Biomedical subjects

Hermis Iatrou

Publications and source records attributed to Hermis Iatrou.

4 recordsLinked to original sources

PubMed2006

Hierarchical ionic self-assembly of rod-comb block copolypeptide-surfactant complexes.

Novel hierarchical nanostructures based on ionically self-assembled complexes of diblock copolypeptides and surfactants are presented. Rod-coil diblock copolypeptide poly(gamma-benzyl-L-glutamate)-block-poly(L-lysine), PBLG-b-PLL (Mn = 25,000 and 8000 for PBLG and PLL, respectively, polydispersity index 1.08), was complexed with anionic surfactants dodecanesulfonic acid (DSA) or dodecyl benzenesulfonic acid (DBSA), denoted as PBLG-b-PLL(DSA)1.0 and PBLG-b-PLL(DBSA)1.0, respectively. The complexation leading to supramolecular rod-comb architectures was studied by transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), Fourier transform infrared spectroscopy (FTIR), and polarized optical microscopy (POM). PBLG-b-PLL, PBLG-b-PLL(DBSA)1.0, and PBLG-b-PLL(DSA)1.0 self-assemble with alternating PBLG lamellae and PLL-containing lamellae with a periodicity of 27-33 nm. Within the PBLG lamellae, the rod-like PBLG helices pack with a periodicity of ca. 1.3 nm. The internal structure of the PLL-containing lamellae depends on the complexation. For pure PBLG-b-PLL, the PLL chains adopt a random coil conformation and the PLL domains are disordered. For PBLG-b-PLL(DSA)1.0, lamellar self-assembly of periodicity of 3.7 nm within the PLL(DSA)1.0 domains is observed due to crystalline packing of the linear n-dodecyl tails. For PBLG-b-PLL(DBSA)1.0 with branched dodecyl tails, a distinct SAXS reflection is observed, suggesting self-assembly within the PLL(DBSA)1.0 domains with a periodicity of 2.9 nm. However, due to the absence of higher order reflections, the internal structure cannot be conclusively assigned. The efficient plasticization which leads to fluid-like liquid crystallinity in PBLG-b-PLL(DBSA)1.0 and an alpha-helical conformation according to FTIR allows us to suggest that the PLL(DBSA)1.0 domains have a hexagonal internal structure. The interplay of self-assembly at different length scales combined with rod-like liquid crystallinity can open new routes to design functional materials.

Benzenesulfonates↗

PubMed2005

Micellization in pH-sensitive amphiphilic block copolymers in aqueous media and the formation of metal nanoparticles.

Dynamic light scattering, potentiometric titration, transmission electron microscopy and atomic force microscopy have been used to investigate the micellar behaviour and metal-nanoparticle formation in poly(ethylene oxide)-block-poly(2-vinylpyridine), PEO-b-P2VP, poly(hexa(ethylene glycol) methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate), PHEGMA-b-PDEAEMA, and PEO-b-PDEAEMA amphiphilic diblock copolymers in water. The hydrophobic block of these copolymers (P2VP or PDEAEMA) is pH-sensitive: at low pH it can be protonated and becomes partially or completely hydrophilic leading to molecular solubility whereas at higher pH micelles are formed. These micelles consist of a P2VP or PDEAEMA core and a PEO or PHEGMA corona, respectively, where the core forming amine units can incorporate metal compounds due to coordination. The metal compounds (e.g., H2PtCl6, K2PtCl6) can either be introduced in a micellar solution, where they are incorporated within the micelle core via coordination with functional groups, or can be added to a unimer solution at low pH, where they lead to a metal-induced micellization. In these micellar nanoreactors, metal nanoparticles nucleate and grow upon reduction with sizes in the range of a few nanometers as observed by TEM. The effect of the metal incorporation method on the characteristics of the micelles and of the synthesized nanoparticles is investigated.

Journal Article↗

PubMed2005

The effect of molecular architecture on the grain growth kinetics of AnBn star block copolymers.

To investigate the effect of molecular architecture on the grain growth kinetics of star block copolymers, a series of AnBn miktoarm star block copolymers with different numbers of arms (n = 1, 2, 4 and 16) was studied. Across this entire series of materials, all the A arms are polystyrene (PS) blocks from the same anionically synthesized batch, and thus all the A arms are identical. Likewise, all the B arms are polyisoprene (PI) blocks from the same anionically synthesized batch, and thus all the B arms are identical. All the stars employed in this study are therefore composed of the same A and B arms liked together in symmetric numbers. The coarsening kinetics of grain growth was monitored in real space by transmission electron microscopy (TEM), followed by subsequent micrograph image analysis. It was found that the molecular architecture influenced the grain growth kinetics of these AnBn star copolymers dramatically. The grain coarsening kinetics was found to follow a scaling law as V approximately t(beta), where V is the characteristic grain volume and t is time. The exponent, beta, was found to be about 0.2 for the diblock copolymer (n = 1) and 0.4 for all three of the star block copolymers (n = 2, 4 and 16) in the series. It is postulated that the difference in grain growth rate between the diblock and the various stars is due to a reduction in molecular entanglements resulting from chain stretching near the junction points in the stars.

Journal Article↗

PubMedDate not supplied

Living polypeptides.

Block copolypeptides, which combine the self-assembly of block copolymers and the highly ordered 3D structures of proteins, are potential candidates for novel supramolecular structures and biotech applications, such as biosensors, tissue engineering, and selective drug delivery. The synthesis of model block copolypeptides through living nucleophilic/basic polymerization of alpha-amino acid N-carboxyanhydrides (NCAs) has been a challenge for more than fifty years, most probably due to traces of impurities in the system. This problem has been overcome, using high vacuum techniques in order to create and maintain the conditions necessary for the living polymerization of NCAs with primary amines. This method is a general one and opens avenues leading to novel, well-defined polypeptides with various architectures.

Carbonic Anhydrases↗