Gels, Volume 2, Issue 1 (March 2016) – 12 articles

In their natural environment, cells are constantly exposed to a cohort of biochemical and biophysical signals that govern their functions and fate. Therefore, materials for biomedical applications, either in vivo or in vitro, should provide a replica of the complex patterns of biological signals. Thus, the development of a novel class of biomaterials requires, on the one side, the understanding of the dynamic interactions occurring at the interface of cells and materials; on the other, it requires the development of technologies able to integrate multiple signals precisely organized in time and space. A large body of studies aimed at investigating the mechanisms underpinning cell-material interactions is mostly based on 2D systems. While these have been instrumental in shaping our understanding of the recognition of and reaction to material stimuli, they lack the ability to capture central features of the natural cellular environment, such as dimensionality, remodelling and degradability. In this work, we review the fundamental traits of material signal sensing and cell response. We then present relevant technologies and materials that enable fabricating systems able to control various aspects of cell behavior, and we highlight potential differences that arise from 2D and 3D settings. Full article

The acoustic properties of the silica aerogel (SA) granules of various sizes from 0.50 to 3.35 mm, distributed into six groups of nominal sizes and measured via a two-microphone impedance tube, are presented. The absorption coefficients of the SA granules were evaluated at ultra- to super-low frequency range from 50–1600 Hz. It was observed that nominal SA granules with sizes of 1.2 mm (AG2) and 1.7 mm (AG3) displayed the best absorption coefficients. When tested with granules filled at 5 cm depth, AG2 and AG3 absorption coefficients peaked at 980 Hz with values of 0.86 and 0.81, respectively. A novel approach to measure transmission loss (TL) by using “inferential” principle is presented. This novel method, named “Inferential Transmission Loss Method” (InTLM), revealed that the average TL, TL_avg for both AG2 and AG3 SA granules was 14.83 dB and 15.35 dB, respectively. Gelatin silica aerogels doped with sodium dodecyl sulfate (GSA–SDS) composites comprising of 1.2 mm (GSA–AG2) and 1.7 mm (GSA–AG3) granules of various configurations were fabricated and evaluated for absorption coefficients and TL with known traditional acoustic panels. The results showed that GSA–AG3 had a better absorption coefficient over other configurations for the same corresponding thickness reaching the peak of 0.6 from 1300 to 1450 Hz with TL_avg between 10.7 and 20.3 decibels. The four-layered GSA–AG2 and GSA–AG3 composites showed exceptionally high absorption from 500 to 800 Hz suitable for narrow band applications. Lastly, the “InTLM” was matched with the sound meter measurements, with high accuracy between 0.3 and 3.2 dB for low-frequency testing (50–1600 Hz). Full article

Poly-N-isopropylacrylamide (PNIPAAm) hydrogels, known for their sensor and actuator capabilities, can be photolithographically structured for microsystem applications. For usage in microsystems, the preparation, and hence the characteristics, of these hydrogels (e.g., degree of swelling, size, cooperative diffusion coefficient) are key features, and have to be as reproducible as possible. A common method of hydrogel fabrication is free radical polymerisation using a thermally-initiated system or a photoinitiator system. Due to the reaction quenching by oxygen, the polymer solution has to be rinsed with protective inert gases like nitrogen or argon before the polymerisation process. In this paper, we focus on the preparation reproducibility of PNIPAAm hydrogels under different conditions, and investigate the influence of oxygen and the UV light source during the photopolymerisation process. The flushing of the polymer solution with inert gas is not sufficient for photostructuring approaches, so a glove box preparation resulting in better quality. Moreover, the usage of a wide-band UV light source yields higher reproducibility to the photostructuring process compared to a narrow-band UV source. Full article

Caffeine (a stimulant) and ethanol (a depressant) may have opposite effects in our body, but under in vitro conditions they can “gel” together. Caffeine, being one of the widely used stimulants, continued to surprise the scientific community with its unprecedented biological, medicinal and physicochemical properties. Here, we disclose the supramolecular self-assembly of anhydrous caffeine in a series of alcoholic and aromatic solvents, rendering a highly entangled microcrystalline network facilitating the encapsulation of the solvents as illustrated using direct imaging, microscopy analysis and NMR studies. Full article

Poly (N-isopropylacrylamide) (pNIPAm)-based hydrogels and hydrogel particles (microgels) have been extensively studied since their discovery a number of decades ago. While their utility seems to have no limit, this feature article is focused on their development and application for sensing small molecules, macromolecules, and biomolecules. We highlight hydrogel/microgel-based photonic materials that have order in one, two, or three dimensions, which exhibit optical properties that depend on the presence and concentration of various analytes. A particular focus is put on one-dimensional materials developed in the Serpe Group. Full article

The gelation properties and mode of self-assembly of six asymmetrical hexaether triphenylene derivatives mono-functionalized with carboxylic and primary amine groups were investigated. The presence of a carboxylic and amine group attached to the triphenylene core generated stable, thermo- and pH-sensitive supramolecular π-organogels with a reversible response to both stimuli. In order to understand the gelation process, we studied the effect of the spacer length and found a different gelation scope for the acid and basic derivatives that accounts for a different supramolecular self-assembly. The presence of the basic group on the amino derivatives was used to guide and catalyze the templated in situ sol-gel polymerization of TEOS and allowed us, under controlled hydrolytic conditions, to prepare an entangled fibrillar network of silica nanotubes. Full article

Poly(vinyl caprolactam) (PNVCL) is one of the most important thermoresponsive polymers because it is similar to poly(N-isopropyl acrylamide). PNVCL precipitates from aqueous solutions in a physiological temperature range (32–34 °C). The use of PNVCL instead of PNIPAM is considered advantageous because of the assumed lower toxicity of PNVCL. PNVCL copolymer gels are sensitive to external stimuli, such as temperature and pH; which gives them a wide range of biomedical applications and consequently attracts considerable scientific interest. This review focuses on the recent studies on PNVCL-based stimuli responsive three dimensional hydrogels (macro, micro, and nano) for biomedical applications. This review also covers the future outlooks of PNVCL-based gels for biomedical applications, particularly in the drug delivery field. Full article

We report the synthesis of conductive and mechanically compliant monolithic carbon aerogels prepared by sol-gel polycondensation of melamine-resorcinol-formaldehyde (MRF) mixtures by incorporating diatomite and carbon black additives. The resulting aerogels composites displayed a well-developed porous structure, confirming that the polymerization of the precursors is not impeded in the presence of either additive. The aerogels retained the porous structure after etching off the siliceous additive, indicating adequate cross-linking of the MRF reactants. However, the presence of diatomite caused a significant fall in the pore volumes, accompanied by coarsening of the average pore size (predominance of large mesopores and macropores). The diatomite also prevented structural shrinkage and deformation of the as-prepared monoliths upon densification by carbonization, even after removal of the siliceous framework. The rigid pristine aerogels became more flexible upon incorporation of the diatomite, favoring implementation of binderless monolithic aerogel electrodes. Full article

The synthesis of new functional monomers based on vanillin is reported. The monomers further were used in the synthesis of different temperature-responsive photo cross-linkable polymers via free radical polymerization with N-isopropyl acrylamide and a maleimide photo cross-linker. These polymers were characterized by NMR, FTIR and UV spectroscopy, as well as gel permeation chromatography (GPC) and differential scanning calorimetry (DSC). Critical solution temperatures were determined by UV spectroscopy. Hydrogel thin films were formed by spin coating of a polymer solution over gold with adhesion promotor followed by cross-linking by UV irradiation. The swelling properties were determined by surface plasmon resonance coupled with optical waveguide spectroscopy. The swelling behavior of the hydrogel films was determined as a function of temperature. The incorporation of a dialkyl amino group compensated the hydrophobic effect of the vanillin monomer. Transition temperatures in the physiological range could be obtained. Full article

Electrofluidodynamics techniques (EFDTs) are emerging methodologies based on liquid atomization induced by electrical forces to obtain a fine suspension of particles from hundreds of micrometers down to nanometer size. As a function of the characteristic size, these particles are interesting for a wide variety of applications, due to the high scalability of chemical and physical properties in comparison to the bulk form. Here, we propose the optimization of EFDT techniques to design chitosan systems in the form of microgels or nanoparticles for several biomedical applications. Different microscopy techniques (Optical, SEM, TEM) have been used to investigate the morphology of chitosan systems at multiple size scale. The proposed study confirms the high versatility and feasibility of EFDTs for creating micro and nano-sized carriers for cells and drug species. Full article

The production of a new composite material embedding aramid honeycomb materials into nano-porous silica aerogels is studied. Our aim is to improve the poor mechanical strength of silica aerogels by aramid honeycombs without losing the amazing properties of the aerogels like little density and low thermal conductivity. The composite materials were prepared using two formulations of silica aerogels in combination with aramid honeycomb materials of different cell sizes. The silica aerogels are prepared using silicon alkoxides methyltrimethoxysilane and tetraethylorthosilicate as precursors in a two-step acid–base sol–gel process. Shortly in advance of the gelation point, the aramid honeycombs were fluted by the sol, gelation occurred and, after the aging process, the gel bodies were supercritically dried. The properties of the received composite materials are satisfying. Even the thermal conductivities and the densities are a bit higher than for pure aerogels. Most importantly, the mechanical strength is improved by a factor of 2.3 compared to aramid honeycomb materials and by a factor of 10 compared to the two silica aerogels themselves. The composite materials have a good prospective to be used as an impressive insulation material. Full article