Ion‐Transfer Electrochemistry of Rat Amylin at the Water–Organogel Microinterface Array and Its Selective Detection in a Protein Mixture

The behavior of proteins and polypeptides at electrified aqueous–organic interfaces is of benefit in label‐free detection strategies. In this work, rat amylin (or islet amyloid polypeptide) was studied at the interface formed between aqueous liquid and gelled organic phases. Amylin is a polypeptide that is co‐secreted with insulin from islet beta‐cells and is implicated in fibril formation. In this study, rat amylin was used, which does not undergo aggregation. The polypeptide underwent an interfacial transfer process, from water to the gelled organic phase, under applied potential stimulation. Cyclic voltammetry revealed steady‐state forward and peak‐shaped reverse voltammograms, which were consistent with diffusion‐controlled water‐to‐organic transfer and thin‐film stripping or desorptive back‐transfer. The diffusion‐controlled forward current was greater when amylin was present in an acidic aqueous phase than when it was present in an aqueous phase at physiological pH; this reflects the greater charge on the polypeptide under acidic conditions. The amylin transfer current was concentration dependent over the range 2–10 μM , at both acidic and physiological pH. At physiological pH, amylin was selectively detected in the presence of a protein mixture, which illustrated the bioanalytical possibilities for this electrochemical behavior.     

A Convenient Synthesis of t-butyl p-Aminobenzoate

A convenient one-pot synthesis of t-butyl p-aminobenzoate is described which involves treatment of p-aminobenzoic acid with thionyl chloride, followed by reaction of the resulting p-sulfinylaminobenzoyl chloride with t-butanol.     

Dicarboxylated ethynylarenes as buffer-dependent chemosensors for Cd(II), Pb(II), and Zn(II)

Two dicarboxylated ethynylarenes were prepared efficiently from condensation of 1,3-bis(3-aminophenylethynyl)benzene with 2 equiv of either succinic anhydride or glutaric anhydride. These compounds behave as fluorescent chemosensors selective for Cd(II), Pb(II), and Zn(II) cations under buffered aqueous conditions, with analyte binding observed as bathochromically shifted, intensified fluorescence. It was noteworthy that the fluorescence responses varied significantly with buffer identity. A conformational restriction mechanism involving reversible interactions between the fluorophore, metal cation, and buffer itself is proposed.     

Asymmetric syntheses of (−)-isoretronecanol and (−)-trachelantamidine

Short and concise total asymmetric syntheses of (−)-isoretronecanol and (−)-trachelantamidine are reported. Oxidative cleavage of tert-butyl (S,S,S,Z)-7-[N-benzyl-N-(α-methylbenzyl)amino]cyclohept-3-ene-1-carboxylate, followed by hydrogenolysis promoted in situ cyclisation/reduction, which provided rapid access to the bicyclic core within (−)-isoretronecanol. Analogous treatment of the C(1)-epimer gave (−)-trachelantamidine. Overall, the syntheses of (−)-isoretronecanol and (−)-trachelantamidine were completed in eight and seven steps and 20 and 9.5% yield, respectively, from commercially available starting materials.     

ABC Triblock Copolymer Micelles: Spherical Versus Worm‐Like Micelles Depending on the Preparation Method

Well‐defined ABC triblock copolymers based on two hydrophilic blocks, A and C, and a hydrophobic block B are synthesized and their self‐assembly behavior is investigated. Interestingly, at the same solvent, concentration, pH, and temperature, different shape micelles are observed, spherical and worm‐like micelles, depending on the preparation method. Specifically, spherical micelles are observed with bulk rehydration while both spherical and worm‐like micelles are observed with film rehydration.

     

Reliable radical stabilization energies from diffusion Monte Carlo calculations

We assess the performance of variational (VMC) and diffusion (DMC) quantum Monte Carlo methods for calculating the radical stabilization energies of a set of 43 carbon-centered radical species. Even using simple single-determinant trial wavefunctions, both methods perform exceptionally well, with mean absolute deviations from reference values well under the chemical accuracy standard of 1 kcal/mol. In addition, the use of DMC results in a highly concentrated spread of errors, with all 43 results within chemical accuracy at the 95% confidence level. These results indicate that DMC is an extremely reliable method for calculating radical stabilization energies and could be used as a benchmark method for larger systems in future.     

Electrochemical potentials from first principles

The electrochemical potential is the fundamental parameter in the theory of electrochemistry. Not only does it determine the position of electrochemical equilibria but also it acts as the driving force for electron transfer reactions, diffusion-migration phenomena, and phase transformations of all kinds. In the present work, the electrochemical potential is defined as the total work done in transferring a single particle of a substance from a universal reference state to a specified location, at constant temperature and pressure. It is the sum of two scalar fields: the electrostatic potential energy and the chemical potential energy. The electrochemical potential is widely underutilized within the fields of solid-state science and electrochemical engineering. For historical reasons, many authors prefer to analyze driving forces in terms of electrode potentials, concentration gradients, or Gibbs free energies. In this paper, the author provides a short introduction to the electrochemical potential and then shows how some of the major branches of electrochemistry can benefit from using it. Topics examined include the Volta potential difference, the membrane potential difference, the scanning Kelvin probe microscope, the electromotive force, the proton motive force, and the activation of electron transfer.

     

Tafel slopes from first principles

Tafel slopes for multistep electrochemical reactions are derived from first principles. The derivation takes place in two stages. First, Dirac’s perturbation theory is used to solve the Schrödinger equation. Second, current–voltage curves are obtained by integrating the single-state results over the full density of states in electrolyte solutions. Thermal equilibrium is assumed throughout. Somewhat surprisingly, it is found that the symmetry factor that appears in the Butler–Volmer equation is different from the symmetry factor that appears in electron transfer theory, and a conversion formula is given. Finally, the Tafel slopes are compiled in a convenient look-up table.     

Bell clapper impact dynamics and the voicing of a carillon

The periodic re-voicing of the bell clappers of the Australian National Carillon in Canberra provided an opportunity for the study of the acoustic effects of this operation. After prolonged playing, the impact of the pear-shaped clapper on a bell produces a significant flat area on both the clapper and the inside surface of the bell. This deformation significantly decreases the duration of the impact event and has the effect of increasing the relative amplitude of higher modes in the bell sound, making it "brighter" or even "clangy." This effect is studied by comparing the spectral envelope of the sounds of several bells before and after voicing. Theoretical analysis shows that the clapper actually strikes the bell and remains in contact with the bell surface until it is ejected by a displacement pulse that has traveled around the complete circumference of the bell. The contact time, typically about 1 ms, is therefore much longer than the effective impact time, which is only a few tenths of a millisecond. Both the impact time and the contact time are reduced by the presence of a flat on the clapper.