Monodisperse nanoparticles of poly(ethylene glycol) macromers and N‐isopropyl acrylamide for biomedical applications

Poly(ethylene glycol)‐based nanoparticles have received significant attention in the field of biomedicine. When they are copolymerized with pH‐ or temperature‐sensitive comonomers, their small size allows them to respond very quickly to changes in the environment, including changes in the pH, ionic strength, and temperature. In addition, the high surface‐to‐volume ratio makes them highly functionalized. In this work, nanoparticles composed of temperature‐sensitive poly(N‐isopropylacrylamide), poly(ethylene glycol) 400 dimethacrylate, and poly(ethylene glycol) 1000 methacrylate were prepared by a thermally initiated, free‐radical dispersion polymerization method. The temperature‐responsive behavior of the hydrogel nanoparticles was characterized by the study of their particle size with photon correlation spectroscopy. The size of the nanoparticles varied from 200 to 1100 nm and was a strong function of the temperature of the system, from 5 to 40°C. The thermal, structural, and morphological characteristics were also investigated. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1678–1684, 2003     

Additive-effects during plating in acid tin methanesulfonate electrolytes

The effects of organic additives on the electrochemical and morphological deposit changes from acid tin methanesulfonate solutions are presented. In the absence of additives, tin deposition is diffusion-controlled with concomitant hydrogen gas evolution and the tin deposits are rough. Addition of polyethylene glycol suppresses hydrogen gas evolution yet has little effect on the mechanism of stannous reduction and the deposit structures. Polypropylene glycol enhances stannous reduction and produces a slightly smoother tin coating. The addition of phenolphthalein to solutions already containing the glycol additives results in a kinetically-controlled tin reduction process and a smooth matte tin deposit.     

Adhesion between oppositely charged polyelectrolytes

The adhesion between a grafted polyelectrolyte layer (brush) and a gel of an oppositely charged polyelectrolyte has been measured as a function of applied pressure, and the interface has been traced using neutron reflectometry. The interface (in aqueous medium at pH 6) between the (polycationic) brush and the (polyanionic) gel has a limited pressure dependence, with a small amount of deformation of the interface at the brush–gel contact. Brushes with a dry thickness of up to 13 nm exhibit weak adhesion (measured using a mechanical force tester) with an adhesive failure when the gel is detached. Thicker brushes result in the gel exhibiting cohesive failure. Reversing the geometry, whereby a polycationic brush is replaced with a polyanion and the polyanionic gel is replaced with a polycation, reveals that the pH dependence of the adhesion is moderately symmetric about pH 6, but that the maximum force required to separate the polycation gel from the polyanion brush over the range of pH is greater than that for the polycation brush and polyanion gel. The polyanion used is poly(methacrylic acid) (PMAA) and polycations of poly[2-(diethylamino)ethyl methacrylate] (PDEAEMA) and poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) were used.     

Characterisation of CYP102A25 from Bacillus marmarensis and CYP102A26 from Pontibacillus halophilus: P450 Homologues of BM3 with Preference towards Hydroxylation of Medium‐Chain Fatty Acids

Cytochrome P450 monooxygenases are highly desired biocatalysts owing to their ability to catalyse a wide variety of chemically challenging C?H activation reactions. The CYP102A subfamily of enzymes are natural catalytically self‐sufficient proteins consisting of a haem and FMN‐FAD reductase domain fused in a single‐component system. They catalyse the oxygenation of saturated and unsaturated fatty acids to produce primarily ω?1, ω?2 and ω?3 hydroxy acids. These monooxygenases have potential applications in biotechnology; however, their substrate range is still limited and there is a continued need to add diversity to this class of biocatalysts. Herein, we present the characterisation of two new members of this class of enzymes, CYP102A25 (BMar) from Bacillus marmarensis and CYP102A26 (PHal) from Pontibacillus halophilus, both of which express readily in a recombinant bacterial host. BMar exhibits the highest activity toward myristic acid and shows moderate activity towards unsaturated fatty acids. PHal exhibits broader activity towards mid‐chain‐saturated (C₁₄–C₁₈) and unsaturated fatty acids. Furthermore, PHal shows good regioselectivity for the hydroxylation of myristic acid, targeting the ω?2 position for C?H activation.     

Morphology of polystyrene/poly(methyl methacrylate) blends: Effects of carbon nanotubes aspect ratio and surface modification

Multiwalled carbon nanotubes (MWCNTs) with aspect ratios (ARs) ranging from 94 to 474 were incorporated into polystyrene (PS)/poly(methyl methacrylate) blends using solution mixing and melt mixing. Also, two functionalized MWCNTs were prepared from the nanotubes having AR 94: one was oxidized by nitric acid while the other was further modified with amine‐terminated PS attached to carboxyl groups to form amides. The two functionalized MWCNTs (1 wt %) were used to show that which phase the carbon nanotubes (CNTs) were located in could be controlled with nanotube surface chemistry. When nanotubes were confined to the minor phase, the size of the minor domain first decreased with adding low AR CNT as expected due to the increased viscosity of the minor phase. However, at higher ARs, the size increased beyond the size for the minor domain with no nanotubes, and at high enough AR, the shape of the minor domain changed from spherical to an elongated irregular shape. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3500–3510, 2015     

Glibenclamide for the Treatment of Ischemic and Hemorrhagic Stroke

Ischemic and hemorrhagic strokes are associated with severe functional disability and high mortality. Except for recombinant tissue plasminogen activator, therapies targeting the underlying pathophysiology of central nervous system (CNS) ischemia and hemorrhage are strikingly lacking. Sur1-regulated channels play essential roles in necrotic cell death and cerebral edema following ischemic insults, and in neuroinflammation after hemorrhagic injuries. Inhibiting endothelial, neuronal, astrocytic and oligodendroglial sulfonylurea receptor 1–transient receptor potential melastatin 4 (Sur1–Trpm4) channels and, in some cases, microglial K_ATP (Sur1–Kir6.2) channels, with glibenclamide is protective in a variety of contexts. Robust preclinical studies have shown that glibenclamide and other sulfonylurea agents reduce infarct volumes, edema and hemorrhagic conversion, and improve outcomes in rodent models of ischemic stroke. Retrospective studies suggest that diabetic patients on sulfonylurea drugs at stroke presentation fare better if they continue on drug. Additional laboratory investigations have implicated Sur1 in the pathophysiology of hemorrhagic CNS insults. In clinically relevant models of subarachnoid hemorrhage, glibenclamide reduces adverse neuroinflammatory and behavioral outcomes. Here, we provide an overview of the preclinical studies of glibenclamide therapy for CNS ischemia and hemorrhage, discuss the available data from clinical investigations, and conclude with promising preclinical results that suggest glibenclamide may be an effective therapeutic option for ischemic and hemorrhagic stroke.     

Infrared Evidence for the Existence of Nitrate Species on Cu-ZSM5 During Isothermal Rate Oscillations in the Decomposition of N2O

Isothermal oscillations in the rate of decomposition of N₂O were studied on an over-exchanged Cu-ZSM-5 catalyst by mass spectroscopy and in situ transient FTIR. Oscillations in the production of O₂ and N₂ were observed to occur in a temperature range of 410–490°C at a total pressure of 1.0 Torr pure N₂O. FTIR has provided the first spectroscopic evidence that surface nitrate species are present under oscillatory conditions. This study confirmed a previously proposed model that predicts a slow build-up of surface nitrates, followed by a rapid nitrate decomposition coupled with an increase in the rate of N₂O decomposition. The IR signature of the surface nitrates suggests they are monodentate nitrate species bound to Cu²⁺ ions. Temperature-programmed desorption studies reveal a strong correlation between the stability of the surface nitrate species and the temperature range in which oscillations occur.     

Refractive index retrievals for polystyrene latex spheres in the spectral range 220–420 nm

The recent development of an Aerosol Extinction Differential Optical Absorption Spectrometer (AE-DOAS) has allowed for the retrieval of wavelength dependent complex refractive indices for polystyrene latex spheres (PSL). The AE-DOAS is a white-type multi-pass gas cell coupled to a UV-Vis spectrometer. Refractive index values are retrieved for wavelengths between 220 and 420 nm by minimizing the χ² goodness-of-fit between measured extinction for five diameters of PSL and model Mie Theory predictions. Comparison to literature shows agreement at wavelengths >360 nm demonstrating the validity of this new instrumental approach while expanding the known refractive index range for PSLs further into the UV where it is previously unreported. In the studied wavelength range, coefficients for the general Cauchy dispersion relationship (A = 1.538(11); B = 0.0043(16) μm²; C = 0.00094(5) μm⁴) for PSLs were determined using the retrieved real portion of the refractive index and the wavelength in microns. In addition, this work indicates that the precision of retrieved values is impacted by the particle diameters chosen for the experiment where retrievals for shorter wavelengths of light benefit from the study of smaller sized particles.

Copyright © 2017 American Association for Aerosol Research