General Aspects and Optimization of Enantioselective Biocatalysis in Organic Solvents: The Use of Lipases [New Synthetic Methods (76)]

Enantioselective biocatalysis in nonaqueous media is becoming increasingly important in preparative synthetic chemistry. This article discusses (1) the general catalytic properties of enzymes in nonaqueous environments, (2) the basic principles that govern lipase-catalyzed enantioselective esterification and transesterification reactions in organic media for the preparation of optically active acids and alcohols, (3) the determination of kinetic and thermodynamic parameters, and (4) the quantitative analysis of published data.     

Damage analysis of tetragonal perovskite structure ceramics implicated by asymptotic field solutions and boundary conditions

Cracking of ceramics with tetragonal perovskite grain structure is known to appear at different sites and scale level. The multiscale character of damage depends on the combined effects of electromechanical coupling, prevailing physical parameters and boundary conditions. These detail features are exhibited by application of the energy density criterion with judicious use of the mode I asymptotic and full field solution in the range of r/a=10⁻⁴ to 10⁻² where r and a are, respectively, the distance to the crack tip and half crack length. Very close to the stationary crack tip, bifurcation is predicted resembling the dislocation emission behavior invoked in the molecular dynamics model. At the macroscopic scale, crack growth is predicted to occur straight ahead with two yield zones to the sides. A multiscale feature of crack tip damage is provided for the first time. Numerical values of the relative distances and bifurcation angles are reported for the PZT-4 ceramic subjected to different electric field to applied stress ratio and boundary conditions that consist of the specification of electric field/mechanical stress, electric displacement/mechanical strain, and mixed conditions. To be emphasized is that the multiscale character of damage in piezoceramics does not appear in general. It occurs only for specific combinations of the external and internal field parameters, elastic/piezoelectric/dielectric constants and specified boundary conditions.     

Characterization of nanochannel delivery membrane systems for the sustained release of resveratrol and atorvastatin: new perspectives on promoting heart health

Novel drug delivery systems capable of continuous sustained release of therapeutics have been studied extensively for use in the prevention and management of chronic diseases. The use of these systems holds promise as a means to achieve higher patient compliance while improving therapeutic index and reducing systemic toxicity. In this work, an implantable nanochannel drug delivery system (nDS) is characterized and evaluated for the long-term sustained release of atorvastatin (ATS) and trans-resveratrol (t-RES), compounds with a proven role in managing atherogenic dyslipidemia and promoting cardioprotection. The primary mediators of drug release in the nDS are nanofluidic membranes with hundreds of thousands of nanochannels (up to 100,000/mm²) that attain zero-order release kinetics by exploiting nanoconfinement and molecule-to-surface interactions that dominate diffusive transport at the nanoscale. These membranes were characterized using gas flow analysis, acetone diffusion, and scanning and transmission electron microscopy (SEM, TEM). The surface properties of the dielectric materials lining the nanochannels, SiO₂ and low-stress silicon nitride, were further investigated using surface charge analysis. Continuous, sustained in vitro release for both ATS and t-RES was established for durations exceeding 1 month. Finally, the influence of the membranes on cell viability was assessed using human microvascular endothelial cells. Morphology changes and adhesion to the surface were analyzed using SEM, while an MTT proliferation assay was used to determine the cell viability. The nanochannel delivery approach, here demonstrated in vitro, not only possesses all requirements for large-scale high-yield industrial fabrication, but also presents the key components for a rapid clinical translation as an implantable delivery system for the sustained administration of cardioprotectants.     

A convenient and sensitive method for haloacetic acid analysis in tap water by on‐line field‐amplified sample‐stacking CE–ESI‐MS

In this study, we propose a simple strategy based on flow injection and field‐amplified sample‐stacking CE–ESI‐MS/MS to analyze haloacetic acids (HAAs) in tap water. Tap water was passed through a desalination cartridge before field‐amplified sample‐stacking CE–ESI‐MS/MS analysis to reduce sample salinity. With this treatment, the signals of the HAAs increased 300‐ to 1400‐fold. The LODs for tap water analysis were in the range of 10 to 100 ng/L, except for the LOD of monochloroacetic acid (1 μg/L in selected‐ion monitoring mode detection). The proposed method is fast, convenient, and sensitive enough to perform on‐line analysis of five HAAs in the tap water of Taipei City. Four HAAs, including trichloroacetic acid, dichloroacetic acid, dibromoacetic acid, and monobromoacetic acid, were detected at concentrations of approximately 1.74, 1.15, 0.16, and 0.15 ppb, respectively.     

Stability and integrity of mechanical joints in flight vehicles: Local and global energy density

A methodology is presented for analyzing the inlfuence of mechanical joint failure on the global instability of flight vehicles. Considered are the ways with which loading, geometry and material of the vehicle can affect the structure instability and/or integrity. The peaks and valleys of the volume energy density function are assumed to coincide with failure by fracture and/or yielding while the distance between their local and global stationary values govern the structure instability. A single length parameter l can thus be applied to provide a measure of stability. The simultaneous occurrence of high energy density and large l at the same location should be avoided as it may have undesirable consequences.A flight vehicle consisting of four cylindrical shell-like structures connected by three tongue-and-groove joints is analyzed. The time-dependent load can be axisymmetric or non-axisymmetric. A semi-analytical finite element program is developed and used to solve for the transient stress and strain distribution from which contours of the volume energy density in the structure are obtained as a function of time. The magnitudes and locations of their local and global stationary values are then calculated and discussed in connection with potential failure by fracture. Stability behavior does not alter appreciably for axisymmetric flight. Considerable fluctuations in the energy density and the dynamic stability length parameter are found when non-axisymmetric loads are considered.     

Dipolar interactions and origin of spin ice in ising pyrochlore magnets

Recent experiments suggest that the Ising pyrochlore magnets Ho2Ti2O7 and Dy2Ti2O7 display qualitative properties of the nearest-neighbor "spin ice" model. We discuss the dipolar energy scale present in both these materials and discuss how spin-ice behavior can occur despite the presence of long-range dipolar interactions. We present results of numerical simulations and a mean field analysis of Ising pyrochlore systems. Based on our quantitative theory, we suggest that the spin-ice behavior in these systems is due to long-range dipolar interactions, and that the nearest-neighbor exchange in Dy2Ti2O7 is antiferromagnetic.     

Nondestructive detection of damage in aluminum: Electromagenetic discharge imaging

Electromagnetic Discharge Imaging (EDI) is applied for the nondestructive detection of imperfections and inhomogeneities in solids. These imperfections were introduced mechanically by drilling holes of different sizes and chemically by applying corrosive agents to aluminum specimens. The results are influenced by a host of variables associated with the waveform generator, the dielectric air gap and the specimen type. Correlation is thus established between the electromagnetic discharge image and the degree of material damage. Detection of material damage was also made possible even when the specimen surface was a layer of opaque insulation material.