Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003     

Einige Bemerkungen zum Vierscheitelsatz

Zusammenfassung. Der Vierscheitelsatz sagt aus, da? die Krümmung einer geschlossenen, sich selbst nicht schneidenden, ebenen Kurve stets mindestens zwei Maxima und zwei Minima besitzt. Er wurde unabh?ngig von Syamadas Mukhopadhyaya und von Adolf Kneser bewiesen, und seitdem hat es eine ganze Reihe weiterer Beweise gegeben. In der vorliegenden Note wird der Satz aus einer elementargeometrischen Aussage über Kreisbogenvielecke durch Grenzübergang hergeleitet und schlie?lich durch Abschw?chung der Differenzierbarkeitsvoraussetzungen verallgemeinert. Eingegangen am 13. Dezember 1994 / Angenommen am 3. M?rz 1995     

Common luminescence intensity fluctuations of single particle and single molecules in non-conducing matrices

Optical spectroscopy in combination with wide field or confocal optical microscopy enables the investigation of single quantum objects such as organic molecules, II/VI semiconductor quantum dots and silicon nanocrystals. They all have fluctuations of luminescence intensities on time scales longer than μs in common. A comparison reveals that despite the large differences of the nature of the respective quantum objects, the intensity fluctuations are related to a slow ionisation process followed by a trapping of the photoejected charge in the non-conducing environment. Detailed aspects of the dynamics are controlled by the dielectric properties of the matrix.     

Compatible Lie Brackets and Integrable Equations of the Principal Chiral Model Type

We consider two classes of integrable nonlinear hyperbolic systems on Lie algebras. These systems generalize the principal chiral model. Each system is related to a pair of compatible Lie brackets and has a Lax representation, which is determined by the direct sum decomposition of the Lie algebra of Laurent series into the subalgebra of Taylor series and the complementary subalgebra corresponding to the pair. New examples of compatible Lie brackets are given.     

Foams and surface rheological properties of β-casein, gliadin and glycinin

Interfacial rheological properties and their suitability for foam production and stability of two vegetable proteins were studied and compared to β-casein. Proteins used ranged from flexible to rigid/globular in the order of β-casein, gliadin and soy glycinin. Experiments were performed at pH 6.7. Network forming properties were characterised by the surface dilational modulus (determined with the ring trough) and the critical falling film length (L_still) at which a stagnant protein film will break. Gliadin had the highest dilational modulus, followed by glycinin and β-casein, whereas glycinin formed the strongest film against fracture in the overflowing cylinder. The rate of decrease in the surface tension was studied at the air–water (Wilhelmy plate method) and the oil–water interface (bursting membrane) and the dynamic surface tension during compression and expansion in the caterpillar. Gliadin had the lowest equilibrium interfacial tensions and β-casein the lowest dynamic surface tension during expansion. Hardly any foam could be formed at a concentration of 0.1 g/l by shaking. At a concentration of 1.4 g/l most foam was formed by β-casein, followed by gliadin and glycinin. It seems that in the first place the rate of adsorption is important for foam formation. For the vegetable proteins, adsorption was slow. This resulted in lower foamability, especially for glycinin.     

Revisiting Gouy phase

The aim of this paper is to highlight the added value of the generalized Gouy phase shift introduced by Siegman. Although suited for optical systems study, including those more complex than free space, we note that it did not meet the use that it deserves so far. The analysis of the whole of the ideas and analytical approaches associated to the important concept of the Gouy phase proves its effectiveness.

Usually, the resonance condition is systematically built on the basis of the equivalent empty cavity. Unfortunately, this approach does not cover some of the useful parameters of the real resonator. By means of the generalized Gouy phase and the self-consistent complex parameter q, we derive here a new approach for the calculation of the resonance condition for the real cavity. Moreover, the use of the generalized Gouy phase clearly simplifies the study of resonators, while making it possible to avoid the use of the Huygens’ Fresnel integral.     

First‐principles calculations of Mössbauer hyperfine parameters for solids and large molecules

Electronic structure calculations based on density functional theory were performed for solids and large molecules. The solids were represented by clusters of 60–100 atoms embedded in the potential of the external crystal. Magnetic moments and Mössbauer hyperfine parameters were derived.     

Matrix effects in the determination of butyltin compounds in environmental samples by GC AA after hydride generation

Experiments for the determination of mono-, di and tri-butyltin (MBT, DBT and TBT) by hydride generation/gas chromatography/atomic absorption spectrometry in various matrices (sediment, suspended matter, mussel, algae and water) have revealed that poor butyltin recoveries are obtained in sediments displaying high sulphur and hydrocarbon contents; very poor recoveries were also observed for TBT in sediments with high chlorophyll pigment contents as well as in algal samples. It was however not clear whether the hydride generatin was inhibited by these infering compounds, as was previously assumed in the case of hydrocarbons, or whether interferences affected the atomization rate. Further studies were performed to solve this problem in order to validate this method in the case of analyses of, for example, oil-contaminated sediment and algae. This paper presents the results obtained. It is concluded here that the poor recoveries were due to an inhibition of hydride generation rather than to interference at the atomization stage.