Tuning Surface Wettability of Poly(3‐sulfopropyl methacrylate) Brushes by Cationic Surfactant‐Driven Interactions

In this communication, polyanionic poly(potassium 3‐sulfopropyl methacrylate) (PSPM) brushes were switched from hydrophilic to hydrophobic by exchange of the counter cations. First, poly(potassium 3‐sulfopropyl methacrylate) brushes were grown by means of atom transfer radical polymerization (ATRP) from thiol monolayers of initiating ω‐mercaptoundecyl bromoisobutyrate and mixed monolayers of thiol initiator and 1‐undecanothiol (blank thiol) attached to gold surfaces. The kinetics of the polymerization reaction were followed by means of the quartz microbalance technique with dissipation (QCM‐D). The collapse of PSPM brushes in the presence of cationic surfactants like quaternary ammonium salts (tetraethylammonium bromide, hexadecyltrimethylammonium bromide) and imidazolium salts (1‐dodecyl‐3‐methylimidazolium bromide, 1H,1H,2H,2H‐perfluoro‐1‐decyl‐3‐methylimidazolium bromide) was shown by QCM‐D. Water contact angle measurements proved that the wettability of the surface could be tuned reversibly from hydrophilic values (<30 °) to hydrophobic ones (>85 °).

     

Thermodynamics of (1-alkanol + linear monoether) systems

Densities, ρ, and speeds of sound, u, of systems formed by 1-heptanol, or 1-octanol, or 1-decanol and dibutylether have been measured at a temperature of (293.15, 298.15, and 303.15) K and atmospheric pressure using a vibrating tube densimeter and sound analyser Anton Paar model DSA-5000. The ρ and u values were used to calculate excess molar volumes, V^E, and deviations from the ideal behaviour of the thermal expansion coefficient, Δα_p and of the isentropic compressibilities, Δκ_S. The available database on molar excess enthalpies, H^E, and V^E for (1-alkanol + linear monoether) systems was used to investigate interactional and structural effects in such mixtures. The enthalpy of the OH?O bonds is lower for methanol solutions, and for the remainder systems, it is practically independent of the mixture compounds. The V^E variation with the chain length of the 1-alkanol points out the existence of structural effects for systems including longer 1-alkanols. The ERAS model is applied to the studied mixtures. ERAS represents quite accurately H^E and V^E data using parameters which consistently depend on the molecular structure.     

Measurement and statistical analysis of single-molecule current-voltage characteristics, transition voltage spectroscopy, and tunneling barrier height

We report on the measurement and statistical study of thousands of current-voltage characteristics and transition voltage spectra (TVS) of single-molecule junctions with different contact geometries that are rapidly acquired using a new break junction method at room temperature. This capability allows one to obtain current-voltage, conductance voltage, and transition voltage histograms, thus adding a new dimension to the previous conductance histogram analysis at a fixed low-bias voltage for single molecules. This method confirms the low-bias conductance values of alkanedithiols and biphenyldithiol reported in literature. However, at high biases the current shows large nonlinearity and asymmetry, and TVS allows for the determination of a critically important parameter, the tunneling barrier height or energy level alignment between the molecule and the electrodes of single-molecule junctions. The energy level alignment is found to depend on the molecule and also on the contact geometry, revealing the role of contact geometry in both the contact resistance and energy level alignment of a molecular junction. Detailed statistical analysis further reveals that, despite the dependence of the energy level alignment on contact geometry, the variation in single-molecule conductance is primarily due to contact resistance rather than variations in the energy level alignment.     

Volumes of activation for dissociation of pentacyanoferrates(II) through pressure and salt effects on reactivity

Summary Dependences of rate constants on pressure (up to 1 kbar) and on added salt concentration (up to 6.0 mol dm^–3 LiNO₃, NaNO₃, NaCl, Na₂SO₄ or KNO₃) have been established for dissociative substitution of pentacyanoferrates(II), [Fe(CN)₅L]^3– with L = 4-cyanopyridine, 4,4-bipyridyl, 4-phenylpyridine and 4-t-butylpyridine. Activation volumes derived directly from pressure effects, and indirectly from salt effects via surface tension dependences and derived surfaces of activation, are reported, compared and discussed.     

“Click” Chemistry Mildly Stabilizes Bifunctional Gold Nanoparticles for Sensing and Catalysis

A large family of bifunctional 1,2,3‐triazole derivatives that contain both a polyethylene glycol (PEG) chain and another functional fragment (e.g., a polymer, dendron, alcohol, carboxylic acid, allyl, fluorescence dye, redox‐robust metal complex, or a β‐cyclodextrin unit) has been synthesized by facile “click” chemistry and mildly coordinated to nanogold particles, thus providing stable water‐soluble gold nanoparticles (AuNPs) in the size range 3.0–11.2 nm with various properties and applications. In particular, the sensing properties of these AuNPs are illustrated through the detection of an analogue of a warfare agent (i.e., sulfur mustard) by means of a fluorescence “turn‐on” assay, and the catalytic activity of the smallest triazole–AuNPs (core of 3.0 nm) is excellent for the reduction of 4‐nitrophenol in water.     

An updated version of the computational package SIMPRE that uses the standard conventions for Stevens crystal field parameters

The crystal field approach used by SIMPRE is analyzed, verifying the exactness of the results concerning energy levels and magnetic properties calculated by the package. To coincide with the prevailing conventions, we reformulate the presentation of the crystal field parameters, so that the results are now, also from a formal point of view, strictly correct. New calculations are presented to test the influence of neglecting the excited J states, a common but critical approximation employed by SIMPRE. For that, we examine the case of Er(trensal) complex (H₃trensal = 2,2′,2″‐tris(salicylideneimino)triethylamine) where the influence of this approximation is found to be minimal. A patched version of the code, SIMPRE 1.1, and an updated version of the user manual are now available. Finally, we comment on “Software package SIMPRE – revisited,” which apparently revisits a software package without inspecting or using the code. © 2014 Wiley Periodicals, Inc.     

Effects of ethylene glycol addition on the aggregation and micellar growth of gemini surfactants

Micellization of three didodecyl dicationic dibromide gemini surfactants with different methylene spacer lengths, 12-s-12,2Br- where s = 3-5 methylene groups, has been investigated in water-ethylene glycol, EG, mixtures with weight percentages of EG up to 50%. Subsequently, effects of the addition of the organic solvent on the micellar growth of these surfactants and on the surfactant concentration range where sphere-to-rod transitions occur were studied by means of steady-state and time-resolved fluorescence quenching and spectroscopic measurements. Results show that an increase in the weight percentage of ethylene glycol added to aqueous 12-s-12,2Br- (s = 3-5) micellar solutions causes the sphere-to-rod transition to occur at higher surfactant concentrations than in pure water. The diminution in the average aggregation number, N(agg), when wt % EG increases, provoked by the decrease in the interfacial Gibbs energy contribution to DeltaG degrees M, is the main factor responsible for this observation. The decrease in N(agg) is accompanied by a decrease in the ionic interactions and the extra packing contribution to the deformation of the surfactants tails, making formation of cylindrical micelles less favorable. Besides, an increase in the solvent content and polarity of the interfacial region does not favor formation of direct ion pairs, decreasing the tendency of micelles to grow.     

Confirmatory and quantitative analysis using experimental design for the extraction and liquid chromatography-UV, liquid chromatography-mass spectrometry and liquid chromatography-mass spectrometry/mass spectrometry determination of quinolones in turkey muscle

The aim of this work is to established methods for determination of quinolones (ciprofloxacin, danofloxacin, enrofloxacin, difloxacin and flumequine), regulated by European Union, and sarafloxacin in turkey muscle. An experimental design has been applied for the optimization of the factors that influence the extraction of quinolones from turkey muscle in order to determine the experimental conditions for their extraction with high recoveries. Liquid chromatography with ultraviolet detection (LC-UV), liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography tandem mass spectrometry (LC-MS/MS) have been used for the simultaneous quantification of quinolones antibiotics in turkey muscle. The proposed methods have been validated according to the Food Drugs Administration guideline and presents the limit of quantification below the maximum residue limits established by the European Union for quinolones in turkey muscle. The methods developed have been applied to quantification of enrofloxacin and its main metabolite ciprofloxacin in samples of turkey muscle obtained from animals treated with enrofloxacin.     

HETEROCYCLIZATION OF AMINOTHIAZOLES

Several new 2-arylidinoamino-4-(3-coumaryl)thiazole derivatives were synthesized via the reaction of 2-amino-4-(coumaryl)thiazole with aromatic aldehydes and other reagents. Structural elucidations were based on elementary analysis and spectral data studies.