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A water soluble fluorescent polymer as a dual colour sensor for temperature and a specific protein
(2013)
We present two thermoresponsive water soluble copolymers prepared via free radical statistical copolymerization of N-isopropylacrylamide (NIPAm) and of oligo(ethylene glycol) methacrylates (OEGMAs), respectively, with a solvatochromic 7-(diethylamino)-3-carboxy-coumarin (DEAC)- functionalized monomer. In aqueous solutions, the NIPAm-based copolymer exhibits characteristic changes in its fluorescence profile in response to a change in solution temperature as well as to the presence of a specific protein, namely an anti-DEAC antibody. This polymer emits only weakly at low temperatures, but exhibits a marked fluorescence enhancement accompanied by a change in its emission colour when heated above its cloud point. Such drastic changes in the fluorescence and absorbance spectra are observed also upon injection of the anti-DEAC antibody, attributed to the specific binding of the antibody to DEAC moieties. Importantly, protein binding occurs exclusively when the polymer is in the well hydrated state below the cloud point, enabling a temperature control on the molecular recognition event. On the other hand, heating of the polymer–antibody complexes releases a fraction of the bound antibody. In the presence of the DEAC-functionalized monomer in this mixture, the released antibody competitively binds to the monomer and the antibody-free chains of the polymer undergo a more effective collapse and inter-aggregation. In contrast, the emission properties of the OEGMA-based analogous copolymer are rather insensitive to the thermally induced phase transition or to antibody binding. These opposite behaviours underline the need for a carefully tailored molecular design of responsive polymers aimed at specific applications, such as biosensing.
Sugar-based molecules and polysaccharide biomass can be turned into porous functional carbonaceous products at comparably low temperatures of 400 °C under a nitrogen atmosphere in the presence of an ionic liquid (IL) or a poly(ionic liquid) (PIL). The IL and PIL act as “activation agents” with own structural contribution, and effectively promote the conversion and pore generation in the biomaterials even at a rather low doping ratio (7 wt%). In addition, this “induced carbonization” and pore forming phenomenon enables the preservation of the biotemplate shape to the highest extent and was employed to fabricate shaped porous carbonaceous materials from carbohydrate-based biotemplates, exemplified here with cellulose filter membranes, coffee filter paper and natural cotton. These carbonized hybrids exhibit comparably good mechanical properties, such as bendability of membranes or shape recovery of foams. Moreover, the nitrogen atoms incorporated in the final products from the IL/PIL precursors further improve the oxidation stability in the fire-retardant tests.
We have used polarized confocal Raman microspectroscopy and scanning near-field optical microscopy with a resolution of 60 nm to characterize photoinscribed grating structures of azobenzene doped polymer films on a glass support. Polarized Raman microscopy allowed determining the reorientation of the chromophores as a function of the grating phase and penetration depth of the inscribing laser in three dimensions. We found periodic patterns, which are not restricted to the surface alone, but appear also well below the surface in the bulk of the material. Near-field optical microscopy with nanoscale resolution revealed lateral two-dimensional optical contrast, which is not observable by atomic force and Raman microscopy.
Continuous synthesis of pyridocarbazoles and initial photophysical and bioprobe characterization
(2013)
Pyridocarbazoles when ligated to transition metals yield high affinity kinase inhibitors. While batch photocyclizations enable the synthesis of these heterocycles, the non-oxidative Mallory reaction only provides modest yields and difficult to purify mixtures. We demonstrate here that a flow-based Mallory cyclization provides superior results and enables observation of a clear isobestic point. The flow method allowed us to rapidly synthesize ten pyridocarbazoles and for the first time to document their interesting photophysical attributes. Preliminary characterization reveals that these molecules might be a new class of fluorescent bioprobe.
Calcium phosphate nanofibers with a diameter of only a few nanometers and a cotton-ball-like aggregate morphology have been reported several times in the literature. Although fiber formation seems reproducible in a variety of conditions, the crystal structure and chemical composition of the fibers have been elusive. Using scanning transmission electron microscopy, low dose electron (nano)diffraction, energy-dispersive X-ray spectroscopy, and energy-filtered transmission electron microscopy, we have assigned crystal structures and chemical compositions to the fibers. Moreover, we demonstrate that the mineralization process yields true polymer/calcium phosphate hybrid materials where the block copolymer template is closely associated with the calcium phosphate.
A polymer analogous reaction for the formation of imidazolium and NHC based porous polymer networks
(2013)
A polymer analogous reaction was carried out to generate a porous polymeric network with N-heterocyclic carbenes (NHC) in the polymer backbone. Using a stepwise approach, first a polyimine network is formed by polymerization of the tetrafunctional amine tetrakis(4-aminophenyl)methane. This polyimine network is converted in the second step into polyimidazolium chloride and finally to a polyNHC network. Furthermore a porous Cu(II)-coordinated polyNHC network can be generated. Supercritical drying generates polymer networks with high permanent surface areas and porosities which can be applied for different catalytic reactions. The catalytic properties were demonstrated for example in the activation of CO2 or in the deoxygenation of sulfoxides to the corresponding sulfides.
4-Phenol diazonium salts undergo Pd-catalyzed Heck reactions with various styrenes to 4’-hydroxy stilbenes. In almost all cases higher yields and fewer side products were observed, compared to the analogous 4-methoxy benzene diazonium salts. In contrast, the reaction fails completely with 2- and 3-phenol diazonium salts. For these substitution patterns the methoxy-substituted derivatives are superior.
Under standard conditions the cross metathesis of allyl alcohols and methyl acrylate is accompanied by the formation of ketones, resulting from uncontrolled and undesired double bond isomerization. By conducting the CM in the presence of phenol, the catalyst loading and the reaction time required for quantiative conversion can be reduced, and isomerization can be suppressed. On the other hand, consecutive isomerization can be deliberately promoted by evaporating excess methyl acrylate after completing cross metathesis and by adding a base or silane as chemical triggers.
We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4]2− moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium)tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4]2− anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g∥ and g⊥, could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.