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Herein we demonstrate the fabrication of arrays of micropillars, achieved through the combination of direct laser writing and nanoimprint lithography. By combining two diacrylate monomers, polycaprolactone dimethacrylate (PCLDMA) and 1,6-hexanediol diacrylate (HDDA), two copolymer formulations that, owing to the varying ratios of the hydrolysable ester functionalities present in the polycaprolactone moiety, can be degraded in the presence of base in a controllable manner. As such, the degradation of the micropillars can be tuned over several days as a function of PCLDMA concentration within the copolymer formulations, and the topography greatly varied over a short space of time, as visualised using scanning electron microscopy and atomic force microscopy. Crosslinked neat HDDA was used as a control material, demonstrating that the presence of the PCL was responsible for the ability of the microstructures to degrade in the controlled manner. In addition, the mass loss of the crosslinked materials was minimal, demonstrating the degradation of microstructured surfaces without loss of bulk properties was possible. Moreover, the compatibility of these crosslinked materials with mammalian cells was explored. The influence of both indirect and direct contact of the materials with A549 cells was assessed by profiling indices reflective of cytotoxicity such as morphology, adhesion, metabolic activity, oxidative balance, and release of injury markers. No significant changes in the aforementioned profile were observed in the cells cultured under these conditions for up to 72 h, with the cell-material interaction suggesting these materials may have potential in microfabrication contexts towards biomedical application purposes.

Stimuli responsive materials are found in a broad range of applications, from energy harvesters to biomolecular sensors. Here, we report the production of poly (L-lactic acid) (PLLA) thin films that exhibit a mechanical stress responsive behaviour. By simply applying a mechanical stress through an AFM tip, a local electrical polarization was generated and measured by Kelvin Probe Force Microscopy. We showed that the magnitude of the stress generated electrical polarization can be manipulated by varying the thickness or crystallization state of the PLLA thin films. Besides exhibiting a mechanical stress-response behaviour with potential for energy harvesting and sensor applications, we show by AFM that these platforms react to mechanical forces with physiological relevance: interaction forces as low as a cell sheet migrating over a substrate or larger ones as the fluid induced stresses in bone tissue. In living tissues, as most mechanical stimuli are transduced as strain gradients for the anatomical structures, these mechanically responsive substrates can be used as ex vivo platforms to study the protein and cells response over a large range of electrical stimuli amplitude. As a proof of concept, selective adsorption of a human fibronectin was demonstrated by local patterning of the stimuli responsive PLLA films. STATEMENT OF SIGNIFICANCE: Bioelectricity is inherent to the formation and repair of living tissues and electrical stimulation has been recognized for promoting regeneration. Given the proven beneficial effects of electric fields and the absence of a suitable method of stimulation, there is a clinical need for smart substrates, which can generate a polarization (charges) to promote tissue regeneration without the need of external devices. In this work, we report the fabrication of poly(L-lactic) acid platforms that exhibit a mechanical stress responsive behaviour when subjected to physiologically relevant forces. This behaviour can be tailored by varying the thickness or crystallization state of the PLLA films. We further demonstrate the biofunctionality of such platforms by exploiting the mechanically-induced charge for adhesion protein adsorption., Competing Interests: Declaration of Competing Interest We wish to confirm that there are no known conflicts of interest associated with this publication and there has been no significant financial support for this work that could have influenced its outcome., (Copyright © 2021 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

Further to conventional linear, branched, crosslinked, and dendritic polymers, single chain cyclized/knotted polymers (SCKPs) have emerged as a new class of polymer structure with unique properties. Herein, the development of bacteria-resistant SCKPs is reported and the effect of this structure on the resistance of polymer materials to bacteria is investigated. Four SCKPs were synthesized by reversible addition fragmentation chain transfer (RAFT) homopolymerization of multivinyl monomers (MVMs) and then crosslinked by UV light to form SCKP films. Regardless of MVM type used, the resulting SCKP films showed much higher resistance to bacteria, and up to 75 % less bacterial attachment and biofilm formation, in comparison with the corresponding non-SCKP films. This is due to the altered surface morphology and hydrophobicity of the SCKP films. These results highlight the critical role of the SCKP structure in enhancing the resistance of polymeric materials to bacteria., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Two polymers, polymethylmethacrylate (PMMA) and cyclic olefin copolymer (COC), containing a range of nano- to micron- roughness surfaces (Ra 0.01, 0.1, 0.4, 1.0, 2.0, 3.2 and 5.0μm) were fabricated using electrical discharge machining (EDM) and replicated using micro injection moulding (μIM). Polymer samples were characterized using optical profilometry, atomic force microscopy (AFM) and water surface contact angle. Cell adhesion tests were carried out using bacterial Pseudomonas fluorescens and mammalian Madin-Darby Canine Kidney (MDCK) cells to determine the effect of surface hydrophobicity, surface roughness and stiffness. It is found that there are features which gave insignificant differences (feature-dependent effect) in cell adhesion, albeit a significant difference in the physicochemical properties (material-dependent effect) of substrata. In bacterial cell adhesion, the strongest feature-dependence is found at Ra 0.4μm surfaces, with material-dependent effects strongest at Ra 0.01μm. Ra 0.1μm surfaces exhibited strongest feature-dependent effects and Ra 5.0μm has strongest material-dependent effects on mammalian cell adhesion. Bacterial cell adhesion is found to be favourable to hydrophobic surfaces (COC), with the lowest adhesion at Ra 0.4μm for both materials. Mammalian cell adhesion is lowest in Ra 0.1μm and highest in Ra 1.0μm, and generally favours hydrophilic surfaces (PMMA). These findings can be used as a basis for developing medical implants or microfluidic devices using micro injection moulding for diagnostic purposes, by tuning the cell adhesion on different areas containing different surface roughnesses on the diagnostic microfluidic devices or medical implants., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Nonviral gene therapy holds great promise but has not delivered treatments for clinical application to date. Lack of safe and efficient gene delivery vectors is the major hurdle. Among nonviral gene delivery vectors, poly(β-amino ester)s are one of the most versatile candidates because of their wide monomer availability, high polymer flexibility, and superior gene transfection performance both in vitro and in vivo. However, to date, all research has been focused on vectors with a linear structure. A well-accepted view is that dendritic or branched polymers have greater potential as gene delivery vectors because of their three-dimensional structure and multiple terminal groups. Nevertheless, to date, the synthesis of dendritic or branched polymers has been proven to be a well-known challenge. We report the design and synthesis of highly branched poly(β-amino ester)s (HPAEs) via a one-pot "A2 + B3 + C2"-type Michael addition approach and evaluate their potential as gene delivery vectors. We find that the branched structure can significantly enhance the transfection efficiency of poly(β-amino ester)s: Up to an 8521-fold enhancement in transfection efficiency was observed across 12 cell types ranging from cell lines, primary cells, to stem cells, over their corresponding linear poly(β-amino ester)s (LPAEs) and the commercial transfection reagents polyethyleneimine, SuperFect, and Lipofectamine 2000. Moreover, we further demonstrate that HPAEs can correct genetic defects in vivo using a recessive dystrophic epidermolysis bullosa graft mouse model. Our findings prove that the A2 + B3 + C2 approach is highly generalizable and flexible for the design and synthesis of HPAEs, which cannot be achieved by the conventional polymerization approach; HPAEs are more efficient vectors in gene transfection than the corresponding LPAEs. This provides valuable insight into the development and applications of nonviral gene delivery and demonstrates great prospect for their translation to a clinical environment.

High aspect ratio (HAR) nanoneedle arrays can be used to tune the intrinsic properties of substrates such as their wettability and reflectivity. Here, a simple and scalable fabrication method for producing dense arrays of freestanding polyethylene glycol (PEG) nanoneedles with sub 50 nm tips and surface coverage up to 83 needles per µm2 is presented. Two distinct sets of silicon nanoneedle master arrays with base diameters between 15 and 265 nm and heights between 146 and 613 nm are fabricated using block copolymer micelle lithography. Replication of selected silicon masters using photocurable polymers produces HAR PEG nanoneedle arrays with feature base diameters ranging between 15 and 292 nm and heights between 133 and 656 nm. At their maximum, the aspect ratio of the pillars is 4.6. PEG nanoneedle arrays are produced using polymers with two different molecular weights as well as two different photoinitiators, showing the versatility of the process. [ABSTRACT FROM AUTHOR]

Further to conventional linear, branched, crosslinked, and dendritic polymers, single chain cyclized/knotted polymers (SCKPs) have emerged as a new class of polymer structure with unique properties. Herein, the development of bacteria‐resistant SCKPs is reported and the effect of this structure on the resistance of polymer materials to bacteria is investigated. Four SCKPs were synthesized by reversible addition fragmentation chain transfer (RAFT) homopolymerization of multivinyl monomers (MVMs) and then crosslinked by UV light to form SCKP films. Regardless of MVM type used, the resulting SCKP films showed much higher resistance to bacteria, and up to 75 % less bacterial attachment and biofilm formation, in comparison with the corresponding non‐SCKP films. This is due to the altered surface morphology and hydrophobicity of the SCKP films. These results highlight the critical role of the SCKP structure in enhancing the resistance of polymeric materials to bacteria. [ABSTRACT FROM AUTHOR]

Time-resolved piezoresponse force spectroscopy (TR-PFS) and spectroscopic imaging are developed to probe the spatial variability of relaxation behavior in nanoscale ferroelectric materials and structures. TR-PFS was applied to study polarization dynamics in polyvinylidine fluoride and trifluoroethylene nanomesas. We demonstrate that polarization relaxation in ferroelectric polymers is slow even on the ∼10 nm length scale of piezoresponse force microscopy (PFM) signal generation. Furthermore, the relaxation times are found to be nonuniform within the nanomesa, indicative of a complex internal structure. The applicability of TR-PFM for studies of polarization dynamics in ferroelectric polymers and relaxors is discussed. [ABSTRACT FROM AUTHOR]

Piezoresponse force microscopy has been used to manipulate and image polarization of ferroelectric polymer Langmuir-Blodgett films at the nanoscale, achieving polarization control with a resolution below 50 nm and imaging resolution below 5 nm. Individual regions showed square polarization-voltage hysteresis loops, demonstrating bistability of the polarization state. Arbitrary polarization patterns could be repeatedly written and erased with a resolution of 25 to 50 nm, limited by grain size, demonstrating the potential for high-density data storage and retrieval at densities exceeding 250 Gbits/in2. [ABSTRACT FROM AUTHOR]

[Display omitted] A library of composite polymer networks (CPNs) were formed by combining Pluronic F127, as the primary gelator, with a range of di-acrylate functionalised PEG polymers, which tune the rheological properties and provide UV crosslinkability. A coarse-grained sol–gel room temperature phase diagram was constructed for the CPN library, which identifies PEG-dependent disruption of micelles as leading to liquefication. Small angle X-ray scattering and rheological measurements provide detailed insight into; (i) micelle-micelle ordering; (ii) micelle-micelle disruption, and; (iii) acrylate-micelle disruption; with contributions that depend on composition, including weak PEG chain length and end group effects. The influence of composition on 3D extrusion printability through modulation of the cohesive/hydrophobic interactions was assessed. It was found that only micelle content provides consistent changes in printing fidelity, controlled largely by printing conditions (pressure and feed rate). Finally, the hydrogels were shown to be UV photo-crosslinkable, which further improves fidelity and structural integrity, and usefully reduces the mesh size. Our results provide a guide for design of 3D-printable CPN inks for future biomedical applications. [ABSTRACT FROM AUTHOR]