Recently, polymerization-induced self-assembly (PISA) has become widely recognized as a robust and efficient route to produce block copolymer nanoparticles of controlled size, morphology, and surface chemistry. Several reviews of this field have been published since 2012, but a substantial number of new papers have been published in the last three years. In this Perspective, we provide a critical appraisal of the various advantages offered by this approach, while also pointing out some of its current drawbacks. Promising future research directions as well as remaining technical challenges and unresolved problems are briefly highlighted.
The formation of ions in nonpolar solvents (with relative permittivity ε r of approximately 2) is more difficult than in polar liquids; however, these charged species play an important role in many applications, such as electrophoretic displays. The low permittivities (ε r) of these solvents mean that charges have to be separated by large distances to be stable (approximately 28 nm or 40 times that in water). The inverse micelles formed by surfactants in these solvents provide an environment to stabilize ions and charges. Common surfactants used are sodium dioctylsulfosuccinate (Aerosol OT or AOT), polyisobutylene succinimide, sorbitan oleate, and zirconyl 2-ethyl hexanoate. The behavior of charged inverse micelles has been studied on both the bulk and on the microscopic scale and can be used to determine the motion of the micelles, their structure, and the nature of the electrostatic double layer. Colloidal particles are only weakly charged in the absence of surfactant, but in the presence of surfactants, many types, including polymers, metal oxides, carbon blacks, and pigments, have been observed to become positively or negatively charged. Several mechanisms have been proposed as the origin of surface charge, including acid-base reactions between the colloid and the inverse micelle, preferential adsorption of charged inverse micelles, or dissolution of surface species. While most studies vary only the concentration of surfactant, systematic variation of the particle surface chemistry or the surfactant structure have provided insight into the origin of charging in nonpolar liquids. By carefully varying system parameters and working to understand the interactions between surfactants and colloidal surfaces, further advances will be made leading to better understanding of the origin of charge and to the development of more effective surfactants.
The aim of this manuscript is to review the potential adverse health effects in humans if exposed to residues of selected veterinary drugs used in food-producing animals. Our other objectives are to briefly inform the reader of why many of these drugs are or were approved for use in livestock production and how drug residues can be mitigated for these drugs. The selected drugs include several antimicrobials, beta agonists, and phenylbutazone. The antimicrobials continue to be of regulatory concern not only because of their acute adverse effects but also because their use as growth promoters have been linked to antimicrobial resistance. Furthermore, nitroimidazoles and arsenicals are no longer approved for use in food animals in most jurisdictions. In recent years, the risk assessment and risk management of beta agonists, have been the focus of national and international agencies and this manuscript attempts to review the pharmacology of these drugs and regulatory challenges. Several of the drugs selected for this review can cause noncancer effects (e.g., penicillins) and others are potential carcinogens (e.g., nitroimidazoles). This review also focuses on how regulatory and independent organizations manage the risk of these veterinary drugs based on data from human health risk assessments.
Low molecular weight gels are formed by the self-assembly of a suitable small molecule gelator into a three-dimensional network of fibrous structures. The gel properties are determined by the fiber structures, the number and type of cross-links and the distribution of the fibers and cross-links in space. Probing these structures and cross-links is difficult. Many reports rely on microscopy of dried gels (xerogels), where the solvent is removed prior to imaging. The assumption is made that this has little effect on the structures, but it is not clear that this assumption is always (or ever) valid. Here, we use small angle neutron scattering (SANS) to probe low molecular weight hydrogels formed by the self-assembly of dipeptides. We compare scattering data for wet and dried gels, as well as following the drying process. We show that the assumption that drying does not affect the network is not always correct.
Modulated differential scanning calorimetry has been used to quantify the glass transitions of small adsorbed amounts of poly(methyl methacrylate) (PMMA) on silica. While a relatively narrow, single glass transition was found for bulk PMMA, broader two-component transitions were found for the adsorbed polymer. A two-state model based on loosely bound polymer (glass transition similar to bulk) and more tightly bound polymer (glass transition centered around 156 degrees C) was used to interpret the thermograms. On the basis of this model, the amount of tightly bound polymer was found to be approximately 1.3 mg/m2, corresponding to a 1.1 nm thick layer. The change in heat capacity for the tightly bound polymer at the glass transition temperature was estimated to be about 16% of that of the bulk polymer.
The concentration-dependent aggregation of two surfactants, anionic sodium dioctylsulfosuccinate (Aerosol OT or AOT) and nonionic pentaethylene glycol monododecyl ether (C12E5), has been studied in cyclohexane-D12 using small-angle neutron scattering (SANS). A clear monomer-to-aggregate transition has been observed for both surfactants, spherical inverse micelles for AOT and hank-like micelles for C12E5. This suggests that a critical micelle concentration exists for surfactants of these kinds in nonpolar solvents. The nature of the transition is different for the two surfactants. AOT aggregates are the same size and shape with decreasing concentration until a sharp critical micelle concentration, after which they cannot be detected. However, C12E5 aggregates gradually decrease in size. These differences demonstrate that the strength of the solvophobic effect can influence the formation of surfactant aggregates in nonaqueous solvents.
A new reagent, 2,4,6-tripyridyl-strlazine (TPTZ), is proposed for the colorimetric determination of iron. The intense violet color formed by TPTZ with iron(ll) is due to the ion Fe(TPTZ)2+2,
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