2016, Ahner, J., Micheel, M., Kötteritzsch, J., Dietzek, B., Hager, M.D.

In order to design a π-conjugated polymer film with tunable optical properties by thermally triggered activation of energy transfer after processing, two monodisperse phenylene ethynylene based oligomers with different optical properties were synthesized and attached to aliphatic polymers as π-conjugated side chains. Subsequently, the exchange of the side chain chromophores between the prepared donor and acceptor graft polymers in the solid state based on a reversible Diels–Alder reaction was studied in detail. The resulting donor–acceptor graft copolymer exhibits intra polymer energy transfer upon excitation of the donor moiety. The photophysical properties of the original and exchanged graft copolymers were investigated by means of absorption and emission spectroscopy. This novel concept opens the possibility for optical tuning of π-conjugated polymer films after processing as well as applications as thermally triggered sensor systems.

2016, Appiah, Clement, Siefermann, Katrin R., Jorewitz, Marcel, Barqawi, Haitham, Binder, Wolfgang H.

A novel and efficient strategy in obtaining series of mono- and bi-armed azobenzene-containing poly(ε-caprolactone)s is described, starting from a commercially available azobenzene dye via azide/alkyne-“click”-reactions. The attachment of alkyne-telechelic poly(ε-caprolactone)s (1 kDa and 3 kDa), followed by chromatographic separation, allowed the attachment of either one or two PCl-chains to either side of the azobenzene-dye. The resulting mono- and bi-armed photo-switchable polymers are fully characterized by 2D-NMR techniques and show a high thermal stability. Additionally liquid chromatography at critical conditions (LCCC) coupled to ESI-TOF allowed us to prove the presence of either one or two polymer chains affixed onto the central azobenzene dye.

2016, Ayub, Khurshid, Ludwig, Ralf

Theoretical mechanistic details for “on water” Wittig reaction of a stabilized ylide with benzaldehyde are presented and compared with a similar reaction under neat conditions. A gas hydrate structure consisting of 20 water molecules has been applied as a water surface for the reaction. The model is chosen to capture non-bonding interactions over a larger area in order to better account for the “on water” effect. The calculated acceleration for the cis-selective Wittig reaction is more than that for the trans-selective Wittig reaction. The “on water” acceleration for the Wittig reaction is due to greater number of non-bonding interactions in the transition state, compared to the starting material. The greater acceleration for the cis-selective Wittig over the trans-selective Wittig has been rationalized on the basis of non-bonding interactions in addition to hydrogen bonding. Besides accelerating the reaction, water also affects the pathway for the reaction. Decomposition of cisOP2 to alkene is estimated as a barrierless process. Moreover OP2 is more stable than OP1 for both cis and trans-selective Wittig reactions, opposite to what is observed for the neat reaction.

2016, Radu, A.I., Ussembayev, Y.Y., Jahn, M., Schubert, U.S., Weber, K., Cialla-May, D., Hoeppener, S., Heisterkamp, A., Popp, J.

Commercial HD DVDs provide a characteristic structure of encoding pits which were utilized to fabricate cost efficiently large area SERS substrates for chemical analysis. The study targets the simulation of the plasmonic structure of the substrates and presents an easily accessible fabrication process to obtain highly sensitive SERS active substrates. The theoretical simulation predicted the formation of supermodes under optimized illumination conditions, which were verified experimentally. First tests of the developed SERS substrates demonstrated their excellent potential for detecting vitamin A and pro-vitamin A at low concentration levels.

2014, Fleischer, Ivana, Pospech, Jola

A mild, regiospecific Brønsted acid-catalyzed hydroarylation of activated olefins, capable of the formation of quinone methide-like intermediates, has been investigated. Variously substituted 2- and 4-vinylphenols, 4-vinylaniline or 6-vinyl-naphthalen-2-ol were successfully implemented in a sequential protonation and Friedel–Crafts-type alkylation reaction of electron-rich arenes.

2017, Bergs, Christian, Brück, Lisa, Rosencrantz, Ruben R., Conrads, Georg, Elling, Lothar, Pich, Andrij

Oxygen is one of the most important substances for physiological reactions and metabolisms in biological systems. Through the tailored design of oxygen-releasing materials it might be possible to control different biological processes. In this work we synthesized for the first time zinc peroxide nanoparticles with controlled sizes and biofunctionalized surfaces using a one-step reaction procedure. The zinc peroxide nanoparticles were obtained with tunable sizes (between 4.0 ± 1.2 nm and 9.4 ± 5.2 nm) and were decorated with glucose 1-phosphate (Glc-1P). The specific interaction of the phosphate function of Glc-1P with the nanoparticle surface was monitored by solid state 31P-NMR and zeta-potential measurements. Furthermore, using fluorescence measurements we demonstrated that anchored glucose molecules on the nanoparticle surface are accessible for specific interactions with lectins. It could be shown that these interactions strongly depend on the amount of Glc-1P attached to the nanoparticle surface. Additionally it was demonstrated that the oxygen release from biofunctionalized zinc peroxide nanoparticles could be tuned according to the chemical composition of the nanoparticles and the pH of the aqueous solution. The antibacterial efficiency of the synthesized nanoparticles against Enterococcus faecalis, Aggregatibacter actinomycetemcomitans, Porphyromonas gingivalis and Prevotella intermedia was evaluated by determination of minimal bactericidal concentration (MIC).

2016, Nisa, Riffat Un, Mahmood, Tariq, Ludwig, Ralf, Ayub, Khurshid

The mechanism of the Zn(II) catalyzed oxidation of benzylic alcohol to benzaldehyde and ester by H2O2 oxidant was investigated through density functional theory methods and compared with the similar oxidation mechanisms of other late transition metals. Both inner sphere and intermediate sphere mechanisms have been analyzed in the presence and absence of pyridine-2-carboxylic acid (ligand). An intermediate sphere mechanism involving the transfer of hydrogen from alcohol to H2O2 was found to be preferred over the competitive inner sphere mechanism involving β-hydride elimination. Kinetic barriers associated with the intermediate sphere mechanism are consistent with the experimental observations, suggesting that the intermediate sphere mechanism is a plausible mechanism under these reaction conditions. The oxidation of alcohols to aldehydes (first step) is kinetically more demanding than the oxidation of hemiacetals to esters (second step). Changing the oxidant to tert-butyl hydrogen peroxide (TBHP) increases the activation barrier for the oxidation of alcohol to aldehyde by 0.4 kcal mol−1, but decreases the activation barrier by 3.24 kcal mol−1 for oxidation of hemiacetal to ester. Replacement of zinc bromide with zinc iodide causes the second step to be more demanding than the first step. Pyridine-2-carboxylic acid ligand remarkably decreases the activation barriers for the intermediate sphere pathway, whereas a less pronounced inverse effect is estimated for the inner sphere mechanism.

2015, Atchison, Jennifer S., Zeiger, Marco, Tolosa, Aura, Funke, Lena M., Jäckel, Nicolas, Presser, Volker

Electrospinning has emerged as a facile technology for the synthesis of ultrafine fibers and even nanofibers of various materials. While carbon nanofibers have been extensively investigated, there have also been studies reported on metal oxide and metal carbide fibers. Yet, comparative studies, especially following the same general synthesis approach, are lacking. In our comprehensive study, we use a sol gel process by which a carrier polymer (cellulose acetate or polyvinylpyrrolidone) is mixed with titanium butoxide, zirconium(IV) acetylacetonate, or niobium n-butoxide to yield nanotextured titania/carbon, zirconia/carbon, or niobia/carbon nonwoven textiles. Carbothermal reduction between 1300 °C and 1700 °C effectively transforms the metal oxide/carbon fibers to metal carbide/carbon nanocomposite while preserving the fiber integrity. As a beneficial effect, the fiber diameter decreases compared to the as-spun state and we obtained ultrafine fibers: 294 ± 108 nm for ZrC/C, 122 ± 28 nm for TiC/C, and 65 ± 36 nm for NbC/C. The highly disordered and porous nature of the carbon matrix engulfing the metal carbide nanocrystals enables a high specific surface area of up to 450 m2 g−1 (TiC/C) after carbothermal reduction.

2016, Davydova, Marina, de los Santos Pereira, Andres, Bruns, Michael, Kromka, Alexander, Ukraintsev, Egor, Hirtz, Michael, Rodriguez-Emmenegger, Cesar

The properties of nanocrystalline diamond (NCD) films offer great potential for the creation of various sensing and photonic devices. A great challenge in order to materialize such applications lies in achieving the micrometrically resolved functionalization of NCD surfaces. In the present work, we introduce a facile approach to meet this challenge employing the novel strain-promoted alkyne–azide cycloaddition “click” chemistry reaction, a catalyst-free ligation protocol compatible with biomolecules. The ability to achieve well-resolved multicomponent patterns with high reproducibility is demonstrated, paving the way for the fabrication of novel devices based on micropatterned NCD films.

2016, Neise, Christin, Rautenberg, Christine, Bentrup, Ursula, Beck, Martin, Ahrenberg, Mathias, Schick, Christoph, Keßler, Olaf, Kragl, Udo

Ionic liquids (ILs) as new media for synthesis and as functional fluids in technical applications are still of high interest. Cooling a steel component from an annealing temperature of nearly 850 °C down to room temperature in a liquid bath is a technically important process. The use of ionic liquids offers advantages avoiding film boiling of the quenching medium. However, such a high immersion temperature exceeds the thermal stability of the IL, for example such as [EMIm][NTf2]. To obtain information about formation of potential toxic decomposition products, potential fragments at varied states of decomposition of [EMIm][NTf2] were studied by various spectroscopic and gravimetric methods. For the first time it was possible to quantify fluorine-containing products via mass spectrometry coupled directly with thermogravimetric (TG) measurements. While chemical and spectroscopic analysis of thermally stressed ILs revealed no hints concerning changes of composition after quenching hot steel for several times, the mass-spectrometer (MS) coupled TG analysis gives information by comparing the decomposition behaviour of fresh and used ILs. A number of fragments were detected in low amounts confirming the proposed decomposition mechanism.