Two‐photon microfabrication of poly(ethylene glycol) diacrylate and a novel biodegradable photopolymer—comparison of processability for biomedical applications

Two‐photon polymerization (2PP) is a versatile microfabrication tool for biomedical applications as it provides unparalleled resolution for accurate three‐dimensional (3D) replication of biological microstructures. To widen the selection of biomaterials suitable for 2PP, this paper presents the processing of a methacrylated poly(ε‐caprolactone)‐based oligomer (PCL‐o) and a poly(ethylene glycol) diacrylate (PEGda) hydrogel into microstructures. PCL‐o is a novel biodegradable photopolymer that has not been previously processed with 2PP, and the fabrication of both polymers with an Nd:YAG laser is reported here for the first time. The overall 2PP processability and achievable resolution were studied by polymerizing arbitrary microstructures on glass substrates. The samples were characterized with scanning electron microscopy. Additionally, the effect of photoinitiator concentration on the resolution was investigated. Also, a preliminary cell attachment test was performed with UV cured films in order to investigate the impact of the used material–initiator combination on cell viability and migration. As a result, laser‐induced polymerization of both PCL‐o and PEGda was successfully demonstrated, and the Nd:YAG laser was proven adequate for the 2PP processing of the novel biodegradable photoresist. Resolution in the order of 1 µm was achieved with PCL‐o. With the easy processing of both PEGda and PCL‐o, these materials have great potential for different biomedical applications. Copyright © 2011 John Wiley & Sons, Ltd.     

MODELLING STRAIN-RATE-DEPENDENCY OF NATURAL SOFT CLAYS COMBINED WITH ANISOTROPY AND DESTRUCTURATION

The paper aims to investigate modelling the strain-rate-dependency of natural soft clays combined with anisotropy and destructuration using an elasto-viscoplastic model.The model is based on Perzyna’s overstress theory and the elastoplastic model S-CLAY1S.Tests at constant strain-rate and creep tests under both one-dimensional and triaxial conditions on several clays are simulated.Simulations highlight the loading scenarios in which it is necessary to account for anisotropy and/or destructuration in order to get accurate predictions.Comparisons between the predicted and measured results demonstrate that the proposed model can successfully reproduce the time-dependent behaviour of natural soft clays under different loading conditions.     

Integrating the original face images and “symmetrical faces” to perform face recognition

Using the original and ‘symmetrical face’ training samples to perform representation based face recognition was first proposed in [1]. It simultaneously used the original and ‘symmetrical face’ training samples to perform a two-step classification and achieved an outstanding classification result. However, in [1] the “symmetrical face” is devised only for one method. In this paper, we do some improvements on the basis of [1] and combine this “symmetrical faces” transformation with several representation based methods. We exploit all original training samples, left “symmetrical face” training samples and right “symmetrical face” training samples for classification and use the score fusion for ultimate face recognition. The symmetry of the face is first used to generate new samples, which is different from original face image but can really reflect some possible appearance of the face. It effectively overcomes the problem of non-sufficient training samples. The experimental results show that the proposed scheme can be used to improve a number of traditional representation based methods including those that are not presented in the paper.     

The effect of chemical and physical characteristics of spruce SEW pulps on enzymatic hydrolysis

Conifers, which are the most abundant biomass species in Nordic countries, USA, Canada and Russia, exhibit strong resistance towards depolymerization by cellulolytic enzymes. At present, it is still not possible to isolate a single structural feature which would govern the rate and degree of enzymatic hydrolysis. On the other hand, the forest residues alone represent an important potential for biochemical production of biofuels. In this study, the effect of substrate properties on the enzymatic hydrolysis of softwood was studied. Stem wood spruce chips were fractionated by SO₂–ethanol–water (SEW) treatment to produce pulps of varying composition by applying different operating conditions. The SEW technology efficiently fractionates different types of lignocellulosic biomass by rapidly dissolving hemicelluloses and lignin. Cellulose remains fully in the solid residue which is then treated by enzymes to release glucose. The differences in enzymatic digestibility of the spruce SEW pulp fibers were interpreted in terms of their chemical and physical characteristics. A strong correlation between the residual lignin content of SEW pulp and enzymatic digestibility was observed whereas cellulose degree of polymerization and hemicellulose content of pulp were not as important. For the pulps containing about 1.5 % (w/w) lignin, 90 % enzymatic digestibility was achieved at 10 FPU enzyme charge and 24 h of hydrolysis time.     

Quantitative detection of well-based DNA array using switchable lanthanide luminescence

In this report a novel wash-free method for multiplexed DNA detection is demonstrated employing target specific probe pairs and switchable lanthanide luminescence technology on a solid-phase array. Four oligonucleotide capture probes, conjugated at 3′ to non-luminescent lanthanide ion carrier chelate, were immobilized as a small array on the bottom of a microtiter plate well onto which a mix of corresponding detection probes, conjugated at 5′ to a light absorbing antenna ligand, were added. In the presence of complementary target nucleic acid both the spotted capture probe and the liquid-phase detection probe hybridize adjacently on the target. Consequently the two non-luminescent label molecules self-assemble and form a luminescent mixed lanthanide chelate complex. Lanthanide luminescence is thereafter measured without a wash step from the spots by scanning in time-resolved mode. The homogeneous solid-phase array-based method resulted in quantitative detection of synthetic target oligonucleotides with 0.32 nM and 0.60 nM detection limits in a single target and multiplexed assay, respectively, corresponding to 3× SD of the background. Also qualitative detection of PCR-amplified target from Escherichia coli is described.     

Trifluoromethanesulfonic acid as a catalyst for the formation of dansylhydrazone derivatives

Trifluoromethanesulfonic acid (TFMSA) is presented as a new, efficient catalyst in the pre-column fluorescent derivatization of the 3-ketosteroid budesonide with dansylhydrazine and compared to the commonly used catalyst trifluoroacetic acid. With TFMSA the derivatization reaction may be carried out at room temperature, with a considerably higher reaction rate compared to previously used acids. The chromatograms also show that TMFSA results in less formation of spurious peaks from the reagent. Derivatization of steroid solutions ranging from 0.5 to 64 μM could be performed using identical reaction conditions.     

Secondary nucleation and accessible surface in insulin amyloid fibril formation

At low pH insulin is highly prone to self-assembly into amyloid fibrils. The process has been proposed to be affected by the existence of secondary nucleation pathways, in which already formed fibrils are able to catalyze the formation of new fibrils. In this work, we studied the fibrillation process of human insulin in a wide range of protein concentrations. Thioflavin T fluorescence was used for its ability to selectively detect amyloid fibrils, by mechanisms that involve the interaction between the dye and the accessible surface of the fibrils. Our results show that the rate of fibrillation and the Thioflavin T fluorescence intensity saturate at high protein concentration and that, surprisingly, the two parameters are proportional to each other. Because Thioflavin T fluorescence is likely to depend on the accessible surface of the fibrils, we suggest that the overall fibrillation kinetics is mainly governed by the accessible surface, through secondary nucleation mechanisms. Moreover, a statistical study of the fibrillation kinetics suggests that the early stages of the process are affected by stochastic nucleation events.     

Kindergartners’ Spontaneous Focusing on Numerosity in Relation to Their Number-Related Utterances During Numerical Picture Book Reading

This study investigated the relationship between kindergartners’ Spontaneous Focusing on Numerosity (SFON) and their number-related utterances during numerical picture book reading. Forty-eight 4- to 5-year-olds were individually interviewed via a SFON Imitation Task and a numerical picture book reading activity. We expected differences in the frequency of number-related utterances during picture book reading between children with a higher SFON score, providing more number-related utterances, and children with a lower SFON score. Our results showed large inter-individual differences in both kindergartners’ SFON and the frequency of their number-related utterances during picture book reading, yet SFON was not related to the frequency of number-related utterances. This unexpected result is discussed in terms of its scientific, methodological, and educational implications.     

Coordination of pyridinethiols in gold(I) complexes

High-yield synthesis of gold(I) thionato complexes, bis(pyridine-2-thionato)gold(I) chloride (1) and bis(pyridine-4-thionato)gold(I) chloride (2), are described. According to their solid-state structures, a linear coordination of Au(I), equiplanar coordination of the ligands and two weak gamma-agostic interactions are found in both of these complexes despite of different relative positions of N and S atoms in the pyridinethionato ligands. Density functional theory calculations on 1 and 2 reproduce the observed X-ray structures. Even though the C-H...Au interactions of Au(I) and two pyridine moieties (2.83 and 2.88 A in 1 and 2.86 A in 2) are relatively weak, according to calculations they seem to provide further stabilization for the coordination and orientation of the ligands. In 1 the shortest Au...Au distances of 3.50 A indicate that aurophilic interactions, even though weak, are present in the solid state, whereas in 2 these interactions are absent.     

High actuation performance offered by simple diene rubbers

Dielectric elastomers are materials well known for their superior actuation behavior under applied electric field. The simplicity of material fabrication and clear working principle of dielectric elastomer actuators (DEAs) can offer various applications of dielectric elastomers. In this work, we have compared a number of different types of commercially available elastomers in terms of actuation performance. It was found that well‐known commercial rubbers like acrylonitrile‐butadiene rubbers (NBR) can offer higher actuation performance in DEAs than the frequently used dielectric elastomers, such as acrylic rubber and silicone. The acrylonitrile content of the NBR was found to play an important role in the dielectric and consequently actuation properties. More interestingly, we observed that addition of organic oil, such as dioctyl adipate, can greatly enhance the actuation performance. Copyright © 2016 John Wiley & Sons, Ltd.