Social and antisocial [3 + 3] Schiff base macrocycles with isomeric backbones

Two new conjugated macrocycles have been prepared in high yield using Schiff base condensation. These are the first Schiff base macrocycles to incorporate phenanthrene, and they contain 66 and 78 atoms, respectively, in their smallest closed ring. Although the backbones of the two macrocycles have nearly the same constitution, one aggregates in chloroform while the other does not. This is rationalized based on the differential overlap of aromatic components in the dimers.     

Molecular polarizability estimates for vibrational spectral interpretation

A scheme is outlined for obtaining estimates of molecular polarizabilities, quadrupole moments, and their derivatives from restricted Hartree-Fock calculations. Results are presented for the test cases H₂, F₂ and Cl₂, and the compared with experiment. This results are found to be lower limits to these quantities, and they are expected to be of use in the interpretation of Raman and of collision-induced infrared absorption spectra.     

Stereochemistry of the Conversion of 2‐Phenoxyethanol into Phenol and Acetaldehyde by Acetobacterium sp.

The conversion of 2‐phenoxyethanol to phenol and acetate by the anaerobic bacterium Acetobacterium sp. strain LuPhet1 proceeds through acetaldehyde with concomitant migration of a H‐atom from C(1) to C(2) of the glycolic moiety. Separate feeding experiments with (R)‐ and (S)‐2‐phenoxy(1‐²H)ethanol, prepared via chemoenzymatic syntheses, indicate that the H‐atom involved in the 1,2‐shift is the pro‐S one of the enantiotopic couple of the alcohol function.     

Detection of methotrexate in a flow system using electrochemical impedance spectroscopy and multivariate data analysis

Methotrexate (MTX), a common pharmaceutical drug in cancer therapy and treatment of rheumatic diseases, is known to cause severe adverse side effects at high dose. As the side effect may be life threatening, there is an urgent need for a continuous, bed-side monitoring of the nominal MTX serum level in a patient while the chemical is being administered. This article describes a detection of MTX using a flow system that consists two modified gold electrodes. Interaction of MTX with the antibodies fixed on the electrode surface is detected by electrochemical impedance spectroscopy and evaluated using singular value decomposition (SVD). The key finding of this work is that the change in the electrode capacitance is found to be quantitative with respect to the concentration of MTX. Moreover a calibration curve constructed using the principal component regression method has a linear range of six orders of magnitude and a detection limit of 1.65 × 10⁻¹⁰ M.     

Chronocoulometric and rotating disc electrode determination of the charge propagation current through poly-4-vinylpyridine films containing hexachloroiridate anions

Charge propagation currents through polymer films coated on electrodes which contain redox active sites are usually determined by potential step methods. The aim of this study was to compare the charge propagation current obtained from chronocoulometric measurements with charge transport through a poly-4-vinylpyridine/IrCl₆²⁻ film during the mediated oxidation of Fe²⁺ at a rotating disc electrode. The two methods gave identical results for the model system chosen.     

Wettability alteration of sandstones by silica nanoparticle dispersions in light and heavy crude oil

Unlike conventional oil production methods, enhanced oil recovery (EOR) processes can recover most oil products from the reservoir. One method, known as wettability alteration, changes the hydrophilicity of the reservoir rock via decreased surface interactions with crude oils. The mitigation of these attractive forces enhances petroleum extraction and increases the accessibility of previously inaccessible rock deposits. In this work, silica nanoparticles (NPs) have been used to alter the wettability of two sandstone surfaces, Berea and Boise. Changes in wettability were assessed by measuring the contact angle and interfacial tension of different systems. The silica NPs were suspended in brine and a combined solution of brine and the Tween®20 nonionic surfactant at concentrations of 0, 0.001, and 0.01 wt% NP with both light and heavy crude oil. The stability of the different nanofluids was characterized by the size, zeta potential, and sedimentation of the particles in suspension. Unlike the NPs, the surfactant had a greater effect on the interfacial tension by influencing the liquid-liquid interactions. The introduction of the surfactant decreased the interfacial tension by 57 and 43% for light and heavy crude oil samples, respectively. Imaging and measurements of the contact angle were used to assess the surface-liquid interactions and to characterize the wettability of the different systems. The images reflect that the contact angle increased with the addition of NPs for both sandstone and oil types. The contact angle in the light crude oil sample was most affected by the addition of 0.001 wt% NP, which altered both sandstones’ wettability. Increases in contact angle approached 101.6% between 0 and 0.001 wt% NPs with light oil on the Berea sandstone. The contact angle however remained relatively unaffected by addition of higher NP concentrations, thus indicating that low NP concentrations can effectively be used for enhancing crude oil recovery. While the contact angle of the light crude oil plateaued, the heavy crude oil continued to increase with an increase in NP concentration; therefore indicating that a maximum contact angle in heavy crude oil was not yet achieved. The introduction of NPs in light and heavy crude oil samples altered both the Berea and Boise sandstone systems’ wettability, which in turn indicated the efficacy of the silica NPs and surfactants in generating a more water-wet reservoir. Consequently, silica NPs and surfactants are most promising for EOR across the range of oil types.     

Polymerization-induced color changes of polydiacetylene-containing liposomes and peptide amphiphile fibers

Polydiacetylenes have received much attention due to their intrinsic optical properties. Their inclination to change color in response to environmental factors has been extensively exploited in the sensing of analytes. In this study we functionalized diacetylene-containing peptide amphiphiles and phospholipids with α-bromo esters so that they could be used as initiators in atom transfer radical polymerization (ATRP) reactions. Subsequently, the supramolecular assemblies formed by these molecules upon their addition to water, namely peptide amphiphile fibers and liposomes, were stabilized by polymerizing the diacetylene moieties present in the molecules. As a result, highly colored, disassembly resistant, macro initiators were created. To investigate whether steric crowding on the surface of these assemblies could influence the color of the polydiacetylenes, we utilized the initiator functionality that had been introduced prior to assembly in ATRP. We found that the chromatic properties of the polydiacetylenes were directly related to the formation of polymer on the surface of peptide amphiphile fibers as well as liposomes. Furthermore, we were able to demonstrate that the progress of this color change could be monitored with UV-visible spectroscopy.