Optically Driven Encapsulation Using Novel Polymeric Hollow Shells Containing an Azobenzene Polymer

A novel method of macromolecule encapsulation using micron‐sized polymeric shells constructed with a photoactive azobenzene containing polyelectrolyte is discussed. Fluorescently labeled dextran molecules were encapsulated using light to remotely shrink and change the wall permeability of new polymeric hollow shells. We observed that the proportion of shells with dye encapsulated increased along with the duration of irradiation. Electron microscopy imaging illustrated significant changes in the surface roughness of shells after being exposed to light. Finally, this new system was shown to possess a high thermal stability.

     

Electron impact studies. CVII—Negative ion mass spectra of the oxime group. Monoximes derived from α-dicarbonyl systems

Specific losses of water are observed from the molecular anions of monoximes of α-diketones. Labelling studies, kinetic energy release values and the +E spectra of ions have been used to aid in the elucidation of the fragmentation pathways. It is proposed that the majority of ions have α-keto nitrile structures.     

Penultimate Propagation Kinetics of Butyl Methacrylate,Butyl Acrylate,and Styrene Terpolymerization

The pulsed‐laser polymerization technique is used to determine the composition‐averaged free‐radical propagation rate coefficient (k_p,ter) for terpolymerization of butyl methacrylate, butyl acrylate, and styrene between 60 and 120 °C. A significant deviation from terminal model predictions is observed for the ternary system, indicating that penultimate kinetics are important at these industrially relevant temperatures. The implicit penultimate propagation model, with all the coefficients taken from previous studies of the binary systems, provides a good prediction of the experimental k_p,ter results.

     

PMMA/Zinc Oxide Nanocomposites Prepared by In‐Situ Bulk Polymerization

Summary: Dispersing surface‐modified zinc oxide nanoparticles (ZnO) in methyl methacrylate (MMA) improves the free radical bulk polymerization process as well as the thermal stability of the formed polymer. Hydroxy groups available on the ZnO surface may induce a degenerative transfer. This suppresses the gel effect, which leads to a better control of the heat evolution during the late stages of polymerization. The formation of chains having vinylidene end groups and head‐to‐head links is suppressed, which shifts the onset of thermal decomposition to the regime where decomposition occurs by random chain scission.

Thermal degradation profiles of PMMA and its composite with ZnO at 11 wt.‐%.     

Facile Synthesis of Self‐Assembled Polyaniline Nanodisks

Polyaniline nanodisks have been synthesized successfully by the chemical oxidation polymerization of aniline by a self‐assembly process without the use of any acid. The thickness and lateral dimensions of the polyaniline nanodisks are in the range of 20–30 nm and 1–2 µm, respectively. The influence of synthetic parameters, such as the concentration of ammonium peroxydisulfate and pH, on the morphologies of polyaniline nanostructures have been investigated.

     

Photo‐Induced Solid‐State Crosslinking of Electrospun Poly(vinyl alcohol) Fibers

Summary: Poly(vinyl alcohol) (PVA) was derivatized by polymer analogous reaction with thienyl acryloyl chloride and processed to submicrometer fibers by electrospinning from aqueous solution. Water solubility of otherwise water‐soluble PVA fibers was reduced considerably by UV crosslinking of thienyl acrylate modified PVA fibers in the solid state. Water stability of these crosslinked fibers was proven by water steam test at 95 °C.

UV/Vis spectrum of PVA‐Thio fibers irradiated for different periods at 300 nm.     

Polymer/Laponite Composite Latexes: Particle Morphology,Film Microstructure,and Properties

Transparent film materials with excellent mechanical and thermal properties were elaborated by drying a latex suspension of armored polymer/Laponite composite particles. Low‐temperature TEM observation of ultrathin cross‐sections of the films indicated a unique network morphology characterized by a “honeycomb” distribution of the Laponite platelets remindful of the original particles morphology.

     

Tuning the Properties of Functional Pyrrolidinium Polymers by (Co)polymerization of Diallyldimethylammonium Ionic Liquids

The synthesis and polymerization of novel diallyldimethylammonium ionic liquid monomers is described. A free‐radical polymerization follows a ring‐closing cyclopolymerization mechanism similar to the one observed previously for diallyldimethylammonium halides that leads to pyrrolidinium functional polymers. As previously observed in other families of polymeric ionic liquids, their physico‐chemical properties are seriously affected by the nature of the counter‐anion. As an example, the thermal stability increases following the trend SCN⁻ < < < bis(trifluoromethane)sulfonamide. Interestingly, this polymerization route may lead to the synthesis of a new family of random copolymers that have a similar poly(diallyldimethylammonium) backbone and a mixture of counter‐anions determined by the comonomer selection.

     

Pore‐Functionalized Nanoporous Materials Derived from Block Copolymers

This review deals with nanoporous materials made from the self‐assembly of block copolymers with a special interest in the chemical functions covering the surface of their nanopores. A detailed overview of the existing methods and strategies to generate well‐defined organic functional groups covering the surface of the pore walls is provided. This further enables to finely tune the affinity of the pore walls and to perform well‐defined chemical reactions onto them, which is essential for further dedicated applications.

     

A Lipase‐Responsive Vehicle Using Amphipathic Polymer Synthesized with the Lipase as Catalyst

We describe an enzyme‐responsive polymeric vehicle, which is of great interest in controlled drug delivery, biosensing, and other related areas. The polymer synthesized using lipase as catalyst in DMSO has a favorable molecular structure that is quickly hydrolyzed by lipase in aqueous phase, and allows a fast release of encapsulated molecules.

     

Supramolecular Hydrogels with CdS Quantum Dots Incorporated by Host–Guest Interactions

In this communication, β‐cyclodextrin modified quantum dots were used as a water‐soluble “supramolecular” cross‐linker (SCL) because of its surface's supramolecular activity. The guest monomer‐loaded SCL (mSCL) can be used to copolymerize with water‐soluble monomers leading to transparent hybrid supramolecular hydrogels. This simple and versatile method opens new venues for the preparation of hybrid supramolecular hydrogels and the host–guest chemistry of cyclodextrins.

     

Electrical Conductivity of an Individual Polyaniline Nanotube Synthesized by a Self‐Assembly Method

Camphor sulfonic acid (CSA) doped polyaniline (PANI) nanotubes (175 nm in outer diameter and 120 nm in inner diameter) were synthesized successfully by a self‐assembly method. It is found that the room‐temperature conductivity of an individual PANI nanotube is 30.5 S · cm⁻¹; in particular, the intrinsic resistance of an individual nanotube (30 kΩ) is much smaller than the contact resistance of crossed nanotubes (500 kΩ).

A SEM image of two crossed PANI‐CSA nanotubes and the attached Pt electrodes.     

Enzyme‐Catalyzed Preparation of Aliphatic Polythioester by Direct Polycondensation of Diacid Diester and Dithiol

Summary: Aliphatic dithiol‐diacid type polythioesters were first enzymatically prepared by the direct polycondensation of hexane‐1,6‐dithiol and diacid diesters using the immobilized lipase from Candida antarctica (lipase CA). As a typical example, diethyl sebacate and hexane‐1,6‐dithiol were polymerized using lipase CA in bulk in the presence of molecular sieves 4A to produce the corresponding polythioester with an of 10 200 in 90% yield. Both the melting and crystallization temperatures of the produced polythioesters were higher when compared to those of the corresponding polyoxyesters. A higher molecular weight polythioester was produced using lipase in a two‐step procedure, i.e., cyclization with subsequent ring‐opening polymerization.

Preparation of polythioester and melting temperature of various polythioesters and polyoxyesters.