
Colin BonduelleUniversity of Bordeaux · CNRS, ENSCBP
Colin Bonduelle
PhD Macromolecular Chemistry
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79
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Introduction
Synthetic polypeptides polymers are simplified proteins analogues that are made of blocks of amino acids. One key aspect of my research is to show that these blocks can adopt tunable secondary structures (such as α-helix or β-sheets). In polymer chemistry, this rare structuring feature is critical to design a new generation of biomaterials that will be safety by design (nanomaterials, gels, membranes and surface coatings). So far, structured polypeptides polymers have found significant interest for a variety of biomedical applications and they can be used to prepare smart materials that are able to mimic the adaptive character of natural proteins, for instance to trigger the release of therapeutics, or to amplify signals in biosensors.
Publications
Publications (79)
Secondary α-helix and β-sheet structures are key scaffolds around which the rest of the residues condense during protein folding. Despite their key role in numerous processes to maintain life, little is known about their properties under force. Their stability under mechanical stress, as constantly experienced in the turbulent environment of cells,...
Peroxidases, like horseradish peroxidase (HRP), are heme metalloenzymes that are powerful biocatalysts for various oxidation reactions. By using simple grafting-from approach, ring-opening polymerization (ROP), and manganese porphyrins, star-shaped polypeptides analogues of HRP capable of catalyzing oxidation reactions with H2O2 is successfully pre...
Protein‐polymer conjugates and polymeric nanomaterials hold great promise in many applications including biomaterials, medicine or nanoelectronics. In this work, we present the first PISA (polymerization‐induced self‐assembly) approach performed in aqueous medium enabling protein‐polymer conjugates and nanoparticles entirely composed of amino acids...
The most economical and efficient route to prepare polypeptides from synthetic chemistry is through the Ring-Opening Polymerization (ROP) of amino acids using N-carboxyanhydride (NCA) monomers. Peptide polymers, in contrast to proteins, consist of repeated amino acid units and are comparatively simpler macromolecules. Despite their simplicity, thes...
At the origin, the emergence of proteins was based on crucial prebiotic stages in which simple amino acids‐based building blocks spontaneously evolved from the prebiotic soup into random proto‐polymers called protoproteins. Despite advances in modern peptide synthesis, these prebiotic chemical routes to protoproteins remain puzzling. We discuss in...
Within this study, an amphiphilic and potentially biodegradable polypeptide library based on poly[(4-aminobutyl)-l-glutamine-stat-hexyl-l-glutamine] [P(AB-l-Gln-stat-Hex-l-Gln)] was investigated for gene delivery. The influence of varying proportions of aliphatic and cationic side chains affecting the physicochemical properties of the polypeptides...
We report that synthetic polymers consisting of L‐proline monomer units exhibit temperature‐driven aggregation in water with unprecedented hysteresis. This protein‐like behavior is robust and governed by the chirality of the proline units. It paves the way to new processes, driven by either temperature or ionic strength changes, such as a simple “w...
Thermoresponsive Polymere unterliegen einer Phasentrennung als Reaktion auf Temperaturänderungen. In ihrer Zuschrift (DOI: 10.1002/ange.202209530) stellen Simon Harrisson, Colin Bonduelle et al. die Verwendung synthetischer Polymere vor, die aus L‐Prolin‐Monomereinheiten bestehen und eine temperaturgesteuerte Aggregation in Wasser mit beispielloser...
Thermoresponsive polymers undergo phase separation in response to changes in temperature. In their Communication (DOI: 10.1002/anie.202209530), Simon Harrisson, Colin Bonduelle et al. present the use of synthetic polymers consisting of L‐proline monomer units exhibiting temperature‐driven aggregation in water with unprecedented hysteresis. This pro...
We report that synthetic polymers consisting of L ‐proline monomer units exhibit temperature‐driven aggregation in water with unprecedented hysteresis. This protein‐like behavior is robust and governed by the chirality of the proline units. It paves the way to new processes, driven by either temperature or ionic strength changes, such as a simple “...
Secondary a-helix and b-sheet structures are key scaffolds around which the rest of the residues condense during protein folding. They are crucial for proteins to adopt their correct native structure. Despite their key role in numerous processes to maintain life, little is known about their properties under force. Their stability under mechanical s...
We developed new macromolecular engineering approaches enabling the preparation of star-like polypeptoids by ring-opening polymerization. Parallely to the evaluation of their cytotoxicity of the HepG2 human cell line, their screening...
N -carboxyanhydrides ring-opening polymerization (ROP) showed that electron-donating groups of the N -alkylation enhanced the ROP kinetic rates through an inductive effect that could counterbalance the steric hindrance during the propagation.
In the present study, three biodegradable block copolymers composed of a poly(ethylene glycol) block and a copolypeptide block with varying compositions of cationic L-lysine (L-Lys) and hydrophobic benzyl-L-glutamate (Bzl-L-Glu) were designed for gene delivery applications. The polypeptides were synthesized by ring opening polymerization (ROP) and...
Polymerization-induced self-assembly (PISA) is an efficient one-step process to obtain nanomaterials. In this work, aqueous ring-opening polymerization induced self-assembly (ROPISA) of α-amino acid N-carboxyanhydride (NCA) affords controllable well-defined nanoassemblies. ROPISA with the PEG5 kDa-NH2 macroinitiator and either the benzyl-L-glutamat...
Cyclic polymers display unique physicochemical and biological properties. However, their development is often limited by their challenging preparation. In this work, we present a simple route to cyclic poly(α-peptoids) from N-alkylated-N-carboxyanhydrides (NNCA) using LiHMDS promoted ring-expansion polymerization (REP) in DMF. This new method allow...
Delicate control over architectures via crystallization-driven self-assembly (CDSA) in aqueous solution, particularly combined with external stimuli, is rare and challenging. Here, we report a stepwise CDSA process thermally initiated from amphiphilic poly(N-allylglycine)-b-poly(N-octylglycine) (PNAG-b-PNOG) conjugated with thiol-terminated triethy...
Antimicrobial peptides (AMPs) are naturally occurring macromolecules made of amino acids that are potent broad-spectrum antibiotics with potential as novel therapeutic agents. This review aims to summarize the fundamental principles concerning the structure and mechanism of action of these AMPs, in order to guide the design of polymeric analogues t...
Nucleobase-containing polymers are an emerging class of building blocks for the self-assembly of nanoobjects with promising applications in nanomedicine and biology. Here we present a macromolecular engineering approach to design nucleobase-containing polypeptide polymers incorporating thymine that further self-assemble in nanomaterials. Diblock an...
A key challenge for designing hybrid materials is the development of chemical tools to control the organization of inorganic nanoobjects at low scales, from mesoscopic (~µm) to nanometric (~nm). So far, the most efficient strategy to align assemblies of nanoparticles consists in a bottom-up approach by decorating block copolymer lamellae with nanoo...
An antikinetoplastid pharmacomodulation study was conducted at position 6 of the 8-nitroquinolin-2(1H)-one pharmacophore. Fifteen new derivatives were synthesized and evaluated in vitro against L. infantum, T. brucei brucei and T. cruzi, in parallel with a cytotoxicity assay on the human HepG2 cell line. A potent and selective 6-bromo-substituted a...
Polymerization‐induced self‐assembly is a facile approach for accessing polymeric nanoparticles based on amphiphilic polymers at high concentration and in a scalable fashion. In their Communication (DOI: 10.1002/anie.201912028), S. Lecommandoux, C. Bonduelle, and co‐workers present the use of aqueous ring‐opening polymerization‐induced self‐assembl...
Polymerisationsinduzierte Selbstorganisation bietet einen einfachen und skalierbaren Zugang zu Polymer‐Nanopartikelnaus amphiphilen Polymeren in hohen Konzentrationen. In ihrer Zuschrift (DOI: 10.1002/ange.201912028) beschreiben S. Lecommandoux, C. Bonduelle et al., wie durch wässrige Ringöffnungspolymerisation induzierte Selbstorganisation (ROPISA...
Sharp as a needle: Reported here is the first aqueous ring‐opening polymerization (ROP) of carboxyanhydrides (NCAs) using α‐amino‐poly(ethylene oxide) as the macroinitiator to protect NCA monomers from hydrolysis through spontaneous in situ self‐assembly (ISA). This ROPISA process affords well‐defined amphiphilic diblock copolymers that simultaneou...
Reported here is the first aqueous ring‐opening polymerization (ROP) of N‐carboxyanhydrides (NCAs) using α‐amino‐poly(ethylene oxide) as a macroinitiator to protect the NCA monomers from hydrolysis through spontaneous in situ self‐assembly (ISA). This ROPISA process affords well‐defined amphiphilic diblock copolymers that simultaneously form origin...
In this work, we implemented a supramolecular approach in order to combine photodynamic therapy (PDT) with gene therapy. We made use of a simple cationic guanidylated porphyrin (H2‑PG) with the hypothesis that porphyrin aggregates should be capable of complexing siRNA through multivalent interactions and thus contribute to its intracellular deliver...
An antikinetoplastid pharmacomodulation study at position 3 of the recently described hit molecule 3‐bromo‐8‐nitroquinolin‐2(1H)‐one was conducted. Twenty‐four derivatives were synthesised using the Suzuki–Miyaura cross‐coupling reaction and evaluated in vitro on both Leishmania infantum axenic amastigotes and Trypanosoma brucei brucei trypomastigo...
Incorporating charged amino-acid side chains in polypeptides polymer backbone to improve solubility, usually leads to reduced secondary structuring. Here we show that highly water-soluble (>15 mg.mL-1), β-sheets structured, ionic polypeptide polymers can be obtained via nucleotide monophosphate grafting onto simple poly(γ-propargyl-L-glutamate) bac...
Stimuli-responsive polypeptides have practical applications in devices and therapeutic delivery. Here we report that coordination to Cd2+ metal species can be used as a robust stimulus to control both, α-helix and β-sheet secondary structuring of polypeptide polymers whose metal responsiveness was achieved in presence of a competitive buffer. As ev...
Synthetic peptide-based polymers represent a unique class of macromolecules able to mimic natural proteins properties in material sciences since 1) they present the same macromolecular backbone than proteins, 2) they can be obtained in large scale and in only one step by using the ROP (Ring-Opening Polymerization) methodology, and 3) they can fold...
Polypeptide polymers can adopt natural protein secondary structures such as α-helices or β-sheets, and this unique feature is at the origin of some intriguing physico–chemical properties. In this work, we present how side chain imidazoylation of a poly(L-lysine) scaffold affords the preparation of poly(histidine) counterparts exhibiting α-helix con...
Synthetic polypeptides are versatile polymers outstandingly relevant to prepare bioinspired materials. In this work, we present a new class of smart polypeptide polymers, called nucleopolypeptides, having lateral chains functionalized with thymidine nucleobases. Structural studies preformed by circular dichroism have revealed that the secondary str...
The symmetric meso-tetrakis(4-aminophenyl)porphyrin was reacted with nonstoichiometric amount of [Formula: see text],[Formula: see text]-bis(tert-butoxycarbonyl)-[Formula: see text]-methylisothiourea with respect to the amine functions of the porphyrin to afford (after deprotection of the Boc residues) the asymmetric guanidiniumphenyl-aminophenyl p...
Synthetic glycopolypeptides are versatile glycopolymers used to conceive bioinspired nanoassemblies. In this work, novel amphiphilic glycopolypeptides were designed to incorporate lactose or galactan in order to prepare polymeric nanoassemblies with sizes below 50 nm. The bioactivity of the two different outer surface sugar units was evaluated by d...
Among the smart polymers, smart polypeptides have a unique polymeric scaffold made of amino acids whose structuring can be controlled by an external stimuli. Herein we present how coordination chemistry to Zn species can be reversibly used to control the helix-to-coil transition of synthetic poly(L-glutamic acid) (PGA) polymers at a neutral pH of 7...
Nano-assemblies prepared from glycosylated macromolecules are promising systems for modulating or mimicking the interactions between natural carbohydrates and their receptors. In the current work, polyester dendrons bearing focal point alkynes and peripheral C-linked α-galactose moieties were synthesized and coupled to helical poly(γ-benzyl-L-gluta...
Two commercial statistical copolymers of ethylene oxide and propylene oxide, Jeffamine® M-2005 (PEO5-st-PPO37) and M-2070 (PEO46-st-PPO13), exhibiting lower critical solution temperature (LCST) in water, were grafted onto the surface of ultra-small superparamagnetic iron oxide nanoparticles (USPIOs) using silanization and amide-bond coupling reacti...
Porous silicon (PSi) nanomaterials combine a high drug loading capacity and tunable surface chemistry with various surface modifications to meet the requirements for biomedical applications. In this work, alkyne-terminated thermally hydrocarbonized porous silicon (THCPSi) nanoparticles were fabricated and postmodified using five bioactive molecules...
Branched amphiphilic copolymers were synthesized through the reversible addition-fragmentation chain transfer (RAFT) chain extension of a poly(methyl acrylate) macro-chain transfer agent using a protected galactose monomer and a polymerizable chain transfer agent branching unit. After galactose deprotection, the copolymers were self-assembled via n...
The development of stimuli-responsive materials is of significant interest for many applications including drug delivery, medical imaging, sensors, and microfluidic devices. Among the available stimuli, light is particularly attractive as it can be applied with high spatial and temporal resolution. We describe here the synthesis of amphiphilic trib...
Biomimetic nanoparticles prepared by self-assembly of iminosugar-based glycopolypeptides evidenced remarkable multivalency properties when inhibiting α-mannosidase activity. This approach paves the way to obtain biologically active drug delivery systems having glycosidase inhibition potency.
Block copolymers combining peptide and saccharide moieties may play a significant role in future applications of polymers in biology, as they can be viewed as simplified synthetic analogues of glycosylated proteins, which display a wide range of biological functions in nature. While a small number of oligosaccharides containing synthetic polypeptid...
The preparation of multilayered polymer films is of significant interest for various applications, but is often hindered by the inherent incompatibilities between polymers. Described here is the use of an epoxidized butyl rubber as a compatibilizer layer. This polymer can be coated onto butyl rubber, despite the small number of epoxidized units (~2...
Butyl rubber-poly(ethylene oxide) (PEO) graft copolymers with high PEO content (40–83 wt %) were synthesized by the functionalization and activation of the double bond moiety of butyl rubber containing high (7 mol %) isoprene content and subsequent reaction with PEO of different molecular weights from 750 to 5000 g/mol. The properties of these copo...
Marseille–Provence is the European Capital of Culture in 2013. In this issue two articles from the Marseille‐based team Chirosciences analyze the role of imidazole alcohol hydrogen bonding in the nucleophlicity of dyad models (see the Full Paper by J. Leclaire, D. Bourissou, F. Fotiadu et al. on page 11301 ff.) and describe a facile synthesis and a...
Glycoproteins are naturally produced by protein glycosylation and are involved in a wide range of cellular functions. This review aims at summarizing the preparation of well-defined synthetic glycoproteins by using chemical routes as well as to highlight the preparation of ideal polymeric analogues of natural glycoproteins: glycopolypeptides. These...
A new family of 2-hydroxyalk(en/yn)ylimidazoles has been evaluated as serine-histidine bare dyad models for the ring-opening reaction of L-lacOCA, a cyclic O-carboxyanhydride. These models were selected to unravel the implication of intramolecular hydrogen bonding and to substantiate its influence on the nucleophilicity of the alcohol moiety, as it...
The cell is certainly one of the most complex and exciting systems in Nature that scientists are still trying to fully understand. Such a challenge pushes material scientists to seek to reproduce its perfection by building biomimetic materials with high-added value and previously unmatched properties. Thanks to their versatility, their robustness a...
Novel synthetic tree-like oligosaccharides-grafted-polypeptides were prepared by using Huisgen 1,3-dipolar cycloaddition between poly(γ-benzyl-L-glutamate)-block-poly(propargylglycine) and two different oligosaccharides, dextran or hyaluronan. By direct solubilisation in water, these tree-like glycopeptides spontaneously form very small assemblies...
The conjugation of dendrons having varying peripheral functionalities to polymer vesicles, commonly referred to as polymersomes, provides an opportunity to significantly alter the polymersome surface chemistry in a single step while leaving intact the block copolymers responsible for assembly. In this work, polymersomes with surface azide groups we...
The covalent immobilization of polymers on surfaces has the potential to impart new properties and functions to surfaces for a wide range of applications. However, most current methods for the production of these surfaces involve multiple chemical steps or do not impart a high degree of control over the chemical functionalities at the surface. Desc...
Polypeptide block copolymers with different block length ratios were obtained by sequential ring-opening polymerization of benzyl-L-glutamate and propargylglycine (PG) N-carboxyanhydrides. Glycosylation of the poly(PG) block was obtained by Huisgens cycloaddition "click" reaction using azide-functionalized galactose. All copolymers were self-assemb...
The patterning of copolymers on surfaces is of interest both for a fundamental understanding of polymer assembly processes and for applications ranging from microelectronics to biomaterials. Graft copolymers can provide new opportunities to control polymer composition and architecture, thus opening possibilities for new assembly processes and patte...
The functionalization of nanomaterials with dendritic surface moieties was recently demonstrated to be an effective means of displaying biological ligands and potentially modulating the biological properties of these materials. With the aim of extending this surface functionalization approach to biodegradable polymer assemblies, poly(ethylene oxide...
Emerging from the shortcomings of modern day therapeutics is a need for a controlled approach in carrier-mediated drug delivery. Polymeric vesicles are a powerful tool to address issues of efficacy, specificity and controlled release of drugs to diseased tissues.These recent structures are able to overcome the body's natural defences, remain stable...
The functionalization of surfaces with poly(ethylene oxide) (PEO) is an effective means of imparting resistance to the adsorption of proteins and the attachment and growth of cells, properties that are critical for many biomedical applications. In this work, a new hyperthermal hydrogen induced cross-linking (HHIC) method was explored as a simple on...
A new mild and clean synthetic method was used for the preparation of butyl rubber-poly(ethylene glycol) (PEG) graft copolymer, and fluorescent protein absorption was employed to reveal novel complex patterns on it through spin-casting. Butyl rubber (1) containing 2.2% isoprene units, with a weight-average molecular weight (Mw) of 400 000 g/mol, we...
The widespread application of cell penetrating agents to clinical therapeutics and imaging agents relies on the ability to prepare them on a large scale and to readily conjugate them to their cargos. Dendritic analogues of cell penetrating peptides, with multiple guanidine groups on their peripheries offer advantages as their high symmetry allows t...
Both lipase PS and Novozym 435 promote the ring-opening polymerization of lacOCA, the O-carboxylic anhydride derived from lactic acid. Accordingly, PLA of relatively high molecular weights (M(n) up to 38400 g/mol) and low polydispersities (M(w)/M(n) < 1.4) are obtained in high yields within a few hours at 80 degrees C. Slight preference for l-lacOC...
L'utilisation de polymères biodégradables synthétiques connaît un grand essor depuis une dizaine d'années. Parmi ces polymères, les polyesters occupent une place privilégiée car ils sont biocompatibles : ils sont d'origine naturelle ou d'origine synthétique. Dans tous les cas, on peut les préparer par polymérisation par ouverture de cycle (ROP) à p...
Well-controlled poly(alpha-hydroxyacids) featuring pendant carboxylic acid groups were prepared under mild conditions via DMAP-catalyzed ROP of the O-carboxyanhydrides derived from glutamic and lactic acids.
Model reactions for the 4-dimethylaminopyridine (DMAP)-catalyzed ring-opening polymerization of lactide and the corresponding lactic O-carboxylic anhydride (lacOCA) have been studied computationally at the B3LYP/6-31G(d) level of theory. The solvent effect of dichloromethane was taken into account through PCM/SCRF single-point calculations at the B...
Artemisinin is an efficient antimalarial drug containing a 1,2,4-trioxane which is able to alkylate heme both in vitro and in vivo, giving rise to covalent heme-artemisinin coupling products. The low valent iron(II) protoporphyrin-IX, which is the prosthetic group of hemoglobin, induces the homolysis of the peroxide bond of artemisinin by an electr...
Extracts of Laetia procera (Flacourtiaceae) displayed significant in vitro activity against Plasmodium falciparum. P. falciparum bioassay guided fractionation of a trunk bark extract of this plant led to the isolation of six clerodane diterpenoids (1-6) and a butanolide (7). Five of these compounds are new and called Laetiaprocerine A-D (3-6) and L...