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Biomedical subjects

Bas G G Lohmeijer

Publications and source records attributed to Bas G G Lohmeijer.

12 recordsLinked to original sources
PubMed2007

Organocatalytic ring opening polymerization of trimethylene carbonate.

A variety of organocatalysts has been surveyed in the ring opening polymerization of trimethylene carbonate. Excellent control was found for several of these catalysts yielding well-defined polycarbonates with molecular weights up to 50,000 g mol(-1), polydispersities below 1.08, and high end-group fidelity. Melt or bulk polymerization was accomplished without loss of control of molecular weight or polydispersity, and random ester-carbonate bulk polymerizations were also demonstrated. Furthermore, by combining disparate polymerization techniques using bifunctional initiators, the mild polymerization conditions allow for the preparation of new block copolymers. Hydrogen-bond activation of monomer and initiator/propagating species is proposed as the underlying mechanism, which can be tuned to mitigate adverse side reactions.

Biochemistry↗
PubMed2006

Organocatalytic living ring-opening polymerization of cyclic carbosiloxanes.

[reaction: see text] An organocatalytic route to narrowly dispersed poly(carbosiloxanes) of predictable molecular weight and end group fidelity is described. N-Heterocyclic carbenes (NHC) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) catalyze the ring opening of cyclic carbosiloxanes. The pK(b) of the catalyst is important in preventing adverse transetherification reactions and obtaining well-defined polymers. Mechanistic studies indicate that hydrogen bonding to TBD or the NHC activates alcohols or silanols for ring-opening reactions.

Journal Article↗
PubMed2006

Triazabicyclodecene: a simple bifunctional organocatalyst for acyl transfer and ring-opening polymerization of cyclic esters.

1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) is an effective organocatalyst for acyl transfer as well as the ring-opening polymerization of cyclic esters. Its high activity is attributed to its ability to simultaneously activate both esters and alcohols, as demonstrated in a model reaction. This unique mechanism makes TBD a remarkably simple example of a bifunctional catalyst. The simplicity of the reaction conditions, the ready commercial availability of the catalyst, and its high activity provide an accessible methodology to allow future studies of tailor-made polyesters.

Journal Article↗
PubMed2006

Monolayered organosilicate toroids and related structures: A phase diagram for templating from block copolymers.

Here we report the controlled generation of micelle-templated organosilicate nanostructures resulting from self-assembly of a block copolymer/organosilicate mixture followed by organosilicate vitrification and copolymer thermolysis. Variation of solution condition and the copolymer/organosilicate mixture composition generates widely different film morphologies ranging from toroids to linear features to contiguous nanoporous monolayers. The use of reactive organosilicates for block copolymer templation generates functional inorganic nanostructures with thermal and mechanical stability.

Acrylamides↗
PubMed2005

Thiourea-based bifunctional organocatalysis: supramolecular recognition for living polymerization.

A versatile, metal-free, organocatalytic approach to the living ring-opening polymerization of lactide using a bifunctional thiourea-tertiary amine catalyst is described. Mild and highly selective polymerization conditions produced poly(lactides) with predictable molecular weights and extremely narrow polydispersities ( approximately 1.05), characteristic of a living polymerization. The extraordinary selectivity of this catalyst system for polymerization relative to transesterification is remarkably unusual. The low polydispersities and exceptional control observed are a consequence of selective transesterification of lactide relative to the open chain esters. Presumably, the ring strain of lactide provides both a driving force for the polymerization and a kinetic preference for polymerization relative to transesterification with catalyst. We postulate that the initiating/propagating alcohol is activated by acid-base interaction with the tertiary amine moiety and the carbonyl of the lactide monomer is simultaneously activated by hydrogen bonding to the thiourea moiety of the catalyst.

Amines↗
PubMed2004

Block copolymer libraries: modular versatility of the macromolecular Lego system.

The synthesis and characterization of a new 4 x 4 library of block copolymers based on polystyrene and poly(ethylene oxide) connected by an asymmetrical octahedral bis(terpyridine) ruthenium complex at the block junction are described, while initial studies on the thin film morphology of the components of the library are presented by the use of Atomic Force Microscopy, demonstrating the impact of a library approach to derive structure-property relationships.

Journal Article↗
PubMed2004

Cylindrical micelles from the aqueous self-assembly of an amphiphilic poly(ethylene oxide)-b-poly(ferrocenylsilane) (PEO-b-PFS) block copolymer with a metallo-supramolecular linker at the block junction.

A supramolecular AB diblock copolymer has been prepared by the sequential self-assembly of terpyridine end-functionalized polymer blocks by using Ru(III)/Ru(II) chemistry. By this synthetic strategy a hydrophobic poly(ferrocenylsilane) (PFS) was attached to a hydrophilic poly(ethylene oxide) (PEO) block to give an amphiphilic metallo-supramolecular diblock copolymer (PEO/PFS block ratio 6:1). This compound was used to form micelles in water that were characterized by a combination of dynamic and static light scattering, transmission electron microscopy, and atomic force microscopy. These complementary techniques showed that the copolymers investigated form rod-like micelles in water; the micelles have a constant diameter but are rather polydisperse in length, and light scattering measurements indicate that they are flexible. Crystallization of the PFS in these micelles was observed by differential scanning calorimetry, and is thought to be the key behind the formation of rod-like structures. The cylindrical micelles can be cleaved into smaller rods whenever the temperature of the solution is increased or they are exposed to ultrasound.

Journal Article↗
PubMed2003

From supramolecular block copolymers to advanced nano-objects.

The formation of asymmetric bis-complexes, based on terpyridine ligands and ruthenium ions, is described as a powerful tool for the self-assembly of polymer blocks end-functionalized with terpyridine units. This is illustrated in this contribution for the synthesis of amphiphilic metallo-supramolecular block copolymers, which are further used to produce aqueous micelles. Finally, the reversibility of the supramolecular bond opens new avenues for the preparation and manipulation of these nano-objects.

Journal Article↗
PubMed2003

Relative binding strength of terpyridine model complexes under matrix-assisted laser desorption/ionization mass spectrometry conditions.

The relative binding strength of a series of terpyridine metal complexes of the type [M(II)L(2)](+) was investigated by using variable laser intensities in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). A model terpyridine ligand, 4'-(1,4,7-trioxa-octyl)-2,2':6',2"-terpyridine, was prepared and complexed with a series of transition metal ions including cadmium, cobalt, copper, iron, manganese, nickel and ruthenium. The relative binding strength of these complexes can be obtained by measuring MALDI mass spectra of the prepared compounds at different laser intensities. The ratio of the signal intensities belonging to the ligand [LH](+) and the complex [ML(2)](+) ([LH](+) /[ML(2)](+)) depends on the laser intensity utilized for the spectrum acquisition. By considering an [LH](+)/[ML(2)](+) ratio > 10 as the point of complete complex dissociation, it is possible to establish a row of complex stabilities depending on the kind of metal ion.

Journal Article↗