Synthesis and properties of new functionalized guanidinium based ionic liquids as non-toxic versatile organic materials

Functionalized guanidinium ionic liquids as a new class of versatile organic materials have been developed. Guanidinium salts containing olefinic functionalities have been prepared and completely characterized. In order to illustrate the versatility of olefinic units, they were brominated and some bromine-containing ionic liquids have been obtained. Relevant physico-chemical properties of the new synthesized salts were evaluated including their melting points, glass transition temperatures, miscibilities, densities, surface tensions and contact angles with glass and Teflon surfaces. Additionally toxicity studies were performed using the human colon carcinoma CaCo-2 cell line. Several new functionalized guanidinium based ILs showed high densities, low contact angles with Teflon, low surface tensions as well as a non-toxic behaviour.     

High-temperature electrical properties of magnesiowustite Mg1 − xFexO and spinel Fe3 − x − yMgxCryO4 ceramics

Phase relationships, thermal expansion and electrical properties of Mg_1 − xFe_xO (x = 0.1-0.45) cubic solid solutions and Fe_{3 − x − y}Mg_xCr_yO_4 ± δ (x = 0.7-0.95; y = 0 or 0.5) spinels were studied at 300-1770 K in the oxygen partial pressure range from 10 Pa to 21 kPa. Increasing iron content enlarges the spinel phase stability domain at reduced oxygen pressures and elevated temperatures. The total conductivity of the spinel ceramics is predominantly n-type electronic and is essentially p(O₂)-independent within the stability domain. The computer simulations using molecular dynamics technique confirmed that overall level of ion diffusion remains low even at high temperatures close to the melting point. Temperature dependencies of the total conductivity in air exhibit a complex behavior associated with changing the dominant defect-chemistry mechanism from prevailing formation of the interstitial cations above 1370-1470 K to the generation of cation vacancies at lower temperatures, and with kinetically frozen cation redistribution in spinel lattice below 700-800 K. The average thermal expansion coefficients of the spinel ceramics calculated from dilatometric data in air vary in the range (9.6-10.0) × 10^− 6 K^− 1 at 300-500 K and (13.2-16.1) × 10^− 6 K^− 1 at 1050-1370 K. Mg_1 − xFe_xO solid solutions undergo partial decomposition on heating under oxidizing and mildly reducing conditions, resulting in the segregation of spinel phase and conductivity decrease.     

Electrochemical permeability of GCO: Estimation of overpotentials

The basic relationships required to analyse permeability data of fluorite-based solid electrolytes are rewritten in order to account for an overpotential term related to slow surface exchange. Results of a gadolinia doped ceria solid electrolyte suggest that surface exchange might limit the permeability especially at low Po₂ and temperature. However, the analysis of the data with different relationships leads to somewhat different estimates of the electron and hole conductivity and overpotential values. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998     

Cu-Ce0.8Gd0.2O2−δ materials as SOFC electrolyte and anode

Co-sintering of Cu-CGO cermet anodes on CGO (Ce_0.8Gd_0.2O_2−δ) electrolyte was conducted at low temperature (1000 °C) by introducing small amounts (2 mol.%) of CuO sintering aid to the electrolytic CGO. The Cu-CGO anodes with Cu contents from 20–50 vol.% were prepared by combustion synthesis followed by sintering and reduction. Symmetrical anode/electrolyte/anode assemblies of Cu-GCO/CGO/Cu-CGO were fabricated by manually depositing the anode combustion powder on a green substrate of the 2 mol% CuO-containing CGO, followed by co-pressing and co-sintering of the assembly at 1000 °C. The low-temperature sintered CGO is submicron with 95–99% relative density. CuO addition has no significant effect on either the total or ionic conductivity of the electrolyte, but p-type conduction in the temperature range, 900–1200 °C, is 25 times higher than that of undoped CGO. Oxygen-ion transference numbers of the Cu-containing CGO lie in the range 0.89–0.99, as determined by the modified e.m.f. technique under an oxygen/air potential gradient. The activation energy for ionic conduction, 83 kJmol⁻¹, is significantly lower than that for p-type electronic transport, 140 kJmol⁻¹. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Protonic conduction in substoichiometric SrZrO3-based ceramics

The transport properties of strontium zirconate based materials were investigated using different characterization techniques. The electrical conductivity is mainly protonic below 610°C, while the contribution of electron holes increases with temperature and oxygen partial pressure. Under extreme reducing conditions, the conductivity is dominated by protons and oxygen ions. Polarization results are consistent with the results obtained. Paper presented at the 2nd Euroconference on Solid State Ionics, Funchal, Madeira, Portugal, Sept. 10–16, 1995     

THE NATURE OF ULTRAVIOLET LIGHT-INDUCED STRAND BREAKAGE IN DNA CONTAINING BROMOURACIL

Abstract— Single-strand breaks are produced in the phosphodiester backbone of ultraviolet-light-irradiated 5–bromodeoxyuridine-containing DNA (BU-DNA) after treatment with alkali. No radiation dependent breakage is observed in thymine-containing DNA (thy-DNA). The relative yields of breaks terminated by 5'-hydroxyl and 5'-phosphate groups was determined by measuring the rate of phosphorylation achieved with polynucleotide kinase in BU-DNA single strands before and after treatment with alkaline phosphatase. The ratio of 5'-phosphate to 5' hydroxyl groups ranged from 2.3 to 2.9 in different experiments. When cysteamine was present during irradiation no new end groups were produced.
In order to identify the nucleoside(s) at the 5'-termini, phosphate groups were removed with alkaline phosphatase and the 5'-hydroxyl groups were phosphorylated with polynucleotide kinase. Electrophoresis of enzymatic digests showed a single ³²P-labeled component migrating more rapidly than any of the four usual 5'-mononucleotides. Upon column chromatography this component resolved into a major peak coincident with 5'-dUMP and a lesser unidentified constituent. No 5'-dBUM³²P was observed among these nucleotides.     

Infrared spectral changes with crystallization in poly(vinylchloride): Correlations with X-ray and density data

The influence of crystallinity and stereoregularity on the infrared (IR) spectrum of atactic PVC in the solid state has been studied by many researchers [1-12]. Although the molecules in commercial PVC consist of both syndiotactic and isotactic sequences, the bulk polymer is not highly stereoregular, having approximately 50% syndiotacticity. Its infrared spectrum is different from that of highly syndiotactic PVC [3,5,7,9,10-12], particularly in the carbon-to-chlorine stretching region where there are three bands located at 610(615), 635, and 690 cm^?1. These three bands are known to be of complex origin, since each band consists of more than one absorption frequency and its relative intensity depends on the physical state or history of the specimen [3,5,7,9,10-12]. The spectrum in this region is most rigorously interpreted in terms of chain conformational structure, the spatial arrangement of the atoms around the C-C1 bond. Thus, while changes in absorbance intensities for the bands with history do not necessarily reflect changes in crystallinity, their history dependence renders these bands potentially useful as crystallinity indicators.     

Raman Scattering Tensors in Biological Molecules and Their Assemblies

INTRODUCTION

The tensor associated with a Raman band plays an important role in determining the band intensity and its structural significance. Each Raman tensor interrelates two electric vectors, that of the exciting radiation (i.e. laser photon) and that of the Raman scattered radiation (i.e. the inelastically scattered photon which results from the exchange of a vibrational quantum between the exciting photon and the molecule). The Raman tensor is obtained formally as the first derivative of the molecular polarizability tensor, the derivative being taken with respect to the vibrational normal coordinate. In other words, the Raman tensor associated with a vibrational Raman band is an indicator of how the polarizability of the molecule oscillates with the molecular normal mode of vibration.     

Investigating the mechanisms of diamond polishing using Raman spectroscopy

Recent research has shown that a phase transformation of diamond to a different form of carbon is involved when diamonds are polished in the traditional fashion. The question as to how this phase transformation is activated and maintained to produce high wear rates is of great technological interest since it may radically change the way we view the processing of diamond. This paper describes the use of Raman spectroscopy to examine debris produced on the diamond polishing wheel, both during its preparation and during polishing. In addition, polished diamond surfaces were examined for the possible existence of non-diamond surface layers in an attempt to identify material removal mechanisms. Raman spectroscopy proves ideal for these analyses because its relatively high spatial resolution is well suited to the analysis of small wear features and debris particles, and because of the wealth of information it reveals about chemical structure. This level of structural information has been lacking in previous analyses of diamond polishing debris. In addition to the non-diamond carbon found in the wear debris, significant quantities of two iron oxides, magnetite (Fe₃O₄) and haematite (α-Fe₂O₃), were also found. An interesting observation was that a transformation from magnetite to haematite could be induced either by using high power laser excitation or by frictional heating during polishing. It is suggested that some of the Raman peaks previously attributed to lonsdaleite might better be explained by the presence of these oxides.