Search

We report a simple process, based on the combination of sol-gel deposition and nano-templating with polycarbonate membranes, for the synthesis of 1D to 3D free-standing silica (SiO 2 ) interconnected nanotube (NT) networks. The thickness and porosity of the SiO 2 nanotube walls can be, respectively, controlled by adjusting the ethanol amount in the sol-gel reaction mixture and by the addition or not of a porogen agent during the synthesis. Internal functionalization of 1D and 3D porous and non-porous SiO 2 NTs by Au nanoparticles (NPs) was then performed using electroless deposition leading to particle sizes ranging from 15 to 20 nm. Characterization of all these systems by SEM-EDX, TEM, ICP and XPS clearly demonstrated the impact of the porosity of SiO 2 on the amount and localization of Au NPs. Selective functionalization of the inner or the inner + outer surfaces of SiO 2 NTs was achieved by keeping or freeing the SiO 2 NTs from the template prior to electroless deposition, respectively. Moreover, UV-visible analysis confirmed plasmon resonance associated with Au NPs in all functionalized systems, paving the way to applications in many fields such as nano-medicine or (photo-)catalysis. In particular, the free-standing interconnected silica-based nanotube systems provide unique features of great interest for use in nanoscale fluidic bioseparation, sensing, and flow (photo)-catalytic chemistry, as demonstrated herein for the photodegradation of methylene blue.

The biogenic calcium phosphate (CaP) crystallization is a process that offers elegant materials design strategies to achieve bioactive and biomechanical challenges. Indeed, many biomimetic approaches have been developed for this process in order to produce mineralized structures with controlled crystallinity and shape. Herein, we propose an advanced biomimetic approach for the design of ordered hybrid mineralized nano-objects with highly anisotropic features. For this purpose, we explore the combination of three key concepts in biomineralization that provide a unique environment to control CaP nucleation and growth: (i) self-assembly and self-organization of biomacromolecules, (ii) enzymatic heterogeneous catalysis, and (iii) mineralization in confinement. We use track-etched templates that display a high density of aligned monodisperse pores so that each nanopore may serve as a miniaturized mineralization bioreactor. We enhance the control of the crystallization in these systems by coassembling type I collagen and enzymes within the nanopores, which allows us to tune the main characteristics of the mineralized nano-objects. Indeed, the synergy between the gradual release of one of the mineral ion precursors by the enzyme and the role of the collagen in the regulation of the mineralization allowed to control their morphology, chemical composition, crystal phase, and mechanical stability. Moreover, we provide clear insight into the prominent role of collagen in the mineralization process in confinement. In the absence of collagen, the fraction of crystalline nano-objects increases to the detriment of amorphous ones when increasing the degree of confinement. By contrast, the presence of collagen-based multilayers disturbs the influence of confinement on the mineralization: platelet-like crystalline hydroxyapatite form, independently of the degree of confinement. This suggests that the incorporation of collagen is an efficient way to supplement the lack of confinement while reinforcing mechanical stability to the highly anisotropic materials. From a bioengineering perspective, this biomineralization-inspired approach opens up new horizons for the design of anisotropic mineralized nano-objects that are highly sought after to develop biomaterials or tend to replicate the complex structure of native mineralized extracellular matrices.

Byline: J-L. Duvail, S. Dubois, S. Demoustier-Champagne, Y. Long, L. Piraux The unique physical properties of nanowires and nanotubes originate from either the small dimensions of the objects, or structural modifications induced by the confined synthesis and surface effects. These features make them very promising for applications in nanoelectronics and nanosensors in particular. In this paper, we review our results on magnetic metallic nanowires and conjugated polymer nanowires and nanotubes prepared by the template method. Their magnetic, electrical and optical properties differ from the bulk counterparts. Mechanisms responsible for these differences have been identified.

Layer-by-layer (LbL) assembly is a versatile technology to construct multifunctional nanomaterials using various supporting substrates, enabled by the large selection freedom of building materials and diversity of possible driving forces. The fine regulation over the film thickness and structure provides an elegant way to tune the physical/chemical properties by mild assembly conditions (e.g. pH, ion strength). In this review, we focus on LbL in nanochannels, which exhibit a different growth mechanism compared to "open", convex substrates. The assembly mechanism in nanochannels is discussed in detail, followed by the summary of applications of LbL assemblies liberated from nanochannel templates which can be used as nanoreactors, drug carriers and transporting channels across cell membranes. For fluidic applications, robust membrane substrates are required to keep in place nanotube arrays for membrane-based separation, purification, biosensing and energy harvesting, which are also discussed. The good compatibility of LbL with crossover technologies from other fields allows researchers to further extend this technology to a broader range of research fields, which is expected to result in an increased number of applications of LbL technology in the future.

Cell culture on microcarriers emerges as an alternative of two-dimensional culture to produce large cell doses, which are required for cell-based therapies. Herein, we report a versatile and easy solvent-free greener fabrication process to prepare microcarriers based on a biosourced and compostable polymer. The preparation of the microcarrier core, which is based on poly(L-lactide) crystallization from a polymer blend, allows us to easily tune the density, porosity, and size of the microparticles. A bioadhesive coating based on biopolymers, devoid of animal protein and optimized to improve cell adhesion, is then successfully deposited on the surface of the microcarriers. The ability of these new microcarriers to expand human adipose-derived stromal cells with good yield, in semistatic and dynamic conditions, is demonstrated. Finally, bead-to-bead cell transfer is shown to increase the yield of cell production without having to stop the culture. These microcarriers are therefore a promising and efficient green alternative to currently existing systems.

The immobilization of proteins to impart specific functions to surfaces is topical for chemical engineering, healthcare and diagnosis. Layer-by-Layer (LbL) self-assembly is one of the most used method to immobilize macromolecules on surfaces. It consists in the alternate adsorption of oppositely charged species, resulting in the formation of a multilayer. This method in principle allows any charged object to be immobilized on any surface, from aqueous solutions. However, when it comes to proteins, the promises of versatility, simplicity and universality that the LbL approach holds are unmet due to the heterogeneity of protein properties. In this review, the literature is analyzed to make a generic approach emerge, with a view to facilitate the LbL assembly of proteins with polyelectrolytes (PEs). In particular, this review aims at guiding the choice of the PE and the building conditions that lead to the successful growth of protein-based multilayered self-assemblies., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The development of a functional in vitro model for microcirculation is an unresolved challenge, with major impact for the creation and regeneration of organs in the tissue engineering. The absence of prevascularized engineered tissues limits enormously their efficacy and integration. Therefore, in this study, the in vitro formation of tubular-like structures with human umbilical vein endothelial cells (HUVECs) is investigated thanks to three-dimensional polycarbonate (PC) microchannel (μCh) scaffolds, surface biofunctionalized with hyaluronic acid/chitosan (HA/CHI) layer-by-layer (LbL) films grafted with adhesive (RGD) and angiogenic (SVV and QK) peptides, alone and in combination. The importance of this work lies in the formation of capillaries in the order of tens of μm, developing spontaneous microvessels, without the complexity of microfluidic approaches, and in a short time-scale. Ellipsometry, confocal laser scanning microscopy, and fluorospectrometry are used to characterize the biofunctionalized microchannels. PC-μCh scaffolds functionalized with (HA/CHI) 12.5 film (PC-LbL) and further grafted with RGD and QK peptides (PC-RGD+QK) or with RGD and SVV peptides (PC-RGD+SVV) are then tested for in vitro blood vessel formation. These assays evidence a rapid formation of tubular-like structures after 2 h of incubation. Moreover, a coculture system involving HUVECs and human pericytes derived from placenta (hPCs-PL) stabilizes the tubes for a longer time.

Here, we report on an in situ study of the spectroelectrochemical behavior of template prepared poly(3,4-ethylenedioxythiophene) (PEDOT) nanowires by UV-Vis-NIR spectroscopy. A comparative analysis between spectra measured on a PEDOT thin film and on nanowires (diameter: 80 nm, 30 nm) has been made. It gives evidence for - enhanced bipolaronic band in the oxidized state, and - more efficient dedoping in the reduced state, for the 30-nm nanowires. This result, analyzed in terms of higher (de)doping level during the redox process for the smaller diameter, demonstrates improved electroactivity and electrochromism, as required for sensors. [ABSTRACT FROM AUTHOR]

A process combining electrochemical nanofabrication by hard templating with the use of a masking strategy and surface functionalization methods, is developed to produce arrays of gold nanopillars of spatially-controlled surface chemistry. Therefore, a gold nanopillar array is first fabricated by performing metal electrochemical deposition into a track-etched membrane supported on a gold substrate. After dissolution of the membrane, a protective polymer layer is deposited on the array and partially etched to specifically reveal the top of the nanopillars. Then, a polythiolactone-based copolymer is grafted on the upper part of the nanopillars. Afterwards, the sacrificial polymer layer is dissolved to reveal the non-functionalized surface corresponding to the lower part of the gold nanopillars and the background surface. This surface is subsequently modified by a self-assembled monolayer (SAM) of alkylthiol molecules which leads to nanostructured surfaces with spatio-selective surface chemistry. The grafting of gold nanoparticles and of a bioadhesive peptide on the top and on the background of the nanopillar array, respectively, is performed to prove the versatility of the approach to produce bifunctionalized nanopillar arrays for biological, biosensing or (bio)catalysis applications., Competing Interests: There are no conflicts of interest to declare., (This journal is © The Royal Society of Chemistry.)

Studying the stimuli-response of polyelectrolyte multilayers (PEMs) towards protein adsorption requires coping with the multiplicity of factors influencing interfacial processes. In this study, we report the design of a nanostructured stimuli-responsive coating based on the sequential layer-by-layer assembly of poly(N-isopropylacrylamide) block copolymers with poly (allylamine hydrochloride) and scrutinize its ability to modulate protein adsorption. The results reveal that the stimuli-response of the film towards protein adsorption under T, pH and I changes is strongly influenced by the type of buffer. This latter parameter has indeed a significant impact on the adsorbed amount of proteins, while it has only slight effect on the stimuli-response of free block copolymer, on the mechanism of PEM growth and the properties of the obtained film. In conditions favorable to protein adsorption, the use of anionic buffer leads to the adsorption of an apparent monolayer of proteins, while in zwitterionic buffer, proteins adsorb in a significantly higher amount. This trend may be explained by a more efficient charge screening of macromolecules by zwitterions which reduce the repulsion between proteins, leading to their accumulation at the interface. Finally, the length of the poly(N-isopropylacrylamide) block is shown to be another key factor impacting the amount of adsorbed proteins. The findings reported in this paper provide relevant information and allow the evaluation of stimuli-response of PEM to be carried out under optimized conditions. [ABSTRACT FROM AUTHOR]

Hybrid nanobiointerfaces were designed as an original contribution to the challenge of synthesizing nanostructured biomaterials integrating a set of cell fate-determining cues, originally provided to cells by the extracellular matrix (ECM). The produced biointerfaces consist of a stiff framework of intersected polypyrrole (PPy) nanotubes supporting a soft multilayer composed of ECM-derived biomacromolecules: collagen (Col) and hyaluronic acid (HA). PPy frameworks with highly tunable characteristics were synthesized through chemical oxidative polymerization of pyrrole monomers, templated within track-etched polycarbonate (PC) membranes featuring a network of intersected nanopores. PPy interfaces with a porosity of 80%, composed of nanotubes with an average diameter ranging from 40 to 300 nm, intersecting at an angle of 90°, were shown to be self-supported. These rigid PPy nanostructured interfaces were functionalized with a self-assembling (HA/Col) multilayer deposited via a layer-by-layer process. Biofunctionalized and unmodified PPy frameworks were both shown to promote sustained cell adhesion, therefore demonstrating the cytocompatibility of the engineered matrices. Such nanobiointerfaces, combining a mechanically-stable framework of tunable dimensions with a soft biopolymeric multilayer of highly versatile nature, pave the way towards cell-instructive biomaterials able to gather a wide range of cues guiding cell behavior. The developed self-supported structures could be used as a coating or as membranes bridging different tissues., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The development of multifunctional surfaces is of general interest for the fabrication of biomedical, catalytic, microfluidic or biosensing devices. Herein, we report on the preparation of copolymer layers immobilized on gold surface and showing both free thiol and amino groups. These layers are produced by aminolysis of a thiolactone-based copolymer in the presence of a diamine, according to a one-step procedure. The free thiol and amino groups present in the modified copolymer layers can be successfully functionalized with respectively thiolated and carboxylic derivatives, in order to produce bifunctionalized surfaces. In addition, we show that the grafted thiolated derivative can be released by cleavage of the disulfide bond under mild reducing conditions. On the other hand, a side cross-linking reaction occurring during the grafting process and resulting in the formation of copolymer aggregates on the metal surface is evidenced. The methodology developed for the preparation of these bifunctionalized redox-responsive layers should be advantageously used to produce bioactive surfaces with drug loading/release properties.

Brushes of vertically-standing enzyme-containing nanotubes are prepared onto planar surfaces by a combination of hard-templating and layer-by-layer assembly. The nanotubes have a core-shell morphology made of two compartments, one for mechanical rigidity, the other containing β-lactamase for bioactivity. We demonstrate inclusion of the enzymatic component either in the core or in the shell part of the nanotubes. Kinetic studies reveal that both types of systems are bioactive but that the activity is significantly better preserved over long time periods when β-lactamase is incorporated in the core of the nanotubes., (Copyright © 2017 Elsevier Inc. All rights reserved.)

Anisotropic nanostructures, such as nanotubes, incorporating bioactive molecules present interesting features for application as drug delivery carriers. Here, we present the synthesis of layer-by-layer (LbL) nanotubes including protein (ovalbumin) layers and go from simple to more complex synergetic combinations of synthetic and natural polyelectrolytes, leading to structures with tunable properties. The rigidity in organic and aqueous media, the stability in buffer solution and the uptake of different LbL tubes by dendritic cells (DCs) are analyzed to contrast size and chemistry. The most rigid studied systems appear as the best candidates to be internalized by cells, regardless of the chemistry of their outermost layers. The successful transport of long protein-loaded robust rigid nanotubes to the cytoplasm of DCs paves the way for their use as new cargo for the delivery of large amounts of antigen to such cells.

The conformation of polymer chains grafted on a substrate influencesprotein adsorption. In a previous study, adsorption/desorption ofalbumin was demonstrated on mixed poly(ethylene oxide) (PEO)/poly(acrylicacid) (PAA) brushes, triggered by solutions of adequate pH and ionicstrength (I). In the present work, homolayers ofPEO or PAA are submitted to saline solutions with pH from 3 to 9 and Ifrom 10–5to 10–1M,and their conformation is evaluated in real time using quartz crystalmicrobalance with dissipation monitoring (QCM-D). Shrinkage/swellingof PAA chains and hydration and salt condensation in the brush areevidenced. The adsorption of human serum albumin (HSA) onto such brushesis also monitored in these different saline solutions, leading toa deep understanding of the influence of polymer chain conformation,modulated by pH and I, on protein adsorption. A detailedmodel of the conformation of PEO/PAA mixed brushes depending on pHand Iis then proposed, providing a rationale forthe identification of conditions for the successive adsorption anddesorption of proteins on such mixed brushes. The adsorption/desorptionof albumin on PEO/PAA is demonstrated using QCM-D [ABSTRACT FROM AUTHOR]