Synthesis and polymerization of a new nitrogen‐containing bis‐ortho‐diynylarene monomer

This study focuses on the preparation, characterization, and optical properties of new bis(3,4‐diphenylethynylphenyl)phenylamine. This is the first nitrogen‐containing bis‐ortho‐diynylarene (BODA) monomer having a nitrogen atom as the spacer group. BODA monomers are usually prepared from common bisphenols, thereby providing great synthetic versatility and the opportunity to develop a wide array of novel polyarylene thermosets by varying the aromatic spacer group. The new bis(3,4‐bisphenylethynylphenyl)phenylamine was synthesized in five steps. This compound emits an intense blue color (λ = 438 nm) upon irradiation by UV light and may be suitable for use as an emitting layer in electroluminescent devices. Bis‐(3,4‐bisphenylethynylphenyl)phenylamine and its polymer have photoluminescence quantum yields 34 and 38%, respectively, and long excited‐state lifetimes of 3.2 and 3.6 ns, respectively. The structure of the monomer and its polymer were characterized using spectroscopic techniques including Ultraviolet–visible Spectrophotometer, Photoluminescence Spectrophotometer, Fourier Transform infrared spectroscopy, and Gel Permeation Chromatography. The polymerizations were studied by Differential Scanning Calorimeter. The amount of weight loss and the thermostability of the nitrogen‐containing polymer were determined from thermogravimetric analysis. The electrical conductivity of neat HCl‐doped BODA‐derived polymer film was measured according to the standard four‐point probe technique. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6988–6996, 2006     

Formation of Amorphous AgI Aggregates Dominating Fast Ion Conductivity in AgI-based Glasses

Precise calorimetry was performed for (AgI)_x(AgPO₃)_1–x and (AgI)_x(Ag₂PO_3.5)_1–x glasses with very high AgI compositions (x0.75). The glasses showed -glass transitions due to the freezing-in of the rearrangement of conductive Ag⁺ ions. Magnitude of the associated heat-capacity jump increased with increasing the AgI composition in the respective glass systems, and was larger in the former system than in the latter when compared at the same AgI composition. All the results were well explained by the amorphous AgI aggregate model for the AgI-based fast ion conducting glasses, indicating the appropriateness of the model for the structure of the glasses with high AgI compositions. The formation of the hypothetical bulk amorphous AgI was also indicated in the glasses at the highest limit of AgI composition.This revised version was published online in November 2005 with corrections to the Cover Date.     

氮杂冠醚与碱金属离子配位反应的研究

滴定量效法是研究反应热化学和热力学的重要手段之一．用这种方法对冠醚与金属离子的配位反应热力学性质进行研究一直受到很大关注【且S习．但是对氨杂冠林，尤其是一系列结构相似的氨杂冠醚体系进行系统的热力学性质研究的报导不多．前文K则曾报导了用自组装的消定量热计对银（I）－a吹体系和铜（11）·N，N’一问位取代革基乙二胺体系的配位反应热化学研究结果·本文报导从（对位取代革基）k杂15冠5卜RPW15CS，R＝CIZH；CHa；CHso）与碘化钠和碘化钾在25T、无水乙过溶液中进行配位反应的消定量效研究结果．讨论了配体上取代基的电…     

Calorimetric approach to tetronic/water interactions

Tetronic^®comprises X-shaped copolymers formed by four poly(propylene oxide) (PPO) andpoly(ethylene oxide) (PEO) block chains bonded to an ethylene diamine centralgroup. Micellization behaviour of three representative Tetronics (T304, T904and T1307) was characterized to gain an insight into the interactions betweenthe copolymer unimers and the state of water in their solutions. The enthalpyof demicellization, recorded at 37°C in an isoperibol microcalorimeter,indicated that the process was in all cases exothermic and the enthalpy rankedin the order T1307≥T904>>T304. Micellization is entropy-driven owing tohydrophobic interactions between the PPO chains.DSC analysisshowed that the crystallization and melting peaks of the free water remainingin T304 and T904 solutions were progressively shifted toward lower temperaturesas the surfactant proportion increased, owing to a colligative effect. Boundwater corresponded to 3 water molecules per EO repeating unit. In the caseof T1307, which has longer PEO chains, a splitting of the melting peak wasobserved, one peak appearing around 0°C due to free water and anotherat –15°C due to interfacial water. As T1307 proportion raised, theenthalpy of the former decreased, whilst the enthalpy of the latter increased.In 40% T1307 solutions, interfacial water overcame the proportion of freewater; there being 1 interfacial and 3 bound water molecules per EO repeatingunit. Gaussian deconvolution of FTIR spectra also enabled to characterizethe evolution of free water as a function of Tetronic proportion. The dependenceof micellization and water interaction behaviour on Tetronics structure shouldbe taken into account to use these copolymers as drug solubilizers and micellarcarriers.     

Solid-state interactions and drug release of teicoplanin in binary combinations with peracetylated α-, β-, and γ-cyclodextrins

Triacetyl α-cyclodextrin, triacetyl β-cyclodextrin and triacetyl γ-cyclodextrin were tested as possible hydrophobic carriers to prolong the release of hydrophilic teicoplanin (TCP). Physical–chemical characterization of individual components, drug-carrier physical mixtures at 0.5, 0.67 and 0.75 mass fraction of carrier, and the respective interaction products by kneading or evaporative crystallization under microwave irradiation was carried out using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). In vitro drug release in pH 7.4 phosphate buffer at 37 °C was determined by intrinsic dissolution rate (IDR) measurements on non disintegrating compressed discs. Solid-state interactions of TCP with triacetyl α-cyclodextrin by evaporative crystallization and kneading and with triacetyl β-cyclodextrin by evaporative crystallization (probably resulting in carrier amorphization) were demonstrated. The role of carrier hydrophobicity, carrier mass fraction and preparation method of solid drug-carrier combinations on solid-state drug-carrier interactions and slowing down of TCP release was assessed. Modulation of drug release can be achieved using TCP-triacetyl γ-cyclodextrin combinations at 0.5 mass fraction of carrier.     

Macroporous poly(methyl methacrylate) produced by phase separation during polymerisation in solution

Polymethyl methacrylate (PMMA) sponges were obtained by polymerization in a solution with monomer/ethanol ratios up to 20:80. The material obtained after the elimination of the solvent present a homogeneous distribution of dispersed pores up to a monomer/ethanol ratio lower than 40:60. For higher ethanol contents in the reacting mixture, the morphology of the sponge corresponds to a network of PMMA microparticles, leaving large empty spaces leading to highly porous structure. The monomer/ethanol ratio during polymerization has a large influence on the porosity, thermal, and mechanical properties of the material and, for large solvent contents, on the size of the polymer microparticles.     

AC calorimetric study of phase transitions in phosphatidylcholine-cholesterol systems

Using an ac calorimetric method, detailed behaviour of the heat capacity in dipalmitoyl-phosphatidylcholine-cholesterol system was studied in the cholesterol concentration less than 5 mol%. It was revealed that the heat capacity near the main transition was composed of at least four anomalies, i.e., multipeak took place in the heat capacity. This fact indicates that a simple theory explaining coexistence of two phases in two component systems does not work in the multipeak region. Then, relation between the multipeak heat capacity and the change of the ripple structure with the cholesterol concentration should be taken into account, when we consider thermodynamical behaviour of the systems.

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Zusammenfassung Mittels AC-Kalorimetrie wurde bei Cholesterol-Konzentrationen von weniger als 5 mol% das Verhalten der Wärmekapazität im System Dipalmitoylphosphatidylcholin-Cholesterol untersucht. Es wurde gezeigt, daß sich die Wärmekapazität in der Nähe der Hauptumwandlung aus mindestens vier Anomalien zusammensetzt, d.h. bei der Wärmekapazität kann ein Multipeak beobachtet werden. Diese Tatsache zeigt, daß eine einfache Theorie, welche die Koexistenz zweier Phasen in einem Zweikomponenten-System erklärt, für die Multipeakregion nicht geeignet ist. Weiterhin sollte bei Überlegungen zum thermodynamischen Verhalten von Systemen eine Beziehung zwischen der Multipeak-Wärmekapazität bzw. der Welligkeitsstruktur und der Cholesterol-Konzentration berücksichtigt werden.

     

Age related changes in the thermal transition of Turkey leg flexor tendon collagen

A differential scanning calorimetric, thermogravimetric and electron microscopic investigation has been carried out on the uncalcified areas of turkey leg flexor tendon as a function of age. Rehydrated samples exhibit an increase of thermal stability with age. The H_D values drop from about 11 cal·g^–1 in the first weeks of life down to 7 cal·g^–1 after the 11th week.At about 11 weeks, the collagen fibril diameter distribution passes from unimodal to multimodal. The DSC curves as well as the TG-DTG curves recorded from dried samples do not show any appreciable difference with ageing. The variations in thermal behaviour of rehydrated samples and fibril diameter distribution could be related to modifications in water binding with ageing.The Authors are grateful to Dr. G. Fabris for discussion and help in the selection of the samples. They also wish to thank Mr. G. Pizzuto for excellent technical assistance. The financial support by Consiglio Nazionale delle Ricerche is gratefully acknowledged.     

离聚体的结构表征——Ⅴ.含氟离聚体中离子微区稳定性的研究

本文用DSC方法研究了羟酸型含氟离聚体中不同金属离子种类、可离子化基团含量、配位结构单元构型及离子微区大小对离聚体中离子微区稳定性的影响。实验表明:离聚体中金属离子配位能力愈强,羟酸含量愈高,离子微区尺寸愈大,则相应离聚体中离子微区稳定性愈大。铅高聚体>锌离聚体>钙离聚体>钠离聚体。     

Thermal Oxidative Stability of Heat-Stabilised Polyamide 66 by Differential Scanning Calorimetry

The thermal stability of heat-stabilised polyamide 66 in an oxidative environment is evaluated by DSC. The oxidative stability of the polyamide decreases as a result of repeated injection moulding. The results also indicate that the presence of glass fibres in the polyamide has a negative influence on the oxidative stability. Both isothermal and dynamic DSC measurements seem to be useful tools for assessing the stability of polyamides and there is a relationship between data determined using both procedures. This revised version was published online in July 2006 with corrections to the Cover Date.