Kouroush Salimi

Controlled graft copolymerization of lactic acid onto starch in a supercritical carbon dioxide medium.

This work presents a new approach for the synthesis of a starch-g-poly L-lactic acid (St-g-PLA) copolymer via the graft copolymerization of LA onto starch using stannous 2-ethyl hexanoate (Sn(Oct)2) as a catalyst in a supercritical carbon dioxide (scCO2) medium. The effects of several process parameters, including the pressure, temperature, scCO2 flow rate and reaction time, on the polymerization yield and grafting degree were studied. Amorphous graft St-g-PLA copolymers with increased thermal stability and processability were produced with a high efficiency. The maximum grafting degree (i.e., 52% PLA) was achieved with the following reaction conditions: 6h, 100°C, 200 bar and a 1:3 (w/w) ratio of St/LA. It was concluded that these low cost biobased graft biopolymers are potential candidates for several environment-friendly applications.

Highly selective magnetic affinity purification of histidine-tagged proteins by Ni2+ carrying monodisperse composite microspheres

A magnetic sorbent with stable and superior magnetic behaviour was developed for His-tagged protein purification by immobilized metal affinity chromatography (IMAC). Magnetic, monodisperse and porous silica microspheres 6 μm in size, with bimodal pore size distribution including both mesoporous and macroporous compartments were synthesized as the base material by a staged-shape template hydrolysis & condensation protocol. The magnetic microspheres were functionalized with iminodiacetic acid (IDA) and Ni2+ ions were attached onto the microspheres by metal-chelate formation via carboxyl groups. The saturation magnetization and carboxyl content of IDA attached magnetic silica microspheres were determined as 22.1 emu g−1 and 19 mmol IDA g−1 microspheres, respectively. A superior magnetic response with respect to the currently available IMAC sorbents in the form of composite magnetic nanoparticles was obtained with the proposed sorbent. The magnetic sorbent was utilized for the isolation of His-tagged green fluorescent protein (GFP) from E. coli lysate in batch-fashion. The maximum equilibrium GFP adsorption was ca. 87 mg GFP per g sorbent. GFP was isolated with high selectivity (>95% purity) and isolation yields up to 68% by changing the magnetic sorbent concentration. The superior isolation performance of the sorbent was explained by the presence of a bimodal pore structure including both macropores facilitating the intraparticular diffusion of GFP, and the mesopores serving a large surface area for parking and adsorption of GFP into the microbeads.

Microwave-assisted rapid synthesis of poly(glycerol-sebacate) elastomers

Poly(glycerol-sebacate) (PGS) was introduced a decade ago as a potential material for soft tissue repair. All of the proposed copolymerization reactions in the literature include a two-stage (prepolymerization and curing) synthesis where the reaction times can take as long as several days. This study, on the other hand, proposes a new route that eliminates these disadvantages and enables a rapid synthesis of PGS elastomers via microwave-assisted prepolymerization in minutes instead of days. No purge gas, catalyst or vacuum is needed in the first prepolymerization step. The curing stage was carried out at 150 °C for 4, 8, 16, and 24 hours. The glass transition temperature (Tg) and melting temperatures for the glycerol and sebacic acid fragments (Tm1 and Tm2 ) of these PGS elastomers were found as -35.61 °C, -15.82 °C, and 61.70 °C, respectively. The Youngs modulus and tensile strength values were found as 0.50 ± 0.02 MPa and 0.27 ± 0.06 MPa, respectively.

Fabrication and characterization of novel starch-grafted poly l-lactic acid/montmorillonite organoclay nanocomposites

In this work, poly(L-lactic acid)-g-starch layered silicate nanocomposites (NCs) (PLLA-g-starch/MMT) were fabricated by intercalative bulk graft copolymerization of LA with starch, in the presence of either stannous octoate acting as a catalyst or LA-MMT organoclay acting as a cocatalyst-nanofiller. This procedure was performed inside a custom vacuum micro-reactor. To better understand the graft copolymerization mechanism, in situ processing types, interfacial interactions and nanostructure formation of PLLA-g-starch/MMT NCs, methods such as FT-IR, XRD, (1)H NMR, (13)C CP/MAS-NMR, DSC/TGA, TEM and SEM were utilized. The morphology and thermal behaviors of nanocomposites were found to be strongly dependent on the loading mass fraction of LA-MMT within the nanocomposite structure and the type of in situ processing such as interfacial, physical and chemical interactions. Preintercalated LA-MMT organoclay exhibited dual functions. It demonstrated the ability to act as a catalyst, essentially accelerating in situ graft copolymerization via esterification of LA carboxyl groups with hydroxyl groups of starch macromolecules, whilst also acting as a nananofiller-compatibilizer.

Novel multifunctional colloidal carbohydrate nanofiber electrolytes with excellent conductivity and responses to bone cancer cells.

This work presents a new approach to fabricating novel polymer nanofiber composites (NFCs) from water solution blends of PVA (hydrolyzed 89%)/ODA-MMT and Na-CMC/ODA-MMT nanocomposites as well as their folic acid (FA) incorporated modifications (NC-3-FA and NC-4-FA) through green electrospinning nanotechnology. The chemical and physical structures and surface morphology of the nanofiber composites were confirmed. Significant improvements in nanofiber morphology and size distribution of the NFC-3-FA and NFC-4-FA nanofibers with lower average means 110 and 113nm compared with those of NFC-1/NFC-2 nanofibers (270 and 323nm) were observed. The structural elements of polymer NFCs, particularly loaded partner NC-2, plays an important role in chemical and physical interfacial interactions, phase separation processing and enables the formation of nanofibers with unique morphology and excellent conductivity (NFC-3-FA 3.25×10(-9)S/cm and NFC-4-FA 8.33×10(-4)S/cm). This is attributed to the higher surface contact areas and multifunctional self-assembled supramacromolecular nanostructures of amorphous colloidal electrolytes. The anticancer activity of FA-containing nanofibers against osteocarcinoma cells were evaluated by cytotoxicity, apoptotic and necrotic analysis methods.

Fabrication and characterization of PVA/ODA-MMT-poly(MA-alt-1-octadecene)-g-graphene oxide e-spun nanofiber electrolytes and their response to bone cancer cells

This work presents a new approach to fabrication and characterization of novel polymer nanofiber electrolytes from intercalated PVA/ODA-MMT nanocomposite as a matrix polymer and encapsulated graphene oxide (GO) nanosheets with amphiphilic reactive copolymer as partner polymers using electrospinning method. The chemical and physical structures, surface morphology, thermal behaviors and electric conductivity of nanocomposites and nanofibers were investigated using analyses methods including FTIR, XRD, SEM, DSC-TGA and conductivity analysis. Significant improvements in nanofiber morphology and size distribution were observed when GO and reactive organoclay were incorporated as reinforcement fillers into various matrix/partner solution blends. The structural factors of matrix-partner polymer nanocomposite particles with higher zeta-potential play important roles in both chemical and physical interfacial interactions and phase separation processing and also lead to the formation of nanofibers with unique surface morphologies and good conductivities. The cytotoxic, necrotic and apoptotic effects of chosen nanofibers on osteocarcinoma cells were also investigated. These multifunctional, self-assembled, nanofibrous surfaces can serve as semi-conductive and bioactive platforms in various electrochemical and bio-engineering processes, as well as reactive matrices used for the immobilization of various biopolymer precursors.

Ti(IV) carrying polydopamine-coated, monodisperse-porous SiO2 microspheres with stable magnetic properties for highly selective enrichment of phosphopeptides

A marked decrease in the saturation magnetization by the formation of functional shells around the magnetic core is an important disadvantage of magnetic core-shell nanoparticles. Another drawback of Ti(IV)-functionalized immobilized metal affinity chromatography (IMAC) sorbents is the acidic character of the binding medium used for Ti4+ attachment onto composite magnetic nanoparticles, which causes an additional decrease in the saturation magnetization owing to the chemical interaction between the acidic moiety and the magnetic core. An IMAC sorbent in the form of magnetic microspheres with superior and stable magnetic properties with respect to magnetic core-shell nanoparticles was designed for phosphopeptide enrichment. Magnetic, monodisperse-porous silica microspheres (MagSiO2) 6μm in size were synthesized by a new staged-shape template hydrolysis-condensation protocol. A porous-silica shell layer was generated around the microspheres to protect the magnetic core from the acidic medium during Ti4+ attachment (MagSiO2@SiO2). The MagSiO2@SiO2 microspheres were coated with a polydopamine shell (MagSiO2@SiO2@PDA) and Ti4+ was attached onto the composite microspheres (MagSiO2@SiO2@PDA@Ti(IV)). Formation of the PDA layer and Ti4+ attachment did not cause any significant decrease in the saturation magnetization. The platform exhibited excellent performance for phosphopeptide enrichment from the digests of phosphorylated proteins. Selectivity was investigated by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. The detection limit for phosphopeptide enrichment by the MagSiO2@SiO2@PDA@Ti(IV) microspheres from the tryptic digests of β-casein was 50 fmol/mL. Usability of the proposed magnetic sorbent with complex biological samples was demonstrated by successful enrichment of four phosphopeptides from human serum. The proposed sorbent showed stable performance over five repeated uses.

Synthesis and characterization of poly(glycerol-co-sebacate-co-ε-caprolactone) elastomers

In this study, poly(glycerol‐co‐sebacate‐co‐ε‐caprolactone) (PGSCL) elastomers were synthesized for the first time from the respective monomers. The structural analysis of PGSCL elastomers by nuclear magnetic resonance (1H‐NMR) and Fourier transform infrared spectroscopy (FTIR) revealed that the elastomers have a high number of hydrogen bonds and crosslinks. X‐ray diffraction (XRD) and thermal analysis indicated an amorphous state. Differential scanning calorimetry (DSC) analysis showed that the elastomers has a glass transition temperature (Tg) of –36.96°C. The Youngs modulus and compression strength values were calculated as 46.08 MPa and 3.192 MPa, respectively. Calculations based on acid number and end groups analysis revealed a number average molecular weight of 148.15 kDa. Even though the foaming studies conducted by using supercritical CO2 resulted in a porous structure; the obtained morphology tended to disappear after 48 h, leaving small cracks on the surface. This phenomenon was interpreted as an indication of self‐healing due to the high number of hydrogen bonds. The PGSCL elastomers synthesized in this study are flexible, robust to compression forces and have self‐healing capacity. Thanks to good biocompatibility and poor cell‐adhesion properties, the elastomers may find diverse applications where a postoperative adhesion barrier is required. Copyright

Highly selective enrichment of phosphopeptides by titanium (IV) attached monodisperse-porous poly(vinylphosphonic acid-co-ethylene dimethacrylate) microspheres

A seeded polymerization protocol was developed for the synthesis of monodisperse-porous poly(vinylphosphonic acid-co-ethylene dimethacrylate), [poly(VPA-co-EDMA)] microspheres with superior porous properties. The protocol allowed the direct synthesis of phosphonic acid functionalized porous microspheres with the mean size of ∼4μm and the specific surface area of 420m2g-1 without applying any complicated post-derivatization protocol for the attachment of phosphonic acid group. The phosphonic acid content of poly(VPA-co-EDMA) microspheres was determined as 1.5mmol H2PO3g-1 microspheres. Ti(IV) ions were attached onto the microspheres via metal-chelate complex formation by phosphonate-groups and Ti(IV) carrying monodisperse-porous poly(vinylphosphonic acid-co-ethylene dimethacrylate), [Ti(IV)@poly(VPA-co-EDMA)] microspheres were obtained as a new sorbent for phosphopeptide enrichment via immobilized metal affinity chromatography. The phosphopeptides in the enriched samples were identified by matrix-assited laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). Four different phosphopeptides were detected with extremely high intensity by the treatment of β-casein digest prepared with the concentration of 10 fmol/mL with Ti(IV)@poly(VPA-co-EDMA) microspheres. Highly selective enrichment of phosphopeptides was also successfully carried out even at trace amounts in a complex mixture of digested proteins (molar ratio of β-casein to BSA, 1:1000) and eight different phosphorylated peptides from BSA digest were successfully identified. Moreover, four highly intense signals of the phosphopeptides in human serum were observed with high S/N ratio and clear background after enrichment by using Ti(IV)@poly(VPA-co-EDMA) microspheres.

Functional Copolymer/Organo-MMT Nanoarchitectures: XXVI. Fabrication and Characterization of Electrospun Nanofibers from PCL/ODA-MMT and Copolymer-g-PLA/ Ag-MMT Blends

We synthesized poly(ϵ-caprolactone)/octadecyl amine-montmorillonite clay nanocomposite as a matrix polymer by solution intercalative method and new amphiphilic poly(maleic anhydrde-alt-1-octadecene)-g-poly(L-lactic acid)/Ag+-montmorillonite clay nanocomposite as a partner polymer by interlamellar graft copolymerization of lactic acid onto anhydride copolymer in the presence of silver salt of montmorillonite clay as catalyst-nanofiller. Novel polymer nanofibers were fabricated by electrospinning of matrix/partner blends with different volume ratios. The nanocomposites and nanofibers were investigated by Fourier transform infrared spectroscopy, thermal gravimetric analysis–differential scanning calorimetry, and scanning electron microscope–transmission electron microscope methods. The diameters, morphologies, and thermal behavior of fibers were strongly depended on the partner-polymer nanocomposites loadings. The fabricated biocompatible and biodegradable nanofibers can be utilized for biomedical and filtration applications. GRAPHICAL ABSTRACT