Reversible redox controlled acids for cationic ring-opening polymerization

Advancements in externally controlled polymerization methodologies have enabled the synthesis of novel polymeric structures and architectures, and they have been pivotal to the development of new photocontrolled lithographic and 3D printing technologies. In particular, the development of externally controlled ring-opening polymerization (ROP) methodologies is of great interest, as these methods provide access to novel biocompatible and biodegradable block polymer structures. Although ROPs mediated by photoacid generators have made significant contributions to the fields of lithography and microelectronics development, these methodologies rely upon catalysts with poor stability and thus poor temporal control. Herein, we report a class of ferrocene-derived acid catalysts whose acidity can be altered through reversible oxidation and reduction of the ferrocenyl moiety to chemically and electrochemically control the ROP of cyclic esters.

A class of ferrocene-derived acid catalysts whose acidity can be altered through reversible oxidation and reduction of the ferrocenyl moiety to chemically and electrochemically control the ROP of cyclic esters is reported.     

Factors affecting the 13.56-MHz radio-frequency-mediated heating of gold nanoparticles

The use of radio-frequency (RF) energy for the thermal activation of tumor-targeted nanoparticles (NPs) is a promising non-invasive hyperthermic treatment because RF waves penetrate deep through tissue. Nonetheless, while the approach has been demonstrated using gold (Au) and iron oxide NPs, the RF-mediated heating mechanism of AuNPs has been controversial. A part of the reason is that measuring and modeling the heating of AuNPs in an RF field is a complex endeavor that depends on the chemical and physical properties of the AuNPs, interfacial phenomena involving AuNP coatings and the sample medium, and the antenna design and characteristics of the RF field. Herein, the mechanisms and factors affecting the 13.56-MHz RF-mediated heating of AuNPs are reviewed, a new factor concerning the thermal isolation of RF antennae is presented, and the ability of a new water-free cooling system to thermally isolate samples from the heat generated by metal RF-induction coils is demonstrated.     

Glycosylation of Volatile Phenols in Grapes following Pre-Harvest (On-Vine) vs. Post-Harvest (Off-Vine) Exposure to Smoke

Taint in grapes and wine following vineyard exposure to bushfire smoke continues to challenge the financial viability of grape and wine producers worldwide. In response, researchers are studying the chemical, sensory and physiological consequences of grapevine smoke exposure. However, studies involving winemaking trials are often limited by the availability of suitable quantities of smoke-affected grapes, either from vineyards exposed to smoke or from field trials involving the application of smoke to grapevines. This study compared the accumulation of volatile phenol glycosides (as compositional markers of smoke taint) in Viognier and Cabernet Sauvignon grapes exposed to smoke pre- vs. post-harvest, and found post-harvest smoke exposure of fruit gave similar levels of volatile phenol glycosides to fruit exposed to smoke pre-harvest. Furthermore, wines made from smoke-affected fruit contained similar levels of smoke-derived volatile phenols and their glycosides, irrespective of whether smoke exposure occurred pre- vs. post-harvest. Post-harvest smoke exposure therefore provides a valid approach to generating smoke-affected grapes in the quantities needed for winemaking trials and/or trials that employ both chemical and sensory analysis of wine.     

Novel and convenient synthesis of 1-(pyridinylmethyl)-2-naphthols and 1-(pyridinylmethylene)-2-tetralones from 2-tetralones

The reaction of 2/4-pyridine carboxaldehyes with 2-tetralone analogs in the presence of catalytic amounts of Pd/C and trimethylsilyl chloride in DMF resulted in the formation of 1-(pyridin-2/4-ylmethyl)-2-naphthols in moderate to good yields as opposed to the expected 1-(pyridin-2/4-ylmethylene)-2-tetralones. 3-Pyridine carboxaldehyde, however, formed 1-(pyridin-3-ylmethylene)-2-tetralones with 2-tetralone analogs under similar conditions. When representative reactions were repeated in the presence of anhydrous HCl gas in acetic acid, including one with 3-pyridine carboxaldehyde, 1-(pyridinylmethyl)-2-naphthols were the only products obtained with significantly improved yields. A possible mechanism explaining these results is discussed.     

Adsorption of cadmium and lead onto oxidized nitrogen-doped multiwall carbon nanotubes in aqueous solution: equilibrium and kinetics

Nitrogen-doped multiwall carbon nanotubes (CNx) were chemically oxidized and tested to adsorb cadmium and lead from aqueous solution. Physicochemical characterization of carbon nanotubes included morphological analysis, textural properties, and chemical composition. In addition, the cadmium adsorption capacity of oxidized-CNx was compared with commercially available activated carbon and single wall carbon nanotubes. Carboxylic and nitro groups on the surface of oxidized CNx shifted the point of zero charge from 6.6 to 3.1, enhancing their adsorption capacity for cadmium and lead to 0.083 and 0.139 mmol/g, respectively, at pH 5 and 25 °C. Moreover, oxidized-CNx had higher selectivity for lead when both metal ions were in solution. Kinetic experiments for adsorption of cadmium showed that the equilibrium was reached at about 4 min. Finally, the small size, geometry, and surface chemical composition of oxidized-CNx are the key factors for their higher adsorption capacity than activated carbon.     

Nanofluids’ stability effects on the thermal performance of heat pipes

Journal of Thermal Analysis and Calorimetry - Nanofluids have been introduced as an alternative to conventional fluids to improve energy efficiency in heat transfer systems. However, their...     

Changes in Silk Feedstock Rheology during Cocoon Construction: The Role of Calcium and Potassium Ions

Variation in silk feedstocks is a barrier both to our understanding of natural spinning and biomimetic endeavors. To address this, compositional changes are investigated in feedstock specimens from the domesticated silkworm (Bombyx mori). It is found that the feedstock viscosity decreased systematically by over two orders of magnitude during cocoon construction. Potential factors such as protein concentration, molecular weight, pH, or the presence of trehalose are excluded, whereas a clear correlation appear between viscosity and the relative concentrations of Ca²⁺ and K⁺ ions. It is expected that Ca²⁺ ions would favor “salt bridges” between acidic (Asp and Glu) amino acids, leading to an increased viscosity, whereas K⁺ ions would compete for these sites, thereby reducing viscosity. Thus, these findings suggest a simple, systematic yet sophisticated control of feedstock viscosity in the silkworm, which in turn can be applied to future industrial silk production.     

A Fluorogenic Probe for Cell Surface Phosphatidylserine Using an Intramolecular Indicator Displacement Sensing Mechanism

The detection of externalized phosphatidylserine (PS) on the cell surface is commonly used to distinguish between living, apoptotic, and necrotic cells. The tools of choice for many researchers to study apoptosis are annexin V‐fluorophore conjugates. However, the use of this 35 kDa protein is associated with several drawbacks, including temperature sensitivity, Ca²⁺ dependence, and slow binding kinetics. Herein, a fluorogenic probe for cell surface PS, P‐IID , is described, which operates by an intramolecular indicator displacement (IID) mechanism. An intramolecularly bound coumarin indicator is released in the presence of cell surface PS, leading to a fluorescence “turn‐on” response. P‐IID demonstrates superior performance when compared to annexin V, for both fluorescence imaging and flow cytometry. This allows P‐IID to be used in time‐lapse imaging of apoptosis using confocal laser scanning microscopy and demonstrates the utility of the IID mechanism in live cells.     

The Riemann–Hilbert approach to the Helmholtz equation in a quarter-plane: Neumann,Robin and Dirichlet boundary conditions

We revisit the Helmholtz equation in a quarter-plane in the framework of the Riemann–Hilbert approach to linear boundary value problems suggested in late 1990s by A. Fokas. We show the role of the Sommerfeld radiation condition in Fokas’ scheme.