Surfactants and wetting at superhydrophobic surfaces: water solutions and non aqueous liquids

Wetting studies regarding amphiphilic molecules and adsorption properties on highly water repellent solid surfaces play key roles in research and technology, with increasing interest both in fundamental and application fields. Nevertheless the wetting properties of aqueous surfactant solutions, non aqueous liquids or immiscible phases on superhydrophobic (SH) solid surfaces have been so far rarely investigated. In this work the authors give an overview on this topic reviewing the literature available together with preliminary results concerning the influence of the distribution properties of surfactants between two immiscible phases. Transition between wetting states can be also considered a possible development of these studies based on switching mechanisms.     

Experimental observation of spin delocalisation onto the aryl-alkynyl ligand in the complexes [Mo(C≡CAr)(Ph2PCH2CH2PPh2)(η-C7H7)]+ (Ar = C6H5, C6H4-4-F; C7H7 = cycloheptatrienyl): an EPR and ENDOR investigation

The paramagnetic aryl-alkynyl complexes [Mo(C≡CAr)(dppe)(η-C(7)H(7))](+) (dppe = Ph(2)PCH(2)CH(2)PPh(2); Ar = C(6)H(5), [1](+); C(6)D(5), [2](+); C(6)H(4)-4-F, [3](+); C(6)H(4)-4-Me, [5](+)) and [Mo(C≡CBu(t))(dppe)(η-C(7)H(7))](+) [4](+), have been investigated in a combined EPR and ENDOR study. Direct experimental evidence for the delocalisation of unpaired spin density over the framework of an aryl-alkynyl ligand has been obtained. The X-band solution EPR spectrum of the 4-fluoro derivative, [3](+), exhibits resolved hyperfine coupling to the remote para position of the aryl group [a(iso)((19)F) = 4.5 MHz, (1.6 G)] in addition to couplings attributable to (95/97)Mo, (31)P and (1)H of the C(7)H(7) ring. A full analysis of the (1)H ENDOR spectra is restricted by the low g anisotropy of the system which prevents the use of orientation selection. However, inter-comparison of the (1)H cw-ENDOR frozen solution spectra of [1](+), [2](+), [4](+) and [5](+), combined with spectral simulation informed by calculated values derived from DFT investigations, has facilitated estimation of the experimental a(iso)((1)H) hyperfine couplings of [1](+) including the ortho, ±3.7 MHz (±1.3 G) and para, ±3.9 MHz (±1.4 G) positions of the C(6)H(5) substituent of the aryl-alkynyl ligand.     

Polycyclic aromatic hydrocarbons (PAHs) in a coal tar standard reference material—SRM 1597a updated

SRM 1597 Complex Mixture of Polycyclic Aromatic Hydrocarbons from Coal Tar, originally issued in 1987, was recently reanalyzed and reissued as SRM 1597a with 34 certified, 46 reference, and 12 information concentrations (as mass fractions) for polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic sulfur heterocycles (PASHs) including methyl-substituted PAHs and PASHs. The certified and reference concentrations (as mass fractions) were based on results of analyses of the coal tar material using multiple analytical techniques including gas chromatography/mass spectrometry on four different stationary phases and reversed-phase liquid chromatography. SRM 1597a is currently the most extensively characterized SRM for PAHs and PASHs.     

Visibility graph approach to the analysis of ocean tidal records

By using the recent method of the visibility graph, three time series of oceanic tide level in central Argentina were investigated. The degree distributions show a rich structure; in particular the maximum is due to the main periodic oscillations at 24 hours and 12 hours and higher harmonics. The degree distributions of the residuals (obtained removing from the original signals the cyclic components) suggest that the local effects, linked with the particular coastal conditions of the sites, are discernible for the degree k < 20, while the global effects, linked with linked with the more general and common atmospheric forcing and ocean current conditions, are visible for k > 100. Although a relationship between the spectral exponent α and the exponent of the degree distribution γ of tidal signals can be recognized, this cannot be simply stated due to the very rich and complex structure of time dynamics of tides. The present study, even if still preliminary, show the importance of the visibility graph method in investigating the complex time dynamics of observational and experimental signals.     

Fourier Expansions of Piecewise Smooth Functions

Although Fourier series or integrals of piecewise smooth functions may be slowly convergent, sometimes it is possible to accelerate their speed of convergence by adding and subtracting suitable combination of known functions.     

Miniaturised technologies for the development of artificial lipid bilayer systems

Artificially reproducing cellular environments is a key aim of synthetic biology, which has the potential to greatly enhance our understanding of cellular mechanisms. Microfluidic and lab-on-a-chip (LOC) techniques, which enable the controlled handling of sub-microlitre volumes of fluids in an automated and high-throughput manner, can play a major role in achieving this by offering alternative and powerful methodologies in an on-chip format. Such techniques have been successfully employed over the last twenty years to provide innovative solutions for chemical analysis and cell-, molecular- and synthetic- biology. In the context of the latter, the formation of artificial cell membranes (or artificial lipid bilayers) that incorporate membrane proteins within miniaturised LOC architectures offers huge potential for the development of highly sensitive molecular sensors and drug screening applications. The aim of this review is to give a comprehensive and critical overview of the field of microsystems for creating and exploiting artificial lipid bilayers. Advantages and limitations of three of the most popular approaches, namely suspended, supported and droplet-based lipid bilayers, are discussed. Examples are reported that show how artificial cell membrane microsystems, by combining together biological procedures and engineering techniques, can provide novel methodologies for basic biological and biophysical research and for the development of biotechnology tools.     

Determination of perfluorinated alkyl acid concentrations in biological standard reference materials

Standard reference materials (SRMs) are homogeneous, well-characterized materials used to validate measurements and improve the quality of analytical data. The National Institute of Standards and Technology (NIST) has a wide range of SRMs that have mass fraction values assigned for legacy pollutants. These SRMs can also serve as test materials for method development, method validation, and measurement for contaminants of emerging concern. Because inter-laboratory comparison studies have revealed substantial variability of measurements of perfluoroalkyl acids (PFAAs), future analytical measurements will benefit from determination of consensus values for PFAAs in SRMs to provide a means to demonstrate method-specific performance. To that end, NIST, in collaboration with other groups, has been measuring concentrations of PFAAs in a variety of SRMs. Here we report levels of PFAAs and perfluorooctane sulfonamide (PFOSA) determined in four biological SRMs: fish tissue (SRM 1946 Lake Superior Fish Tissue, SRM 1947 Lake Michigan Fish Tissue), bovine liver (SRM 1577c), and mussel tissue (SRM 2974a). We also report concentrations for three in-house quality-control materials: beluga whale liver, pygmy sperm whale liver, and white-sided dolphin liver. Measurements in SRMs show an array of PFAAs, with perfluorooctane sulfonate (PFOS) being the most frequently detected. Reference and information values are reported for PFAAs measured in these biological SRMs.

Chemical analysis of surgical smoke by infrared laser spectroscopy

The chemical composition of surgical smoke, a gaseous by-product of some surgical devices??lasers, drills, vessel sealing devices??is of great interest due to the many toxic components that have been found to date. For the first time, surgical smoke samples collected during routine keyhole surgery were analyzed with infrared laser spectroscopy. Traces (ppm range) of methane, ethane, ethylene, carbon monoxide and sevoflurane were detected in the samples which consisted mostly of carbon dioxide and water vapor. Except for the anaesthetic sevoflurane, none of the compounds were present at dangerous concentrations. Negative effects on the health of operation room personnel can be excluded for many toxic compounds found in earlier studies, since their concentrations are below recommended exposure limits.     

Highly stable gel electrolytes for dye solar cells based on chemically engineered polymethacrylic hosts

Four different species of ionically conductive polymers were synthesized and successfully implemented to formulate novel quasi-solid electrolytes for dye solar cells. A power conversion efficiency superior to 85% of the correspondent liquid electrolyte as well as an excellent cell's stability was demonstrated after 500 days of storage.     

Precision measurements and computations of transition energies in rotationally cold triatomic hydrogen ions up to the midvisible spectral range

First-principles computations and experimental measurements of transition energies are carried out for vibrational overtone lines of the triatomic hydrogen ion H(3)(+) corresponding to floppy vibrations high above the barrier to linearity. Action spectroscopy is improved to detect extremely weak visible-light spectral lines on cold trapped H(3)(+) ions. A highly accurate potential surface is obtained from variational calculations using explicitly correlated Gaussian wave function expansions. After nonadiabatic corrections, the floppy H(3)(+) vibrational spectrum is reproduced at the 0.1 cm(-1) level up to 16600 cm(-1).