Fast and "green" living cationic ring opening polymerization of 2-ethyl-2-oxazoline in ionic liquids under microwave irradiation

The living cationic ring opening polymerization of 2-ethyl-2-oxazoline performed in an ionic liquid under microwave irradiation showed an enhanced polymerization rate in comparison to the reaction in common organic solvents; the ionic liquid was efficiently recovered and reused in new reaction cycles, completely avoiding the use of organic volatile compounds.     

The Effect of Hofmeister Salts on the LCST Transition of Poly(2‐oxazoline)s with Varying Hydrophilicity

The influence of Hofmeister salts was investigated on the cloud point of three poly(2‐oxazoline)s, namely poly(2‐ethyl‐2‐oxazoline) [PEtOx], poly(2‐n‐propyl‐2‐oxazoline) [PnPropOx], and poly(2‐isopropyl‐2‐oxazoline) [PiPropOx]. In addition, a comb polymer based on oligo‐2‐ethyl‐2‐oxazoline side chains and a methacrylate backbone (POEtOxMA) was included in this investigation. It was found that the ionic response of the poly(2‐oxazoline)s strongly depends on their hydrophilicity. The comb polymer POEtOxMA revealed a strikingly similar response to the salts as linear PEtOx even though the cloud points of the polymers in water differ. This indicates that the architecture does not significantly influence the effect of the Hofmeister ions, even though there is a difference in the absolute cloud point.

     

Multifunctional Poly(2‐oxazoline) Nanoparticles for Biological Applications

New multifunctional copoly(2‐oxazoline) nanoparticles were prepared for cell studies. The polymer contains double‐bond side chains as potential reaction sites for “thio”‐click reactions as well as a fluorescein label covalently bound to the polymer backbone. Using the nanoprecipitation technique, spherical nanoparticles of 200–800 nm were obtained. Confocal laser scanning microscopy measurements revealed the cellular uptake of the nanoparticles.

     

Solution prepolymerization as a new route for preparing aliphatic polyurethane prepolymers using high‐throughput experimentation

High‐throughput experimentation (HTE) represents a promising and versatile approach for polyurethane (PU) research as a tool to screen and characterize a large number of samples in an automated way. For the realization of a HTE workflow for PUs, the use of a Chemspeed Accelerator? SLT106 automated parallel synthesizer was explored. To evaluate the possibility of these techniques for PUs, we studied the synthesis of prepolymers from isophorone diisocyanate and polypropylene glycol in mass and solution. Several optimization steps, transfer to solution polymerization, and downscaling prepolymerizations have been carried out in a manual way before implementing them into the Chemspeed Accelerator?. As a next step, reproducibility investigations and kinetic studies were performed in an automated manner. All experiments were evaluated by characterization with gel permeation chromatography, MALDI–TOF mass spectrometry and ¹H NMR spectroscopy. These results provide a basis to use the HTE technique for screening different PU prepolymers in the future. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3729–3739, 2009     

Aqueous polymeric sensors based on temperature-induced polymer phase transitions and solvatochromic dyes

This feature article provides, for the first time, an overview of the research that guided the way from fundamental studies of the thermo-responsive phase separation of aqueous polymer solutions to polymeric sensor systems. The incorporation of solvatochromic dyes into thermoresponsive polymers as well as the concepts of polymeric sensors are presented and discussed in detail.     

Characterization of poly(2-oxazoline) homo- and copolymers by liquid chromatography at critical conditions

In this study liquid chromatography at critical conditions for poly(2-ethyl-2-oxazoline)s (PEtOx) has been performed for the first time in order to analyze functional PEtOx homopolymers and block copolymers. Besides the verification of the critical point of adsorption with two series of ester end group functionalized PEtOx homopolymers, to evaluate the effect of both the chain length dependence and the end group polarity, using a cyano column with a solvent combination of 2-propanol and water, also two-dimensional liquid chromatography (2D-LC) has been applied for a poly(2-oxazoline) block copolymer. The combined characterization techniques provided further information about the polymerization procedure with regard to the formation of side-products by separation of the block copolymer from the corresponding homopolymer impurities. In addition, hyphenation of LCCC with MALDI-TOF MS and ESI-Q-TOF tandem mass spectrometry verified the obtained results.     

Preparation of polyurethane elastomers (PUEs) in a high‐throughput workflow

High‐throughput experimentation (HTE) represents a promising and versatile approach for polyurethane (PU) research as a tool to rapidly screen and characterize a large number of samples in an automated way. To realize a unique HTE workflow for the research and development of PU elastomers (PUEs), the use of parallel automated formulation and coating platforms at Flamac were explored. To evaluate the applicability of HTE for PUEs, four different PU systems were investigated with different reactivities and viscosities. All prepared PUEs were evaluated by conventional physical testing methods measuring the E‐modulus, tensile‐elongation and the hardness properties revealing similar trends as conventionally prepared PUEs indicating the viability of the HTE approach. In addition, the properties of the PUEs were also investigated using downscaled microtensile bars as well as depth‐sensing indentation, again, revealing similar trends. With this proof of principle study, we demonstrated for the first time that HTE can also be extended to polymeric materials based on high reactive and viscous raw materials in combination with complex technologies. The reported results provide a basis for the use of HTE approaches for preparing, screening and characterizing large numbers of PUEs for R&D purposes. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Well‐Defined Thermoresponsive Polymethacrylamide Copolymers with Ester Pendent Groups through One‐Pot Statistical Postpolymerization Modification of Poly(2‐Isopropenyl‐2‐Oxazoline) with Multiple Carboxylic Acids

Thermoresponsive polymers that undergo a solubility phase transition in water are important as basis for the development for a wide variety of responsive and smart materials. In this study, the synthesis of thermoresponsive copolymers is demonstrated by the straightforward one‐pot statistical postpolymerization modification of well‐defined poly(2‐isopropenyl‐2‐oxazoline) (PiPOx) by ring‐opening reaction with multiple carboxylic acids. The reactions are carried out using dual, triple, and quadruple mixtures of up to four different aliphatic carboxylic acids. The cloud point temperatures of the resulting polymethacrylamide copolymers with ester pendent groups can be finely tuned by adjusting the feed ratio and the hydrophilic–hydrophobic balance of the acids that are used for the ring‐opening modification of PiPOx. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 360–366     

Polychlorinated dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxins,dibenzofurans and biphenyls in fish from the Netherlands: concentrations,profiles and comparison with DR CALUX® bioassay results

A liquid chromatography–particle-beam mass spectrometer (LC–PB/MS) with interchangeable electron-impact (EI) and glow-discharge (GD) ion sources was evaluated for future application in analysis of botanical extracts. In this work a green tea tincture was characterized for a series of catechin components (catechin, epicatechin, epigallocatechin, and epigallocatechin gallate (EGCG)) and caffeine. Special emphasis was given to EGCG and caffeine, because they are important in determining the possible health effects of the green tea. The effects of instrument operating conditions were evaluated for the EI and GD ionization sources to determine their effect on analyte intensities and fragmentation patterns. These studies furnished information about the effects of these conditions in determining possible ionization pathways in the two ion sources. The mass spectra of these compounds obtained with the GD ion source are EI-like in appearance, with clearly identified molecular ions and fragmentation patterns that are easily rationalized. The absolute limits of detection for EGCG and caffeine were, respectively, 11 ng and 0.77 ng for the EI source and 3.2 ng and 0.61 ng for the GD source. The PB/EIMS and PB/GDMS combinations can be operated in a flow-injection mode, wherein the analyte is injected directly into the mobile phase, or coupled to high-performance liquid chromatography (HPLC), enabling LC–MS analysis of complex mixtures. A reversed-phase chromatographic separation of the green tea tincture was performed on a commercial C₁₈ column using a gradient of water (containing 0.1% TFA) and ACN. Quantification of EGCG and caffeine was performed by the standard addition method. The amounts of EGCG and caffeine in the tested green tea tincture were each ∼14 mg mL⁻¹.