Alba Marcellan

Nanoparticle solutions as adhesives for gels and biological tissues

Adhesives are made of polymers because, unlike other materials, polymers ensure good contact between surfaces by covering asperities, and retard the fracture of adhesive joints by dissipating energy under stress. But using polymers to ‘glue’ together polymer gels is difficult, requiring chemical reactions, heating, pH changes, ultraviolet irradiation or an electric field. Here we show that strong, rapid adhesion between two hydrogels can be achieved at room temperature by spreading a droplet of a nanoparticle solution on one gel’s surface and then bringing the other gel into contact with it. The method relies on the nanoparticles’ ability to adsorb onto polymer gels and to act as connectors between polymer chains, and on the ability of polymer chains to reorganize and dissipate energy under stress when adsorbed onto nanoparticles. We demonstrate this approach by pressing together pieces of hydrogels, for approximately 30 seconds, that have the same or different chemical properties or rigidities, using various solutions of silica nanoparticles, to achieve a strong bond. Furthermore, we show that carbon nanotubes and cellulose nanocrystals that do not bond hydrogels together become adhesive when their surface chemistry is modified. To illustrate the promise of the method for biological tissues, we also glued together two cut pieces of calf’s liver using a solution of silica nanoparticles. As a rapid, simple and efficient way to assemble gels or tissues, this method is desirable for many emerging technological and medical applications such as microfluidics, actuation, tissue engineering and surgery.

Nano-hybrid self-crosslinked PDMA/silica hydrogels

We discovered that the free radical polymerization of N,N-dimethylacrylamide in water can lead, above a certain concentration, to gels without any added difunctional crosslinker. These so called “self-crosslinked” hydrogels were prepared and their weak mechanical properties were improved by introducing silica nanoparticles. From swelling experiments performed at equilibrium in aqueous media, it was shown that silica particles behave as adhesive fillers and strongly interact with PDMA chains. These interactions are responsible for the reinforcement of mechanical properties. From initial elastic moduli, determined in the preparation state, we show that the elastic behaviour of these hydrogels mainly originates from entanglements and from physical crosslinks that can be controlled by the polymer concentration and the ratio between silica particles and polymer chains, respectively. The mechanical behaviour was characterized using: monotonic tensile tests, loading-unloading cycles at large strains and stress relaxation experiments in order to investigate long time behaviour. The introduction of silica highly increases the stiffness of the network without greatly reducing its extensibility, implying that strong interactions take place between PDMA chains and silica surfaces. Non-linear behavior was pointed out: softening at small deformations and hardening at high deformations which is related to finite chain extensibility. All these effects have been shown to strongly depend on the silica content. The analysis of hysteresis and residual strains induced by cycles, clearly indicate that contrary to chemical crosslinkers, hybrid interactions increase the dissipative process.

Organ Repair, Hemostasis, and In Vivo Bonding of Medical Devices by Aqueous Solutions of Nanoparticles**

Sutures are traumatic to soft connective tissues, such as liver or lungs. Polymer tissue adhesives require complex in vivo control of polymerization or cross-linking reactions and currently suffer from being toxic, weak, or inefficient within the wet conditions of the body. Herein, we demonstrate using Stöber silica or iron oxide nanoparticles that nanobridging, that is, adhesion by aqueous nanoparticle solutions, can be used in vivo in rats to achieve rapid and strong closure and healing of deep wounds in skin and liver. Nanoparticles were also used to fix polymer membranes to tissues even in the presence of blood flow, such as occurring after liver resection, yielding permanent hemostasis within a minute. Furthermore, medical devices and tissue engineering constructs were fixed to organs such as a beating heart. The simplicity, rapidity, and robustness of nanobridging bode well for clinical applications, surgery, and regenerative medicine.

Effect of polymer–particle interaction on the fracture toughness of silica filled hydrogels

We have investigated the mechanical and fracture properties of hybrid hydrogels made of chemically crosslinked polyacrylamide (PAAm) and silica nanoparticles. Unlike the case where the polymer is poly(dimethylacrylamide) (PDMA), the introduction of silica nanoparticles at 6–7 vol% does not lead to any significant reinforcement in the mechanical properties (modulus, hysteresis and fracture toughness) of the hydrogels. The key difference between the two hybrid gels is that PAAm does not absorb on silica while PDMA does [L. Petit, L. Bouteiller, A. Brulet, F. Lafuma and D. Hourdet, Langmuir0, 2007, 23(1), 147–158]. These results stress the importance of polymer/filler interactions in controlling the macroscopic mechanical properties of hybrid hydrogels and suggest that a strong but breakable interaction leads to superior fracture toughness.

Thermoresponsive Toughening with Crack Bifurcation in Phase‐Separated Hydrogels under Isochoric Conditions

A novel mode of gel toughening displaying crack bifurcation is highlighted in phase-separated hydrogels. By exploring original covalent network topologies, phase-separated gels under isochoric conditions demonstrate advanced thermoresponsive mechanical properties: excellent fatigue resistance, self-healing, and remarkable fracture energies. Beyond the phase-transition temperature, the fracture proceeds by a systematic crack-bifurcation process, unreported so far in gels.

Recognition-mediated hydrogel swelling controlled by interaction with a negative thermoresponsive LCST polymer

Abstract Most polymeric thermoresponsive hydrogels contract upon heating beyond the lower critical solution temperature (LCST) of the polymers used. Herein, we report a supramolecular hydrogel system that shows the opposite temperature dependence. When the non‐thermosesponsive hydrogel NaphtGel, containing dialkoxynaphthalene guest molecules, becomes complexed with the tetra cationic macrocyclic host CBPQT4+, swelling occurred as a result of host–guest complex formation leading to charge repulsion between the host units, as well as an osmotic contribution of chloride counter‐ions embedded in the network. The immersion of NaphtGel in a solution of poly(N‐isopropylacrylamide) with tetrathiafulvalene (TTF) end groups complexed with CBPQT4+ induced positive thermoresponsive behaviour. The LCST‐induced dethreading of the polymer‐based pseudorotaxane upon heating led to transfer of the CBPQT4+ host and a concomitant swelling of NaphtGel. Subsequent cooling led to reformation of the TTF‐based host–guest complexes in solution and contraction of the hydrogel.

Recent advances in studying single bacteria and biofilm mechanics

Bacterial biofilms correspond to surface-associated bacterial communities embedded in hydrogel-like matrix, in which high cell density, reduced diffusion and physico-chemical heterogeneity play a protective role and induce novel behaviors. In this review, we present recent advances on the understanding of how bacterial mechanical properties, from single cell to high-cell density community, determine biofilm tri-dimensional growth and eventual dispersion and we attempt to draw a parallel between these properties and the mechanical properties of other well-studied hydrogels and living systems.

Hydrogels with Dual Thermoresponsive Mechanical Performance

Dual thermoresponsive chemical hydrogels, combining poly(N-isopropylacrylamide) side-chains within a poly(N-acryloylglycinamide) network, are designed following a simple and versatile procedure. These hydrogels exhibit two phase transitions both at low (upper critical solution temperature) and high (lower critical solution temperature) temperatures, thereby modifying their swelling, rheological, and mechanical properties. These novel thermo-schizophrenic hydrogels pave the way for the development of thermotoughening wet materials in a broad range of temperatures.

Testing and characterization of fibers

Abstract Characterizing fibers—both natural and synthetic—is challenging, especially when the fiber diameter can be as small as just a few microns. Nevertheless, mechanical testing at the single fiber scale is the only unambiguous means of characterizing fibers or exploring their morphologies. Traditionally the properties of fibers have been normalized to their linear weight because of the difficulties of measuring fiber cross sections exactly; however, precise measuring techniques are now available, which allow their properties to be expressed in engineering terms familiar to all engineers working on structural materials. Traditional and conventional engineering units will both be found in this book, usually with an explanation of how to convert from one to the other. The identification of the mechanical responses together with understanding the micromechanisms involved are invaluable in guiding the design and use of fibers with advanced properties. The fiber structure can be rather complex and involves multiple characteristic length scales that demand specific techniques, e.g., from spectroscopic techniques to probe molecular or atomic structures, X-ray diffraction to identify crystalline or amorphous domains or both optical and electron microscopy. Tomography techniques are new tools allowing the internal morphology of fibers to be imaged and recent developments in this direction open up previously unimagined prospects of exploring fiber structure.