Synthesis and Characterization of Chitosan Grafted Oligo(L‐lactic acid)

Chitosan grafted oligo(L ‐lactic acid) copolymers with different length of side chain were prepared through the reaction of terminal aldehyde group of oligo(L ‐lactic acid) (OLLA) and amino groups of chitosan. The mean molecular mass of the grafting OLLA chain was ca. 600 ～ 5 000. The graft copolymers are soluble in DMSO, DMF and acetic acid. The synthesis method and structure described here provide chitosan‐g‐OLLA copolymers with broad applicability.

Structure of chitosan‐g‐oligo(L ‐lactic acid).     

Self‐Catalysis of Phthaloylchitosan for Graft Copolymerization of ε‐Caprolactone with Chitosan

Summary: A protection‐graft‐deprotection method was developed to prepare chitosan‐g‐polycaprolactone graft copolymers, during which the ring‐opening copolymerization of ε‐caprolactone onto phthaloylchitosan (PHCS) happened without any additional catalysis. The intermediate PHCS was introduced primarily to protect the active amino group of chitosan. After controlled experiments, the phthalimido compound was proposed to be a novel kind of organic catalyst for the ring‐opening polymerization of caprolactone monomers, while the hydroxyl group acted as an initiator. Hence, in this graft system, PHCS was endowed with both self‐catalysis and self‐initiation at the same time, and the PCL side chains grew from the hydroxyl groups of the chitosan backbone.

     

Spontaneous Birefringence in Layer‐by‐Layer Films of Chitosan and Azo Dye Sunset Yellow

Layer‐by‐layer (LBL) films consisting of layers of the azo dye Sunset Yellow alternated with chitosan display spontaneous birefringence, which is attributed to the film anisotropy imparted by the LBL method. This is unusual for azobenzene‐containing materials as they normally form films with randomly oriented molecules, presenting birefringence only due to photoinduced isomerization cycles. Spontaneous birefringence does not appear in cast films, but occurs for LBL films obtained under various experimental conditions.

Chemical structures of (a) Sunset Yellow and (b) chitosan.     

Chemoenzymatic Synthesis of Amylose‐Grafted Chitosan

An amylose‐grafted chitosan has been synthesized by a chemoenzymatic method according to the following two reactions. First, maltoheptaose is introduced to chitosan by a reductive amination using sodium cyanotrihydroborate in a mixed solvent of 1.0 mol · L⁻¹ aqueous acetic acid and methanol at room temperature to produce a maltoheptaose‐grafted chitosan that has a well‐defined molecular structure. A phosphorylase‐catalyzed enzymatic polymerization of α‐D ‐glucose 1‐phosphate is then performed from the maltoheptaose‐grafted chitosan to obtain the amylose‐grafted chitosan. This material does not dissolve in any solvent, e.g., aqueous acetic acid and dimethyl sufoxide, which are good solvents for chitosan and amylose, respectively.

     

A Catalytic Approach to Functional Poly(1,4‐ketone)s Bearing Pendant Monosaccharide Fragments

Summary: Novel alternating polyketone‐based polymers bearing pendant saccharide units that are accessible by polymerization catalysis are presented. The materials were synthesized by polymerization of carbon monoxide and α‐olefins containing protected glucose or N‐acetyl glucosamine residues. The dicationic Pd^II bis(phoshine) complex [Pd(dppp)(NCCH₃)₂](BF₄)₂ was used as a catalyst precursor. An O‐deacetylation of the copolymers afforded materials with amphiphilic character.

Structure of the poly(1,4‐ketone) copolymers synthesized here.     

Preparation of Crosslinked Chitosan/Silk Fibroin Blend Films for Drug Delivery System

Crosslinked chitosan/silk fibroin blend films were prepared by a solution casting technique using glutaraldehyde as crosslinking agent. Drug release characteristics of the blend films with various blend compositions were investigated. Theophylline, diclofenac sodium, amoxicillin trihydrate, and salicylic acid were used as model drugs. The release studies were performed at 37 °C in buffer solutions at pH 2.0, 5.5, and 7.2. It was found that the blend films with 80% chitosan content showed the maximum amount of model drug release at pH 2.0 for all the drugs studied here. This result corresponded to the swelling ability of the blend films. From a swelling study, the maximum degrees of swelling of the drug‐loaded blend films were obtained at this pH and blend composition. The amount of drugs released from the films with 80% chitosan content, from the highest to the lowest values, occurred in the following sequence: salicylic acid > theophylline > diclofenac sodium > amoxicillin.

Comparison of the amounts of drug released from chitosan and the blend film with 80% chitosan content at pH 2.0: (filled) chitosan film, and (blank) blend film with 80% chitosan content (SAL = salicylic acid, THEO = theophylline, DFS = diclofenac sodium, AMX = amoxicillin).     

A Click Approach to Chiral‐Dendronized Polyfluorene Derivatives

A new kind of chiral‐dendronized binaphthyl‐containing polyfluorene derivatives has been synthesized through “click chemistry” efficiently. The resulting copolymers exhibited desirable properties, such as excellent solubility, good thermal stability, and considerably high molecular weights. The photophysical properties of the copolymers were investigated in details, and the results indicated that the combination of chiral binaphthyl unit and bulky dendron could effectively suppress intermolecular packing and aggregation. In addition, the investigation of circular dichroism behavior of these chiral‐dendronized copolymers showed a strong Cotton effect at long wavelength (373–379 nm), indicating that the chirality of the binaphthyl units was transferred to the whole polyfluorene backbone.

     

Chemical Modification of Chitosan, 17

The Michael reaction of chitosan with acrylic acid was carried out successfully, even in water alone as the reaction medium. As a consequence of its good solubility in water, the reaction product, N‐carboxyethylchitosan, showed excellent biodegradable properties with standard activated sludge.

     

Porphyrinated Nanofibers via Copolymerization and Electrospinning

Summary: The first example of the synthesis of acrylonitrile copolymers with porphyrin pendants and the subsequent electrospinning of the resultant copolymers into nanofibers is presented in this communication. Vinyl porphyrin monomers have been synthesized and copolymerized with acrylonitrile through solution polymerization. FT‐IR, NMR, UV‐vis, and fluorescence spectroscopy are used to characterize the copolymers. Preliminary quantum chemical calculations have also been carried out to reveal the activity of the vinyl porphyrin monomers. Nanofibers with a diameter of around 330 nm are prepared by electrospinning the copolymer solutions. Their morphology and porphyrination are clearly observed by field‐emission scanning electron microscopy and fluorescence microscopy. It is speculated that this type of nanofiber may be a latent support of porphyrins for various purposes such as catalysis, molecular imprinting, sensors, and light/energy conversion.

The formation of luminescent nanofibers from porphyrinated polymers.     

Automated Parallel Synthesis of MADIX (Co)Polymers

An automated parallel synthetic approach has been developed for synthesizing polymer libraries by the Macromolecular Design via the Interchange of Xanthates (MADIX) process. The experimental set‐up, parallel polymerizations, characterization, and reproducibility tests are detailed. Examples of acrylic diblock copolymers synthesized in this way are given.

Automated MADIX polymerizations of BA in the presence of a X₁ ‐capped PEA.     

Binary Reactive/Inert Non‐Fouling Polymeric Surfaces

Binary reactive/inert antifouling polymer brushes were grafted via a two step surface initiated polymerization from printed initiator monolayer and provided robust, effective polymeric surfaces for bioattachment with distinguishably reduced non‐specific adsorption. This synthetic strategy can be harnessed to build complex binary polymeric structures on substrate surfaces and the polymer brush surfaces reported in the present paper can be widely used for versatile biological study.

     

Direct Synthesis of Poly(dimethylsiloxane) Copolymers with TPE‐Properties via CuAAC (Click Chemistry)

Poly(dimethylsiloxane) copolymers were synthesized directly from AA/BB monomers employing a CuAAC reaction (click chemistry) in a polyaddition approach. Using organic dialkynes and oligo(siloxane)s end‐functionalized with azide moieties it was possible to obtain siloxane‐based copolymers with TPE properties by click chemistry for the first time. As seen from DSC experiments, properties were strongly dependent on the incorporated organic comonomer.

     

Drug Delivery Systems Based on Porous Chitosan/Polyacrylic acid Microspheres

Porous microspheres have been prepared by suspension free radical polymerization of acrylic acid (AA) in the presence of chitosan (CHI). The microspheres were characterized by FTIR and environmental SEM. The PAA content of the microspheres was estimated to be in the range 45–50 wt.‐%. The swelling degree of these particles is almost constant in the range 2 < pH < 5, but it increases considerably as the pH is raised from 5 to 10. The release profiles of microspheres loaded with meclofenamic acid (MF) were determined at pH 2, 7.4, and 10. The in vitro release of MF at different pHs was modulated by the solubility of the drug. These microcapsules are biodegradable and presented good biocompatibility and biodegradability during in vivo experiments.

ESEM microphotograph of the porous PAA/CHI microspheres.     

Nanostructured Thermosetting Systems from Epoxidized Styrene Butadiene Block Copolymers

Summary: Nanostructured thermosetting materials were prepared by modification of an epoxy resin with 30 wt.‐% epoxidized polystyrene‐block‐polybutadiene copolymer (PS‐b‐PepB). The copolymer self‐assembles into a well‐defined hexagonal nanoordered structure, of around 30‐nm diameter, thus establishing its use as structure‐directing agent to generate nanostructured thermosetting materials. The study confirms pathways towards tailoring interactions between thermosetting matrices and immiscible block copolymers by using the concept of functionalization to build nanostructured polymer matrices.

Structure of diglycidyl ether of bisphenol‐A/4,4′‐methylenebis(3‐chloro 2,6‐diethylaniline) cured blend containing 30 wt.‐% PS‐b‐PepB61 block copolymer.     

Mechanical Reinforcement of Continuous Flow Spun Polyelectrolyte Complex Fibers

A simple continuous flow wet‐spinning method to achieve mechanical reinforcement of the two oppositely charged biopolymers chitosan and gellan gum is described. The mechanical properties of these biopolymers are influenced by the order of addition. Using a facile method for mechanical reinforcement of gellan gum/chitosan fibers resulted in increases in Young's modulus, tensile strength, and toughness. Spinning gellan gum into chitosan resulted in the strongest fibers. We show that our fibers can provide a mechanical alternative for bio‐fibers without the need of cross‐linking. It is demonstrated that the fibers become ionically conducting in the presence of water vapor.

     

Step‐Growth Radical Addition‐Coupling Polymerization (RACP) for Synthesis of Alternating Copolymers

We report a new type of step‐growth radical addition‐coupling polymerization (RACP) involving consecutive addition of carbon‐centered radical derived from α,α′‐dibromo dibasic ester to NO double bond of C‐nitroso compound followed by cross‐coupling of carbon‐centered radical and in situ formed nitroxyl radical, which produces alternating copolymers with high molecular weight and unimodal molecular weight distribution from saturated and unsaturated monomers.

     

On‐Chip Alginate Microencapsulation of Functional Cells

We report the use of a PTFE‐based microfluidic device for the encapsulation of living, therapeutically‐active cells within monodisperse alginate microspheres. We present a novel microfluidic platform and a flexible experimental method for the production of alginate microspheres. Cell lines HEK293, U‐2 OS and PC12 were separately encapsulated using this method, with minimal loss of cell viability.

     

Sorption of Hydrophobic Organic Compounds by Aqueous Latexes

Summary: Optical absorption measurements are used for the first time to investigate the uptake of pure organic solvents or solutions by latex particles. Sorption into glassy polymer particles is a two‐stage process with distinctly different characteristic times, which reflects that an initial softening of the outer particle layer facilitates further uptake. The sorption of solutions containing highly water‐insoluble compounds allows the preparation of composite nanoparticles, which are hardly accessible by other routes.

Photograph of the neat 100 nm latex (right) particles and the particles after dying by sorption with the hydrophobic pigment Sudan IV (left).     

Ultra‐Fast RAFT‐HDA Click Conjugation: An Efficient Route to High Molecular Weight Block Copolymers

The use of the reversible addition fragmentation chain transfer—hetero Diels–Alder (RAFT‐HDA) click reaction for the modular construction of block copolymers is extended to the generation of high molecular weight materials. Cyclopentadienyl end‐functionalized polystyrene (PS‐Cp) prepared via both atom transfer radical polymerization (ATRP) and the RAFT process are conjugated to poly(isobornyl acrylate) (PiBoA) (also prepared via RAFT polymerization) to achieve well‐defined block copolymers with molecular weights ranging from 34 000 to over 100 000 g · mol⁻¹ and with small polydispersities (PDI < 1.2). The conjugation reactions proceeded in a very rapid fashion (less than 10 min in the majority of cases) under ambient conditions of temperature and atmosphere. The present study demonstrates—for the first time—that RAFT‐HDA click chemistry can provide access to high molecular weight block copolymers in a simple and straight‐forward fashion.

     

Linear Azo Polymer Containing Conjugated 5,5′‐Azodisalicylic Acid Segments in the Main Chain: Synthesis,Characterization, and Degradation

Summary: Copolymers of poly(ethylene oxide) (PEO) and 5,5′‐azodisalicylic acid (Olsalazine, OLZ) were synthesized and evaluated by hydrolysis and in‐vitro biodegradation with azoreductase. It was found that changing the molecular weight of the PEO blocks affected the loading ratio of OLZ, and resulted in significant differences in the hydration and degradability of the copolymers. These novel azo‐containing copolymers can be used in colon‐specific drug delivery.

Release of 5‐ASA from OLZ and PEO‐OLZ copolymers incubated with rat cecum content in the presence of benzyl viologen and α‐D ‐glucose.