Modification of hyaluronic acid to enable click chemistry photo-crosslinking of hydrogels with tailorable degradation profiles.

Hyaluronic acid (HA) is a naturally occurring mucopolysaccharide that, due to its inherent bioactivity and extracellular matrix-like structure, has the potential to be utilised extensively in tissue engineering. However, this glycosaminoglycan lacks the properties required for cellular adhesion and photo-crosslinking by UV light, which significantly hinders this polymers applicability. This research presents a method for modifying hyaluronic acid via thiolation and methacrylation to generate a novel photo-crosslinkable polymer with improved physicochemical properties, biocompatibility and the potential to customize biodegradability according to the ratio of monomers used. A decrease in stiffness proportional to increasing thiol concentration was observed when testing the compressive strength of hydrogels. Conversely, it was noted that the storage moduli of hydrogels increased proportionally to thiol concentration indicating a greater degree of cross-linking with the addition of thiol. The addition of thiol to HA increased the biocompatibility of the material in both neuronal and glial cell lines and improved the degradability of methacrylated HA. Due to the enhanced physicochemical properties and biocompatibility imparted by the introduction of thiolated HA, this novel hydrogel system could have numerous bioengineering applications.

Review: Recent advancements and moving trends in chemical analysis of fire debris.

This review describes recent advances and current trends in fire debris analysis from 2014 to 2021. Onsite analytical techniques used for fire scene investigation, identifying samples of interest for later analysis as well as onsite confirmatory techniques are examined. Laboratory techniques are reviewed both from a perspective of instrumentation and data analysis. Advances in analytical techniques include GC x GC-TOFMS, DART-MS, HS-GC-IMS. New and emerging methods of data analysis including those using machine learning are assessed. Each aspect is essential for forensic scientists to obtain the correct conclusion when collecting, examining, analysing, and interpreting fire debris. This review concludes that there is a need for the validity and certainty of all methods to be assessed if they are to be used to generate reports or draw conclusions.

A Comparative Analysis of Conventional and Deep Eutectic Solvent (DES)-Mediated Strategies for the Extraction of Chitin from Marine Crustacean Shells.

Chitin, the second most abundant biopolymer on earth, is utilised in a wide range of applications including wastewater treatment, drug delivery, wound healing, tissue engineering, and stem cell technology among others. This review compares the most prevalent strategies for the extraction of chitin from crustacean sources including chemical methods that involve the use of harsh solvents and emerging methods using deep eutectic solvents (DES). In recent years, a significant amount of research has been carried out to identify and develop environmentally friendly processes which might facilitate the replacement of problematic chemicals utilised in conventional chemical extraction strategies with DES. This article provides an overview of different experimental parameters used in the DES-mediated extraction of chitin while also comparing the purity and yields of associated extracts with conventional methods. As part of this review, we compare the relative proportions of chitin and extraneous materials in different marine crustaceans. We show the importance of the species of crustacean shell in relation to chitin purity and discuss the significance of varying process parameters associated with different extraction strategies. The review also describes some recent applications associated with chitin. Following on from this review, we suggest recommendations for further investigation into chitin extraction, especially for experimental research pertaining to the enhancement of the "environmentally friendly" nature of the process. It is hoped that this article will provide researchers with a platform to better understand the benefits and limitations of DES-mediated extractions thereby further promoting knowledge in this area.

The dynamic kinetic resolution of azlactones with thiol nucleophiles catalyzed by arylated, deoxygenated cinchona alkaloids.

A significant improvement of the available organocatalytic methods (in terms of product substrate scope and product enantiomeric excess) for the generation of enantioenriched α-amino acid thioesters via the dynamic kinetic resolution of azlactones is reported. C-9 arylated cinchona alkaloid catalysts have been found to be considerably superior to other bifunctional alkaloid catalysts as the promoters of this asymmetric process.

Highly tunable arylated cinchona alkaloids as bifunctional catalysts.

We report the design and evaluation of a library of chiral bifunctional organocatalysts in which the distance between the catalytically active units can be systematically varied.

Organocatalytic asymmetric addition of alcohols and thiols to activated electrophiles: efficient dynamic kinetic resolution and desymmetrization protocols.

Bifunctional urea-based cinchona alkaloid derivatives have been shown to promote highly efficient DKR reactions of azalactones using an alcohol nucleophile. The optimum catalyst is remarkably insensitive to the steric bulk of the amino acid residue, allowing alanine-, methionine-, and phenylalanine-derived azalactones to undergo DKR with unprecedented levels of enantioselectivity using a synthetic catalyst. The first DKR of these substrates by thiols and the highly enantioselective desymmetrization of a meso-glutaric anhydride by thiolysis are also reported.

Computational study-led organocatalyst design: a novel, highly active urea-based catalyst for addition reactions to epoxides.

An in silico study examined the stabilities of hydrogen-bonded complexes between simple thiourea catalysts and three different electrophiles and identified a novel, highly active N-tosyl urea catalyst for the promotion of addition reactions to epoxide electrophiles. Synthesis and evaluation of 6 revealed it to be a powerful catalyst for the addition of 1,2-dimethylindole to styrene oxide under conditions in which simple N,N-bis-aryl ureas and thioureas (including 1) are inactive. Subsequent studies determined 6 to be compatible with a range of indole and epoxide substrates (including (E)-stilbene oxide) and found that relatively poor nucleophiles such as sterically and electronically deactivated anilines, thiophenol, and benzyl alcohol could be efficiently and regioselectively added to oxiranes under mild conditions.