Biomacromolecules Update: Welcome to Our New Editors and New Procedure for Review Submission

Despite the pandemic and the difficulties posed by it to researchers around the world, 2020 has been a great year for Biomacromolecules as it achieved some significant milestones in the past year. First, Biomacromolecules reached the highest level in history with a record impact factor of above 6.0. Furthermore, what a year I have had! I have truly enjoyed my first year as Editor-in-Chief. Thanks to all at the ACS, from the journal office to production to marketing to the leadership at ACS Publications, for making the transition smooth and providing me all the support to continue to expand the influence of Biomacromolecules. A special thanks to our Managing Editor, Dr. Paulomi Majumder, for her unwavering support. In an effort to provide our community with fast, smooth, fair, and ethical editing and review processes, we have implemented and continue to implement several processes. For instance, we now have established a new procedure to optimize the process for a review proposal. Even if the majority of reviews are solicited by members of the editorial board in accordance with editorial policy, the editorial office welcomes suggestions for reviews that may be suitable for the journal

Polymer vesicles (from virus to cell biomimicry)

Les polymersomes, obtenus par auto-assemblage en solution aqueuse de copolymères à blocs amphiphiles en structure vésiculaire, sont présentés comme d excellent mimes synthétiques des virus, dont les propriétés membranaires principalement élasticité, perméabilité, fonctionnalité- peuvent être très proches. Il y a ainsi un fort engouement quant à leur utilisation en biotechnologie et surtout en vectorisation d actifs pharmaceutiques ou cosmétiques. Afin d aller encore plus loin dans le biomimétisme ou la bio-inspiration, une étape devait être franchie : encapsuler ces polymersomes les uns dans les autres. Ce cloisonnement ou multi-compartimentalisation permet de mimer cette fois la structure d une cellule dite eukaryote, elle-même constituée de compartiments internes (organelles) et d un cytoplasme (lui conférant entre autres une certaine stabilité mécanique) contenues dans le compartiment externe représenté par la membrane cellulaire. Toutefois, l obtention d un simple mime structural d une structure si complexe représente déjà un challenge en soi, nécessitant maîtrise de la physico-chimie des systèmes, de la stabilisation des interfaces et des outils de formulation. Une méthode d émulsion-centrifugation a été développée et a permis d obtenir de telles structures compartimentalisées (mimes d organelles) à cavité gélifiée (mime de cytoplasme). Finalement, différentes voies d exploitation de ces systèmes sont présentées, allant de l encapsulation multiple, la libération contrôlée jusqu au développement de réactions enzymatiques en cascade confinées, mimant ainsi le métabolisme cellulaire.Amphiphilic block copolymers self-assemble in water into vesicles, coined polymersomes ; these vesicles are described as excellent synthetic mimics of viral capsids due to the resemblance of their respective membrane properties (in terms of elasticity, permeability, and functionality). As a result, they were massively investigated over the last years regarding applications in biotechnology and more particularly for the targeted delivery of pharmaceutical or cosmetic actives.In order to go further towards bio-inspiration and cell biomimicry, the next step required the encapsulation of polymersomes in other polymersomes. This multicompartmentalization indeed enables to mimic the structure of an eukaryotic cell; an outer cellular membrane compartment encloses internal compartments (organelles) and a cytoplasm responsible amongst others for a certain mechanic stability. However, alone the controlled formation of a system mimicking such a complex structure represents a technological challenge in terms of control over the physical chemistry of these systems, the stabilization of their interfaces and their formulation. A formation method based upon an emulsion-centrifugation has been developed and enabled the formation of such multicompartmentalized structures (organelle mimics) with a gelified lumen (cytoplasm mimic). Finally, various potential applications of these systems are presented: from multiple encapsulation, controlled drug release, to the development of enzymatic and confined cascade reactions that mimick the cellular metabolism.BORDEAUX1-Bib.electronique (335229901) / SudocSudocFranceF

Assemblages de copolymères à blocs pour la vectorisation de siRNA

Les siRNA sont des molécules double brin d acide ribonucléique capables d inhiber l expression d un gène spécifique, présentant ainsi un fort potentiel thérapeutique pour les maladies génétiques, les cancers et les infections virales. Cependant, son utilisation in vivo est restreinte par sa sensibilité à la dégradation enzymatique. Le projet de thèse consiste à créer un système de vectorisation des siRNA pour des applications in vivo. Nous avons synthétisé des copolymères à blocs amphiphiles biocompatibles et biodégradables capable de s auto-assembler en diverses structures et d encapsuler les siRNA. Les propriétés physico-chimiques des assemblages formées et l évaluation cellulaire préliminaire est réaliséeAmphiphilic block copolymers are molecules composed of hydrophilic and hydrophobic segments having the capacity to spontaneously self-assemble into a variety of supramolecular structures like micelles and vesicles. Here, we propose an original way to self-assemble amphiphilic block copolymers into a supported bilayer membrane for defined coating of nanoparticles. The heart of the method rests on a change of the amphiphilicity of the copolymer that can be turned off and on by varying the polarity of the solvent. In this condition, the assembly process can take advantage of specific molecular interactions in both organic solvent and water. The higher gene silencing activity of the copolymer-modified complexes over the complexes alone shows the potential of this new type of nanoconstructs for biological applications, especially for the delivery of therapeutic biomolecules.BORDEAUX1-Bib.electronique (335229901) / SudocSudocFranceF

Organogels from trehalose difatty esters amphiphiles

International audienceSaccharide diesters have been recently shown to be excellent gelators of vegetable oils. In this paper, different fatty acid trehalose diesters were synthesized by a selective enzymatic transesterification performed only on the primary hydroxyl group of the trehalose. The resulting trehalose diesters demonstrated their ability to self-assemble in a large variety of edible vegetable oils with a minimum gelation concentration of 0.25 wt%/v. Microscopic analysis and X-ray scattering studies indicate that the gels are obtained by the self-assembly of trehalose diesters in crystalline fibers constituting the tridimensional network. The rheological study revealed that the properties of the gels depend on the kind of fatty acid grafted on the trehalose but are also influenced by the vegetable oil composition

Controlling Polymersome Size through Microfluidic-Assisted Self-Assembly: Enabling 'Ready to Use' formulations for biological applications

The self-assembly of poly(ethylene glycol)-block-poly(trimethylene carbonate) PEG-b-PTMC copolymers into vesicles, also referred as polymersomes, was evaluated by solvent displacement using microfluidic systems. Two microfluidic chips with different flow regimes (micromixer and Herringbone) were used and the impact of process conditions on vesicle formation was evaluated. As polymersomes are sensitive to osmotic variations, their preparation under conditions allowing their direct use in biological medium is of major importance. We therefore developed a solvent exchange approach from DMSO (Dimethylsulfoxide) to aqueous media with an osmolarity of 300 mOsm.L-1, allowing their direct use for biological evaluation. We evidenced that the organic/aqueous solvent ratio does not impact vesicle size, but the total flow rate and copolymer concentration have been observed to influence the size of polymersomes. Finally, nanoparticles with diameters ranging from 76 nm to 224 nm were confirmed to be vesicles through the use of multi-angle light scattering in combination with cryo-TEM (Cryo-Transmission Electron Microscopy) characterization

Thermosensitive polymer-grafted iron oxide nanoparticles studied by in situ dynamic light backscattering under magnetic hyperthermia

© 2015 IOP Publishing Ltd. Thermometry at the nanoscale is an emerging area fostered by intensive research on nanoparticles (NPs) that are capable of converting electromagnetic waves into heat. Recent results suggest that stationary gradients can be maintained between the surface of NPs and the bulk solvent, a phenomenon sometimes referred to as \u27cold hyperthermia\u27. However, the measurement of such highly localized temperatures is particularly challenging. We describe here a new approach to probing the temperature at the surface of iron oxide NPs and enhancing the understanding of this phenomenon. This approach involves the grafting of thermosensitive polymer chains to the NP surface followed by the measurement of macroscopic properties of the resulting NP suspension and comparison to a calibration curve built up by macroscopic heating. Superparamagnetic iron oxide NPs were prepared by the coprecipitation of ferrous and ferric salts and functionalized with amines, then azides using a sol-gel route followed by a dehydrative coupling reaction. Thermosensitive poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA) with an alkyne end-group was synthesized by controlled radical polymerization and was grafted using a copper assisted azide-alkyne cycloaddition reaction. Measurement of the colloidal properties by dynamic light scattering (DLS) indicated that the thermosensitive NPs exhibited changes in their Zeta potential and hydrodynamic diameter as a function of pH and temperature due to the grafted PDMAEMA chains. These changes were accompanied by changes in the relaxivities of the NPs, suggesting application as thermosensitive contrast agents for magnetic resonance imaging (MRI). In addition, a new fibre-based backscattering setup enabled positioning of the DLS remote-head as close as possible to the coil of a magnetic heating inductor to afford in situ probing of the backscattered light intensity, hydrodynamic diameter, and temperature. This approach provides a promising platform for estimating the response of magnetic NPs to application of a radiofrequency magnetic field or for understanding the behaviour of other thermogenic NPs

Multivalent Elastin-Like Glycopolypeptides: Subtle Chemical Structure Modifications with High Impact on Lectin Binding Affinity

A library of synthetic elastin-like glycopolypeptides were synthesized and screened by microscale thermophoresis to identify key structural parameters affecting lectin binding efficacy. While polypeptide backbone size and glycovalency were found to have little influence, the presence of a linker at the anomeric position of galactose and the absence of positive charge on the polypeptide residue holding the sugar unit were found to be critical for the binding to RCA120.Développement de squelettes polypeptidiques recombinants pour la synthèse de glycoconjugués multivalents parfaitement défini

Avidin Localizations in pH-Responsive Polymersomes for Probing the Docking of Biotinylated (Macro)molecules in the Membrane and Lumen

To mimic organelles and cells and to construct next-generation therapeutics, asymmetric functionalization and location of proteins for artificial vesicles is thoroughly needed to emphasize the complex interplay of biological units and systems through spatially separated and spatiotemporal controlled actions, release, and communications. For the challenge of vesicle (= polymersome) construction, the membrane permeability and the location of the cargo are important key characteristics that determine their potential applications. Herein, an in situ and post loading process of avidin in pH-responsive and photo-cross-linked polymersomes is developed and characterized. First, loading efficiency, main location (inside, lumen, outside), and release of avidin under different conditions have been validated, including the pH-stable presence of avidin in polymersomes’ membrane outside and inside. This advantageous approach allows us to selectively functionalize the outer and inner membranes as well as the lumen with several bio(macro)molecules, generally suited for the construction of asymmetrically functionalized artificial organelles. In addition, a fluorescence resonance energy transfer (FRET) effect was used to study the permeability or uptake of the polymersome membrane against a broad range of biotinylated (macro)molecules (different typology, sizes, and shapes) under different conditions

Biomacromolecules

Three-dimensional (3D) bioprinting offers a great alternative to traditional techniques in tissue reconstruction, based on seeding cells manually into a scaffold, to better reproduce organs' complexity. When a suitable bioink is engineered with appropriate physicochemical properties, such a process can advantageously provide a spatial control of the patterning that improves tissue reconstruction. The design of an adequate bioink must fulfill a long list of criteria including biocompatibility, printability, and stability. In this context, we have developed a bioink containing a precisely controlled recombinant biopolymer, namely, elastin-like polypeptide (ELP). This material was further chemoselectively modified with cross-linkable moieties to provide a 3D network through photopolymerization. ELP chains were additionally either functionalized with a peptide sequence Gly-Arg-Gly-Asp-Ser (GRGDS) or combined with collagen I to enable cell adhesion. Our ELP-based bioinks were found to be printable, while providing excellent mechanical properties such as stiffness and elasticity in their cross-linked form. Besides, they were demonstrated to be biocompatible, showing viability and adhesion of dermal normal human fibroblasts (NHF). Expressions of specific extracellular matrix (ECM) protein markers as pro-collagen I, elastin, fibrillin, and fibronectin were revealed within the 3D network containing cells after only 18 days of culture, showing the great potential of ELP-based bioinks for tissue engineering