Fluorous gallic acid derivatives as versatile gelators. Self-assembly into nanosized fibers or balls

A new class of low molecular mass organogelators, the fluorous derivatives of gallic acid 1–3, is described. The gelation properties have been examined in a large variety of organic liquids. The corresponding analogs possessing alkyl instead of semiperfluoroalkyl chains (4–6) do not display any gelation properties, thus revealing the key role of perfluorinated chains in the aggregation/gelation process. Gels have been studied by scanning electron microscopy, revealing the presence of three-dimensional networks of nanosized fibers. In the case of an instable gel, SEM images showed that these elongated fibers curl up into nanoballs, failing to create the entangled network responsible for solvent entrapment.     

Desktop near-field thermal-lens microscope for thermo-optical detection in microfluidics

A new compact near-field desktop-sized diode laser thermal-lens microscope for analysis in microfluidics was proposed. A novel beam-alignment and detection systems provided high signal stability and, along with reduced number of optical elements rendered the instrument portable. The detection of nonfluorescent model species (Fe(II)-bathophenanthroline chelate) in water showed good linearity in the range of 5 × 10(-9) to 1 × 10(-4) M, and the limit of detection was 3.5 × 10(-9) M, which corresponded to 3.5 × 10(-7) absorbance units and provided a 20-fold enhancement in sensitivity compared with existing schematic.     

Co-doped ZnO nanoparticles synthesized by an adapted sol–gel method: effects on the structural,optical, photocatalytic and antibacterial properties

Pure and Co-doped ZnO nanoparticles were synthesized with different cobalt levels (1–10 mol%) via adapted sol–gel method using water as solvent and characterized by X-ray diffraction, transmission electron microscopy, Raman spectroscopy and photoacoustic absorption spectroscopy. The results showed that all the samples have hexagonal wurtzite structure, with no evidence of any secondary phases until 10 mol% of the dopant. The average crystallite size of the samples was in the range of 25–50 nm, do not showing significant differences with the increase of the dopant level. However, the band gap energy of the nanoparticles decreases from 2.98 eV (pure ZnO) to 1.95 eV (10 mol% of Co). The photocatalytic activity of the samples was evaluated on the removal of methylene blue under visible light irradiation, which revealed an efficiency reduction by Co-doping ZnO. The antibacterial property was carried out indicating activity of the prepared samples against gram-positive bacteria.     

An Alternative to the Classical α‐Arylation: The Transfer of an Intact 2‐Iodoaryl from ArI(O2CCF3)2

The α‐arylation of carbonyl compounds is generally accomplished under basic conditions, both under metal catalysis and via aryl transfer from the diaryl λ³‐iodanes. Here, we describe an alternative metal‐free α‐arylation using ArI(O₂CCF₃)₂ as the source of a 2‐iodoaryl group. The reaction is applicable to activated ketones, such as α‐cyanoketones, and works with substituted aryliodanes. This formal C? H functionalization reaction is thought to proceed through a [3,3] rearrangement of an iodonium enolate. The final α‐(2‐iodoaryl)ketones are versatile synthetic building blocks.     

Determination of lead(II) in aqueous solution using carbon nanotubes paste electrodes modified with Amberlite IR-120

A new composite electrode is described for anodic stripping voltammetry determination of Pb(II) at trace level in aqueous solution. The electrode is based on the use of multiwalled carbon nanotubes and Amberlite IR-120. The anodic stripping voltammograms depend, to a large extent, on the composition of the modified electrode and the preconcentration conditions. Under optimum conditions, the anodic peak current at around ?0.57 V is linearly related to the concentration of Pb(II) in the range from 9.6?×?10^?8 to 1.7?×?10^?6 mol L^?1 (R?=?0.998). The detection limit is 2.1?×?10^?8 mol L^?1, and the relative standard deviation (RSD) at 0.24?×?10^?6 mol L^?1 is 1.7% (n?=?6). The modified electrode was applied to the determination of Pb(II) using the standard addition method; the results showed average relative recoveries of 95% for the samples analysed.

Cationic liposomes in mixed didodecyldimethylammonium bromide and dioctadecyldimethylammonium bromide aqueous dispersions studied by differential scanning calorimetry, Nile Red fluorescence, and turbidity

The thermotropic phase behavior of cationic liposomes in mixtures of two of the most investigated liposome-forming double-chain lipids, dioctadecyldimethylammonium bromide (DODAB) and didodecyldimethylammonium bromide (DDAB), was investigated by differential scanning calorimetry (DSC), turbidity, and Nile Red fluorescence. The dispersions were investigated at 1.0 mM total surfactant concentration and varying DODAB and DDAB concentrations. The gel to liquid-crystalline phase transition temperatures (Tm) of neat DDAB and DODAB in aqueous dispersions are around 16 and 43 degrees C, respectively, and we aim to investigate the Tm behavior for mixtures of these cationic lipids. Overall, DDAB reduces the Tm of DODAB, the transition temperature depending on the DDAB content, but the Tm of DDAB is roughly independent of the DODAB concentration. Both DSC and fluorescence measurements show that, within the mixture, at room temperature (ca. 22 degrees C), the DDAB-rich liposomes are in the liquid-crystalline state, whereas the DODAB-rich liposomes are in the gel state. DSC results point to a higher affinity of DDAB for DODAB liposomes than the reverse, resulting in two populations of mixed DDAB/DODAB liposomes with distinctive phase behavior. Fluorescence measurements also show that the presence of a small amount of DODAB in DDAB-rich liposomes causes a pronounced effect in Nile Red emission, due to the increase in liposome size, as inferred from turbidity results.     

Critical evolution of the local order parameters related to the nanopolar domains in Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> ceramics

In the present paper, Pb(Mg_1/3Nb_2/3)O₃ (PMN) ceramics prepared by the columbite method were investigated. The dielectric study indicates typical relaxor properties, with a frequency dispersion in the range of 200–350 K. The relaxor-to-paraelectric phase transition was evidenced by the continuous decrease of the local order parameter derived from the permittivity-temperature data. As a result of the critical behavior, the main Raman modes show anomalies at: (i) ∼150 K; (ii) ∼220 K (i.e. close to the critical temperature reported for the field-induced ferroelectric state in PMN single crystal); (iii) ∼260 K (i.e. the temperature of the permittivity maximum); (iv) ∼350 K (the temperature for initiation of the cluster freezing process T ^*); (v) ∼620 K (Burns temperature). The frequency split of the doublet at ∼605 and ∼500 cm⁻¹ presents a critical behavior related to the local symmetry lowering and to the structure ordering due to a phase transformation which takes place below T ^*. The tunability in the paraelectric state was interpreted in terms of reorientation of the non-interacting nanopolar clusters in a double-well potential. The temperature dependence of the nanopolar domain size also shows anomalies in the range of T ^*. The size and dynamics of the polar nanodomains is essential in determining the functional properties of the Pb(Mg_1/3Nb_2/3)O₃ relaxor.     

Note on Joseph's inequalities in stability theory

Résumé Pour la stabilité linéaire d'un écoulement parallèle, le premier théorème de Joseph [1] a donné le domaine de la stabilité à l'aide de deux courbesM ₁ etM ₂. Nous avons amélioré ce théorème en employant l'enveloppe d'une famille de courbes à laquelle appartiennentM ₁ etM ₂. Nos résultats ci-dessus et ceux de Joseph ont été améliorés encore à l'aide de l'inégalitéI ₂ ² 4I ₁ ² au lieu de .Les simples inégalités nous permettent de faire une limitation plus forte pour la vitesse de l'amplification de la perturbation que celles connues jusqu'à présent en stabilité hydrodynamique.     

Domain Formation in DODAB–Cholesterol Mixed Systems Monitored via Nile Red Anisotropy

The effect of the cholesterol (ch) on liposomes composed of the cationic lipid dioctadecyldimethylammonium bromide (DODAB) was assessed by studying both the steady-state and time-resolved fluorescence anisotropy of the dye Nile Red. The information obtained combined with analysis of the steady-state emission and fluorescence lifetime of Nile Red (NR) for different cholesterol concentrations (5–50%) elucidated the presence of “condensed complexes” and cholesterol-rich domains in these mixed systems. The steady-state fluorescence spectra were decomposed into the sum of two lognormal emissions, emanating from two different states, and the effect of temperature on the anisotropy decay of Nile Red for different cholesterol concentrations was observed. At room temperature, the time-resolved anisotropy decays are indicative of NR being relatively immobile (manifest by a high r _∞ value). At higher temperature, rotational times ca. 1 ns were obtained throughout and a trend in increasing hindrance was seen with increase of Ch content.