David Plackett

Sustainable films and coatings from hemicelluloses: a review.

This review summarizes the results of past research on films and coatings from hemicelluloses, biopolymers that are as yet relatively unexploited commercially. The targeted uses of hemicelluloses have primarily been packaging films and coatings for foodstuffs as well as biomedical applications. Oxygen permeability of hemicellulose films, an important characteristic for food packaging, was typically comparable to values found for other biopolymer films such as amylose and amylopectin. As expected, the modification of hemicelluloses to create more hydrophobic films reduced the water vapor permeability. However, modified hemicellulose coatings intended for food still exhibited water vapor permeabilities several magnitudes higher than those of other polymers currently used for this purpose. Research on hemicelluloses for biomedical applications has included biocompatible hydrogels and coatings and material surfaces with enhanced cell affinity. Numerous possibilities exist for chemically modifying hemicelluloses, and fundamental studies of films from modified hemicelluloses have identified other potential applications, including selective membranes.

Transparent Films Based on PLA and Montmorillonite with Tunable Oxygen Barrier Properties

Polylactide (PLA) is viewed as a potential material to replace synthetic plastics (e.g., poly(ethylene terephthalate) (PET)) in food packaging, and there have been a number of developments in this direction. However, for PLA to be competitive in more demanding uses such as the packaging of oxygen-sensitive foods, the oxygen permeability coefficient (OP) needs to be reduced by a factor of ~10. To achieve this, a layer-by-layer (Lbl) approach was used to assemble alternating layers of montmorillonite clay and chitosan on extruded PLA film surfaces. When 70 bilayers were applied, the OP was reduced by 99 and 96%, respectively, at 20 and 50% RH. These are, to our knowledge, the best improvements in oxygen barrier properties ever reported for a PLA/clay-based film. The process of assembling such multilayer structures was characterized using a quartz crystal microbalance with dissipation monitoring. Transmission electron microscopy revealed a well-ordered laminar structure in the deposited multilayer coatings, and light transmittance results demonstrated the high optical clarity of the coated PLA films.

Combining asymmetrical flow field-flow fractionation with light-scattering and inductively coupled plasma mass spectrometric detection for characterization of nanoclay used in biopolymer nanocomposites.

It is expected that biopolymers obtained from renewable resources will in due course become fully competitive with fossil fuel-derived plastics as food-packaging materials. In this context, biopolymer nanocomposites are a field of emerging interest since such materials can exhibit improved mechanical and barrier properties and be more suitable for a wider range of food-packaging applications. Natural or synthetic clay nanofillers are being investigated for this purpose in a project called NanoPack funded by the Danish Strategic Research Council. In order to detect and characterize the size of clay nanoparticulates, an analytical system combining asymmetrical flow field-flow fractionation (AF4) with multi-angle light-scattering detection (MALS) and inductively coupled plasma mass spectrometry (ICP-MS) is presented. In a migration study, we tested a biopolymer nanocomposite consisting of polylactide (PLA) with 5% Cloisite®30B (a derivatized montmorillonite clay) as a filler. Based on AF4-MALS analyses, we found that particles ranging from 50 to 800 nm in radius indeed migrated into the 95% ethanol used as a food simulant. The full hyphenated AF4-MALS-ICP-MS system showed, however, that none of the characteristic clay minerals was detectable, and it is concluded that clay nanoparticles were absent in the migrate. Finally, by means of centrifugation experiments, a platelet aspect ratio of 320 was calculated for montmorillonite clay using AF4-MALS for platelet size measurements.

Migration of nanosized layered double hydroxide platelets from polylactide nanocomposite films

Melt-extruded L-polylactide (PLA) nanocomposite films were prepared from commercially available PLA and laurate-modified Mg–Al layered double hydroxide (LDH-C12). Three films were tested for total migration as well as specific migration of LDH, tin, laurate and low molecular weight PLA oligomers (OLLA). This is the first reported investigation on the migration properties of PLA-LDH nanocomposite films. The tests were carried out as part of an overall assessment of the suitability of such films for use as food contact materials (FCM). Total migration was determined according to a European standard method. All three films showed migration of nanosized LDH, which was quantified using acid digestion followed by inductively coupled plasma mass spectrometric (ICP–MS) detection of 26Mg. Migration of LDH from the films was also confirmed by examining migrates using transmission electron microscopy (TEM) and was attributed indirectly to the significant PLA molecular weight reduction observed in extruded PLA-LDH-C12 films. Migration of tin was detected in two of the film samples prepared by dispersion of LDH-C12 using a masterbatch technique and migration of the laurate organomodifier took place from all three film types. The results indicate that the material properties are in compliance with the migration limits for total migration and specific lauric acid migration as set down by the EU legislation for FCM, at least if a reduction factor for fresh meat is taken into consideration. The tin detected arises from the use of organotin catalysts in the manufacture of PLA.

Composite Films of Arabinoxylan and Fibrous Sepiolite: Morphological, Mechanical, and Barrier Properties

Hemicelluloses represent a largely unutilized resource for future bioderived films in packaging and other applications. However, improvement of film properties is needed in order to transfer this potential into reality. In this context, sepiolite, a fibrous clay, was investigated as an additive to enhance the properties of rye flour arabinoxylan. Composite films cast from arabinoxylan solutions and sepiolite suspensions in water were transparent or semitransparent at additive loadings in the 2.5-10 wt % range. Scanning electron microscopy showed that the sepiolite was well dispersed in the arabinoxylan films and sepiolite fiber aggregation was not found. FT-IR spectroscopy provided some evidence for hydrogen bonding between sepiolite and arabinoxylan. Consistent with these findings, mechanical testing showed increases in film stiffness and strength with sepiolite addition and the effect of poly(ethylene glycol) methyl ether (mPEG) plasticizer addition. Incorporation of sepiolite did not significantly influence the thermal degradation or the gas barrier properties of arabinoxylan films, which is likely a consequence of sepiolite fiber morphology. In summary, sepiolite was shown to have potential as an additive to obtain stronger hemicellulose films although other approaches, possibly in combination with the use of sepiolite, would be needed if enhanced film barrier properties are required for specific applications.

PLGA and PHBV Microsphere Formulations and Solid-State Characterization: Possible Implications for Local Delivery of Fusidic Acid for the Treatment and Prevention of Orthopaedic Infections

PurposeTo develop and characterize the solid-state properties of poly(DL-lactic-co-glycolic acid) (PLGA) and poly(3-hydroxybutyric acid-co-3-hydroxyvaleric acid) (PHBV) microspheres for the localized and controlled release of fusidic acid (FA).MethodsThe effects of FA loading and polymer composition on the mean diameter, encapsulation efficiency and FA released from the microspheres were determined. The solid-state and phase separation properties of the microspheres were characterized using DSC, XRPD, Raman spectroscopy, SEM, laser confocal and real time recording of single microspheres formation.ResultsAbove a loading of 1% (w/w) FA phase separated from PLGA polymer and formed distinct spherical FA-rich amorphous microdomains throughout the PLGA microsphere. For FA-loaded PLGA microspheres, encapsulation efficiency and cumulative release increased with initial drug loading. Similarly, cumulative release from FA-loaded PHBV microspheres was increased by FA loading. After the initial burst release, FA was released from PLGA microspheres much slower compared to PHBV microspheres.ConclusionsA unique phase separation phenomenon of FA in PLGA but not in PHBV polymers was observed, driven by coalescence of liquid microdroplets of a DCM-FA-rich phase in the forming microsphere.

Drug intercalation in layered double hydroxide clay: Application in the development of a nanocomposite film for guided tissue regeneration

It has been proposed that localized and controlled delivery of alendronate and tetracycline to periodontal pocket fluids via guided tissue regeneration (GTR) membranes may be a valuable adjunctive treatment for advanced periodontitis. The objectives of this work were to develop a co-loaded, controlled release tetracycline and alendronate nanocomposite plasticized poly(lactic-co-glycolic acid) (PLGA) film that would form a suitable matrix supporting osteoblast proliferation and differentiation. Alendronate release was successfully controlled, with complete suppression of the burst phase of release by intercalation of alendronate anions in magnesium/aluminum layered double hydroxide (LDH) clay nanoparticles and dispersed in the PLGA film matrix. Tetracycline, loaded as free drug into the film together with alendronate-LDH clay complex released more rapidly than alendronate, but showed evidence of intercalation in the LDH clay particles. The dual drug loaded nanocomposite films were biocompatible with osteoblasts and after 5 week incubations, significant increase in alkaline phosphatase activity and bone nodule formation were observed.

Synthesis and characterization of birch wood xylan succinoylated in 1-n-butyl-3-methylimidazolium chloride

The chemical modification of birch wood xylan was undertaken in the ionic liquid 1-n-butyl-3-methylimidazolium chloride (C4mimCl) using three different long-chain succinic anhydrides: n-octenyl succinic anhydride (n-OSA), n-dodecenyl succinic anhydride (n-DDSA) and n-octadecenyl succinic anhydride (n-ODSA). Reactions were performed at temperatures of 80–100 °C and reaction times of 0.5–22 hours resulting in a degree of substitution (DS) of 0.08–0.27. The formation of the desired products was confirmed through the use of 1H NMR and FT-IR, while DS was determined by titration. Thermogravimetric analysis of the modified and native xylans showed a slight lowering of thermal stability with functionalization. Contact angle measurements on spin-coated surfaces of modified xylan films showed a significant increase in hydrophobicity with the introduction of the alkenyl-functionalized succinic anhydride moieties.

A simple passive equilibration method for loading carboplatin into pre-formed liposomes incubated with ethanol as a temperature dependent permeability enhancer

ABSTRACT A passive equilibration method which relies on addition of candidate drugs to pre‐formed liposomes is described as an alternative method for preparing liposome encapsulated drugs. The method is simple, rapid and applicable to liposomes prepared with high (45 mol%) or low (< 20 mol%) levels of cholesterol. Passive equilibration is performed in 4‐steps: (i) formation of liposomes, (ii) addition of the candidate drug to the liposomes in combination with a permeability enhancing agent, (iii) incubation at a temperature that facilitates diffusion of the added compound across the lipid bilayer, and (iv) quenching the enhanced membrane permeability by reduction in temperature and/or removal of the permeabilization enhancer. The method is fully exemplified here using ethanol as the permeabilization enhancer and carboplatin (CBDCA) as the drug candidate. It is demonstrated that ethanol can be added to liposomes prepared with 1,2‐distearoyl‐sn‐glycero‐3‐phosphocholine (DSPC) and Cholesterol (Chol) (55:45 mol ratio) in amounts up to 30% (v/v) with no change in liposome size, even when incubated at temperatures > 60 °C. Super‐saturated solutions of CBDCA (40 mg/mL) can be prepared at 70 °C and these are stable in the presence of ethanol even when the temperature is reduced to < 30 °C. maximum CBDCA encapsulation is achieved within 1 h after the CBDCA solution is added to pre‐formed DSPC/Chol liposomes in the presence of 30% (v/v) ethanol at 60 °C. When the pre‐formed liposomes are mixed with ethanol (30% v/v) at or below 40 °C, the encapsulation efficiency is reduced by an order of magnitude. The method was also applied to liposomes prepared from other compositions include a cholesterol free formulations (containing 1,2‐distearoyl‐sn‐glycero‐3‐phosphoethanolamine‐N‐[carboxy(polyethylene glycol)‐2000] (DSPE‐PEG2000)) and a low Chol (< 20 mol%) formulations prepared with the distearoyl‐sn‐glycero‐3‐phospho‐(1′‐rac‐glycerol) DSPG)). The cytotoxic activity of CBDCA was unaffected when prepared in this manner and two of the resultant formulations exhibited good stability in vitro and in vivo. The cytotoxic activity of CBDCA was unaffected when prepared in this manner and the resultant formulations exhibited good stability in vitro and in vivo. Pharmacokinetics studies in CD‐1 mice indicated that the resulting formulations increased the circulation half life of the associated CBDCA significantly (AUC0–24 h of CBDCA = 0.016 &mgr;g·hr/mL; AUC0–24h of the DSPC/Chol CBDCA formulation = 1014.0 &mgr;g·hr/mL and AUC0–24h of the DSPC/DSPG/Chol CBDCA formulation = 583.96 &mgr;g·hr/mL). Preliminary efficacy studies in Rag‐2M mice with established subcutaneous H1975 and U‐251 tumors suggest that the therapeutic activity of CBDCA is improved when administered in liposomal formulations. The encapsulation method described here has not been disclosed previously and will have broad applications to drugs that would normally be encapsulated during liposome manufacturing.

Carbohydrate analysis of hemicelluloses by gas chromatography–mass spectrometry of acetylated methyl glycosides

A method based on gas chromatography–mass spectrometry analysis of acetylated methyl glycosides was developed in order to analyze monosaccharides obtained from various hemicelluloses. The derivatives of monosaccharide standards, arabinose, glucose, and xylose were studied in detail and 13C-labeled analogues were used for identification and quantitative analysis. Excellent chromatographic separation of the monosaccharide derivatives was found and identification of the anomeric configuration was feasible through a prepared and identified pure methyl 2,3,4,6-tetra-O-acetyl-β-d-glucopyranoside. The electron ionization mass spectrum and fragmentation path was studied for each monosaccharide derivative. Fragment ion pairs of labeled and unlabeled monosaccharides were used for quantification; m/z 243/248 for glucose, 128/132 for xylose, and 217/218 for arabinose. Using the intensity ratios obtained from the extracted ion chromatograms, accurate quantification of monosaccharide constituents of selected hemicelluloses was demonstrated.