Scott D. Kimmins

Chemical amination of the enzyme was demonstrated to favor immobilization onto polydopamine (PDA)-coated magnetic nanoparticles (MNPs) for the first time, to the best of the author’s knowledge. MNPs prepared via hydrothermal synthesis were coated with PDA for the immobilization of naringinase. X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy showed that the MNPs were composed mainly of Fe₃O₄ with an average size of 38.9 nm, and coated with a 15.1 nm PDA layer. Although the specific activities of α-L-rhamnosidase (RAM) and β-D-glucosidase (GLU) of free naringinase decreased with amination, the immobilization yields of the aminated enzyme increased by more than 40% for RAM and more than 10-fold for GLU. The immobilization improved the enzyme’s thermal stability (at 50 °C), reaching a half-life of 40.7 and 23.1 h for RAM and GLU activities, respectively. The biocatalyst was successfully used for the debittering of grapefruit juice, detecting a reduction in naringin of 56% after 24 h. These results demonstrate that the enzyme amination is an effective strategy to enhance the immobilization on a PDA coating and could be applied to other enzymes in order to obtain an easily recoverable biocatalyst using a simple immobilization methodology.

Crosslinking of an unsaturated aliphatic polyester poly(globalide) (PGl) by bistriazolinediones (bisTADs) is reported. First, a monofunctional model compound, phenyl–TAD (PTAD), was tested for PGl functionalisation. ¹H-NMR showed that PTAD–ene reaction was highly efficient with conversions up to 97%. Subsequently, hexamethylene bisTAD (HM–bisTAD) and methylene diphenyl bisTAD (MDP–bisTAD) were used to crosslink electrospun PGl fibres via one- and two-step approaches. In the one-step approach, PGl fibres were collected in a bisTAD solution for in situ crosslinking, which resulted in incomplete crosslinking. In the two-step approach, a light crosslinking of fibres was first achieved in a PGl non-solvent. Subsequent incubation in a fibre swelling bisTAD solution resulted in fully amorphous crosslinked fibres. SEM analysis revealed that the fibres’ morphology was uncompromised by the crosslinking. A significant increase of tensile strength from 0.3 ± 0.08 MPa to 2.7 ± 0.8 MPa and 3.9 ± 0.5 MPa was observed when PGI fibres were crosslinked by HM–bisTAD and MDP–bisTAD, respectively. The reported methodology allows the design of electrospun fibres from biocompatible polyesters and the modulation of their mechanical and thermal properties. It also opens future opportunities for drug delivery applications by selected drug loading.

Printing of novel linear polypeptide hydrogel bioinks and stabilisation of structures by post-printing UV-triggered crosslinking through catalyst free thiol–yne click chemistry of cysteine and propiolated 4-arm PEG.

Owing to their wide range of inherent functionality, hydrolytic stability, biodegradability, and low toxicity, polypeptide‐based materials have been increasingly exploited for controlled drug release applications. More recently, the incorporation of poly(α‐peptoid)s such as poly(sarcosine) into polypeptide‐based materials has been investigated owing to their potential as naturally derived “stealth polymers.” Here the synthesis of novel amphiphilic polypept(o)ide nanoparticles is described utilizing silica templates as a macroinitiator for the ring‐opening copolymerization of l‐tryptophan and d/l‐phenylalanine NCAs and subsequent chain extension with sarcosine NCA. These particles are subsequently crosslinked utilizing the TAD‐indole “click” chemistry and the silica templates are eroded via treatment with HF yielding core crosslinked amphiphilic polypept(o)ide nanostructures. This synthetic strategy offers a unique platform to yield naturally‐derived degradable core‐crosslinked nanostructures, which may have the potential to be utilized in the future as delivery vehicles for hydrophobic small molecules.

Crosslinking of tryptophan (Trp) containing copolypeptides with varying ratios of benzyl-l-glutamate (BLG) and Nα-(carbobenzyloxy)-l-lysine (Z-Lys) is achieved by the selective reaction with hexamethylene-bis-TAD (bisTAD). Conversion of the resulting organogels into biocompatible hydrogels by full BLG or Z-Lys deprotection is demonstrated. Moreover, diffusion controlled deprotection allows the design of macroscopic hybrid organohydrogels comprising hydrophilic as well as hydrophobic regions at a desired ratio and position. FTIR and SEM analysis confirm the coexistence of both hydrophilic and hydrophobic segments in one copolypeptide piece. Selective loading of hydrogel and organogel segments with hydrophilic and hydrophobic dyes, respectively, is observed on macroscopic amphiphilic gels and films. These materials offer significant potential as dual-loaded drug release gels as well as tissue engineering platforms.

Electrospinning is considered a relatively simple and versatile technique to form high porosity porous scaffolds with micron to nanoscale fibers for biomedical applications. Here, electrospinning of unsaturated aliphatic polyglobalide (PGl) into well-defined fibers with an average diameter of 9 μm is demonstrated. Addition of a dithiol cross-linker and a photoinitiator to the polymer solution enabled the UV-triggered intracross-linking of the fibers during the spinning process. The in situ cross-linking of the fibers resulted in amorphous material able to swell up to 14% in tetrahydrofurane (THF) without losing the fiber morphology. Seeding mesenchymal stem cells (MSCs) onto both cross-linked and non-cross-linked PGl fibers proved their compatibility with MSCs and suitability as scaffolds for cell growth and proliferation of MSCs. Moreover, the ability to directly load cross-linked PGl with hydrophobic molecules by soaking the fiber mesh in solution is shown with Rhodamine B and Indomethacin, a hydrophobic anti-inflammatory drug. This marks an advantage over conventional aliphatic polyesters and opens opportunities for the design of drug loaded polyester scaffolds for biomedical applications or tissue engineering.