Polymerization of higher α‐olefins using a Cs‐symmetry hafnium metallocene catalyst. Kinetics of the polymerization and microstructural analysis

The C_s‐symmetry hafnium metallocene [(p‐Et₃Si)C₆H₄]₂C(2,7‐di‐tert‐BuFlu)(C₅H₄)Hf(CH₃)₂ and tetrakis(pentafluorophenyl) borate dimethylanilinium salt ([B(C₆F₅)₄]^?[Me₂NHPh]⁺) were used as the catalytic system for the polymerization of higher α‐olefins (from hexene‐1 to hexadecene‐1) in toluene at 0 °C. The evolution of the polymerization was studied regarding the variation of the molecular weight, molecular weight distribution and yield with time. The effect of the monomer structure on the polymerization kinetics was established. The role of trioctylaluminum in accelerating the polymerization was investigated. ¹³C NMR spectroscopy was used to study the microstructure of the poly(α‐olefins) by the determination of the pentad monomer sequences. The thermal properties of the polymers were obtained by differential scanning calorimetry, DSC. The results were discussed in connection with the polymer microstructure. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4314–4325, 2009     

Bioconjugated quantum dots as fluorescent probes for bioanalytical applications

Quantum dots (QDs) are inorganic semiconductor nanocrystals that have unique optoelectronic properties responsible for bringing together multidisciplinary research to impel their potential bioanalytical applications. In recent years, the many remarkable optical properties of QDs have been combined with the ability to make them increasingly biocompatible and specific to the target. With this great development, QDs hold particular promise as the next generation of fluorescent probes. This review describes the developments in functionalizing QDs making use of different bioconjugation and capping approaches. The progress offered by QDs is evidenced by examples on QD-based biosensing, biolabeling, and delivery of therapeutic agents. In the near future, QD technology still faces some challenges towards the envisioned broad bioanalytical purposes.      

Asymptotics for Hessenberg Matrices for the Bergman Shift Operator on Jordan Regions

Let $G$ be a bounded Jordan domain in the complex plane. The Bergman polynomials $\{p_n\}_{n=0}^\infty $ of $G$ are the orthonormal polynomials with respect to the area measure over $G$ . They are uniquely defined by the entries of an infinite upper Hessenberg matrix $M$ . This matrix represents the Bergman shift operator of $G$ . The main purpose of the paper is to describe and analyze a close relation between $M$ and the Toeplitz matrix with symbol the normalized conformal map of the exterior of the unit circle onto the complement of $\overline{G}$ . Our results are based on the strong asymptotics of $p_n$ . As an application, we describe and analyze an algorithm for recovering the shape of $G$ from its area moments.     

Anion recognition by functionalized single wall carbon nanotubes

Amidoferrocenyl-functionalised single wall carbon nanotubes (Fc-SWNT) are efficient exoreceptors for the redox recognition of H2PO4-.     

Absolutely minimising generalised solutions to the equations of vectorial calculus of variations in $$L^\infty $$

Consider the supremal functional

$$\begin{aligned} E_\infty (u,A) := \Vert \mathscr {L}(\cdot ,u,\mathrm {D}u)\Vert _{L^\infty (A)},\quad A\subseteq \Omega , \end{aligned}$$

(1)

applied to \(W^{1,\infty }\) maps \(u:\Omega \subseteq \mathbb {R}\longrightarrow \mathbb {R}^N\), \(N\ge 1\). Under certain assumptions on \(\mathscr {L}\), we prove for any given boundary data the existence of a map which is:

1. (i)
   a vectorial Absolute Minimiser of (1) in the sense of Aronsson,
    
2. (ii)
   a generalised solution to the ODE system associated to (1) as the analogue of the Euler-Lagrange equations,
    
3. (iii)
   a limit of minimisers of the respective \(L^p\) functionals as \(p\rightarrow \infty \) for any \(q\ge 1\) in the strong \(W^{1,q}\) topology and
    
4. (iv)
   partially \(C^2\) on \(\Omega \) off an exceptional compact nowhere dense set.
    

Our method is based on \(L^p\) approximations and stable a priori partial regularity estimates. For item ii) we utilise the recently proposed by the author notion of \(\mathcal {D}\)-solutions in order to characterise the limit as a generalised solution. Our results are motivated from and apply to Data Assimilation in Meteorology.

     

Anionic polymerization of styrenic macromonomers of polyisoprene,polybutadiene, and polystyrene

Anionic polymerization and high‐vacuum techniques were used to prepare a series of well‐defined polyisoprene, polybutadiene, and polystyrene polymacromonomers. The procedure involved (1) the synthesis of styrenic macromonomers in benzene by the selective reaction of the corresponding macroanion with the chlorine of 4‐(chlorodimethylsilyl)styrene (CDMSS) and (2) the in situ anionic polymerization of the macromonomer without previous isolation. The synthesis of the macromonomers [polyisoprene macromonomer: 11 samples, weight‐average molecular weight (M_w) = 1000–18,000; polybutadiene macromonomer: 5 samples, M_w = 2000–4000; and polystyrene macromonomer: 2 samples, M_w = 1300 and 3600] was monitored by size exclusion chromatography with refractive index/ultraviolet detectors. Selectivity studies with CDMSS indicated that polybutadienyllithum had the highest selectivity, and polystryryllithium the lowest. From kinetic studies it was concluded that the polymerization half‐life times were longer but comparable to those of styrene, and they appeared to only slightly depend on the molecular weight of the macromonomer chain (at least for low degrees of polymerization of the polymacromonomer and for M_w < 7000 for the macromonomer side chain). Dependence on the polymerization degree of the polymacromonomer product was also observed. All the prepared polymacromonomers were characterized by size exclusion chromatography with refractive index, ultraviolet and two‐angle laser light scattering detectors, and NMR spectroscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1038–1048, 2005     

Hydrodynamic properties of model 3-miktoarm star copolymers

The synthesis of well-defined, nearly monodispersed, 3-miktoarm (from the greek word μlkτós meaning mixed) star copolymer of the A₂B type is described. A and B is either polystyrene (PS), polybutadiene (PBd), or polyisoprene (PI). The sequential controlled addition of living anionic B and A chains to methyltrichlorosilane leads to narrow molecular weight distribution miktoarm star copolymers with homogeneous composition. Characterization was carried out by size exclusion chromatography, low-angle laser light scattering, laser differential refractometry, membrane and vapor pressure osmometry, nuclear magnetic resonance and ultraviolet spectroscopy. Analysis of [η], R_H and R_v of the A₂B and one A₂B₂ miktoarm copolymers, suggests that a small expansion of the copolymer occurs either in a good solvent for both species or in a Θ solvent for one of them, as compared with the corresponding star homopolymers. This is in contrast to results obtained on linear block copolymers, and is due to the increased occurrence of heterocontacts in the miktoarm starshaped architecture. © 1995 John Wiley & Sons, Inc.     

Nearest neighbor ising model with added local 4-spin interaction

The effects of adding a local 4-spin term to the nearest neighbor Ising model are studied. The relevant parameter isx, the ratio of the four- to the two-spin interaction strength. We have evaluated the first six terms of the high temperature susceptibility expansion and found them to be consistent with the value 1.75 of the critical exponent γ. The critical exponent α is shown to remain zero to first order inx, provided that the free energy is analytic inx. We also demonstrate the equivalence of the model examined to an elastic spin system with pure two-spin interactions.