritical carbon dioxide (scCO₂) media based applications, for which the effective solubilization of materials in the supercritical phase is generally not possible because of solubility problems faced when CO₂ is involved. Initially, a difunctional fluorinated initiator was synthesized in two steps. First, 4,4′‐azobis‐4‐cyanovaleric acid was chlorinated with SOCl₂, and then the product, 4,4′‐azobis‐4‐cyanovaleryl chloride, was reacted with a fluorinated alcohol to obtain the initiator for the polymerization reactions. The synthesized triblock co‐oligomers consisted of fluorinated side blocks and a hydrocarbon intermediate block. Efficient solubilization of the materials in scCO₂ was observed. It was experimentally shown that the solubility efficiency was affected by specific interactions between CO₂ and the oligomers, and these were determined by the nature and size of the inner block and by the chain length of the fluorinated side blocks in comparison with the inner block. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5312–5322, 2005     

Chemoenzymatic polymerization of hydrazone functionalized phenol

Hydrazone substituted oligophenol was synthesized via enzymatic oxidative polymerization of (E)-2-((2-phenylhydrazono)methyl)phenol. Enzymatic polymerization catalyzed by Horseradish peroxidase (HRP) enzyme and H₂O₂ oxidizer yielded oligophenol with hydrazone functionality on the side-chain. Effects of various factors including solvent system, reaction pH and temperature on the polymerization were studied. Optimum polymerization conditions with the highest yield (84%) and molecular weight (M_n = 8 × 10³, DP ≈ 37, PDI = 1.11) was achieved using MeOH/pH 6.0 buffer (1: 1 vol %) at 25°C in 24 h under air. Synthesized oligomer was characterized by ¹H and ¹³C NMR, FTIR, UV–Vis spectroscopy, GPC, cyclic voltammetry and thermogravimetric analyses. The polymerization involved hydrogen elimination from the monomer, and terminal units of the oligomer structure consisted of phenolic hydroxyl (–OH) end groups. The oligomer backbone possessed phenylene and oxyphenylene repeat units. The resulting oligomer was completely soluble in common organic solvents. The oligomer was thermally robust and exhibited 5% mass loss at 375°C and 50% mass loss at 440°C.     

Generic approach for the sensitive absolute quantification of large undigested peptides in plasma using a particular liquid chromatography-mass spectrometry setup

A generic LC-MS approach for the absolute quantification of undigested peptides in plasma at mid-picomolar levels is described. Nine human peptides namely, brain natriuretic peptide (BNP), substance P (SubP), parathyroid hormone 1-34 (PTH), C-peptide, orexines A and B (Orex-A and -B), oxytocin (Oxy), gonadoliberin-1 (gonadothropin releasing-hormone or luteinizing hormone-releasing hormone, LHRH) and α-melanotropin (α-MSH) were targeted. Plasma samples were extracted via a 2-step procedure: protein precipitation using 1vol of acetonitrile followed by ultrafiltration of supernatants on membranes with a MW cut-off of 30 kDa. By applying a specific LC-MS setup, large volumes of filtrates (e.g., 2×750 μL) were injected and the peptides were trapped on a 1mm i.d.×10 mm length C8 column using a 10× on-line dilution. Then, the peptides were back-flushed and a second on-line dilution (2×) was applied during the transfer step. The refocalized peptides were resolved on a 0.3mm i.d. C18 analytical column. Extraction recovery, matrix effect and limits of detection were evaluated. Our comprehensive protocol demonstrates a simple and efficient sample preparation procedure followed by the analysis of peptides with limits of detection in the mid-picomolar range. This generic approach can be applied for the determination of most therapeutic peptides and possibly for endogenous peptides with latest state-of-the-art instruments.     

Reactive layer-by-layer deposition of poly(ethylene imine) and a precursor of TiO2: influence of the sodium chloride concentration on the film growth, interaction with hexacyanoferrate anions, and particle distribution in the film

Films prepared according to a layer-by-layer (LBL) manner find increasing importance in many applications such as coatings with dedicated optical or electronic properties, particularly when including nanomaterials. An alternative way to prepare such hybrid layer-by-layer coatings is to perform sol-gel chemistry in a layer-by-layer manner. In this article, we highlight the importance of the NaCl concentration as a parameter to control the growth as well as the properties of LBL films made from poly(ethylene imine) as the organic counterpart and titanium IV (bisammoniumlactato)dihydroxyde ([Ti(lac)(2)(OH)(2)](2-)) as the precursor of TiO(2). An increase in the sodium chloride concentration leads to the faster growth of the film and to a decrease in the number of hexacyanoferrate anions remaining in the film after a buffer rinse. This may be due to a progressive increase in the fraction of negatively charged TiO(2) as suggested by transmission electron microscopy. In the presence of 0.5 M NaCl, the fraction of TiO(2) is close to 60% in mass. As a surprising finding, the films produced from 0.15 M NaCl are not homogeneously filled with TiO(2) even if the film is produced in an LBL fashion. The increased concentration of TiO(2) at the film-solution interface could constitute a barrier for the incorporation of the negatively charged redox probe.     

New imine compounds and their copper complexes: synthesis,characterization and comparative investigations of morphologic,mesomorphic, thermotropic,thermo-optical and thermodynamical properties

Investigations of the morphologic, mesomorphic, thermotropic, thermo-optical and thermodynamical properties of new imine compounds and their copper complexes, synthesized by our group, have been carried out. Temperature transformations of typical textures for mesophases, taking place in imine compounds and copper complexes, and the peculiarities of the biphasic regions at the direct and reverse mesophase–isotropic liquid and isotropic liquid–mesophase phase transitions have been investigated.     

Experimental assessment of the phonon confinement in TiO2 anatase nanocrystallites by Raman spectroscopy

TiO₂ aerogels prepared by sol‐gel method and followed by supercritical drying have been annealed at temperatures ranging between 400 and 550 °C. The obtained TiO₂ anatase crystallites with the mean size between 6.4 and 13.9 nm, as obtained from transmission electron microscopy measurements, have been further investigated by Raman spectroscopy. It was found that the peak position and full width at half maximum (FWHM) of the TiO₂ anatase Raman bands located around 144, 398, and 638 cm⁻¹ are influenced by crystallite dimension. These spectral changes can be assigned to the combined action of several nanosize effects such as phonon confinement, phonon coupling, strain, and stoichiometry defects. Surprisingly, the best discrimination of the FWHM change with the nanocrystallite mean size was achieved for the 638 cm⁻¹ band, whereas the best discrimination for the peak position was found for the 398 cm⁻¹ band. The critical size values obtained from the peak position and FWHM evaluation were between 12.7 and 13.1 nm. Taking into consideration that only the phonon confinement and inhomogeneous strain can induce an asymmetric broadening of the Raman signal, the bands asymmetry was evaluated, and the critical size values of the nanocrystallites were determined to be between 10 and 11 nm. For a symmetric size distribution of TiO₂ anatase crystallites with dimensions between 6.4 and 13.9 nm, the obtained result indicates that the phonon confinement contribution to the overall size effects is more than 75%. No evidence about the influence of the phonon coupling and vacancies on the Raman features was observed. The comparison of the data derived from the experimental analysis with those obtained by applying the theoretical phonon confinement model indicates the necessity of developing an improved phonon confinement model. The asymmetry approach can be applied for a great variety of nanostructures, as a measure of the confinement effect. Copyright © 2011 John Wiley & Sons, Ltd.     

Injection-seeded, gain-switched tunable Cr:ZnSe laser

We report a narrow-linewidth, tunable, gain-switched Cr:ZnSe laser operating between 2255 and 2455 nm. The spectral width of the laser was reduced from 125 nm to 0.3 nm by using injection seeding. Seeding was achieved with a second tunable CW Cr:ZnSe laser. The output wavelength was varied by tuning the wavelength of the seed laser. The seeded oscillator produced as high as 157 μJ pulses with 598 μJ incident pump pulse energy at a repetition rate of 1 kHz. The slope efficiency was determined to be 26%.     

(Liquid + liquid) equilibria of (water + lactic acid + alcohol) ternary systems

(Liquid + liquid) equilibrium (LLE) measurements of the solubility (binodal) curves and tie-line end compositions were carried out for {water (1) + lactic acid (2) + octanol, or nonanol, or decanol (3)} at T = 298.15 K and 101.3 ± 0.7 kPa. The relative mutual solubility of lactic acid is higher in the water layers than in the organic layers. The reliability of the experimental tie-line data was confirmed by using the Othmer–Tobias correlation. The LLE results for the ternary systems were predicted by UNIFAC method. Distribution coefficients and separation factors were evaluated for the immiscibility region.