Advantages of block copolymer synthesis by RAFT-controlled dispersion polymerization in supercritical carbon dioxide

Reversible addition-fragmentation chain transfer (RAFT)-controlled block copolymer synthesis using dispersion polymerization in supercritical carbon dioxide (scCO2) shows unprecedented control over blocking efficiency. For PMMA-b-PBzMA and PMMA-b-PSt the blocking efficiency was quantified by measuring homopolymer contaminants using the techniques of GPC deconvolution, gradient polymer elution chromatography (GPEC), and GPC dual RI/UV detection. A new, promising method was also developed which combined GPC deconvolution and GPEC. All techniques showed that blocking efficiency was significantly improved by reducing the radical concentration and target molecular weight. Estimated values agreed well with (and occasionally exceeded) theory for PMMA-b-PBzMA. The heterogeneous process in scCO2 appeared to cause little or no further hindrance to the block copolymerization procedure when reaction conditions were optimized. High blocking efficiencies were achieved (up to 82%) even at high conversion of MMA (>95%) and high molecular weight. These data compare favorably to numerous published reports of heterogeneous syntheses of block copolymers

New fluorescent pH sensors based on covalently linkable PET rhodamines

Financial support from the Austrian Science Fund FWF (Project no. P 21192-N17) and from the Spanish Ministry of Education (Joint Project no. AT2009-0019) is gratefully acknowledged. The authors thank the Institute of Organic Chemistry, Graz University of Technology, particularly Jana Rentner, MSc for kind support in performing LC-MS. Furthermore, we thank Johann Pichler, Institute of Inorganic Chemistry, Graz University of Technology, for acquiring 19F-NMR spectra, as well as Sarah Schiller and Stefan Schobesberger.A new class of rhodamines for the application as indicator dyes in fluorescent pH sensors is presented. Their pH-sensitivity derives from photoinduced electron transfer between non-protonated amino groups and the excited chromophore which results in effective fluorescence quenching at increasing pH. The new indicator class carries a pentafluorophenyl group at the 9-position of the xanthene core where other rhodamines bear 2-carboxyphenyl substituents instead. The pentafluorophenyl group is used for covalent coupling to sensor matrices by “click” reaction with mercapto groups. Photophysical properties are similar to “classical” rhodamines carrying 2′-carboxy groups. pH sensors have been prepared with two different matrix materials, silica gel and poly(2-hydroxyethylmethacrylate). Both sensors show high luminescence brightness (absolute fluorescence quantum yield ΦF≈0.6) and high pH-sensitivity at pH 5–7 which makes them suitable for monitoring biotechnological samples. To underline practical applicability, a dually lifetime referenced sensor containing Cr(III)-doped Al2O3 as reference material is presented.Austrian Science Fund (FWF) P 21192-N17Spanish Government AT2009-001

Understanding the Role of omega-End Groups and Molecular Weight in the Interaction of PNIPAM with Gold Surfaces

Modification of nanoparticle surfaces by adsorption or grafting of polymers allows fine control of hybrid materials propertieds for diverse applications. To obtain such a control, it is of paramount importance to understand the impact of the polymer structure on the nature and strength of its interaction with teh nanoparticle. We investigated here a simple model of hybrid materials made of poly(N-isopropylacrylamide) of different molar masses and end groups interacting with gold surfaces. A series of poly(N-isopropylacrylamide) with number-average molar masses ranging from 3700 to 10000 g.mol(-1) were synthesized by reversible addition-fragmentation chain transfer/macromolecular design by interchange of xanthates (RAFT/MADIX): The terminal xanthate group was then reduced into either a thiol or a hydrogen group. Quartz crystal microbalance adsorption/desorption experiments demonstrated that the polymer termini have a strong impact on the mechanism of polymer adsorption on flat gold surface\u27s. These differences in polymer structure have, in return, a Strong influence on the colloidal stability and growth mechanism of nanoparticles directly synthesized in polymer solution. For those properties, the effect of xanthate group compared very favorably to the conventional thiol moiety. Interestingly, the properties of nanohybrids were, poorly affected by the molar mass of the polymer

Factors influencing the synthesis and the post-modification of PEGylated pentafluorophenyl acrylate containing copolymers

Copolymerization reactions involving oligoethylene glycol acrylate (OEGA) or diethylene glycol acrylate (DEGA) with pentafluorophenyl acrylate (PFPA) have been performed by reversible addition fragmentation transfer (RAFT) polymerization. The effect of the reaction conditions on the nucleophilic acyl substitution reactions of PFPA was studied using a model amine (furfuryl amine). The resulting PEG/PFP functional copolymers were then used as scaffolds to produce a library of polymers by reaction with a range of amines

Polymer-gold nanohybrids with potential use in bimodal MRI/CT: Enhancing the relaxometric properties of Gd(III) complexes

We present a new synthetic strategy to produce Gd(III)-decorated gold nanoparticles (AuNPs) for potential use as bimodal contrast agents (CA) for computed X-ray tomography (CT) and magnetic resonance imaging (MRI). The hybrid AuNPs exhibit high molar relaxivities (>12 000 mM−1 s−1 per particle), indicative of highly efficient CT/MRI CAs

Audiological and electrophysiological assessment of professional pop/rock musicians

In the present study, we evaluated peripheral and central auditory pathways in professional musicians (with and without hearing loss) compared to non-musicians. The goal was to verify if music exposure could affect auditory pathways as a whole. This is a prospective study that compared the results obtained between three groups (musicians with and without hearing loss and non-musicians). Thirty-two male individuals participated and they were assessed by: Immittance measurements, pure-tone air conduction thresholds at all frequencies from 0.25 to 20 kHz, Transient Evoked Otoacoustic Emissions, Auditory Brainstem Response (ABR), and Cognitive Potential. The musicians showed worse hearing thresholds in both conventional and high frequency audiometry when compared to the non-musicians; the mean amplitude of Transient Evoked Otoacoustic Emissions was smaller in the musicians group, but the mean latencies of Auditory Brainstem Response and Cognitive Potential were diminished in the musicians when compared to the non-musicians. Our findings suggest that the population of musicians is at risk for developing music-induced hearing loss. However, the electrophysiological evaluation showed that latency waves of ABR and P300 were diminished in musicians, which may suggest that the auditory training to which these musicians are exposed acts as a facilitator of the acoustic signal transmission to the cortex.FAPESP (The State of Sao Paulo Research Foundation)FAPESP (The State of Sao Paulo Research Foundation

Larval Zebrafish Lateral Line as a Model for Acoustic Trauma

Excessive noise exposure damages sensory hair cells, leading to permanent hearing loss. Zebrafish are a highly tractable model that have advanced our understanding of drug-induced hair cell death, yet no comparable model exists for noise exposure research. We demonstrate the utility of zebrafish as model to increase understanding of hair cell damage from acoustic trauma and develop protective therapies. We created an acoustic trauma system using underwater cavitation to stimulate lateral line hair cells. We found that acoustic stimulation resulted in exposure time- and intensity-dependent lateral line and saccular hair cell damage that is maximal at 48-72 h post-trauma. The number of TUNEL+ lateral line hair cells increased 72 h post-exposure, whereas no increase was observed in TUNEL+ supporting cells, demonstrating that acoustic stimulation causes hair cell-specific damage. Lateral line hair cells damaged by acoustic stimulation regenerate within 3 d, consistent with prior regeneration studies utilizing ototoxic drugs. Acoustic stimulation-induced hair cell damage is attenuated by pharmacological inhibition of protein synthesis or caspase activation, suggesting a requirement for translation and activation of apoptotic signaling cascades. Surviving hair cells exposed to acoustic stimulation showed signs of synaptopathy, consistent with mammalian studies. Finally, we demonstrate the feasibility of this platform to identify compounds that prevent acoustic trauma by screening a small redox library for protective compounds. Our data suggest that acoustic stimulation results in lateral line hair cell damage consistent with acoustic trauma research in mammals, providing a highly tractable model for high-throughput genetic and drug discovery studies

Advantages of Block Copolymer Synthesis by RAFT-Controlled Dispersion Polymerization in Supercritical Carbon Dioxide

Reversible addition–fragmentation chain transfer (RAFT)-controlled block copolymer synthesis using dispersion polymerization in supercritical carbon dioxide (scCO₂) shows unprecedented control over blocking efficiency. For PMMA<i>-<i>b</i>-</i>PBzMA and PMMA<i>-<i>b</i>-</i>PSt the blocking efficiency was quantified by measuring homopolymer contaminants using the techniques of GPC deconvolution, gradient polymer elution chromatography (GPEC), and GPC dual RI/UV detection. A new, promising method was also developed which combined GPC deconvolution and GPEC. All techniques showed that blocking efficiency was significantly improved by reducing the radical concentration and target molecular weight. Estimated values agreed well with (and occasionally exceeded) theory for PMMA<i>-<i>b</i>-</i>PBzMA. The heterogeneous process in scCO₂ appeared to cause little or no further hindrance to the block copolymerization procedure when reaction conditions were optimized. High blocking efficiencies were achieved (up to 82%) even at high conversion of MMA (>95%) and high molecular weight. These data compare favorably to numerous published reports of heterogeneous syntheses of block copolymers

One-Pot Synthesis of Block Copolymers in Supercritical Carbon Dioxide: A Simple Versatile Route to Nanostructured Microparticles

We present a one-pot synthesis for well-defined nanostructured polymeric microparticles formed from block copolymers that could easily be adapted to commercial scale. We have utilized reversible addition–fragmentation chain transfer (RAFT) polymerization to prepare block copolymers in a dispersion polymerization in supercritical carbon dioxide, an efficient process which uses no additional solvents and hence is environmentally acceptable. We demonstrate that a wide range of monomer types, including methacrylates, acrylamides, and styrenics, can be utilized leading to block copolymer materials that are amphiphilic (e.g., poly­(methyl methacrylate)-<i>b</i>-poly­(<i>N</i>,<i>N</i>-dimethylacrylamide)) and/or mechanically diverse (e.g., poly­(methyl methacrylate)-<i>b</i>-poly­(<i>N</i>,<i>N</i>-dimethylaminoethylmethacrylate)). Interrogation of the internal structure of the microparticles reveals an array of nanoscale morphologies, including multilayered, curved cylindrical, and spherical domains. Surprisingly, control can also be exerted by changing the chemical nature of the constituent blocks and it is clear that selective CO₂ sorption must strongly influence the block copolymer phase behavior, resulting in kinetically trapped morphologies that are different from those conventionally observed for block copolymer thin films formed in absence of CO₂