Studies of photooxidative degradation of poly(vinyl chloride)/poly(ethylene oxide) blends

The photooxidative degradation of blends (in a full range of compositions) of amorphous poly(vinyl chloride) (PVC) with semicrystalline poly(ethylene oxide) (PEO) in the form of thin films is investigated using absorption spectroscopy (UV–visible and Fourier transform infrared) and atomic force microscopy (AFM). The amount of insoluble gel formed as a result of photocrosslinking is estimated gravimetrically. It is found that the PVC/PEO blendsí susceptibility to photooxidative degradation differs from that pure of the components and depends on the blend composition and morphology. Photoreactions such as degradation and oxidation are accelerated whereas dehydrochlorination is retarded in blends. The photocrosslinking efficiency in PVC/PEO blends is higher than in PVC; moreover, PEO is also involved in this process. AFM images showing the lamellar structure of semicrystalline PEO in the blend lead to the conclusion that the presence of PVC does not disturb the crystallization process of PEO. The changes induced by UV irradiation allow the observation of more of the distinct PEO crystallites. This is probably caused by recrystallization of short, more mobile chains in degraded PEO or by partial removal of the less stable amorphous phase from the film surface. These results confirm previous information on the miscibility of PVC with PEO. The mechanism of the interactions between the components and the blend photodegradation are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 585–602, 2004     

Two-Color Two-Photon Excitation of Fluorescence

Abstract— We report the observation of two-photon excitation of an organic fluorophore with two different wavelengths, a phenomenon we refer to as two-color two-photon (2C2P) excitation. Ultraviolet emission of p -Merphenyl at 340 nm was observed when the sample was illuminated with both 375 and 750 nm pulses from a picosecond dye laser. The emission of p -terphenyl was about 100-fold and more than 1000-fold less for illumination at only 375 or 750 nm, respectively. Observation of the 2C2P signal required temporal and spatial overlap of the 375 and 750 nm pulses. The amplitude of the signal depended on the polarization of each beam. 2C2P excitation can have applications in fluorescence microscopy and elsewhere when spatially localized excitation is desirable.     

Spectrophotometric determination of Fe(II) in milligram solid samples

The analytical procedure of determination of Fe(II) in the presence of Fe(III) in milligram samples is proposed. A solid sample is dissolved in hydrochloric acid in argon atmosphere. Subsequently, the pH-value of the solution is fixed and Fe(III) complexed by phosphoric buffer. At the next step Fe(II) is oxidized by -molybdosilicic acid. Finally, the intensity of colouring caused by the reduced form of the acid is measured at the wavelength 770 nm. The proper treatment of the sample during oxidation, and immediately before, is decisive for the accuracy of the analysis. The method was verified by means of the analysis of synthetic magnetite. The theoretical content of Fe(II) was 24.12%, the determined one was 24.02 ± 0.10%. The method was applied to the determination of the homogeneity of an iron catalyst for ammonia synthesis.     

Analysis of data transmission technique based on pulsed laser

Pulsed lasers are used mainly in lidar systems as sources of short and highly energetic light pulses. In data transmission systems continuous wave lasers are typically applied, however it is also possible to use pulsed lasers in such systems. Such approach seems to be especially reasonable for devices where a pulsed laser is applied anyway and executes another function (rangefinding). The article discusses a data transmission concept based on a pulsed laser technology. Advantages and limits of such a transmission method are described. Influence of individual transmission elements on the effective data transmission speed is analysed.     

ELEMENTAL SULFUR REACTIONS WITH 2-PICOLINE

Abstract

A study of the reaction of the elemental sulfur with 2-picoline is reported. The process was carried out at the boiling point of the 2-picoline under argon. After removing unreacted solids, the reaction products were identified by means of LC. GC and GC-MS. The following products have been identified by mass spectrometry: 1,2-di/2-pyridyl/-ethane. 1,2-di/2-pyridyl/-ethene. 2-methyl-x-[/2-pyridyl/methyl]pyridines, 2-mercapto-methyl-[x/2-pyridyl/methyl]-pyridines, l-mercapto-1,2-di/2-pyridyl/-ethane, 5,6-di/2-pyridyl/-5H-cyclopenta-[b]pyridine, 5,6-di/2-pyridyl/-7H-cyclopenta[b]pyridine, 1,2,3-tri/2-pyridyl/-propane. 1,2-di/2-pyridyl/-1-[x-/2-methyl/-pyridyl]-ethane, 5,6-di/2-pyridyl/-7-[/2-pyridyl/methyl]-7H-cyclopenta[b]pyridine, 5,6-di/2-pyridyl/-5-[/2-pyridyl/-methyl]-5H-cyclopenta-[b]pyridine. Di{7-[5,6-di/2-pyridyl/-7H-cyclopenta[b]pyridyl]} sulfide and di(7-[5,6-di/2-pyridyl/-7H-cyclopentalblpyridyl]} disulfide.     

Elimination of autofluorescence background from fluorescence tissue images by use of time-gated detection and the AzaDiOxaTriAngulenium (ADOTA) fluorophore

Sample autofluorescence (fluorescence of inherent components of tissue and fixative-induced fluorescence) is a significant problem in direct imaging of molecular processes in biological samples. A large variety of naturally occurring fluorescent components in tissue results in broad emission that overlaps the emission of typical fluorescent dyes used for tissue labeling. In addition, autofluorescence is characterized by complex fluorescence intensity decay composed of multiple components whose lifetimes range from sub-nanoseconds to a few nanoseconds. For these reasons, the real fluorescence signal of the probe is difficult to separate from the unwanted autofluorescence. Here we present a method for reducing the autofluorescence problem by utilizing an azadioxatriangulenium (ADOTA) dye with a fluorescence lifetime of approximately 15 ns, much longer than those of most of the components of autofluorescence. A probe with such a long lifetime enables us to use time-gated intensity imaging to separate the signal of the targeting dye from the autofluorescence. We have shown experimentally that by discarding photons detected within the first 20 ns of the excitation pulse, the signal-to-background ratio is improved fivefold. This time-gating eliminates over 96 % of autofluorescence. Analysis using a variable time-gate may enable quantitative determination of the bound probe without the contributions from the background.     

STM/STS investigation of carbon nanotube junctions

In this paper we present scanning tunneling microscopy/spectroscopy investigations of multiwall carbon nanotube junctions. We concentrated on bent and narrowing junctions, which my be formed by introducing pentagon–heptagon defects into a hexagonal network of a carbon nanotube. It was expected that the defects introduced to the nanotube could cause changes in the local density of states. The scanning tunneling spectroscopy results were used to search for and identify these defects. We also discuss a hypothesis for a combination of a telescope junction and a pentagon–heptagon induced junction. PACS 68.37.Ef; 73.22.–f; 61.46.Fg; 71.20.Tx     

Room and high-temperature scanning tunnelling microscopy and spectroscopy (HT-STM/STS) investigations of surface nanomodifications created on the TiO2(1 1 0) surface

High-temperature scanning tunnelling microscopy, scanning tunnelling spectroscopy and current imaging tunnelling spectroscopy (HT-STM/STS/CITS) were used to study the topographic and electronic structures changes due to surface modifications of the TiO₂(1 1 0) surface caused by the STM tip. In situ high-temperature STM results showed that the created modifications were stable even at elevated temperatures. The STS/CITS results showed the presence of energy gap below the Fermi level on the untreated regions. The disappearance of energy gap below the Fermi level on the modifications created by the tip was observed. It is assumed that the presence of the tip can change the chemical stoichiometry of the surface from TiO_2−x towards Ti₂O₃.     

Magnetic properties of UT2Si2 and UT2Ge2 (T = Co,Ni, Cu) intermetallic systems

Neutron diffraction and magnetization measurements indicate that, at low temperatures, long-range magnetic order is present in UCO₂Si₂, UNi₂Si₂, UCu₂Si₂, UNi₂Ge₂, and UCo₂Ge₂. UCo₂Si₂ and UNi₂Ge₂ are simple collinear antiferromagnets of +-+- type, UCu₂Si₂ a simple collinear ferromagnet. In UNi₂Si₂, a magnetic phase transition from a LSW type structure to collinear antiferromagnetism of +-+- type was found, while in UCu₂Ge₂, the antiferromagnetic structure of ++-- transforms into collinear ferromagnetism. Crystal structure and magnetic parameters are given. No magnetic moment on transition metal ions was found within the accuracy of a powder neutron diffraction experiment. The stability of particular magnetic ordering schemes is discussed in terms of an isotropic RKKY mechanism.