A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions

A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X -band electron paramagnetic resonance spectroscopy

Molecular environment and reactivity in gels and colloidal solutions under identical conditions

A PEG-Tyr block copolymer forms a kinetically stable colloidal solution in water at room temperature which undergoes an irreversible conversion to a gel phase upon heating. A micellar solution and a gel can therefore be studied under identical experimental conditions. This made it possible to compare physical properties and chemical reactivity of micelles and gels in identical chemical environments and under identical conditions. EPR spectra of the spin-labelled copolymer showed that tyrosine mobility in gels was slightly reduced compared to micelles. Chemical reactivity was studied using photochemical degradation of tyrosine and tyrosine dimerization, in the absence and in the presence of an Fe(iii) salt. The reactivity trends were explained by reduced tyrosine mobility in the gel environment. The largest reactivity difference in gels and micelles was observed for bimolecular dityrosine formation which was also attributed to the reduction in molecular mobility

Magnetically-Triggered Release of Entrapped Bioactive Proteins from Thermally Responsive Polymer-Coated Iron Oxide Nanoparticles for Stem Cell Proliferation

Nanoparticles could conceal bioactive proteins during therapeutic delivery, avoiding side effects. Superparamagnetic iron oxide nanoparticles (SPIONs) coated with a temperature-sensitive polymer were tested for protein release. We show that coated SPIONs can entrap test proteins and release them in a temperature-controlled manner in a biological system. Magnetically heating SPIONs triggered protein release at bulk solution temperatures below polymer transition. The entrapped growth factor Wnt3a was inactive until magnetically-triggered release, upon which it could increase mesenchymal stem cell proliferation. Once chemically adjusting polymer transition above body temperature this system could be used for targeted cell stimulation in model animals and humans

Enhanced Mechanistic Understanding Through the Detection of Radical Intermediates in Organic Reactions

Two applications of a radical trap based on a homolytic substitution reaction (SH2') are presented for the trapping of short-lived radical intermediates in organic reactions. The first example is a photochemical cyanomethylation catalyzed by a Ru complex. Two intermediate radicals in the radical chain propagation have been trapped and detected using mass spectrometry (MS), along with the starting materials, products and catalyst degradation fragments. Although qualitative, these results helped to elucidate the reaction mechanism. In the second example, the trapping method was applied to study the radical initiation catalyzed by a triethylboronoxygen mixture. In this case, the concentration of trapped radicals was sufficiently high to enable their detection by nuclear magnetic resonance (NMR). Quantitative measurements made it possible to characterize the radical flux in the system under different reaction conditions (including variations of solvent, temperature and concentration) where modelling was complicated by chain reactions and heterogeneous mass transfer

Conductive gels based on modified agarose embedded with gold nanoparticles and their application as a conducting support for Shewanella oneidensis MR-1

Shewanella oneidensis is an electrogenic microbe which could be more widely applied in biosensing and fuel cell applications if better methods existed to promote electrode-biofilm formation. This paper reports a simple procedure that converts agarose, a cheap and readily available polymer, into a modified “MAgarose” material which will form biocompatible hydrogels that embed gold nanoparticles (AuNPs) along the fibers to yield a composite material with a conductivity ca. 80 times higher than an unmodified agarose-AuNP gel. Proof-of-concept bioelectrochemical experiments using Shewanella oneidensis show that when these MAgarose-AuNP gels are used to coat carbon veil there is a 10-fold increase in oxidative microbial current production when tested in a 3-electrode cell set-up. Microscopy results show that this can be attributed to the ability of the composite hydrogel to support MR-1 growth throughout the 3D matrix

Functional magnetic nanoparticles for protein delivery applications : understanding protein-nanoparticle interactions

Iron oxide nanoparticles (IONPs) surface functionalised with thermo-responsive polymers can encapsulate therapeutic proteins and release them upon heating with an alternating magnetic field above the lower critical solution temperature (LCST). In order to make this delivery system clinically-relevant, we prepared IONPs coated with poly-N-isopropylmethacrylamide (PNIPMAM), a polymer with LCST above human body temperature. The optimal polymer chain length and nanoparticle size to achieve LCST of ca. 45 °C were 19 kDa PNIPMAM and 16 nm IONPs. The PNIPMAM-coated IONPs could encapsulate a range of proteins which were released upon heating above LCST in the presence of a competitor protein or serum. A small amount of encapsulated protein leakage was observed below LCST. The efficiency of protein encapsulation and release was correlated with molecular weight and glycosylation state of the proteins. Magnetic heating resulted in a faster protein release as compared to conventional heating without significant temperature increase of the bulk solution

Reversible Photoreduction as a Trigger for Photoresponsive Gels

We present here a new type of photoresponsive, reversible low molecular weight gel. All previous examples rely on a photoisomerisation, ring-closing or dimerization. We show that photoreduction of a perylene bisimide gelator results in the formation of a stable radical anion. The formation of the radical anion results in a change in the packing of the perylene bisimides in the self-assembled aggregates, leading to a change in fibrous network and an increase in the rheological properties of the gels. An increase in the rheological properties is extremely rare for a photoresponsive gel; normally, irradiation results in a gel-to-sol transition, and the gel falling apart. As the radical anion decays, which takes several hours in air, the original gel properties are restored. This photoreduction can be cycled many times. Finally, we show that the mechanical properties are different between irradiated and nonirradiated sections in a patterned gel

A UV Sensitive Integrated Micromegas with Timepix Readout

This article presents a detector system consisting of three components, a CMOS imaging array, a gaseous-detector structure with a Micromegas layout and a UV-photon sensitive CsI reflective photocathode. All three elements have been monolithically integrated using simple post-processing steps. The Micromegas structure and the CMOS imaging chip are not impacted by the CsI deposition. The detector operated reliably in He/isobutane mixtures and attained charge gains with single photons up to a level of 6 \cdot 10^4. The Timepix CMOS array permitted high resolution imaging of single UV-photons. The system has an MTF50 of 0.4 lp/pixel which corresponds to app. 7 lp/mm.Comment: 4 pages with 8 figures. Submitted to Nucl. Instr. and Meth. A (Elsevier) for proceedings of VCI 2010

Photochemical Initiation and Reactions of Thiyl Radicals Studied with SH2’ Radical Traps

A radical trapping method based on an SH2’ homolytic substitution reaction was applied to study the mechanism of a photochemical spirocyclisation of indole-ynones in the presence of thiols. Starting material, products and a range of trapped radical intermediates were simultaneously detected in reaction mixtures by mass spectrometry (MS). The trapped intermediates included both initiating and main chain propagating radicals. These data made it possible to propose a self-initiation mechanism consistent with the originally postulated photoexcitation of an intramolecular electron donor-acceptor complex of the substrate. The effect of thiol structure on the MS peak intensity of the reaction components was rationalised in terms of the relative stability of the radical intermediates. The results were compared to a simpler related reaction, a photochemical thiol-ene addition where reagents, products and trapped intermediate radicals were also detected by MS. Relative MS peak intensities were again explained by a combination of electronic and steric effects on the stability of intermediate radicals. Overall, SH2’ radical trapping was demonstrated to be a powerful experimental technique for providing mechanistic evidence on photochemical and other organic radical reactions