Fabrication of bio-inspired hydrophobic self-assembled electrospun nanofiber based hierarchical structures

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this record.In this letter, we present a facile approach to fabricate hydrophobic surfaces based on electrostatic field assisted self-assembly of fibers onto conductive micropillars. Hydrophobic patterns fabricated in this work are inspired by an underwater fern Salvinia molesta. Hydrophilic cellulose acetate nanofibers were electrospun on a conducting micro-patterned surface to create a hierarchical structure. The water contact angle increased from just below 70° (hydrophilic) on the micro-patterned structures to ∼140° (hydrophobic) for the hierarchical structures. Introduced hydrophobicity is due to the pinning of the water droplet to suspended hydrophilic nanofibers and a reduced solid-water interface.This work is supported by DST-UKIERI (IND/CONT/E/14-15/370 & DST/INT/UK/P-92/14) project. MK acknowledges assistance with the use of FESEM facility at the University of Exeter. Authors acknowledge IIT Hyderabad for providing research facilities required for carrying out experiment

Preparation and characterization of polycaprolactone microspheres by electrospraying

This is the author accepted manuscript. Published online: 13 Sep 2016. The final version to be made available from the publisher via the DOI in this record.The ability to reproducibly produce and effectively collect electrosprayed polymeric microspheres with controlled morphology and size in bulk form is challenging. In this study, microparticles were produced by electrospraying polycaprolactone (PCL) of various molecular weights and solution concentrations in chloroform, and by collecting materials on different substrates. The resultant PCL microparticles were characterized by optical and electron microscopy to investigate the effect of molecular weight, solution concentration, applied voltage, working distance and flow rate on their morphology and size. The work demonstrates the key role of a moderate molecular weight and/or solution concentration in the formation of spherical PCL particles via an electrospraying process. Increasing the applied voltage was found to produce smaller and more uniform PCL microparticles. There was a relatively low increase in the particle average size with an increase in the working distance and flow rate. Four types of substrates were adopted to collect electrosprayed PCL particles: a glass slide, aluminium foil, liquid bath and copper wire. Unlike 2D bulk structures collected on the other substrates, a 3D tubular structure of microspheres was formed on the copper wire and could find application in the construction of 3D tumour mimics.The financial support received from the Cancer Research UK (CRUK) and Engineering and Physical Sciences Research Council (ESPRC) Cancer Imaging Centre in Cambridge and Manchester (C8742/A18097) is acknowledged

Orientation of cellulose nanocrystals in electrospun polymer fibres (dataset)

Dataset supporting the open access article.Polystyrene and poly(vinyl alcohol) nanofibres containing cellulose nanocrystals (CNCs) were successfully produced by electrospinning. Knowledge of the local orientation of CNCs in electrospun fibres is critical to understand and exploit their mechanical properties. The orientation of CNCs in these electrospun fibres was investigated using transmission electron microscopy (TEM) and Raman spectroscopy. A Raman band located at ~1095 cm−1, associated with the C–O ring stretching of the cellulose backbone, was used to quantify the orientation of the CNCs within the fibres. Raman spectra were fitted using a theoretical model to characterize the extent of orientation. From these data, it is observed that the CNCs have little orientation along the direction parallel to the axis of the fibres. Evidences for both oriented and non-oriented regions of CNCs in the fibres are presented from TEM images of nanofibres. These results contradict previously published work in this area and micromechanical modelling calculations suggest a uniform orientation of CNCs in electrospun polymer fibres. It is demonstrated that this explains why the mechanical properties of electrospun fibre mats containing CNCs are not always the same as that would be expected for a fully oriented system

Deformation mechanisms in ionic liquid spun cellulose fibers

This is the final version of the article. Available from the publisher via the DOI in this record.The molecular deformation and crystal orientation of a range of next generation regenerated cellulose fibers, produced from an ionic liquid solvent spinning system, are correlated with macroscopic fiber properties. Fibers are drawn at the spinning stage to increase both molecular and crystal orientation in order to achieve a high tensile strength and Young’s modulus for potential use in engineering applications. Raman spectroscopy was utilized to quantify both molecular strain and orientation of fibers deformed in tension. X-ray diffraction was used to characterize crystal orientation of single fibers. These techniques are shown to provide complimentary information on the microstructure of the fibers. A shift in the position of a characteristic Raman band, initially located at ∼1095 cm−1, emanating from the backbone structure of the cellulose polymer chains was followed under tensile deformation. It is shown that the shift rate of this band with respect to strain increases with the draw ratio of the fibers, indicative of an increase in the axial molecular alignment and subsequent deformation of the cellulose chains. A linear relationship between the Raman band shift rate and the modulus was established, indicating that the fibers possess a series aggregate structure of aligned crystalline and amorphous domains. Wide-angle X-ray diffraction data show that crystal orientation increases with an increase in the draw ratio, and a crystalline chain slip model was used to fit the change in orientation with fiber draw ratio. In addition to this a new model is proposed for a series aggregate structure that takes into better account the molecular deformation of the fibers. Using this model a prediction for the crystal modulus of a cellulose-II structure is made (83 GPa) which is shown to be in good agreement with other experimental approaches for its determination.The Engineering and Physical Sciences Research Council (EPSRC) is acknowledged for funding provided under Grant No. EP/L017679/1

Structure of Spherulites in Insulin, β-Lactoglobulin, and Amyloid β

Under denaturing conditions such as low pH and elevated temperatures, proteins in vitro can misfold and aggregate to form long rigid rods called amyloid fibrils; further self-assembly can lead to larger structures termed spherulites. Both of these aggregates resemble amyloid tangles and plaques associated with Alzheimer’s disease in vivo. The ability to form such aggregates in a multitude of different proteins suggests that it is a generic ability in their mechanism to form. Little is known about the structure of these large spherulites ranging from 5 to 100 microns and whether they can reproducibly form in amyloid β (1-40) (Aβ40), a 40-amino acid residue peptide, which is one of the major components of Alzheimer’s amyloid deposits. Here, we show that spherulites can readily form in Aβ40 under certain monomerization and denaturing conditions. Using polarized and nonpolarized Raman spectroscopy, we analyzed the secondary structure of spherulites formed from three different proteins: insulin, β-lactoglobulin (BLG), and Aβ40. Visually, these spherulites have a characteristic “Maltese Cross” structure under crossed polarizers through an optical microscope. However, our results indicate that insulin and Aβ40 spherulites have similar core structures consisting mostly of random coils with radiating fibrils, whereas BLG mostly contains β-sheets and fibrils that are likely to be spiraling from the core to the edge

Understanding the interactions of cellulose fibres and deep eutectic solvent of choline chloride and urea

This is the author accepted manuscript. The final version is available from Springer Verlag via the DOI in this record.A deep eutectic solvent composed of choline chloride (ChCl) and urea has been recently introduced as a promising cellulose compatible medium that enables e.g. fibre spinning. This paper clarifies the influence of such a solvent system on the structure and chemical composition of the cellulosic pulp fibres. Special emphasis was placed on the probable alterations of the chemical composition due to the dissolution of the fibre components and/or due to the chemical derivatisation taking place during the DES treatment. Possible changes in fibre morphology were studied with atomic force microscopy and scanning electron microscopy. Chemical compositions of pulp fibres were determined from the carbohydrate content, and by analysing the elemental content. Detailed structural characterisation of the fibres was carried out using spectroscopic methods; namely X-Ray Photoelectron Spectroscopy, solid state Nuclear Magnetic Resonance and Raman Spectroscopy. No changes with respect to fibre morphology were revealed and negligible changes in the carbohydrate composition were noted. The most significant change was related to the nitrogen content of the pulp after the DES treatment. Comprehensive examination using spectroscopic methods revealed that the nitrogen originated from strongly bound ChCl residuals that could not be removed with a mild ethanol washing procedure. According to Raman spectroscopic data and methylene blue adsorption tests, the cationic groups of ChCl seems to be attached to the anionic groups of pulp by electrostatic forces. These findings will facilitate the efficient utilisation of DES as a cellulose compatible medium without significantly affecting the native fibre structure.The authors acknowledge the Finnish Funding Agency for Innovation (TEKES) for funding the work via Design Driven Value Chains in the World of Cellulose 2.0 project. The Academy of Finland (Project ID 300367) is acknowledged for enabling the research mobility of T.T. to the University of Exeter, UK. Unto Tapper (VTT) is thanked for the SEM imaging, Atte Mikkelson, Ritva Heinonen and Marita Ikonen (VTT) for the chemical analysis and Robertus Nugroho (Aalto University) for the AFM imaging

Superbase ionic liquids for effective cellulose processing from dissolution to carbonisation

This is the author accepted manuscript. The final version is available from Royal Society of Chemistry via the DOI in this recordA range of superbase derived ionic liquids (SILs) was synthesised and characterised. Their ability to dissolve cellulose and the characteristics of the produced fibres were correlated to their specific structural and solvent properties. 17 ionic liquids (ILs) (including 9 novel) were analysed and six ILs were selected to produce fibres: 1-ethyl-3-methylimidazolium acetate [C2C1im][OAc], 1-ethyl-3-methylimidazolium diethyl phosphate [C2C1im][DEP] and the SILs 1-ethyl-1,8-diazabicyclo[5.4.0]undec-7-enium diethylphosphate [DBUEt][DEP], 1,8-diazabicyclo[5.4.0]undec-7-enium acetate [DBUH][OAc], 1,5-diazabicyclo[4.3.0]non-5-enium acetate [DBNH][OAc] and 1-ethyl-1,5-diazabicyclo[4.3.0]non-5-enium diethylphsophate [DBNEt][DEP]. The mechanical properties of these fibres were investigated. The obtained fibres were then carbonised to explore possible application as carbon fibre precursors. The fibres obtained using a mixture of 1,5-diazabicyclo[4.3.0]non-5-enium based SILs with acetate and hexanoate anions (9 : 1), [DBNH][OAc][Hex], showed a promising combination of strength, stiffness and strain at failure values for applications in textiles and fibre reinforcement in renewable composites. Using Raman spectroscopy it is demonstrated that these fibres exhibit a relatively high degree of structural order, with fewer defects than the other materials. On the other hand, analogous fibres based on imidazolium cation with acetate and hexanoate anions (9 : 1), [C2C1im][OAc][Hex] showed a decline in the quality of the produced fibres compared to the fibres produced from [C2C1im][OAc], [C2C1im][DEP] or [DBNH][OAc][Hex].We would like to thank the EPSRC grant number EP/L017679/01 for financial support (AERO RB1717)

Stress transfer quantification in gelatin-matrix natural composites with tunable optical properties

© 2015 American Chemical Society.This work reports on the preparation and characterization of natural composite materials prepared from bacterial cellulose (BC) incorporated into a gelatin matrix. Composite morphology was studied using scanning electron microscopy and 2D Raman imaging revealing an inhomogeneous dispersion of BC within the gelatin matrix. The composite materials showed controllable degrees of transparency to visible light and opacity to UV light depending on BC weight fraction. By adding a 10 wt % fraction of BC in gelatin, visible (= 550 nm) and UV (= 350 nm) transmittances were found to decrease by ∼35 and 40%, respectively. Additionally, stress transfer occurring between the gelatin and BC fibrils was quantified using Raman spectroscopy. This is the first report for a gelatin-matrix composite containing cellulose. As a function of strain, two distinct domains, both showing linear relationships, were observed for which an average initial shift rate with respect to strain of -0.63 ± 0.2 cm-1%-1 was observed, followed by an average shift rate of -0.25 ± 0.03 cm-1%-1. The average initial Raman band shift rate value corresponds to an average effective Youngs modulus of 39 ± 13 GPa and 73 ± 25 GPa, respectively, for either a 2D and 3D network of BC fibrils embedded in the gelatin matrix. As a function of stress, a linear relationship was observed with a Raman band shift rate of -27 ± 3 cm-1GPa-1. The potential use of these composite materials as a UV blocking food coating is discussed

Optimization of admixture and three-layer particleboard made from oil palm empty fruit bunch and rubberwood clones

Empty fruit bunch (EFB) is a biomass that is widely available and has the potential to be used as industrial raw material especially in wood-based industries. This study focuses on producing a particleboard by incorporating EFB with two different rubberwood clones: Prang Besar (PB) 260 and RRIM 2002, respectively. PB 260 is a commercially planted clone and wood from matured (>25 year-old) trees are used by wood-based panel manufacturers. RRIM 2002 is a new clone planted at the Malaysian Rubber Board (MRB) research trial plots and consists of only 4-year-old trees. Two types of particleboards (admixture and three-layer) with different ratios were produced. The Japanese Industrial Standard (JIS-5908 2003 particleboard) was used to evaluate mechanical and dimensional stability properties of the particleboards. From the study, it was found that admixture particleboards showed superior properties compared to three-layer particleboards. Layering EFB and rubberwood significantly decreased board performance for all properties (except internal bonding). The optimum ratios of EFB and both rubberwood clones are found to be 1:1 (50% EFB: 50% rubberwood). Meanwhile, increasing the rubberwood clones ratio to 70% lowered board performance especially for EFB (30%):RRIM 2002 clone (70%) boards which showed the lowest values for all properties for both admixture and three-layer board