Self-Assembly Pathway Influence on Dehydropeptide-Based Gel Properties and Drug Release.

Low-molecular-weight peptide-based hydrogels formed through self-assembly have emerged as promising candidates for biomedical applications. While the self-assembly process is known to affect the network morphology, its impact on mechanical properties and drug delivery remains poorly understood. In this work, it is explored how different gelation conditions influence the morphology, properties, and drug release profiles of dehydropeptide-based gels.

Tripeptides Featuring Dehydrophenylalanine and Homophenylalanine: Homo- Versus Hetero-Chirality and Sequence Effects on Self-Assembly and Gelation.

Over the years, our research group developed dehydrodipeptides -capped with aromatic moieties as protease-resistant efficacious hydrogelators, affording self-assembled hydrogels at low (critical) concentrations. Dehydrotripeptides, with different dipeptide sequences and (,) stereochemistry, open a wider chemical space for the development of self-assembled soft nanomaterials. In this work, a small library of -succinylated dehydrotripeptides containing a -terminal dehydrophenylalanine (∆Phe) residue and a scrambled dipeptide sequence with phenylalanine (Phe) and homophenylalanine (Hph) (-Phe-,-Hph and ,-Hph--Phe) was synthesized and characterized as a potential hydrogelator.

Hybrid Carrageenans Versus Kappa-Iota-Carrageenan Blends: A Comparative Study of Hydrogel Elastic Properties.

A comparison between the gel properties of blends of kappa- and iota-carrageenans (K+Is) and hybrid carrageenans (KIs) with equivalent chemical compositions is here presented. The objective is to assess under which conditions hybrid carrageenans are valuable alternative to blends of kappa- and iota-carrageenans for gelling applications and to contribute to the identification of phase-separated structures or co-aggregated helices. Phase states constructed in sodium chloride and in potassium chloride confirm that KIs build gels under a much narrower range of ionic strength and polysaccharide concentration.

Role of the Molecular Mass on the Elastic Properties of Hybrid Carrageenan Hydrogels.

A set of carrageenans produced in the potassium form and with chemical structures varying from pure iota-carrageenans to nearly pure kappa-carrageenans is submitted to ultrasonication to reduce their molecular masses Mw while maintaining a constant chemical structure and a polydispersity index around 2. The kinetics of ultrasound-induced chain scission are found to be slower for polysaccharides richer in kappa-carrageenan disaccharide units. From the elasticity of samples directly gelled in a rheometer at 1 /% in 0.

New Supramolecular Hydrogels Based on Diastereomeric Dehydrotripeptide Mixtures for Potential Drug Delivery Applications.

Self-assembly of peptide building blocks offers unique opportunities for bottom-up preparation of exquisite nanostructures, nanoarchitectures, and nanostructured bulk materials, namely hydrogels. In this work we describe the synthesis, characterization, gelation, and rheological properties of new dehydrotripeptides, Cbz--Lys(Cbz)-,-Asp-∆Phe-OH and (2-Naph)--Lys(2-Naph)-,-Asp-∆Phe-OH, containing a -terminal lysine residue --capped with carboxybenzyl (Cbz) and 2-Naphthylacetyl (2-Naph) aromatic moieties, an aspartic acid residue (Asp), and a -terminal dehydrophenylalanine (∆Phe) residue. The dehydrotripeptides were obtained as diastereomeric mixtures (,, and ,,Z), presumably via aspartimide chemistry.

Structure-Elasticity Relationships in Hybrid-Carrageenan Hydrogels Studied by Image Dynamic Light Scattering, Ultra-Small-Angle Light Scattering and Dynamic Rheometry.

Hybrid-carrageenan hydrogels are characterized using novel techniques based on high-resolution speckle imaging, namely image dynamic light scattering (IDLS) and ultra-small-angle light scattering (USALS). These techniques, used to probe the microscopic structure of the system in sol-gel phase separation and at different concentrations in the gel phase, give access to a better understanding of the network's topology on the basis of fractals in the dense phase. Observations of the architecture and the spatial and the size distributions of gel phase and fractal dimension were performed by USALS.

Viscoelastic Reversibility of Carrageenan Hydrogels under Large Amplitude Oscillatory Shear: Hybrid Carrageenans versus Blends.

The viscoelastic response of carrageenan hydrogels to large amplitude oscillatory shear (LAOS) has not received much attention in the literature in spite of its relevance in industrial application. A set of hybrid carrageenans with differing chemical compositions are gelled in the presence of KCl or NaCl, and their nonlinear viscoelastic responses are systematically compared with mixtures of kappa- and iota-carrageenans of equivalent kappa-carrageenan contents. Two categories of LAOS response are identified: strain softening and strain hardening gels.

Multifunctional magneto-plasmonic lipogel based on peptide hydrogel for application in combined cancer therapy.

Supramolecular hydrogels, particularly low-molecular-weight peptide hydrogels, are promising drug delivery systems due to their ability to change the solubility, targeting, metabolism and toxicity of drugs. Magneto-plasmonic liposomes, in addition to being remotely controllable with the application of an external magnetic field, also increase the efficiency of encapsulated drug release through thermal stimulation, for example, with magnetic and optical hyperthermia. Thus, the combination of those two materials-giving magneto-plasmonic lipogels-brings together several functionalities, among which are hyperthermia and spatiotemporally controlled drug delivery.

Multilayer Film Comprising Polybutylene Adipate Terephthalate and Cellulose Nanocrystals with High Barrier and Compostable Properties.

In the present study, a multilayer, high-barrier, thin blown film based on a polybutylene adipate terephthalate (PBAT) blend with polyhydroxyalkanoate (PHA), and composed of four layers including a cellulose nanocrystal (CNC) barrier layer and an electrospun poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) hot-tack layer, was characterized in terms of the surface roughness, surface tension, migration, mechanical and peel performance, barrier properties, and disintegration rate. The results showed that the film exhibited a smooth surface. The overall migration tests showed that the material is suitable to be used as a food contact layer.

Experimental Validation of a Micro-Extrusion Set-Up with In-Line Rheometry for the Production and Monitoring of Filaments for 3D-Printing.

The main objective of this work is to validate an in-line micro-slit rheometer and a micro-extrusion line, both designed for the in-line monitoring and production of filaments for 3D printing using small amounts of material. The micro-filament extrusion line is first presented and its operational window is assessed. The throughputs ranged between 0.

From Seaweeds to Hydrogels: Recent Progress in Kappa-2 Carrageenans.

Hybrid carrageenans, also called kappa-2 (K2) or weak kappa, are a class of sulfated polysaccharides with thermo-reversible gelling properties in water and are extracted from a specific family of red seaweeds. K2 are known in the industry for their texturizing properties which are intermediate between those of kappa-carrageenans (K) and iota-carrageenans (I). As such, K2 are gaining industrial interest, as they can replace blends of K and I (K + I) in some niche applications.

Unveiling the Role of Capping Groups in Naphthalene N-Capped Dehydrodipeptide Hydrogels.

Self-assembled peptide-based hydrogels are archetypical nanostructured materials with a plethora of foreseeable applications in nanomedicine and as biomaterials. N-protected di- and tri-peptides are effective minimalist (molecular) hydrogelators. Independent variation of the capping group, peptide sequence and side chain modifications allows a wide chemical space to be explored and hydrogel properties to be tuned.

Can Biomass Mastication Assist the Downstreaming of Polyhydroxyalkanoates Produced from Mixed Microbial Cultures?

Polyhydroxyalkanoates (PHAs) are natural polyesters which biodegrade in soils and oceans but have more than double the cost of comparable oil-based polymers. PHA downstreaming from its biomass represents 50% of its overall cost. Here, in an attempt to assist downstreaming, mastication of wet biomasses is tested as a new mechanical continuous biomass pretreatment with potential for industrial upscaling.

Plasmonic lipogels: driving co-assembly of composites with peptide-based gels for controlled drug release.

Supramolecular short peptide-based gels are promising materials for the controlled release of drugs ( chemotherapeutic drugs) owing to the biocompatibility and similarity to cell matrix. However, the drug encapsulation and control over its release, mainly the hydrophilic drugs, can be a cumbersome task. This can be overcome through encapsulation/compartmentalization of drugs in liposomes, which can also enable spatiotemporal control and enhanced drug release through a trigger, such as photothermia.

An injectable, naproxen-conjugated, supramolecular hydrogel with ultra-low critical gelation concentration-prepared from a known folate receptor ligand.

Short peptides capped on the N-terminus with aromatic groups are often able to form supramolecular hydrogels-self-assembled networks of fibrils able to trap water molecules. Typically, these hydrogelators can form stiff gels at concentrations of 0.1 to 1.

Tuning the drug multimodal release through a co-assembly strategy based on magnetic gels.

Self-assembled short peptide-based gels are highly promising drug delivery systems. However, implementing a stimulus often requires screening different structures to obtain gels with suitable properties, and drugs might not be well encapsulated and/or cause undesirable effects on the gel's properties. To overcome this challenge, a new design approach is presented to modulate the release of doxorubicin as a model chemotherapeutic drug through the interplay of (di)phenylalanine-coated magnetic nanoparticles, PEGylated liposomes and doxorubicin co-assembly in dehydropeptide-based gels.

Rheologically Assisted Design of Conductive Adhesives for Stencil Printing on PCB.

Driven by the need to deliver new, lead-free, eco-friendly solder pastes for soldering electronic components to Printed Circuit Boards (PCB), electrically conductive adhesives (ECAs) based on epoxy, carbon nanotubes (CNT), and exfoliated graphite (EG) were designed. The rheology of the adhesives prepared is paramount for the success of the deposition process, which is based on stencil printing. Thus, a rheological analysis of the process was first performed.

Structure-Elastic Properties Relationships in Gelling Carrageenans.

Gelling carrageenans are polysaccharides extracted from the Gigartinales order of red algae. These are additives used essentially in the food industry for texturizing, stabilizing or gelling various formulations. Although a consensual gel mechanism has been reached which encompasses a coil-to-helix transition followed by the self-assembling of helices in a network, the structure-elastic relationships in the network are still to be clearly established.

In-Line Rheo-Optical Investigation of the Dispersion of Organoclay in a Polymer Matrix during Twin-Screw Compounding.

The dispersion mechanisms in a clay-based polymer nanocomposite (CPNC) during twin-screw extrusion are studied by in-situ rheo-optical techniques, which relate the CPNC morphology with its viscosity. This methodology avoids the problems associated with post extrusion structural rearrangement. The polydimethylsiloxane (PDMS) matrix, which can be processed at ambient and low temperatures, is used to bypass any issues associated with thermal degradation.

High-Oxygen-Barrier Multilayer Films Based on Polyhydroxyalkanoates and Cellulose Nanocrystals.

This study reports on the development and characterization of organic recyclable high-oxygen-barrier multilayer films based on different commercial polyhydroxyalkanoate (PHA) materials, including a blend with commercial poly(butylene adipate--terephthalate) (PBAT), which contained an inner layer of cellulose nanocrystals (CNCs) and an electrospun hot-tack adhesive layer of poly(3-hydroxybutyrate--3-hydroxyvalerate) (PHBV) derived from cheese whey (CW). As a result, the full multilayer structures were made from bio-based and/or compostable materials. A characterization of the produced films was carried out in terms of morphological, optical, mechanical, and barrier properties with respect to water vapor, limonene, and oxygen.

Bolaamphiphilic Bis-Dehydropeptide Hydrogels as Potential Drug Release Systems.

The self-assembly of nanometric structures from molecular building blocks is an effective way to make new functional materials for biological and technological applications. In this work, four symmetrical bolaamphiphiles based on dehydrodipeptides (phenylalanyldehydrophenylalanine and tyrosyldehydrophenylalanine) linked through phenyl or naphthyl linkers (terephthalic acid and 2,6-naphthalenedicarboxylic acid) were prepared, and their self-assembly properties were studied. The results showed that all compounds, with the exception of the bolaamphiphile of tyrosyldehydrophenylalanine and 2,6-naphthalene dicarboxylic acid, gave self-standing hydrogels with critical gelation concentrations of 0.

Evaluation of a Model Photo-Caged Dehydropeptide as a Stimuli-Responsive Supramolecular Hydrogel.

Short peptides capped on the -terminus with aromatic groups are often able to form supramolecular hydrogels, via self-assembly, in aqueous media. The rheological properties of these readily tunable hydrogels resemble those of the extracellular matrix (ECM) and therefore have potential for various biological applications, such as tissue engineering, biosensors, 3D bioprinting, drug delivery systems and wound dressings. We herein report a new photo-responsive supramolecular hydrogel based on a "caged" dehydropeptide (CNB-Phe-ΔPhe-OH ), containing a photo-cleavable carboxy-2-nitrobenzyl (CNB) group.

Supramolecular ultra-short carboxybenzyl-protected dehydropeptide-based hydrogels for drug delivery.

Self-assembled peptide-based hydrogels are promising materials for biomedical research owing to biocompatibility and similarity to the extracellular matrix, amenable synthesis and functionalization and structural tailoring of the rheological properties. Wider developments of self-assembled peptide-based hydrogels in biomedical research and clinical translation are hampered by limited commercial availability allied to prohibitive costs. In this work a focused library of Cbz-protected dehydrodipeptides Cbz-L-Xaa-Z-ΔPhe-OH (Xaa= Met, Phe, Tyr, Ala, Gly) was synthesised and evaluated as minimalist hydrogels.

Impact of Citrate and Lipid-Functionalized Magnetic Nanoparticles in Dehydropeptide Supramolecular Magnetogels: Properties, Design and Drug Release.

Currently, the nanoparticle functionalization effect on supramolecular peptide-based hydrogels remains undescribed, but is expected to affect the hydrogels' self-assembly and final magnetic gel properties. Herein, two different functionalized nanoparticles: citrate-stabilized (14.4 ± 2.