Sulfobetaine‐containing diblock and triblock copolymers via reversible addition‐fragmentation chain transfer polymerization in aqueous media

A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by ¹H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003     

Lein?l, Lein?lfirniss und Oelfarben

Ohne Zusammenfassung     

Experimental characterization of hexatic smectic phases through electro-optic studies and dielectric relaxation spectroscopy

The electro-optic and complex dielectric behaviour of an antiferroelectric liquid crystal 4-(1-methylheptyloxycarbonyl)phenyl 4'-(n-butanoyloxyprop-1-oxy)biphenyl-4-carboxylate, having chiral SmC_A* and hexatic smectic phases, have been investigated. Complex dielectric permittivities were measured as a function of frequency, d.c. bias field and temperature. Spontaneous polarization was measured by the current reversal technique; tilt angle was measured under a polarizing microscope using a low frequency electric field. The electro-optic properties and dielectric behaviour of the material are compared with results obtained by DSC and polarizing optical microscopy. Dielectric relaxation processes in SmC_A* and hexatic smectic phases were determined. The dielectric strength at the SmC_A* to hexatic smectic phase transition is discussed in terms of coupling between the long range bond orientational order and smectic C director. It seems from the results of spontaneous polarization and dielectric relaxation spectroscopy that the material might possess an additional phase between the SmC_A* and hexatic smectic I* phases.     

Ultrasonic spectroscopic evaluation of the ring‐opening metathesis polymerization of dicyclopentadiene

An in situ ultrasonic spectroscopy technique was used to study the ring‐opening metathesis polymerization of dicyclopentadiene catalyzed by bis(tricyclohexylphosphine)benzylidene ruthenium dichloride. A reaction cell employing a flexible poly(ethylene terephthalate) window for pulse echo ultrasonic spectroscopy was used to monitor the polymerization. The changes in the density, wave speed, acoustic modulus, and attenuation were all simultaneously monitored. In comparison with Fourier transform infrared (FTIR) spectroscopy data, the changes in the density, velocity, and modulus only accurately measured the rate constant for the metathesis of the cyclopentyl unsaturation. The ultrasonic values were within 6% of the values determined by FTIR. The activation energy for metathesis of the cyclopentyl unsaturation was 84 kJ mol^?1, following first‐order kinetics. Rate constants for the polymerization of the norbornyl unsaturation could not be determined by ultrasound. The gel point, vitrification, and qualitative information about the reaction rate could be determined from the change in the attenuation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1323–1333, 2003     

Arsenic determination in marine sediment using ultrasound for sample preparation.

This work deals with As determination in marine sediment using ultrasound for sample preparation. It is shown that As can be quantitatively extracted from marine sediment using 20% (v/v) HCl and sonication. The slurry is centrifuged and the analyte is determined in the supernatant by hydride generation atomic absorption spectrometry (HG AAS). A flow injection (FI) system is employed for hydride generation, with 0.5% (m/v) NaBH(4) used as reducdant and a 20% (v/v) HCl used as sample carrier. The limit of quantification is 1.6 microg g(-1) of As, which is based on 800 microl of sample solution and 0.200 g of sample mass in a volume of 50 mL. Certified and non certified marine sediment samples were analyzed; the results were in accordance with the certified or reference values. Speciation analysis by HPLC-ICP-MS showed that As(V) is the only detectable As species present in the supernatant of the centrifuged sample.     

PERIODIC ENVIRONMENTS AND PERIODIC HARVESTING

ABSTRACT. We consider autonomous population models under periodic harvesting and population models in periodic environments and seek conditions under which there is an asymptotically stable periodic solution.     

Study of the dynamic structure factor of strong glasses

The dynamic structure factors (DSFs) of several strong glasses (SF6, SF10, BK7, SUPRASIL) measured by Brillouin light scattering spectroscopy are reported. Spectra have been collected, at and above room temperature, at two scattering angles, θ=90° and θ=180° corresponding to exchanged wavevector q values ranging from 0.0256 to 0.0448 nm⁻¹. In particular we find that the isotropic spectral lineshapes are in all cases well described by the simple hydrodynamic theory of an amorphous solid. The width of the Brillouin peaks are found to be consistent with the predicted q² dependence at both investigated temperatures. This damping is however found to account only partially for the strong asymmetry of the Brillouin line clearly visible on a logarithmic intensity scale. As a matter of fact there is an excess intensity in the very low frequency plateau underlying the central component. The height of this plateau and hence the entire lineshape is well reproduced if a relaxation process is taken into account in the hydrodynamic equations. Owing to the intense elastic scattering we are able to determine unambiguously only the ratio between amplitude and characteristic time of this process which quantifies the sound dispersion to be of the order of a few percent in all samples. The temperature dependence of the parameters indicates that this relaxation cannot be attributed to thermally activated relaxation phenomena. These general findings favorably compare with molecular dynamics simulation results on similar systems.     

Closed-form solutions for a rectangular layer with central crack under anti-plane shear stress

We consider the problem of determining the stress distributionin a finite rectangular elastic layer containing a Griffithcrack which is opened by internal shear stress acting alongthe length of the crack. The mode III crack is assumed to belocated in the middle plane of the rectangular layer. The followingtwo problems are considered: (A) the central crack is perpendicularto the two fixed lateral surfaces and parallel to the othertwo stress-free surfaces; (B) all the lateral surfaces of therectangular layer are clamped and the central crack is parallelto the two lateral surfaces. By using Fourier transformations,we reduce the solution of each problem to the solution of dualintegral equations with sine kernels and a weight function whichare solved exactly. Finally, we derive closed-form expressionsfor the stress intensity factor at the tip of the crack andthe numerical values for the stress intensity factor at theedges of the cracks are presented in the form of tables.     

Combined supercritical-fluid chromatography/mass spectrometry in the analysis of diuron in plasma using on-line phase-system switching

On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL.     

Direct numerical simulation of settling of a large solid particle during bioconvection

Settling of a large solid particle in bioconvection flow caused by gyrotactic microorganisms is investigated. The particle is released from the top of the bioconvection chamber; its settling pattern depends on whether it is released in the centre of the bioconvection plume or at its periphery. The Chimera method is utilized; a subgrid is generated around a moving particle. The method suggested by Liu and Wang (Comput. Fluid 2004; 33 :223–255) is further developed to account for the presence of a moving boundary in the streamfunction‐vorticity formulation using the finite‐difference method. A number of cases for different release positions of the particle are computed. It is demonstrated that bioconvection can either accelerate or decelerate settling of the particle depending on the initial position of the particle relative to the plume centre. It is also shown that the particle impacts bioconvection plume by changing its shape and location in the chamber. Copyright © 2005 John Wiley & Sons, Ltd.