Electrochemical properties of two-component polymers of palladium and pyrrolidine and piperazine derivatives of C60

Redox-active films have been generated via electrochemical reduction in a solution containing palladium(II) acetate and [C₆₀]fullerene, or derivatives of C₆₀. The C₆₀ derivatives include piperazine (piperazine-C₆₀), pyrrolidine (CH₃-pyr-C₆₀), and a pyrrolidine salt, [(CH₃)₂-pyr-C₆₀]⁺ attached to the fullerene unit. In these films, fullerene moieties are covalently bonded to palladium atoms to form a polymeric network. The polymer yields involving the piperazine and pyrrolidine derivatives of C₆₀ are significantly lower than the yield of the C₆₀/Pd film. The CH₃-pyr-C₆₀/Pd and [(CH₃)₂-pyr-C₆₀]⁺/Pd films are electrochemically active in the negative potential region due to the reduction of the fullerene moiety. Reduction of the CH₃-pyr-C₆₀/Pd film is accompanied by the transport of supporting electrolyte cations from the solution into the film. In the first reduction step of the [(CH₃)₂-pyr-C₆₀]⁺/Pd film, both cations and anions of the supporting electrolyte are involved. The piperazine-C₆₀/Pd film exhibits electrochemical activity at both negative and positive potentials. In the negative potential region, reduction of the fullerene cage takes place. Oxidation of the piperazine moiety is responsible for the observed current in the positive potential range. Here, the oxidation process of this polymer is significantly influenced by the presence of metallic palladium particles in the film.     

Polynomial-Time Algorithms for Energy Games with Special Weight Structures

Energy games belong to a class of turn-based two-player infinite-duration games played on a weighted directed graph. It is one of the rare and intriguing combinatorial problems that lie in NP∩co-NP, but are not known to be in P. The existence of polynomial-time algorithms has been a major open problem for decades and apart from pseudopolynomial algorithms there is no algorithm that solves any non-trivial subclass in polynomial time. In this paper, we give several results based on the weight structures of the graph. First, we identify a notion of penalty and present a polynomial-time algorithm when the penalty is large. Our algorithm is the first polynomial-time algorithm on a large class of weighted graphs. It includes several worst-case instances on which previous algorithms, such as value iteration and random facet algorithms, require at least sub-exponential time. Our main technique is developing the first non-trivial approximation algorithm and showing how to convert it to an exact algorithm. Moreover, we show that in a practical case in verification where weights are clustered around a constant number of values, the energy game problem can be solved in polynomial time. We also show that the problem is still as hard as in general when the clique-width is bounded or the graph is strongly ergodic, suggesting that restricting the graph structure does not necessarily help.     

Contents List and Abstracts from the Journal of the Adhesion Society of Japan

FTIR reflection spectroscopy was used to characterize thin films of a cyanurate prepolymer on evaporated aluminium and on silicon single crystal wafers. Both substrates are covered by their native oxides. The optical function of the prepolymer is derived from ATR measurements. The measured thin film reflectance spectra have to be interpreted in comparison with the corresponding bulk spectra obtained by simulation. All samples re-produce the bulk composition. The cyanate groups of the prepolymer are not involved in specific intermolecular interactions or in preferential orientation. This is also found for the triazine rings on Si. On Al, however, a considerable excess of triazine rings are oriented parallel to the interface. The vibration frequencies of the triazine groupings that are perpendicular to the Al substrate show a red shift to some 2–8 c^?1. This special interaction effect does not occur on Si. Both the preferential orientation and the specific inter-molecular interaction act at least 100 nm into the prepolymer layer.     

Highly Enantioselective Production of (R)-Halohydrins with Whole Cells of Rhodotorula rubra KCh 82 Culture

Biotransformation of ten α-haloacetophenones in the growing culture of the strain Rhodotorula rubra KCh 82 has been carried out. Nine of the substrates underwent an effective enantioselective reduction to the respective (R)-alcohols according to Prelog’s rule, with the exception of 2-chloro-1,2-diphenylethan-1-one that was not transformed by this strain. The expected reduction proceeded without dehalogenation, leading to the respective (R)-halohydrins in high yields. The use of this biocatalyst yielded (R)-2-bromo-1-phenyl-ethan-1-ol (enantiomeric excess (ee) = 97%) and its derivatives: 4''-Bromo- (ee = 99%); 4''-Chloro- (ee > 99%); 4''-Methoxy- (ee = 96%); 3''-Methoxy- (ee = 93%); 2''-Methoxy- (ee = 98%). There were also obtained and characterized 2,4''-dichloro-, 2,2'',4''-trichloro- and 2-chloro-4''-fluoro-phenyetan-1-ol with >99% of enantiomeric excesses.     

Chitosan–silver nanocomposites: New functional biomaterial for health-care applications

Chitosan–silver nanocomposites (CS-HDA-AgNCs) was prepared using chitosan, biogenic silver nanocomposites, and crosslinker, hexamethylene 1,6-di(amino carboxysulfonate) (HDA). The film is flexible and transparent. Its physical, mechanical, thermal, hydrophilicity, and swelling properties were improved by HDA (2.5%). The antimicrobial activity of CS-HDA-AgNCs were not displayed any remarkable zone of inhibition but showed toxic effect in the presence of normal 3T3 fibroblasts and cancer HeLa cells. It decreases to ca. 5–7% for both cell lines. In conclusion, it can be mentioned that the CS-HDA-AgNCs, a kind of new functional biomaterial, could be useful for health-care applications.     

Strength of pure alumina ceramics above 1 GPa

Up to now, commercially available alumina ceramics were claimed to have strength between 400 and 550 MPa. However, our study shows strength ~ 2 times higher for commercially available alumina than commonly believed. The average and characteristic strength, measured on 31 pure alumina ceramic discs by ball on three balls (B3B) test, were 1205 ± 93 MPa and 1257 MPa, respectively, with a Weibull modulus of m = 11.8. Tested specimens were in form of discs with a diameter of 5 mm and thickness 0.5 mm. The grain size distribution of the alumina is bimodal with an average grain size of ~ 850 nm measured at the surface. The fracture reveals a mixed transgranular / intergranular failure mode. To avoid incorporation of additional flaws, the discs were tested as sintered. The characteristic flexural strength measured in B3B was recalculated according to Weibull theory for standard 4-point bending bars of size 3 × 4 × 45 mm as bend 856 MPa. The measured strength of nearly 900 MPa shows the potential of strength for high purity alumina ceramics.     

3D printing hybrid organometallic polymer‐based biomaterials via laser two‐photon polymerization

Materials with microscale structures are gaining increasing interest due to their range of technical and medical applications. Additive manufacturing approaches to such objects via laser two‐photon polymerization, also known as multiphoton fabrication, enable the creation of new materials with diverse and tunable properties. Here, we investigate the properties of 3D structures composed of organometallic polymers incorporating aluminium, titanium, vanadium and zirconium. The organometallic polymer‐based materials were analysed using a variety of techniques including SEM, energy‐dispersive X‐ray spectroscopy, X‐ray photoelectron spectroscopy analysis and contact angle measurements and their biocompatibility was tested in vitro. Cell viability and mode of death were determined by 3‐(4,5‐dimethyl‐2‐thiazolyl)‐2,5‐diphenyl‐2H‐tetrazolium bromide (MTT) assay and acridine orange/ethidium bromide staining. Polymers incorporating Al, Ti and Zr supported cell adhesion and proliferation, and showed low toxicity in vitro, whereas the organometallic polymer incorporating V was shown to be cytotoxic. Inductively coupled plasma optical emission spectrometry suggested that leaching of the V from the organometallic polymer is the likely cause of this. The preparation of the organometallic polymers is straightforward and both simple 2D and complex 3D structures can be fabricated with ease. Resolution tests of the newly developed organometallic polymer incorporating Al show that suspended lines with widths down to 200 nm can be fabricated. We believe that the materials described in this work show promising properties for the development of objects with sub‐micron features for biomedical applications (e.g. biosensors, drug delivery devices, tissue scaffolds etc.). © 2019 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.     

Associations between Oil Yield and Profile of Fatty Acids,Sterols, Squalene,Carotenoids, and Tocopherols in Seed Oil of Selected Japanese Quince Genotypes during Fruit Development

Tocopherols, phytosterols, carotenoids, and squalene are present in mature seeds of Japanese quince. Yet, little is known about the relationship between these compounds and oil yield during fruit and seed development. The profile change of lipophilic compounds during fruit and seed development in Japanese quince cultivars “Darius,” “Rondo,” and “Rasa” is investigated. It is shown here that during fruit and seed development, there is a significant reduction, three‐ to over tenfold, in the concentration of minor bioactive compounds in seed oil. It is recorded that delay between synthesis of tocopherols and oil in Japanese quince seeds during the fruit development results in a logarithmic relationship between the oil content and tocopherols concentration in the seed oil (R² = 0.980). Similar trends are observed between oil yield and phytosterols, and carotenoids (R² = 0.927 and R² = 0.959, respectively). The profile of fatty acids during the development of the seeds significantly is changed. The reduction of linoleic, palmitic, and gondoic acids levels and increment of oleic acid is noted. The oil content, profile of fatty acids, and concentration of bioactive compounds in all three genotypes of Japanese quince do not change significantly statistically during the last month of fruit development. Practical Applications: Some fruits are harvested at different degrees of maturity mainly due to a logistic issue and uneven ripening of fruits, which affects the chemical composition of whole fruit including seeds. Therefore, it would be good to know how the chemical composition is changing in plant material during development especially in the last month before harvest. Production of Japanese quince continues to rise year to year and with it the volume of generated by‐products such as seeds. This study demonstrates how it changes the oil content, profile of fatty acid, and concentration of tocopherols, squalene, phytosterols, and carotenoids in the seeds and seed oil of three Japanese quince cultivars “Rondo,” “Darius,” and “Rasa” during plant development. The provided information can be very useful for the manufactories oriented on the processing of by‐products, mainly seeds, generated by other branches of industry, for instance, fruit‐processing.