Immobilization of Adenosine Derivatives onto Cellulose Nanocrystals via Click Chemistry for Biocatalysis Applications.

Adenosine triphosphate (ATP) is a central molecule of organisms and is involved in many biological processes. It is also widely used in biocatalytic processes, especially as a substrate and precursor of many cofactors─such as nicotinamide adenine dinucleotide phosphate (NADP(H)), coenzyme A (CoA), and S-adenosylmethionine (SAM). Despite its great scientific interest and pivotal role, its use in industrial processes is impeded by its prohibitory cost. To overcome this limitation, we developed a greener synthesis of adenosine derivatives and efficiently selectively grafted them onto organic nanoparticles. In this study, cellulose nanocrystals were used as a model combined with click chemistry via a copper-catalyzed azide/alkyne cycloaddition reaction (CuAAC). The grafted adenosine triphosphate derivative fully retains its biocatalytic capability, enabling heterobiocatalysis for modern biochemical processes.

RAFT Polymerisation by the Radical Decarboxylation of Carboxylic Acids.

The controlled grafting of polymers from small- and macro-molecular substrates is an essential process for many advanced polymer applications. This usually requires the pre-functionalisation of substrates with an appropriate functional group, such as a RAFT agent or ATRP initiator, which requires additional synthetic steps. In this paper, we describe the direct grafting of RAFT polymers from carboxylate containing small molecules and polymers via photochemical radical decarboxylation. This method utilises the innate functional groups present in the substrates, and achieves efficient polymer initiation in a single step with excellent control of molecular weight and dispersity.

Thermoresponsive Poly(N-isopropylacrylamide) Grafted from Cellulose Nanofibers via Silver-Promoted Decarboxylative Radical Polymerization.

A family of thermoresponsive poly(N-isopropylacrylamide) [PNIPAM]-grafted cellulose nanofibers (CNFs) was synthesized via a novel silver-promoted decarboxylative polymerization approach. This method relies on the oxidative decarboxylation of carboxylic acid groups to initiate free radicals on the surface of CNFs. The polymerization reaction employs relatively mild reaction conditions and can be performed in a one-step, one-pot fashion. This rapid reaction forms a C─C bond between CNF and PNIPAM, along with the formation of free polymer in solution. The degree of functionalization (DF) and the amount of PNIPAM grafted can be controlled by the Ag concentration in the reaction. Similar to native bulk PNIPAM, PNIPAM-grafted CNFs (PNIPAM-g-CNFs) show remarkable thermoresponsive properties, albeit exhibiting a slight hysteresis between the heating and cooling stages. Grafting PNIPAM from CNFs changes its cloud point from about 32 to 36 °C, influenced by the hydrophilic nature of CNFs. Unlike physical blending, covalently tethering PNIPAM transforms the originally inert CNFs into thermosensitive biomaterials. The Ag concentration used does not significantly change the cloud point of PNIPAM-g-CNFs, while the cloud point slightly decreases with fiber concentration. Rheological studies demonstrated the sol-gel transition of PNIPAM-g-CNFs and revealed that the storage modulus (G') above cloud point increases with the amount of PNIPAM grafted. The novel chemistry developed paves the way for the polymerization of any vinyl monomer from the surface of CNFs and carbohydrates. This study validates a novel approach to graft PNIPAM from CNFs for the synthesis of new thermoresponsive and transparent hydrogels for a wide range of applications.

Nanocrystallisation and self-assembly of biosourced ferulic acid derivative in polylactic acid elastomeric blends.

HYPOTHESIS: The crystallisation of biosourced ferulic acid derivatives - Bis-O-feruloyl-1,4-butanediol (BDF) - in a polylactic acid (PLA) matrix produces thermoplastic elastomeric blends that are transparent and biodegradable. Elastomeric and transparency are controlled by the domain size. PLA-BDF blends up to a threshold BDF concentration providing elastomeric properties show no evidence of BDF crystallisation. Heat treatment weakens the PLA-BDF interaction, give BDF molecules mobility to interact with nearby BDF molecules, leading to BDF nano-crystallisation. EXPERIMENTS: PLA-BDF blends were synthesised by hot-melt processing by mixing pure PLA with different concentrations of BDF (0-40 wt%) at 180 °C for 13 min. One set of blends was annealed at 50 °C for 24 h and compared with the unannealed set. The BDF crystallisation in the blends is studied by combining SAXS, SEM, XRD and Polarised Optical Microscopy. Monte-Carlo simulations were performed to validate SAXS data analysis. FINDINGS: Unannealed PLA-BDF blends of up to the threshold of 20 wt% BDF are dominated by the semicrystalline behaviour of PLA, without any trace of BDF crystallisation. Surprisingly, the PLA-BDF 40 wt% blend shows BDF crystallisation in the form of large and nanoscale structures bonded together by weak interparticle interaction. At concentrations up to 20 wt%, the BDF molecules are homogenously dispersed and bonded with PLA. Increasing BDF to 40 wt% brings the BDF molecules close enough to crystallise at room temperature, as the BDF molecules are still bonded with the PLA network. Annealing of PLA-BDF blends led to BDF nanocrystallisation and self-assembling in the PLA network. Both BDF nanoparticle size and interparticle distance decrease as the BDF concentration increases. However, the number density of BDF nanocrystals increases. The formed BDF nanocrystals have size ranging between 100 and 380 Å with interparticle distance of 120-180 Å. The structure factor and potential mean force confirm the strong interparticle interaction at the higher BDF concentration. Heat treatment weakens the PLA -BDF interaction, which provides mobility to the BDF molecules to change conformation and interact with the nearby BDF molecules, leading to BDF crystallisation. This novel BDF crystallisation and self-assembly mechanism can be used to develop biodegradable shape memory PLA blends for biomedical, shape memory, packaging and energy applications.

Controlling the transparency and rheology of nanocellulose gels with the extent of carboxylation.

TEMPO and periodate are combined in a one-shot reaction to oxidise cellulose and produce nanocellulose gels with a wide range of degree of substitution (DS). Highly-oxidised cellulose nanofibres with a high charge of -80 mV were produced. The strong electrical repulsion between TEMPO-periodate oxidised nanofibres (TPOF) results in the formation of well-separated nanofibres with a diameter of 2-4 nm, albeit depolymerised due to high oxidation. TPOF produces highly-transparent gels due to smaller aspect ratio and high surface charge. These properties induce a reduced viscosity and moduli of the gels by decreasing fibre entanglement. TPOF gels are more stable at basic pH and high ionic strength than TEMPO-oxidised gels due to their higher surface charge. Freeze-dried TPOF gels also exhibit remarkable water holding capacity due to enhanced immobilisation of water molecules. The excellent optical properties of the highly transparent gel for red blood cells analysis open new possibilities in diagnostics application.

One-shot TEMPO-periodate oxidation of native cellulose.

TEMPO/NaClO/NaBr and sodium periodate were combined in a one-shot reaction to oxidise cellulose from bleached pulp. Oxidation of cellulose forms two fractions: a highly-carboxylated water-insoluble (up to 1.9 mmol COO-/g, DS = 0.39) and a water-soluble fraction (up to 4 mmol COO-/g, DS = 1.1). Results show that these regioselective oxidants work in synergy to produce fully-oxidised 2,3,6-tricarboxycellulose. Increasing the periodate concentration results in fibrillation and extensive depolymerisation of the pulp cellulose as more residual aldehyde groups participate in the depolymerisation process. X-ray diffraction (XRD) reveals that the addition of periodate increases cellulose crystallinity, retains crystal size but slightly alters the XRD pattern. The degree of substitution (DS), which governs the solubility of carboxylated cellulose, can be controlled by varying the periodate concentration. Combining TEMPO/NaBr/NaClO with sodium periodate simultaneously in a one-shot reaction produces low-cost cellulose with controlled level of carboxylation and unique properties.

Health-promoting bioactivities of betalains from red dragon fruit (Hylocereus polyrhizus (Weber) Britton and Rose) peels as affected by carbohydrate encapsulation.

BACKGROUND: Betalains, which are red-purple and yellow pigments, are ideal alternatives to synthetic colorants as they possess strong coloring potential and excellent health-contributing properties. However, the instability of betalains toward normal storage and biological conditions, in addition to the limited number of betalain sources, impedes their food application and diminishes their bioactivities. This study aimed to evaluate the health-promoting bioactivities of betalains from red dragon fruit (Hylocereus polyrhizus (Weber) Britton and Rose) peels as affected by encapsulation in maltodextrin-gum Arabic and maltodextrin-pectin matrices. RESULTS: Encapsulation in maltodextrin-gum Arabic and maltodextrin-pectin matrices afforded dry betalain powders after lyophilization. Optical microscopy imaging showed that the betalain powders consisted of matrix-type and shard-like microparticles. ABTS antioxidant assay revealed that maltodextrin-gum Arabic-betalain (MGB) and maltodextrin-pectin-betalain (MPB) microparticles possessed higher antioxidant capacities (195.39 ± 8.63 and 201.76 ± 4.06 µmol Trolox g-1 microparticles respectively) than the non-encapsulated betalain extract (151.07 ± 2.57 µmol Trolox g-1 extract). Duck embryo chorioallantoic membrane (CAM) vascular irritation assay showed that the anti-inflammatory activity of encapsulated betalains was five- to six-fold higher than that of non-encapsulated betalains (P ≤ 0.05). Antiangiogenic activity, as evaluated by duck embryo CAM assay, was enhanced two- to four-fold by carbohydrate encapsulation. Glutathione S-transferase (GST)-inducing activity of betalains was likewise improved four- to five-fold. CONCLUSION: The study showed that the antioxidant, anti-inflammatory, antiangiogenic and GST-inducing activities of betalains from red dragon fruit peels were enhanced through carbohydrate encapsulation. © 2016 Society of Chemical Industry.