Functionalization of poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) films via surface‐initiated atom transfer radical polymerization: Comparison with the conventional free‐radical grafting procedure

We modified hydrophobic poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBHV) films with hydrophilic chains to control their surface properties. We designed and investigated surface‐initiated atom transfer radical polymerization (SI‐ATRP) to modify the PHBHV films by grafting poly(2‐hydroxyethyl methacrylate) (PHEMA) from the surface. This method consisted of two steps. In the first step, amino functions were formed on the surface by aminolysis; this was followed by the immobilization of an atom transfer radical polymerization initiator, 2‐bromoisobutyryl bromide. In the second step, the PHEMA chains were grafted to the substrate by a polymerization process initiated by the surface‐bound initiator. The SI‐ATRP technique was expected to favor a polymerization process with a controlled manner. The experimental results demonstrate that the grafting density was controlled by the reaction conditions in the first step. The grafted films were analyzed by Fourier transform infrared spectroscopy, contact angle testing, scanning electron microscopy, and energy‐dispersive X‐ray spectroscopy. The results show that grafted chains under the SI‐ATRP method were preferentially located on the surface for surface grafting and in the bulk for conventional free‐radical polymerization initiated by benzoyl peroxide. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The Omnipresence of DYRK1A in Human Diseases

The increasing population will challenge healthcare, particularly because the worldwide population has never been older. Therapeutic solutions to age-related disease will be increasingly critical. Kinases are key regulators of human health and represent promising therapeutic targets for novel drug candidates. The dual-specificity tyrosine-regulated kinase (DYRKs) family is of particular interest and, among them, DYRK1A has been implicated ubiquitously in varied human diseases. Herein, we focus on the characteristics of DYRK1A, its regulation and functional role in different human diseases, which leads us to an overview of future research on this protein of promising therapeutic potential.     

Semi-automated sample preparation for plasma proteomics

The discovery of new biomarkers will be an essential step to enhance our ability to better diagnose and treat human disease. The proteomics research community has recently increased its use of human blood (plasma/serum) as a sample source for these discoveries. However, while blood is fairly non-invasive and readily available as a specimen, it is not easily analyzed by liquid chromatography (LC)/mass spectrometry (MS), because of its complexity. Therefore, sample preparation is a crucial step prior to the analysis of blood. This sample preparation must also be standardized in order to gain the most information from these valuable samples and to ensure reproducibility. We have designed a semi-automated and highly parallel procedure for the preparation of human plasma samples. Our process takes the samples through eight successive steps before analysis by LC/MS: (1) receipt, (2) reformatting, (3) filtration, (4) depletion, (5) concentration determination and normalization, (6) digestion, (7) extraction, and (8) randomization, triplication, and lyophilization. These steps utilize a number of different liquid handlers and liquid chromatography (LC) systems. This process enhances our ability to discover new biomarkers from human plasma.     

Effectiveness of Portable Indoor Air Cleaners: Sensory Testing Results

The objective of this study was to test the effectiveness of individual commercially available portable indoor air cleaning units in removing dust particulates, tobacco smoke particulate and vapor phase constituents (nicotine and vinyl pyridine), viable and total fungal spores, pollen, and gaseous contaminants (carbon monoxide[CO], nitrogen dioxide[NO²], and formaldehyde[HCHO]), in a clean air test chamber. The air cleaner chamber results presented here represent initial-use results. In general, High Efficiency Particulate Air (HEPA) and electrostatic precipitator systems demonstrated the highest efficiencies with respect to particulate, contaminants, followed closely by electret filter systems. Ionizers and ozone generators were least effective in particulate removal. Systems which included sufficient sorbent material (i.e. activated carbon or potassium permanganate) were marginally effective at gaseous contaminant removal. None of the systems tested were effective at carbon monoxide removal. Sensory testing was conducted to discern potential correlation between human perceptive response and measured air cleaner performance (with respect to tobacco smoke removal). An electret filter (EF) loaded with carbon sorbent received the best ratings with respect to odor strength, nasal irritation, eye irritation, and overall air acceptability.     

Amperometric ATP microbiosensors for the analysis of chemosensitivity at rat carotid bodies

The physiological application of amperometric adenosine triphosphate (ATP) microbiosensors for characterizing the stimulus-response at rat carotid bodies superfused with high potassium concentrations, during normoxic hypercapnia, and during hypoxia is demonstrated using the peripheral arterial chemoreceptors in the carotid body of rats as a model system. Amperometric microbiosensors based on glucose oxidase (GOD) and hexokinase (HEX) immobilized within a polymer matrix at the surface of Pt disk microelectrodes (diameter: 25 microm) are positioned at a distance of approximately 100 microm above the carotid body surface for detecting extracellular ATP. A linear calibration function of ATP microbiosensors in the physiologically relevant concentration range of 0-40 microM ATP enables quantitative detection of ATP released at the carotid body surface in response to physiological stimuli. It is shown that these stimuli induce extracellular ATP release from the carotid body at levels of 4-10 microM. Other electroactive neurotransmitters such as, e.g., catecholamines are coreleased by the carotid body at hypercapnic, hypoxic and high-potassium stimulus, are simultaneously detected utilizing a dual-electrode assembly with an ATP microbiosensor and a second bare channel providing a colocalized reference measurement for ATP quantification.     

High glass transition temperature bio-based copolyesters from poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and isosorbide

New renewable copolymers were prepared from reactive bis-hydroxylated poly(3-hydroxybutyrate-co-3-hydroxyvalerate) oligomers (PHBHV-diol), isosorbide and 1,4-phenylene diisocyanate. First, microwave (MW)-assisted alcoholysis in the presence of ethylene glycol provides a rapid and straightforward method for engineering PHBHV-diol, with molar masses ranging from 700 to 4100 g mol^?1. These well-defined oligoesters were further used for the preparation of random copolymers of PHBHV-diol and isosorbide bridged with 1,4-phenylene diisocyanate via urethanization. The molar masses (M_n) of most copolyesters are about 10,000 g mol^?1 with polydispersities (DPI) in the range of 1.2–1.9. The dependence of the solid-state structures on the length of PHBHV block was carefully investigated. The incorporation of isosorbide units into the PHBHV backbone increased the glass-transition temperatures from +5 °C up to +34 °C.     

Development of a new azido-oxazoline monomer for the preparation of amphiphilic graft copolymers by combination of cationic ring-opening polymerization and click chemistry

A new monomer (2-(5-azidopentyl)-2-oxazoline) bearing an azido group was synthesized. The cationic ring-opening copolymerization of this monomer with 2-methyl-2-oxazoline resulted in a well-defined linear polymer backbone with pendant azido groups. Alkynyl-poly(d,l-lactide) was grafted onto the azido groups of poly(oxazoline) via a Huisgen 1,3-dipolar cycloaddition reaction to give a novel amphiphilic graft copolymer [poly(2-methyl-2-oxazoline-co-2-pentyl-2-oxazoline)-g-poly(d,l-lactide)] (P[(MeOx-co-PentOx)-g-LA]). Different graft copolymers were prepared with PLA of different lengths. Preliminary results of the self-association of this copolymer in water indicated the formation of nanoparticles, which suggests this copolymer may have applications as vehicles for drug delivery.     

Identification of xanthones as selective killers of cancer cells overexpressing the ABC transporter MRP1

Multidrug‐resistance protein 1 (MRP1) belongs to the ATP‐binding cassette (ABC) transporter family. MRP1 mediates MDR (multidrug resistance) by causing drug efflux either by conjugation to glutathione (GSH) or by co‐transport with free GSH (without covalent bonding between the drug and GSH). We recently reported that the calcium channel blocker verapamil can activate massive GSH efflux in MRP1‐overexpressing cells, leading to cell death through apoptosis. However, clinical use of verapamil is hampered by its cardiotoxicity. Then, in the search for compounds that act similarly to verapamil, but without major side effects, we investigated xanthones. Herein we show that xanthones induce apoptosis among resistant cells overexpressing MRP1 similarly to the verapamil effect. Among the xanthones studied, 1,3‐dihydroxy‐6‐methoxyxanthone was identified as the most active derivative, able to specifically kill cells transfected with human MRP1 with even greater potency than verapamil. Under the same conditions, the active xanthones have no toxic effect on control (sensitive) cells. Xanthones could therefore be considered as new potential anticancer agents for the selective treatment of MRP1‐positive tumors.     

Designing exopolysaccharide-graft-poly(3-hydroxyalkanoate) copolymers for electrospun scaffolds

Poly(3-hydroxyalkanoate)s PHAs have been demonstrated to be a family of biopolyester with good biodegradability and biocompatibility. A glycosaminoglycan-like marine exopolysaccharide EPS HE800 was here incorporated to enhance cell adhesion. Novel graft copolymer HE800-g-PHA were prepared to improve the compatibility between hydrophobic PHA and hydrophilic HE800. The carboxylic end groups of PHA oligomers were activated with acyl chloride functions, allowing coupling to hydroxyl groups of HE800. Fibrous scaffolds were prepared by a modified electrospinning system which combined simultaneously PHA electrospinning and HE800-g-PHA copolymer electrospraying. Adhesion and growth of human mesenchymal stem cells on the HE800-g-PHA scaffolds showed a notable improvement over those on PHAs matrices.     

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