Experimental visualization of bubble formation from an orifice in microgravity in the presence of electric fields

 The formation of air bubbles injected into a stagnant, isothermal liquid in microgravity through an orifice was studied. The bubbles grew very large in microgravity. They attained a nearly spherical shape and showed pronounced affinity towards coalescence in the absence of electric fields and other perturbations. Under the influence of electric fields, periodic detachment was observed, with bubble sizes larger than in terrestrial conditions. The bubble shape was elongated. After detachment, the bubbles moved away from the electrode at which they formed without coalescing with other bubbles. Experimental data on bubble shape and size at detachment showed good agreement with models. Received: 26 March 2001 / Accepted: 16 August 2001     

Solid‐Contact Potentiometric Sensor Based on Polyaniline and Unsubstituted Pillar[5]Arene

A novel potentiometric sensor based on screen‐printed carbon electrode covered with electropolymerized polyaniline (PANI) and unsubstituted pillar[5]arene as ionophore has been developed and tested in potentiometric measurements of pH and metal ions. The introduction of pillar[5]arene improved the reversibility of the pH response in the range from 2.0 to 9.0 with the slope of 45 mV/pH. Among metal cations, the response to Fe³⁺ and Ag⁺ ions was referred to PANI redox conversion whereas the signal toward Cu²⁺ in the range from 1.0×10^?6 to 1.0×10^?2 M (limit of detection (LOD) 3.0×10^?7 M) to specific interaction with the macrocycle.     

Comparing Cyclophellitol N‐Alkyl and N‐Acyl Cyclophellitol Aziridines as Activity‐Based Glycosidase Probes

The synthesis and evaluation as activity‐based probes (ABPs) of three configurationally distinct, fluorescent N‐alkyl cyclophellitol aziridine isosteres for profiling GH1 β‐glucosidase (GBA), GH27 α‐galactosidase (GLA) and GH29 α‐fucosidase (FUCA) is described. In comparison with the corresponding acyl aziridine ABPs reported previously, the alkyl aziridine ABPs are synthesized easily and are more stable in mild acidic and basic media, and are thus easier to handle. The β‐glucose‐configured alkyl aziridine ABP proves equally effective in labeling GBA as its N‐acyl counterpart, whereas the N‐acyl aziridines targeting GLA and FUCA outperform their N‐alkyl counterparts. Alkyl aziridines can therefore be an attractive alternative in retaining glycosidase ABP design, but in targeting a new retaining glycosidase both N‐alkyl and N‐acyl aziridines are best considered at the onset of a new study.     

β-Octafluorinated tetrakis(ethoxycarbonyl)porphyrin

Tetrakis(alloxycarbonyl)porphyrin and its β-octafluoro-substituted derivatives were synthesized via Lindsey method and transformed to their zinc complexes.Single crystal X-ray structures of corresponding Zn(Ⅱ) porphyrins revealed that β-octafluorination will give more compactness of porphyrin moieties in the crystal structure owing to the hydrogen bonding interactions involving β-fluorine atoms.An unusual six-coordinated Zn(Ⅱ) was found via intramolecular coordination of oxygen atom of meso-substituents with central Zn(Ⅱ).     

Limitations of temperature measurements with holographic interferometry in the presence of pressure variations

In recent years oscillatory flows have shown to be a promising strategy to enhance heat transfer. However, the mechanisms underlying oscillatory heat transfer enhancement are not yet completely understood. One problem, when investigating heat transfer in oscillatory flows experimentally, is to resolve the temperature distribution as a function of time. This is one reason that most studies reported in the literature so far were restricted to frequencies of a few hertz. As shown in this paper, an appropriate tool to investigate oscillatory heat transfer phenomena at higher frequencies (1000 Hz) is real time holographic interferometry (HI) combined with high-speed cinematography. In the present paper HI was applied to study acoustically driven flow. To apply HI to such a physical situation it was necessary to expand its applicability to cases where changes in the refractive index are caused not only by temperature changes but also by pressure variations. For this purpose a new evaluation formula that accounts for pressure variations was derived. On the example of the acoustic field, we discuss the impact of the pressure variations on temperature measurements. Additionally, an image processing algorithm was developed that allows the measurement of time dependent temperature distributions. The uncertainties of the temperature measurements introduced by the image processing algorithm were found to be in the range of thermocouple measurements.     

Polyelectrolyte coatings prevent interferences from charged nanoparticles in SPME speciation analysis

In this work we present a new approach for protection of the fiber in solid phase microextraction (SPME) from interfering charged particles present in the sample medium. It involves coating of commercial poly(dimethylsiloxane) extraction phase with polyelectrolyte layer composed of poly(diallyldimethylammonium chloride), and poly(sodium 4-styrenesulfonate). The modified fiber provides reproducible, convenient and fast extraction capabilities toward the model analyte, triclosan (TCS). A negatively charged polyelectrolyte coating prevents sorbing oxidic nanoparticles from both partitioning into the PDMS phase and aggregation at its surface. The results for the TCS/nanoparticle sample show that the polyelectrolyte layer-modified solid phase extracts just the free form of the organic compound and enables dynamic speciation analysis of the nanoparticulate target analyte complex.     

Determining equilibrium constants for dimerization reactions from molecular dynamics simulations

With today's available computer power, free energy calculations from equilibrium molecular dynamics simulations "via counting" become feasible for an increasing number of reactions. An example is the dimerization reaction of transmembrane alpha-helices. If an extended simulation of the two helices covers sufficiently many dimerization and dissociation events, their binding free energy is readily derived from the fraction of time during which the two helices are observed in dimeric form. Exactly how the correct value for the free energy is to be calculated, however, is unclear, and indeed several different and contradictory approaches have been used. In particular, results obtained via Boltzmann statistics differ from those determined via the law of mass action. Here, we develop a theory that resolves this discrepancy. We show that for simulation systems containing two molecules, the dimerization free energy is given by a formula of the form ΔG ∝ ln(P(1) /P(0) ). Our theory is also applicable to high concentrations that typically have to be used in molecular dynamics simulations to keep the simulation system small, where the textbook dilute approximations fail. It also covers simulations with an arbitrary number of monomers and dimers and provides rigorous error estimates. Comparison with test simulations of a simple Lennard Jones system with various particle numbers as well as with reference free energy values obtained from radial distribution functions show full agreement for both binding free energies and dimerization statistics.     

Preparation and characterization of 5,10,15,20‐tetraphenylporphyrin Langmuir films for gas chemsensor applications

In this work is reported the preparation and characterization of 5,10,15,20‐tetraphenylporphyrin (H₂TPP) films at the water‐air interfaces. The surface pressure‐area isotherms (π‐A) and UV‐Vis spectroscopy were used to investigate the effect of the spreading methods and parameters on the porphyrin monolayer formation. Also, Langmuir‐Blodgett (LB) and Langmuir‐Schaefer (LS) films were deposited onto glass substrates in order to study the conformation changes in porphyrin molecular packing. Quartz crystal microbalance (QCM) was utilized as the active solid substrate for the development of the NO₂ gas sensor based on the H₂TPP molecular films. The results of π‐A curves have clearly shown the significant contribution of the preparation methods and processing parameters on the conformation of porphyrin molecular films. The UV‐Vis spectroscopy results using polarized absorption dichroism have indicated different molecular packing for porphyrin films deposited by LB and LS methods, with relative tilted angles of 50° ± 5° and 35° ± 5°, respectively. Moreover, the QCM response has given strong evidence that H₂TPP porphyrin molecular films have performed as NO₂ chemsensor. Copyright © 2011 John Wiley & Sons, Ltd.