Synthesis and characterization of spirobifluorene‐based polyimides

The synthesis and properties of organosoluble aromatic polyimides, containing spiro‐skeletal units in the polymer backbone on the basis of the spiro‐diamine monomer, 2,2′‐diamino‐9,9′‐spirobifluorene, are described. In the case of the spiro segment, the two fluorene rings are orthogonally arranged and connected through a tetrahedral bonding carbon atom, the spiro center. As a consequence, the polymer chain is periodically zigzagged with a 90° angle at each spiro center. This structural feature minimizes interchain interactions and restricts the close packing of the polymer chains, resulting in amorphous polyimides that have good solubility in organic solvents. Compared with their fluorene‐based cardo analogues, the spirobifluorene‐based polyimides have an improved solubility. Furthermore, the main‐chain rigidity of the polyimide appears to be preserved because of the presence of the spiro structure, which restricts the free segmental mobility. As a result, these polyimides exhibit a high glass‐transition temperature (T_g's) and good thermal stability. The T_g's of these polyimides were in the range of 287–374 °C, and the decomposition temperatures in nitrogen for a 10% weight loss occurred at temperatures above 570 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3615–3621, 2002     

Characterization of deep sea sediments by INAA for radioactive waste management purposes

An instrumental neutron activation analysis method, using both reactor flux and epi-cadmium neutrons, has been developed for the determination of major, minor and trace elements in sub-seabed sediments. The method involves two different irradiations followed by three different counting periods using high-resolution Ge(Li) and low-energy photon detectors. The list of elements determined includes Ag, Al, As, Ba, Br, Ca, Ce, Cl, Co, Cr, Cs, Dy, Eu, Fe, Ga, Gd, Hf, Hg, I, In, K, La, Lu, Mg, Mn, Mo, Na, Nd, Ni, Pt, Rb, Re, Rh, Sb, Sc, Se, Si, Sm, Sn, Sr, Ta, Tb, Th, Ti, Tm, U, V. W, Yb, Zn, and Zr. The accuracy of the method has been evaluated by analyzing four different standard reference materials. The method has been applied to core samples collected from the Great Meteor East and the South Nares Abyssal Plain which are being evaluated as potential sites for the possible disposal of vitrified highly active waste.     

Thermal analysis of magnesium hydroxide

Natural brucite and two precipitated Mg(OH)₂ samples were analysed in a simultaneous TG-DTG-DSC analyser. The initial dehydroxylation temperature of natural brucite is lower than those of the precipitated samples, but the maximum and final temperatures of the former are higher than those of the latter. The maximum temperatures of individual samples obtained from DTG and DSC curves are almost the same. Heats of reaction derived from peak areas for the three samples are not exactly the same, as they are influenced by the specific surface area of the individual sample. Activation energies deduced by Freeman and Carroll's method are very different from one another. This is attributed to the difference in pressure when the sample is crimped. A linear relationship is observed between the deduced activation energy and the specific height of the DSC peak.

---

Zusammenfassung Natürlicher Brucit und zwei gefällte Mg(OH)₂-Proben wurden in einem simultanen TG-DTG-DSC-Analysator geprüft. Die Anfangstemperatur der Dehydroxylierung des natürlichen Brucits ist niedriger als die der gefällten Proben, doch sind Maximal- und Endtemperaturen des ersteren höher als jene der letzteren. Die an Hand von DTG und DSC-Kurven erhaltenen Maximaltemperaturen der einzelnen Proben sind fast identisch. Die aus den Peakflächen der drei Proben errechneten Reaktionswärmen sind nicht genau dieselben, da sie von der spezifischen Peakfläche der einzelnen Proben beeinflußt werden. Die mittels der Methode von Freeman und Carroll abgeleiteten Aktivierungsenergien sind von einander sehr verschieden. Sie werden den Unterschieden im Druck bei dem Schrumpfen der Probe zugeschrieben. Ein linearer Zusammenhang zwischen der abgeleiteten Aktivierungsenergie und der spezifischen Höhe der DSC-Peaks wurde beobachtet.

---

Résumé La brucite naturelle et deux échantillons de Mg(OH)₂ précipités ont été étudiés par TG-TGD et DSC simultanées. La température initiale de la déshydroxylation de la brucite naturelle est plus faible que celle des deux échantillons précipités, mais les températures maximale et finale de déshydroxylation de la brucite sont plus élevées que celles des échantillons précipités. Les chaleurs de réaction déduites de l'aire des pics DSC des trois échantillons ne sont pas exactement les mêmes, puisqu'elles sont influencées par l'état de surface des échantillons individuels. Les énergies d'activation trouvées en appliquant la méthode de Freeman et Carroll sont très différentes les unes des autres. Elles sont attribuées à la différence de pression au niveau de l'échantillon. On a observé une relation linéaire entre l'énergie d'activation déduite et la hauteur spécifique du pic DSC.

---

Mg(OH)₂ -- . , , - , . - , , . , , , , . , —, , . - .

---

---

The authors wish to thank Dr. T. C. W. Mak, Department of Chemistry, The Chinese University of Hong Kong, for taking the X-ray diffraction data.     

Evaluation of kinetic parameters from thermogravimetric curves: Part I. Combined numerical method

A new method is proposed to evaluate kinetic parameters from thermogravimetric traces. The method consists of two steps, α, T and dα/dT values are first employed to estimate kinetic parameters by linear least squares fitting, using the five types of mechanism for solid phase reactions suggested by ?esták. From the different sets of parameters thus obtained, the most probable mechanism type is decided. The resultant parameters for the chosen type of mechanism may further be improved by differential correction method, if necessary, using the more accurate data of α and T. The proposed method was tested with artificial data and the data for the thermal dehydration of gypsum by ?esták et al. The results were very satisfactory.     

Temperature control technology by heat capacity change upon lock and key binding

We propose an innovative temperature control technology wherein a heat capacity change upon lock and key binding is applied. A proof-of-principle calculation is performed using a three-dimensional integral equation theory of a statistical mechanics of fluid (Ornstein-Zernike theory coupled by HNC closure). Logical correctness of the temperature control technology is verified by this calculation. The performance of the heat pump is discussed. In addition, a more effective condition of the heat pump is also discussed to improve the performance.     

Chromium Speciation Using Ion Chromatography-Atomic Absorption System with On-Line Preconcentration

A method using ion chromatography-atomic absorption system (IC-AA) with on-line preconcentration unit is developed for the speciation of chromium in aqueous samples. Both Cr(III) and Cr(VI) species are pre-treated with sodium salt of ethylenediaminetetraacetic acid (EDTA) in consecutive steps. The treated samples can then be injected into an on-line preconcentration unit followed by ion chromatographic separation with UV or selective flame AA detection. Both chromium species can be separated within 10 minutes, and the method is applicable for aqueous samples with ppm levels of chromium.     

A tunable gas sensor using an acoustic waveguide

A tunable gas sensor using surface acoustic waves (SAW) is described. It is designed on the basis of a waveguide delay line fabricated on a piezoelectric substrate made of 128° Y-cut LiNbO₃. A voltage applied between the waveguide and two electrodes causes a local change in the properties of the substrate near the waveguide and differently affects the sensor’s response to the vapors of various analytes. Some results of the experimental study of the sensor, which show the change in the selectivity under the effect of voltage, are presented. The analytes used for testing include a number of alcohols and deionized water. The possibilities for employing such a sensor in the sensor arrays of gas analyzers of the electronic nose type are discussed.     

Photolithographic patterning of highly conductive PEDOT:PSS and its application in organic light‐emitting diodes

Photolithographically patterned highly conductive (～1400 S/cm) poly(3,4‐ethylenedioxythio‐phene):poly(styrenesulfonate) (PEDOT:PSS) films are demonstrated as electrodes for organic light emitting diodes (OLEDs). With the assistance of hydrofluoroether (HFE) solvents and fluorinated photoresists, high‐resolution passive‐matrix OLEDs with PEDOT:PSS electrodes are fabricated, in which the OLEDs show comparable performance to those devices prepared on the indium tin oxide (ITO) electrodes. This photolithographic patterning process for PEDTO:PSS has great potential for applications which require flexible electrodes. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1221–1226     

Characterization of new metabolites from in vivo biotransformation of 2‐amino‐ 3‐methylimidazo[4,5‐f]quinoline in mouse by mass spectrometry

In studying the metabolic pathways underlying the mechanism of carcinogenesis of the heterocyclic amine of 2‐amino‐3‐methylimidazo[4,5‐f]quinoline (IQ), we recently found a new metabolite which gave an [M + H]⁺ ion of m/z 217 when subjected to electrospray ionization (ESI) in positive‐ion mode. Following ip injection of this metabolite of m/z 217 (designated as m/z 217) to beta‐naphthoflavone‐treated mice, 57% of the total radioactivity was recovered in a 24‐h mouse urine sample. HPLC separation followed by MS analysis indicates that the urine sample contained m/z 217 (36 ± 3% of total recovered radioactivity) and two other peaks that gave rise to the [M + H]⁺ ions of m/z 393 (31 ± 4%, designated as m/z 393) and m/z 233 (14 ± 1%, designated as m/z 233). Beta‐glucuronidase treatment of m/z 393 resulted in a radioactive peak corresponding to m/z 217. ESI in combination with various mass spectrometry techniques, including multiple‐stage mass spectrometry, exact mass measurements and H/D exchange followed by tandem mass spectrometry, was used for structural characterization. The urinary metabolites of m/z 217, 393 and 233 were identified as 1,2‐dihydro‐2‐amino‐5‐hydroxy‐3‐methylimidazo[4,5‐f]quinoline, 1,2‐dihydro‐2‐amino‐5‐O‐glucuronide‐3‐methylimidazo[4,5‐f]quinoline and 1,2‐dihydro‐2‐amino‐5,7‐dihydroxy‐3‐methylimidazo[4,5‐f]quinoline, respectively. Our results demonstrated that m/z 217 is biotransformed in vivo to m/z 393 by O‐glucuronidation and to m/z 233 by oxidation. The observation of these more polar metabolites relative to IQ suggests that they may arise from a previously undescribed detoxicification pathway. Copyright © 2009 John Wiley & Sons, Ltd.