Predicting the wetting dynamics of a two-liquid system

We propose a new theoretical model of dynamic wetting for systems comprising two immiscible liquids, in which one liquid displaces another from the surface of a solid. Such systems are important in many industrial processes and the natural world. The new model is an extension of the molecular-kinetic theory of wetting and offers a way to predict the dynamics of a two-liquid system from the individual wetting dynamics of its parent liquids. We also present the results of large-scale molecular dynamics simulations for one- and two-liquid systems and show them to be in good agreement with the new model. Finally, we show that the new model is consistent with the limited data currently available from experiment.     

Can we predict the spreading of a two-liquid system from the spreading of the corresponding liquid-air systems?

We present new data obtained from the spreading of a series of oil droplets, on top of a hydrophobic grafted silicon substrate, in air and immersed in water. We follow the contact angle and radius dynamics of hexane, dodecane, hexadecane, dibutyl phthalate, and squalane from the first milliseconds to approximately 1 s. Analysis of the images allows us to make several hundred contact angle and droplet radius measurements with great accuracy. The G-Dyna (Seveno et al. Langmuir 2010, 25, 13034) software is then used to fit the data with one of the wetting theories, the molecular-kinetic theory (MKT) (Blake et al. J. Colloid Interface Sci.1969, 30, 421), which takes into account the dissipation at the three-phase zone at the contact line. This theory allows us to extract the coefficient of friction of the contact line, which expresses the relationship between the driving force, that is, the unbalanced Young force, and the contact-line velocity V. It is first shown that the MKT is appropriate to describe the experimental data and then that the contact-line friction is a linear function of the viscosity as theoretically predicted. This is checked for oil-air and oil-water systems. A linear relation between the contact-line friction measured in oil-water systems and the contact-line frictions of the parent single liquid system seems plausible. To the best of our knowledge, this is the first trial to establish a link between the dynamics of wetting in liquid-liquid and in liquid-air systems.     

An FTIR Study on the Solid-State Copolymerization of bis(2-hydroxyethyl)terephthalate and Poly(butylene terephthalate) and the Resulting Copolymers

Summary: The first aim of this work was to study the solid-state copolymerization (SSP) of bis(2-hydroxyethyl)terephthalate (BHET) with poly(butylene terephthalate) (PBT) by FTIR spectroscopy. The development of the chemical microstructure during the SSP-reaction was examined as a function of the BHET content, showing the different regimes. The thermal behaviour of the resulting copolymers with different BHET contents was also investigated during cooling using infra-red dynamic spectra. For low BHET-concentrations, only crystallization of PBT-sequences was observed, while for high BHET-concentrations, only crystallization of PET-sequences was detectable with a cross-over behaviour for intermediate concentrations.     

1‐[4‐(Methyl­sulfonyl)­phenyl]‐5‐phenyl‐1H‐pyrazole derivatives

Three related compounds containing a pyrazole moiety with vicinal phenyl rings featuring a methyl­sulfonyl substituent are described, namely 3‐methyl‐1‐[4‐(methyl­sulfonyl)­phenyl]‐5‐phenyl‐1H‐pyrazole, C₁₇H₁₆N₂O₂S, ethyl 1‐[4‐(methyl­sul­fonyl)­phenyl]‐5‐phenyl‐1H‐pyrazole‐3‐carboxyl­ate, C₁₉H₁₈N₂O₄S, and 1‐[4‐(methyl­sulfonyl)­phenyl]‐3‐[3‐(morpholino)­phenoxy­methyl]‐5‐phenyl‐1H‐pyrazole, C₂₇H₂₇N₃O₄S. The design of these compounds was based on celecoxib, a selective cyclo­oxy­genase‐2 (COX‐2) inhibitor, in order to study the influence of various substituents on COX‐2 and 5‐lipoxy­genase (5‐LOX) inhibition.     

Response of DNA fragments to potentiometric sensors studied using HPLC

Potentiometric sensors are studied as viable candidates for the construction of high throughput DNA arrays. For preliminary investigations, such sensors were used in an HPLC setup in the present work. This avoided errors due to ionic contaminants or additives in the commercial samples. The oligonucleotides dT(10), dT(20) and dT(30) were used as test substances. The potentiometric sensors were of the coated wire type, containing PVC, DOP, MTDDACl and a synthetic podand urea receptor. The HPLC system consisted of a reversed phase column eluted with a phosphate buffer, triethylammoniumacetate (TEAA), and an acetonitrile gradient. Molar responses and sensitivities increased with increasing chain length of oligonucleotides, yielding detection limits as low as 10(-6)M (dT(30), injected concentration). The slopes of the calibration graphs were at least 23 mV/decade (dT(10)), which was much higher than expected. The results are discussed in view of the potential use of this sensor type in high throughput microarrays.     

Ritz and harmonic Ritz values and the convergence of FOM and GMRES

The Ritz and harmonic Ritz values are approximate eigenvalues, which can be computed cheaply within the FOM and GMRES Krylov subspace iterative methods for solving non‐symmetric linear systems. They are also the zeros of the residual polynomials of FOM and GMRES, respectively. In this paper we show that the Walker–Zhou interpretation of GMRES enables us to formulate the relation between the harmonic Ritz values and GMRES in the same way as the relation between the Ritz values and FOM. We present an upper bound for the norm of the difference between the matrices from which the Ritz and harmonic Ritz values are computed. The differences between the Ritz and harmonic Ritz values enable us to describe the breakdown of FOM and stagnation of GMRES. Copyright © 1999 John Wiley & Sons, Ltd.     

Conformationally constrained dipeptides. Obtention of enantiomerically pure 6‐acetamido‐5‐oxo‐1,2,3,5,6,7‐hexahydro‐3‐indolizine carboxylic acid

The separation of a stereoisomeric mixture of esters 6, and the synthesis of the new enantiomerically pure unsaturated 6,5‐fused bicyclic lactam 2 are described. The key‐step involves trimethylsilyl iodide cleavage, without racemization, of a vinylogous carbamate. The cis N‐ acetylamino acid 2 is a new scaffold for the synthesis of rigid β‐turn mimetics.     

Infrared Monitoring of the Modification of Styrene Acrylonitrile Copolymers with Oxazoline and Its Interfacial Reaction with Acid-Containing Polymers

The kinetics of the modification of styrene acrylonitrile (SAN) with aminoethanol to oxazoline-containing copolymers has been monitored with FTIR spectroscopy. Further, the interfacial reaction in bilayer samples of the oxazoline groups of these copolymers and the carboxylic acid groups of poly(ethylene-co-methacrylic acid) (PE-co-MA) copolymers has been studied by FTIR at different temperatures. The interfacial formation of ester-amides has been measured quantitatively by FTIR difference spectroscopy.     

Antioxidant Properties and Aldehyde Reactivity of PD-L1 Targeted Aryl-Pyrazolone Anticancer Agents

Small molecules targeting the PD-1/PD-L1 checkpoint are actively searched to complement the anticancer arsenal. Different molecular scaffolds have been reported, including phenyl-pyrazolone derivatives which potently inhibit binding of PD-L1 to PD-1. These molecules are structurally close to antioxidant drug edaravone (EDA) used to treat amyotrophic lateral sclerosis. For this reason, we investigated the capacity of five PD-L1-binding phenyl-pyrazolone compounds (1–5) to scavenge the formation of oxygen free radicals using electron spin resonance spectroscopy with DPPH/DMPO probes. In addition, the reactivity of the compounds toward the oxidized base 5-formyluracil (5fU) was assessed using chromatography coupled to mass spectrometry and photodiode array detectors. The data revealed that the phenyl-pyrazolone derivatives display antioxidant properties and exhibit a variable reactivity toward 5fU. Compound 2 with a N-dichlorophenyl-pyrazolone moiety cumulates the three properties, being a potent PD-L1 binder, a robust antioxidant and an aldehyde-reactive compound. On the opposite, the adamantane derivative 5 is a potent PD-L1 binding with a reduced antioxidant potential and no aldehyde reactivity. The nature of the substituent on the phenyl-pyrazolone core modulates the antioxidant capacity and reactivity toward aromatic aldehydes. The molecular signature of the compound can be adapted at will, to confer additional properties to these PD-L1 binders.