Precise Synthesis and Thin Film Self-Assembly of PLLA-b-PS Bottlebrush Block Copolymers

The ability of bottlebrush block copolymers (BBCPs) to self-assemble into ordered large periodic structures could greatly expand the scope of photonic and membrane technologies. In this paper, we describe a two-step synthesis of poly(l-lactide)-b-polystyrene (PLLA-b-PS) BBCPs and their rapid thin-film self-assembly. PLLA chains were grown from exo-5-norbornene-2-methanol via ring-opening polymerization (ROP) of l-lactide to produce norbornene-terminated PLLA. Norbonene-terminated PS was prepared using anionic polymerization followed by a termination reaction with exo-5-norbornene-2-carbonyl chloride. PLLA-b-PS BBCPs were prepared from these two norbornenyl macromonomers by a one-pot sequential ring opening metathesis polymerization (ROMP). PLLA-b-PS BBCPs thin-films exhibited cylindrical and lamellar morphologies depending on the relative block volume fractions, with domain sizes of 46–58 nm and periodicities of 70–102 nm. Additionally, nanoporous templates were produced by the selective etching of PLLA blocks from ordered structures. The findings described in this work provide further insight into the controlled synthesis of BBCPs leading to various possible morphologies for applications requiring large periodicities. Moreover, the rapid thin film patterning strategy demonstrated (>5 min) highlights the advantages of using PLLA-b-PS BBCP materials beyond their linear BCP analogues in terms of both dimensions achievable and reduced processing time.     

Neutral Community Theory: How Stochasticity and Dispersal-Limitation Can Explain Species Coexistence

Neutral community theory explains biodiversity, i.e. the coexistence of several species, as the result of a stochastic balance between immigration and extinction on a local level, and between speciation and extinction on a regional level. The most popular model, presented by Hubbell in 2001, has seen many analytical developments in recent years, which can be used in model analysis, model testing and model comparison. We review these developments here, and present alternative derivations and shine previously unnoticed lights on them.     

Etude structurale des sulfotellurures de terres rares (LS)2Te1+x (L = Tb,Dy, Ho,Er, Tm et Y). I. Sous-structure de la phase ordonnée de (HoS)2Te1,34. Structure de la phase desordonnée de (TbS)2Te

The lanthanide sulfotellurides (LS)₂Te_1+x (0 ≤ x < 0.50) show order-disorder phenomena. Above 450°C, they crystallize in a partially disordered structure, orthorhombic with cell parameters a, b, and c close to 4.1, 5.2, and 13.6 Å, respectively. This structure is determined from diffractometer data on a (HoS)₂Te_1.34 crystal (R = 0.061). It is built up along the c axis from (L₄S) tetrahedra layers, separated by Te planes. Disorder and nonstoichiometry are related to the two vacant Te sites.     

Charge-changing cross sections of the neutron-rich isotopes8,9,11Li

Total charge-changing cross sections have been measured for⁸Li on C and Pb targets, for⁹Li on C, Al, Cu, Sn and Pb targets, as well as for¹¹Li on C, Sn and Pb targets at about 80 MeV/nucleon. These data are compared to measured total reaction cross sections and Glauber-type calculations using Hartree-Fock density distributions. These comparisons allow to draw conclusions on the proton density distribution of the neutronrich lithium isotopes. The results show that even for the most exotic nucleus¹¹Li the proton distribution is only very weakly influenced by the long tail in the neutron density distribution already established in several experiments.     

On the uniqueness of minimizing harmonic maps to a closed hemisphere

We study the uniqueness of minimizing harmonic maps to a closed hemisphere. We are able to describe the boundary data for which there are more than one minimizer, and to describe in these cases the corresponding set of minimizers. This is a limiting case for a former result of W.Jäger and H.Kaul.This article was processed by the author using the Springer-Verlag T_EX PJourlg macro package 1991.     

111In–L–LDL and 153Gd–L–LDL as radiotracers for detection of AR4‐2J rat pancreatic tumors

Pancreatic cancer has an extremely poor prognosis, due, in part, to lack of methods for early diagnosis. The present study was designed to evaluate the potential of labeling low‐density lipoprotein (LDL) with a radionuclide using a lipid chelating agent, bis(stearylamide) of diethylenetriaminepentaacetic acid (L), to detect pancreatic tumors by gamma‐scintigraphy. Previous studies indicated that the difficulty of visualization of pancreatic tumors was due to their poor vascularization. This study compares the ability of two radiotracers, ¹¹¹In–L–LDL and ¹⁵³Gd–L–LDL to target highly vascularized rat pancreatic tumors (AR4‐2J) implanted in nude mice. Biodistribution studies showed that the tumor uptake of ¹¹¹In–L–LDL and ¹⁵³Gd–L–LDL tracers was twofold and fivefold higher respectively than with the controls (¹¹¹In citrate and ¹⁵³Gd citrate respectively). These tracers would thus be suitable for scintigraphic imaging. We show here that LDL could be employed as a delivery system for tracers such as ¹¹¹In or ¹⁵³Gd when these two radionuclides are complexed by a lipid‐chelating anchor, and that ¹¹¹In–L–LDL and ¹⁵³Gd–L–LDL enabled better visualization of the pancreatic tumor tissues, with a better result with ¹⁵³Gd–L–LDL. Copyright © 2004 John Wiley & Sons, Ltd.     

Rate of Convergence of a Stochastic Particle System for the Smoluchowski Coagulation Equation

By continuing the probabilistic approach of Deaconu et al. (2001), we derive a stochastic particle approximation for the Smoluchowski coagulation equations. A convergence result for this model is obtained. Under quite stringent hypothesis we obtain a central limit theorem associated with our convergence. In spite of these restrictive technical assumptions, the rate of convergence result is interesting because it is the first obtained in this direction and seems to hold numerically under weaker hypothesis. This result answers a question closely connected to the Open Problem 16 formulated by Aldous (1999).     

Oxidative deamination of benzylamine by electrogenerated quinonoid systems as mimics of amine oxidoreductases cofactors

The reactions of a new type of quinonoid system with benzylamine have been investigated in methanol in order to mimic the reactions occurring in the course of the enzymatic oxidation of amines by quinone cofactors. Under strictly anaerobic conditions, unstable quinonoid species 1(ox)()-4(ox)() have been selectively electrogenerated using anodic-controlled potential electrolysis. Thus, we have demonstrated that 3,4-quinone 1(ox)() is incapable of deaminating benzylamine, while 3,4-iminoquinone species 3(ox)() and 4(ox)() act as efficient catalysts for the autorecycling oxidation of benzylamine: the reaction efficiency reached 64 turnovers. Additional mechanistic investigations reveal that the oxidation of benzylamine by our quinonoid model cofactors proceeds unambiguously via a transamination mechanism, as suggested for many enzymatic systems.     

Tribological properties of ormosil coatings

Transparent plastics are not scratch resistant. The damage leads to a loss of optical properties. Coatings prepared using either tetraethoxysilane or colloidal silica particles embedded in glymo is a way to avoid these disadvantages. Tribological experiments are carried out to better understand the surface modification due to a sliding friction. It is shown that the wear track is not directly related to usual mechanical properties such as Young's modulus and the hardness of the coating. The different stages leading to material loss are discussed in term of particle removal and debris circulation (accumulation or elimination) through the friction track. The mechanical properties of the film combined with the film to substrate adhesion are expected to play an important role as it can be deduced from results obtained as a function of the coating composition.