Thermogravimetry and differential scanning calorimetry of natural and synthetic melanins

The thermal stability of natural melanins from bovine eyes, black human hair and the hard core of banana peel, synthetic melanins obtained enzymatically or by autoxidation of various precursors, and chemically modified synthetic melanins was studied by DSC and TG analysis. It was shown that the resistance of melanins to thermal degradation depends on their origin. Synthetic melanins were found to be more stable to thermal decomposition than natural melanins. Methylation of melanins caused a significant increase in thermal stability. The DSC curves of melanins reveal typical relaxation phenomena in the temperature range 293–413 K.

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Zusammenfassung Mittels DSC und TG wurde die thermische Stabilität von natürlichen Melaninen aus Rindsaugen, aus schwarzem menschlichen Haar und aus Hartteilen von Bananenschalen, weiterhin von enzymatisch oder durch Autoxidation aus verschiedenen Präkursoren synthetisierten Melaninen sowie von chemisch modifizierten synthetischen Melaninen untersucht. Es zeigte sich, daß die Beständigkeit von Melaninen gegenüber thermischem Abbau von ihrem Ursprung abhängt. Synthetische Melanine erwiesen sich in der thermischen Zersetzung als stabiler als Melanine natürlichen Ursprunges. Durch Methylierung wird eine eindeutige Steigerung der thermischen Stabilität verursacht. Im Temperaturbereich 293–413 K zeigen weisen die DSC-Kurven der Melanine typische Relaxationserscheinungen auf.

     

Facile synthesis of potassium tetrathiooxalate – The “true” monomer for the preparation of electron-conductive poly(nickel-ethylenetetrathiolate)

Herein, aiming at optimization of the polymerization process leading to a family of hole- and electron-conducting 1,1,2,2-ethenetetrathiolate-based polymers, such as poly(nickel-1,1,2,2-ethenetetrathiolate), poly[K_x(Ni-ett)], we investigated transformations of the monomer precursor 1,3,4,6-tetrathiapentalene-2,5-dione (TPD) occurring under polymerization conditions. We found that only one ring of TPD opens upon its reaction with potassium methoxide under inert conditions at room temperature which leads to the formation of potassium 2-oxo-1,3-dithiol-4,5-dithiolate (K₂[3]). Heating of K₂[3] under reflux in methanol solution under inert conditions opens the second ring, however the resulting product is not potassium ethenetetrathiolate (K₄[2]), the product of an exhaustive methanolysis of TPD, but potassium tetrathiooxalate (K₂[4]), the product of the decarbonylation of K₂[3]. Preliminary experiments reveal that the involvement of K₂[4] in the polymerization process is beneficial for reproducible formation of high quality 1,1,2,2-ethenetetrathiolate-based polymers suitable for thermoelectric applications.     

Supercontinuum generation in all-solid photonic crystal fiber with low index core

In this paper we report on the fabrication and characterization of an all-solid photonic band gap fiber with high contrast and low index core. The fiber cladding is composed of high index lead-silicate rods while borosilicate NC21 glass is used as a background glass. A 70 nm wide photonic band gap at 875 nm central wavelength is experimentally identified and compared with a numerical model. We also present a novel method for photonic band gap measurement using a femtosecond pulsed laser. The method is verified against standard one and discussed.     

Wettability conversion on the liquid flame spray generated superhydrophobic TiO2 nanoparticle coating on paper and board by photocatalytic decomposition of spontaneously accumulated carbonaceous overlayer

Titanium dioxide (TiO₂) is a photoactive material with various interesting and useful properties. One of those is the perfect wettability of TiO₂ surface after ultraviolet (UV) illumination. Wettability of a solid surface plays an important role in the field of printing, coating, and adhesion among others. Here we report on a superhydrophobic and photoactive liquid flame spray (LFS) generated TiO₂ nanoparticle coating that can be applied on web-like materials such as paper and board in one-step roll-to-roll process. The LFS TiO₂ nanoparticle coated paper and board were superhydrophobic instantly after the coating procedure because of spontaneously accumulated carbonaceous overlayer on TiO₂, and thus there was no need for any type of separate hydrophobization treatment. The highly photoactive LFS TiO₂ nanoparticle coating could be converted steplessly from superhydrophobic to superhydrophilic by UV-illumination, and the coating gave strong response to natural daylight illumination even in the shade. The superhydrophobic LFS TiO₂ coated surface can be used as an intelligent substrate, where photo-generated hydrophilic patterns guide the fluid setting and figure formation. Our study reveals that the wettability changes on the LFS TiO₂ surface were primarily caused by the photocatalytic removal of the carbonaceous material from TiO₂ during the UV-illumination and spontaneous accumulation of the carbonaceous material on the surface of the metal oxide during storage in the dark. The latter mechanism was found to be a temperature activated process which could be significantly speeded up by heat treatment. If other mechanisms such as surface oxidization, increment of hydroxyl groups, or charge separation played a role in the wetting phenomena on TiO₂, their effect was rather secondary as the removal and accumulation of the carbonaceous material dominated the wettability changes on the surface. Our study gives valuable information on the complex issue of photo-induced wettability changes on TiO₂.     

Switchable water absorption of paper via liquid flame spray nanoparticle coating

Surface wetting/anti-wetting and liquid absorption are relevant properties of many porous solids including paper and other cellulose-based materials. Here we demonstrate how surface wetting by water and water absorption of commercially available kraft paper can be altered by thin nanoparticle coatings fabricated by liquid flame spray in facile and continuous one-step process. Surface wettability and absorption properties of paper increased with silica and decreased with titania (TiO₂) nanoparticle coatings. Moreover, the water-repellent (superhydrophobic) TiO₂ nanoparticle coated paper could be switched to superhydrophilic and water absorbing by ultraviolet illumination. The experiments revealed that although surface wetting and liquid absorption of nanoparticle coated paper are strongly related to each other, they are two distinct phenomena which do not necessarily correlate. We propose wetting regimes on the nanoparticle coated paper samples on the basis of the experimental observations.     

On Formality of a Class of Compact Homogeneous Spaces

We prove the formality property of any homogeneous space G/G generated by an automorphism of finite order of a compact simple Lie group G.     

Development of thermally stable tellurite glasses designed for fabrication of microstructured optical fibers

We optimize the composition of tellurite glass for the manufacture of photonic crystal fibers with a large spectrum of transparency. The glasses, synthesized in four and five component (TeO₂-WO₃-Na₂O-Nb₂O₅ and TeO₂-WO₃-PbO-Na₂O-Nb₂O₅) oxide systems with variable contents of WO₃ (5-38 mol%) and PbO (0-18 mol%), are designed and manufactured, and the transmission properties of the obtained glasses for the spectral range of 200 nm-7 μm have been determined. Thermal expansion coefficients and glass characteristic temperatures are determined by the dilatometer and Leitz heat microscope methods. Differential Scanning Calorimetry (DSC) measurements as well as crystallization tests by isothermal heat treatment are used to measure the thermal stability of the glasses and their ability to crystallize. Diffractive X-ray (XRD) measurements are used to determine the crystalline phases of the glass samples and the glasses with the highest resistance to recrystallization during thermal treatment were selected and used for the manufacture of photonic crystal fibers.     

Characterization of a large core photonic crystal fiber made of lead–bismuth–gallium oxide glass for broadband infrared transmission

We report on characterization of a large solid core, photonic crystal fiber dedicated to broadband transmission range from visible to mid-infrared. We have fabricated a multi-mode photonic crystal fiber, made of a heavy metal-oxide glass based on the $\hbox {PbO}{-}\hbox {Bi}_{2}\hbox {O}_{3}{-}\hbox {Ga}_{2}\hbox {O}_{3}$ system, modified with $\hbox {SiO}_{2}$ and CdO, synthesized in-house, which shows good transmission up to $4.5\,\upmu \hbox {m}$ , as well as good rheological properties that permit multiple thermal processing steps without crystallization. The core of the fiber is created by replacement of central 60 tubes with solid rods. The photonic cladding is composed of 8 rings of air holes with a filling factor of 0.42. Simulation results shows that the fiber can be used for broadband transmission in the range of 430–3,000 nm. Calculated effective mode area of the fiber is $295\,\upmu \hbox {m}^{2}$ . We have measured attenuation of the fiber in the range 800–1,700 nm and its sensitivity to bending losses. Attenuation ranges from 1 to 4 dB/m in the considered range and bending losses are below 0.7 dB.     

A new model for the rationalization of the thermal behavior of carbonated apatites

A new model for the location and distribution of carbonate ions in carbonated apatite was used to assign the IR spectra of A- and AB-carbonated apatites. The percentage of total carbonate as measured by the mass loss in the TGA of these compounds is in good agreement with the percentage obtained by combustion analysis. The decomposition of pure A-type carbonate appears at temperatures of 985–1123 °C, whereas the decomposition of AB-type carbonated apatites occurs in the range of 600–800 °C. This difference is attributed to changes in the environment of channel carbonate brought about by B-type substitution of carbonate for phosphate. In the presence of sodium ions, the channel is changed by substitution of sodium for calcium in order to accommodate the difference between the charge of the carbonate and phosphate ions. A thermodynamic cycle is introduced to rationalize the differences in decomposition temperatures of A- and B-type carbonate. Preferential loss of B-type carbonate upon heating to 600 °C also suggests the migration of B-type carbonate to A-sites.