Effect of maleic anhydride content on the rheology and phase behavior of poly(styrene-co -maleic anhydride)/ poly(methyl methacrylate) blends

 We investigated the thermo- rheological behavior of high glass transition, high molecular weight and small dynamic asymmetry blends of poly(styrene-co-maleic anhydride) (SMA) and poly (methyl methacrylate) (PMMA) with varying amounts of maleic anhydride (MA) content, namely 8 wt%, 14 wt% and 32 wt%, in the SMA component. The phase separation (binodal) temperature of each blend was determined rheologically using a combination of dynamic frequency and temperature sweeps in parallel plate geometry; it was marked by a change in slope of the elastic modulus and the occurrence of a peak in tan δ in temperature sweeps. Failure of the time-temperature superposition principle and observation of two peaks in the Cole-Cole plots corroborated these findings. The blends displayed lower critical solution temperature (LCST) behavior with the critical temperatures exhibiting a non-monotonic dependence on the MA content. From rheological and thermal measurements it was concluded that SMA/PMMA blends containing 14% MA were more miscible than those containing 8% or 32% MA, a finding attributed to the compositional dependence of the interplay between SMA-SMA and SMA-PMMA interactions in the different samples. MA also influenced the dynamic asymmetry and pretransitional concentration fluctuations. The phase diagrams corresponding to each blend were modeled using a two-parameter temperature dependent interaction parameter, based on the concept of generalized Gibbs free energy of mixing. The fitted values of interaction parameter were in good agreement with values calculated explicitly using the Flory-Huggins theory. Received: 16 February 2001 Accepted: 11 July 2001     

Directed self-organized critical patterns emerging from fractional Brownian paths

We discuss a family of clusters corresponding to the region whose boundary is formed by a fractional Brownian path y(i) and by the moving average function . Our model generates fractal directed patterns showing spatio-temporal complexity, and we demonstrate that the cluster area, length and duration exhibit the characteristic scaling behavior of SOC clusters. The function C_n(i) acts as a magnifying lens, zooming in (or out) the ‘avalanches’ formed by the cluster construction rule, where the magnifying power of the zoom is set by the value of the amplitude window n. On the basis of the construction rule of the clusters and of the relationship among the exponents, we hypothesize that our model might be considered to be a generalized stochastic directed model, including the Dhar–Ramaswamy (DR) model and the stochastic models as particular cases. As in the DR model, the growth and annihilation of our clusters are obtained from the set of intersections of two random walk paths, and we argue that our model is a variant of the directed self-organized criticality scheme of the DR model.     

Finite-sized Heisenberg chains and magnetism of one-dimensional metal systems

We present a combined experimental and theoretical study of the magnetization of one-dimensional atomic cobalt chains deposited on a platinum surface. We discuss the intrinsic magnetization parameters derived by X-ray magnetic circular dichroism measurements and the observation of ferromagnetic order in one dimension in connection with the presence of strong, dimensionality-dependent anisotropy energy barriers of magnetocrystalline origin. An explicit transfer matrix formalism is developed to treat atomic chains of finite length within the anisotropic Heisenberg model. This model allows us to fit the experimental magnetization curves of cobalt monatomic chains, measured parallel to the easy and hard axes, and provides values of the exchange coupling parameter and the magnetic anisotropy energy consistent with those reported in the literature. The analysis of the spin–spin correlation as a function of temperature provides further insight into the tendency to magnetic order in finite-sized one-dimensional systems. PACS 57.10.Pq; 75.30.-m; 75.30.Gw; 78.70.Dm     

Adhesion control by inflation: implications from biology to artificial attachment device

There is an increasing demand for materials that incorporate advanced adhesion properties, such as an ability to adhere in a reversible and controllable manner. In biological systems, these features are known from adhesive pads of the tree frog, Litoria caerulea, and the bush-cricket, Tettigonia viridissima. These species have convergently developed soft, hemispherically shaped pads that might be able to control their adhesion through active changing the curvature of the pad. Inspired by these biological systems, an artificial model system is developed here. It consists of an inflatable membrane clamped to the metallic cylinder and filled with air. Pull-off force measurements of the membrane surface were conducted in contact with the membrane at five different radii of curvature r _c with (1) a smooth polyvinylsiloxane membrane and (2) mushroom-shaped adhesive microstructured membrane made of the same polymer. The hypothesis that an increased internal pressure, acting on the membrane, reduces the radius of the membrane curvature, resulting in turn in a lower pull-off force, is verified. Such an active control of adhesion, inspired by biological models, will lead to the development of industrial pick-and-drop devices with controllable adhesive properties.     

An enantiopure diselenide based on a chiral bicyclic backbone—synthesis and configuration assignment

An enantiomerically pure diselenide containing two chiral bicyclic subunits was prepared from the respective halides. The stereochemical outcome of the reaction was established via NMR spectroscopy and X-ray diffraction measurements.     

Minimization over the $$\ell _1$$ -ball using an active-set non-monotone projected gradient

Computational Optimization and Applications - The $$\ell _1$$ -ball is a nicely structured feasible set that is widely used in many fields (e.g., machine learning, statistics and signal analysis)...     

Chemical characterisation of old cabbage (Brassica oleracea L. var. acephala) seed oil by liquid chromatography and different spectroscopic detection systems

We report an extensive chemical characterisation of fatty acids, triacylglycerols, tocopherols, carotenoids and polyphenols contained in the oil extracted from old cabbage (Brassica oleracea L. var. acephala) by cold-pressing of the seeds. Analyses were performed by GC-FID combined with mass spectrometry, HPLC with photodiode array, fluorescence and mass spectrometry detection. The 94% of the total fatty acids were unsaturated, rappresented by erucic acid (more than 50%) followed by linoleic, linolenic and oleic acids accounting for approximately 10% each. The most abundant triacylglycerols (>13%) were represented by erucic–gadolenic–linoleic, erucic–eruci–linoleic and erucic–erucic–oleic. Among tocopherols, γ-tocopherol accounted for over 70% of the total content. Thirteen carotenoids and 11 polyphenols were identified and measured. In particular, the total content in carotenoids was 10.9 ppm and all-E-lutein was the main component (7.7 ppm); among polyphenols, six hydroxycinnamic acids and five flavonoids, were identified by combining information from retention times, PDA and MS data.     

Application of dosimetry tools for the assessment of e-cigarette aerosol and cigarette smoke generated on two different in vitro exposure systems

The diluted aerosols from a cigarette (3R4F) and an e-cigarette (Vype ePen) were compared in two commercially available in vitro exposure systems: the Borgwaldt RM20S and Vitrocell VC10. Dosimetry was assessed by measuring deposited aerosol mass in the exposure chambers via quartz crystal microbalances, followed by quantification of deposited nicotine on their surface. The two exposure systems were shown to generate the same aerosols (pre-dilution) within analytically quantified nicotine concentration levels (p = 0.105). The dosimetry methods employed enabled assessment of the diluted aerosol at the exposure interface. At a common dilution, the per puff e-cigarette aerosol deposited mass was greater than cigarette smoke. At four dilutions, the RM20S produced deposited mass ranging 0.1–0.5 µg/cm²/puff for cigarette and 0.1–0.9 µg/cm²/puff for e-cigarette; the VC10 ranged 0.4–2.1 µg/cm²/puff for cigarette and 0.3–3.3 µg/cm²/puff for e-cigarette. In contrast nicotine delivery was much greater from the cigarette than from the e-cigarette at a common dilution, but consistent with the differing nicotine percentages in the respective aerosols. On the RM20S, nicotine ranged 2.5–16.8 ng/cm²/puff for the cigarette and 1.2–5.6 ng/cm²/puff for the e-cigarette. On the VC10, nicotine concentration ranged 10.0–93.9 ng/cm²/puff for the cigarette and 4.0–12.3 ng/cm²/puff for the e-cigarette. The deposited aerosol from a conventional cigarette and an e-cigarette in vitro are compositionally different; this emphasises the importance of understanding and characterising different product aerosols using dosimetry tools. This will enable easier extrapolation and comparison of pre-clinical data and consumer use studies, to help further explore the reduced risk potential of next generation nicotine products.

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Graphical abstract A cigarette and an e-cigarette (top left) were assessed on two different in vitro exposure systems, the Borgwaldt RM20S (top right) and the VC 10 (bottom right). Compositionally the product aerosols were different, but there was no difference between the same product on different machines (bottom left).

     

Tautomers of a Fluorescent G Surrogate and Their Distinct Photophysics Provide Additional Information Channels

Thienoguanosine (^thG) is an isomorphic nucleoside analogue acting as a faithful fluorescent substitute of G, with respectable quantum yield in oligonucleotides. Photophysical analysis of ^thG reveals the existence of two ground‐state tautomers with significantly shifted absorption and emission wavelengths, and high quantum yield in buffer. Using (TD)‐DFT calculations, the tautomers were identified as the H1 and H3 keto‐amino tautomers. When incorporated into the loop of (?)PBS, the (?)DNA copy of the HIV‐1 primer binding site, both tautomers are observed and show differential sensitivity to protein binding. The red‐shifted H1 tautomer is strongly favored in matched (?)/(+)PBS duplexes, while the relative emission of the H3 tautomer can be used to detect single nucleotide polymorphisms. These tautomers and their distinct environmental sensitivity provide unprecedented information channels for analyzing G residues in oligonucleotides and their complexes.     

Abstract simplicity of complete Kac-Moody groups over finite fields

Let G be a Kac-Moody group over a finite field corresponding to a generalized Cartan matrix A, as constructed by Tits. It is known that G admits the structure of a BN-pair, and acts on its corresponding building. We study the complete Kac-Moody group which is defined to be the closure of G in the automorphism group of its building. Our main goal is to determine when complete Kac-Moody groups are abstractly simple, that is have no proper non-trivial normal subgroups. Abstract simplicity of was previously known to hold when A is of affine type. We extend this result to many indefinite cases, including all hyperbolic generalized Cartan matrices A of rank at least four. Our proof uses Tits’ simplicity theorem for groups with a BN-pair and methods from the theory of pro-p groups.