Facile fabrication of fast recyclable and multiple self‐healing epoxy materials through diels‐alder adduct cross‐linker

A reversibly cross‐linked epoxy resin with efficient reprocessing and intrinsic self‐healing was prepared from a diamine Diels‐Alder (DA) adduct cross‐linker and a commercial epoxy oligomer. The newly synthesized diamine cross‐linker, comprising a DA adduct of furan and maleimide moieties, can cure epoxy monomer/oligomer with thermal reversibility. The reversible transition between cross‐linked state and linear architecture endows the cured epoxy with rapid recyclability and repeated healability. The reversibly cross‐linked epoxy fundamentally behaves as typical thermosets at ambient conditions yet can be fast reprocessed at elevated temperature like thermoplastics. As a potential reversible adhesive, the epoxy polymer with adhesive strength values about 3 MPa showed full recovery after repeated fracture‐thermal healing processes. The methodology explored in this contribution provides new insights in modification of conventional engineering plastics as functional materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2094–2103     

Hydrophobically directed selective reduction of ketones using amine boranes

Amine boranes bearing hydrophobic substituents were used to reduce aryl ketones in competition with a methyl ketone. Their high stability in protic solvents combined with their ease of preparation made amine boranes useful compounds in the study of hydrophobically directed selective reductions. Several characteristics of the reducing agent were found to be important in determining the reaction selectivity, including available hydrocarbon surface area, degree of fluorination, and proximity of the hydrophobic group to the active hydrides.     

Amperometric Detection of Catechol and Catecholamines by Immobilized Laccase from DeniLite

DeniLite laccase immobilized Pt electrode was used for detection of catechol and catecholamines. The enzymatically oxidized substrates were measured amperometrically. The sensitivities are 210, 75, 60 and 45 nA/μM with the upper limits of linear ranges of 58, 40, 55 and 55 μM and the detection limits (S/N=3) of 0.07, 0.2, 0.3 and 0.4 μM for catechol, dopamine (DA), norepinephrine (NEPI) and epinephrine (EPI), respectively. The response time (t_90%) is about 2 seconds for each substrate and the long‐term stability is around 40–50 days with retaining 80% of initial activity. The very fast response and the remarkable long‐term stability are the principal advantages of this sensor. In case of catechol, the pH response of the sensor is mainly determined by enzyme's pH profile, however, in case of catecholamines, both enzyme's pH profile and reversibility of the substrate are operated and the optimal pHs for NEPI and EPI shift towards acidic range compared to that for DA. The presence of ascorbic acid (<50 μM) did not interfere with the measurement.     

Temperature effect on deposition rate of silicon nitride films

Temperature effects on deposition rate of silicon nitride films were characterized by building a neural network prediction model. The silicon nitride films were deposited by using a plasma enhanced chemical vapor deposition system and process parameter effects were systematically characterized by 2⁶⁻¹ fractional factorial experiment. The process parameters involved include a radio frequency power, pressure, temperature, SiH₄, N₂, and NH₃ flow rates. The prediction performance of generalized regression neural network was drastically improved by optimizing multi-valued training factors using a genetic algorithm. Several 3D plots were generated to investigate parameter effects at various temperatures. Predicted variations were experimentally validated. The temperature effect on the deposition rate was a complex function of parameters but N₂ flow rate. Larger decreases in the deposition rate with the temperature were only noticed at lower SiH₄ (or higher NH₃) flow rates. Typical effects of SiH₄ or NH₃ flow rate were only observed at higher or lower temperatures. A comparison with the refractive index model facilitated a selective choice of either SiH₄ or NH₃ for process optimization.     

Recycling in telomerization of butadiene with D‐xylose: Pd(TPPTS)n‐KF/Al2O3 as an active catalyst

A palladium‐TPPTS catalyst heterogenized on KF/alumina has been shown to be effective and recyclable for the selective formation of monooctadienylxylopyranosides via the telomerization of butadiene with D ‐xylose. Copyright © 2007 John Wiley & Sons, Ltd.     

UV curing of a novel resin derived from poly(ethylene terephthalate)

The synthesis and characterization of photopolymerizable unsaturated polyester resins based on PET waste are described. The resins came from a depolymerization process based on the glycolysis of PET by diethylene glycol (DEG). Different molecular weights of glycolysates were synthesized. Then, the latter was functionalized by a methyl hemiester of maleic acid to obtain unsatured α,ω‐bismaleate PET oligomers. In the presence of an electron donor monomer, such as triethylene glycol divinyl ether, these electron acceptor oligomers were copolymerized by way of charge‐transfer complexes under UV irradiation. The reaction was monitored in situ by real‐time IR spectroscopy to study the kinetics of photopolymerization. This one was studied in relation with the physical and chemical characteristics of oligoesters and the composition of mixtures containing divinyl ethers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1324–1335, 2007     

Phenol biosensor based on electrochemically controlled integration of tyrosinase in a redox polymer

An amperometric biosensor for the detection of phenolic compounds was developed based on the immobilization of tyrosinase within an Os-complex functionalized electrodeposition polymer. Integration of tyrosinase within the redox polymer assures efficient catechol recycling between the enzyme and the polymer bound redox sites. The non-manual immobilization procedure improves the reproducibility of fabrication process, greatly reduces the desorption of the enzyme from the immobilization layer, and, most importantly prevents fast inactivation of the enzyme by its substrate due to fast redox cycling. A two-layer sensor architecture was developed involving ascorbic acid oxidase entrapped within an electrodeposition polymer in a second layer on top of the redox polymer/tyrosinase layer. Using this sensor architecture it was possible to eliminate the current interference arising from direct ascorbate oxidation up to a concentration of 630 μM ascorbic acid. The effects of the polymer thickness, the enzyme/polymer ratio, and the applied potential were evaluated with respect to optimal sensor properties. The sensitivity of the optimized sensors for catechol was 6.1 nA μM⁻¹ with a detection limit of 10 nM, and for phenol 0.15 nA μM⁻¹ with a detection limit of 100 nM.     

Dendrimers and combinatorial chemistry—tools for fluorescent enhancement in protease assays

FRET based systems are some of the best methods available to detect and monitor proteolytic activity. To enhance fluorescent signals and hence assay sensitivity, two different systems were developed using two different dendrimeric constructs. In the first case, a triple branched dendrimer bearing three dansyl groups was used to enhance assay sensitivity and showed a significant enhancement of fluorescence following enzymatic cleavage. In another example, a tris-fluorescein probe, that undergoes self-quenching, was utilized in a combinatorial library synthesis to map the substrate specificity of proteases.     

Recycling Chiral Organocatalyst （4S）-Phenoxy-（S）-proline for Direct Asymmetric Aldol Reaction in Ionic Liquid （bmim）PF6

Room temperature ionic liquid (bmim)PF6 was evaluated for recycling an organocatalyst (4S)-phenoxy-(S)-proline for direct asymmetric aldol reactions. The desired aldol products were obtained with good yields up to 93.2% and enantioselectivities up to 88.5%, and isolation of the products by simple extraction allowed recycling the ionic liquid containing the immobilized catalyst in subsequent reactions without significant decrease of yields and enantioselectivities.