Solubility and preferential solvation of acetaminophen in methanol + water mixtures at 298.15 K

The equilibrium solubility of acetaminophen in methanol + water binary mixtures at 298.15 K was determined and correlated with the Jouyban–Acree model. Preferential solvation parameters by methanol (δx_1,3) were derived from their thermodynamic solution properties by means of the inverse Kirkwood–Buff integrals method. δx_1,3 values are negative in water-rich mixtures but positive in compositions from 0.32 in mole fraction of methanol to pure methanol. It is conjecturable that in the former case, the hydrophobic hydration around non-polar groups plays a relevant role in the solvation. The higher solvation by methanol in mixtures of similar cosolvent compositions and methanol-rich mixtures could be explained in terms of the higher basic behavior of this cosolvent.     

Preparation of a sulfonated fused-silica capillary and its application in capillary electrophoresis and electrochromatography

In the present paper, two new methods, sol-gel and chemical bonding methods, were proposed for preparation of sulfonated fused-silica capillaries. In the sol-gel method, a fused-silica capillary was coated with the sol solution obtained by hydrolysis of 3-mercaptopropyltrimethoxysilane (MPTS) and tetramethoxysilane, and followed by age; while in the chemical bonding method, a capillary was chemically bonded directly with MPTS. Then, both the resulting capillaries were oxidized with an aqueous solution of hydrogen peroxide solution (H2O2) (30%, m/m) to obtain the sulfonated capillaries. The electroosmotic flow (EOF) for the sulfonated capillaries was found to remain almost constant within the studied pH range, and greater than that of the uncoated capillary. However, the coating efficiency of the capillary prepared by chemical bonding method was higher than that by sol-gel method, by comparing their magnitude of the EOF, the degree of disguise of the silanol and reproducibility of preparation procedure. The effects of the electrolyte's concentration and the content of methanol (MeOH) on the EOF were also studied. Especially, the study of the apparent pH (pH*) on the EOF in a water-MeOH system was reported. Finally, capillary electrophoretic separation of seven organic acids was achieved within 6.5 min under optimal condition using the chemically bonded sulfonated capillary. Moreover, separation of four alkaloids on the sulfonated capillary was compared with that on uncoated capillary in different conditions. Ion-exchange mechanism was found to play a key role for separation of these four basic analytes on the sulfonated capillary.     

Pareto optimization in computational protein design with multiple objectives

The optimization for function in computational design requires the treatment of, often competing, multiple objectives. Current algorithms reduce the problem to a single objective optimization problem, with the consequent loss of relevant solutions. We present a procedure, based on a variant of a Pareto algorithm, to optimize various competing objectives in protein design that allows reducing in several orders of magnitude the search of the solution space. Our methodology maintains the diversity of solutions and provides an iterative way to incorporate automatic design methods in the design of functional proteins. We have applied our systematic procedure to design enzymes optimized for both catalysis and stability. However, this methodology can be applied to any computational chemistry application requiring multi-objective combinatorial optimization techniques.     

Convenient Preparation of Cycloalkenyl Boronic Acid Pinacol Esters

A practical method for the preparation of cycloalkenyl boronic acid pinacol esters is described. These important synthetic intermediates are typically made using more expensive methods like transition metal-catalyzed borylation of alkenyl halides or triflates. In this work, they are obtained from the simple corresponding cycloalkanones, which are subjected to Shapiro reaction conditions followed by trapping with a borate ester. The requisite products are obtained in very good to excellent yields, and the reactions can be scaled up to multigram amounts. By providing a simple alternative to common methods that make use of expensive transition-metal catalysts and formation of sensitive intermediates, this convenient method will be useful for the synthesis of ring-containing partners for Suzuki–Miyaura cross-coupling and other reactions employing boronic esters as substrates.     

Complex dynamics of epidemic models on adaptive networks

There has been a substantial amount of well mixing epidemic models devoted to characterizing the observed complex phenomena (such as bistability, hysteresis, oscillations, etc.) during the transmission of many infectious diseases. A comprehensive explanation of these phenomena by epidemic models on complex networks is still lacking. In this paper we study epidemic dynamics in an adaptive network proposed by Gross et al., where the susceptibles are able to avoid contact with the infectious by rewiring their network connections. Such rewiring of the local connections changes the topology of the network, and inevitably has a profound effect on the transmission of the disease, which in turn influences the rewiring process. We rigorously prove that the adaptive epidemic model investigated in this paper exhibits degenerate Hopf bifurcation, homoclinic bifurcation and Bogdanov–Takens bifurcation. Our study shows that adaptive behaviors during an epidemic may induce complex dynamics of disease transmission, including bistability, transient and sustained oscillations, which contrast sharply to the dynamics of classical network models. Our results yield deeper insights into the interplay between topology of networks and the dynamics of disease transmission on networks.     

On Type I Singularities of the Local Axi-Symmetric Solutions of the Navier–Stokes Equations

Local regularity of axially symmetric solutions to the Navier–Stokes equations is studied. It is shown that under certain natural assumptions there are no singularities of Type I.     

The Hirota bilinear method for the coupled Burgers equation and the high-order Boussinesq–Burgers equation

This paper studies the coupled Burgers equation and the high-order Boussinesq–Burgers equation. The Hirota bilinear method is applied to show that the two equations are completely integrable. Multiple-kink (soliton) solutions and multiple-singular-kink (soliton) solutions are derived for the two equations.