From Nature-Sourced Polysaccharide Particles to Advanced Functional Materials.

Polysaccharides constitute over 90% of the carbohydrate mass in nature, which makes them a promising feedstock for manufacturing sustainable materials. Polysaccharide particles (PSPs) are used as effective scavengers, carriers of chemical and biological cargos, and building blocks for the fabrication of macroscopic materials. The biocompatibility and degradability of PSPs are advantageous for their uses as biomaterials with more environmental friendliness. This review highlights the progresses in PSP applications as advanced functional materials, by describing PSP extraction, preparation, and surface functionalization with a variety of functional groups, polymers, nanoparticles, and biologically active species. This review also outlines the fabrication of PSP-derived macroscopic materials, as well as their applications in soft robotics, sensing, scavenging, water harvesting, drug delivery, and bioengineering. The paper is concluded with an outlook providing perspectives in the development and applications of PSP-derived materials.

Intrafibrillar Crosslinking Enables Decoupling of Mechanical Properties and Structure of a Composite Fibrous Hydrogel.

The fibrous network of an extracellular matrix (ECM) possesses mechanical properties that convey critical biological functions in cell mechanotransduction. Engineered fibrous hydrogels show promise in emulating key aspects of ECM structure and functions. However, varying hydrogel mechanics without changing its architecture remains a challenge. A composite fibrous hydrogel is developed to vary gel stiffness without affecting its structure by controlling intrafibrillar crosslinking. The hydrogel is formed from aldehyde-modified cellulose nanocrystals and gelatin methacryloyl that provide the capability of intrafibrillar photocrosslinking. By varying the degree of gelatin functionalization with methacryloyl groups and/or photoirradiation time, the hydrogel's elastic modulus is changed by more than an order of magnitude, while preserving the same fiber diameter and pore size. The hydrogel is used to seed primary mouse lung fibroblasts and test the role of ECM stiffness on fibroblast contraction and activation. Increasing hydrogel stiffness by stronger intrafibrillar crosslinking results in enhanced fibroblast activation and increased fibroblast contraction force, yet at a reduced contraction speed. The developed approach enables the fabrication of biomimetic hydrogels with decoupled structural and mechanical properties, facilitating studies of ECM mechanics on tissue development and disease progression.

Nanogels designed for cell-free nucleic acid sequestration.

Chronic wounds exhibit over-expression of cell-free deoxyribonucleic acid (cfDNA), leading to a prolonged inflammation and non-healing wounds. Scavenging excessive cfDNA molecules is a promising strategy for chronic wound treatment. Nanoscopic particles act as efficient cfDNA scavengers due to their large surface area, however their efficiency in cfDNA uptake was limited by adsorption solely on the nanoparticle surface. In contrast, nanogels may provide multiple cfDNA binding sites in the nanoparticle interior, however their use for cfDNA scavenging is yet to be explored. Herein, we report cationic nanogels derived from a copolymer of chitosan and poly{2-[(acryloyloxy)ethyl]trimethylammonium chloride} end-grafted to the chitosan backbone as side chains. The nanogels retain their positive charge at the pH and ionic strength of chronic wound exudate, enabling electrostatically driven cfDNA scavenging. The network structure of the nanogels leads to the cfDNA sequestration in the nanogel interior, in addition to surface attachment. A key factor in cfDNA sequestration is the ratio of the pore size of the nanogel-to-cfDNA molecular dimensions. The enhanced cfDNA scavenging efficiency, along with biocompatibility of the nanogels, makes them a promising component of dressings for chronic wound treatment.

Stimulus-Responsive Nanoconjugates Derived from Phytoglycogen Nanoparticles.

Plant-derived phytoglycogen nanoparticles (PhG NPs) have the advantages of size uniformity, dispersibility in water, excellent lubrication properties, and lack of cytotoxicity; however, their chemical functionalization may lead to loss of NP structural integrity. Here, we report a straightforward approach to the generation of PhG NP conjugates with biologically active molecules. Hydrogen bonding of bovine serum albumin with electroneutral PhG NPs endows them with additional ligand binding affinity and enables the electrostatically governed attachment of methotrexate (MTX), a therapeutic agent commonly used in the treatment of cancer and arthritis diseases, to the protein-capped NPs. We showed stimuli-responsive release of MTX from the PhG-based nanoconjugates under physiological cues such as temperature and ionic strength. The results of this study stimulate future exploration of biomedical applications of nanoconjugates of PhG NPs.

Phytoglycogen Nanoparticles: Nature-Derived Superlubricants.

Phytoglycogen nanoparticles (PhG NPs), a single-molecule highly branched polysaccharide, exhibit excellent water retention, due to the abundance of close-packed hydroxyl groups forming hydrogen bonds with water. Here we report lubrication properties of close-packed adsorbed monolayers of PhG NPs acting as boundary lubricants. Using direct surface force measurements, we show that the hydrated nature of the NP layer results in its striking lubrication performance, with two distinct confinement-controlled friction coefficients. In the weak- to moderate-confinement regime, when the NP layer is compressed down to 8% of its original thickness under a normal pressure of up to 2.4 MPa, the NPs lubricate the surface with a friction coefficient of 10-3. In the strong-confinement regime, with 6.5% of the original layer thickness under a normal pressure of up to 8.1 MPa, the friction coefficient was 10-2. Analysis of the water content and energy dissipation in the confined NP film reveals that the lubrication is governed by synergistic contributions of unbound and bound water molecules, with the former contributing to lubrication properties in the weak- to moderate-confinement regime and the latter being responsible for the lubrication in the strong-confinement regime. These results unravel mechanistic insights that are essential for the design of lubricating systems based on strongly hydrated NPs.

Luminescence properties, energy transfer and thermal stability of white emitting phosphor Sr3(PO4)2:Ce3+/Tb3+/Mn2+ for white LEDs.

A series of Sr3(PO4)2:Ce3+/Mn2+/Tb3+ phosphors were synthesized by a high temperature solid phase method. After introducing Ce3+ as sensitizer in Sr3(PO4)2:Ce3+/Mn2+, the efficient energy transfer from Ce3+ to Mn2+ was observed and analyzed in detail, and Sr3(PO4)2:Ce3+/Mn2+ was demonstrated to be color tunable, changing from blue to orange red. In addition, Tb3+ ion, which mainly emits green light, was further added into the Sr3(PO4)2:Ce3+/Mn2+. Due to the addition of this green emission, the white emitting phosphors with good quality were obtained. At the same time, the energy transfer mechanisms among Ce3+, Tb3+ and Mn2+ ions were also analyzed in detail. The results show that Sr3(PO4)2:Ce3+/Mn2+/Tb3+ is a promising candidate for white light emitting diodes.

Impact of phase separation morphology on release mechanism of amorphous solid dispersions.

Amorphous solid dispersions (ASDs) can phase separate in the gel phase during dissolution, lowering the chemical potential and thus the driving force for drug release. The purpose of this study is to explore the connection between amorphous phase separation in the hydrated ASD and its resulting release rate. Poorly soluble model compounds - indomethacin (IND) and ritonavir (RTV) - were formulated as ASDs using PVP as carrier. Rotating disk dissolution studies with varying drug loading levels of IND-PVP and RTV-PVP showed that the drug release was fastest at an intermediate drug loading level. This was in part due to faster erosion of the ASD at lower drug loading levels. More interestingly, at low drug loading levels, PVP and the drug co-eroded, while at high drug loading levels, PVP was released preferentially. In the case of RTV-PVP, the loading level corresponding to this transition was correlated with the change in phase separation morphology as probed by confocal fluorescence imaging studies. At low drug loading levels, the hydrophobic domains were discrete domains while at high drug loading levels, hydrophobic domains were continuous. Our results suggest that at low drug loadings, release is mediated by erosion of the polymer along with embedded drug rich droplets, whereas at high drug loadings, formation of a drug-rich domain continuous morphology leads to preferential release of the polymer-rich domains. The transition from hydrophobic discrete to hydrophobic continuous morphology occurs at the percolation threshold. We discuss the two mechanisms of phase separation and its impact on the drug release from ASDs in the context of the ternary phase diagram.