Hydrogels Based on Natural Polymers Loaded with Bentonite and/or Halloysite: Composition Impact on Spectroscopic, Thermal, and Swelling Properties.

Hydrogels are characterized by their property of absorbing and releasing a high content of water and water-based liquids; thus, they can be applied in agriculture as controlled-release water and fertilizer products. The focus of this research was efficient and low-cost natural polymer-based hydrogels obtained by crosslinking gellan gum (GGLA) and starch (ST) with acetic acid (CA) and loading them with either bentonite (BET) and/or halloysite (HAL). The hydrogels were obtained by mixing 100, 75, 50, 25, and 0 wt.% of GGLA with 0, 25, 50, 75, and 100 wt.% ST water solutions. To obtain the networks, they were crosslinked with 10, 5, and 2 wt.% of CA and loaded with 2, 5, and 10 wt.% of BET and/or HAL. The samples were analyzed by infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), their swelling in water, and the state of bound water properties. The results of these analyses point to the formation of a polymeric network with a decomposition temperature of >250 °C, and tailorable swelling properties that vary between 3 and 77, depending on the hydrogel composition. In summary, GGLA-ST-BET/HAL hydrogels are a good option for eco-friendly agriculture materials.

Preparation of Well-Dispersed Chitosan/Alginate Hollow Multilayered Microcapsules for Enhanced Cellular Internalization.

Hollow multilayered capsules have shown massive potential for being used in the biomedical and biotechnology fields, in applications such as cellular internalization, intracellular trafficking, drug delivery, or tissue engineering. In particular, hollow microcapsules, developed by resorting to porous calcium carbonate sacrificial templates, natural-origin building blocks and the prominent Layer-by-Layer (LbL) technology, have attracted increasing attention owing to their key features. However, these microcapsules revealed a great tendency to aggregate, which represents a major hurdle when aiming for cellular internalization and intracellular therapeutics delivery. Herein, we report the preparation of well-dispersed polysaccharide-based hollow multilayered microcapsules by combining the LbL technique with an optimized purification process. Cationic chitosan (CHT) and anionic alginate (ALG) were chosen as the marine origin polysaccharides due to their biocompatibility and structural similarity to the extracellular matrices of living tissues. Moreover, the inexpensive and highly versatile LbL technology was used to fabricate core-shell microparticles and hollow multilayered microcapsules, with precise control over their composition and physicochemical properties, by repeating the alternate deposition of both materials. The microcapsules' synthesis procedure was optimized to extensively reduce their natural aggregation tendency, as shown by the morphological analysis monitored by advanced microscopy techniques. The well-dispersed microcapsules showed an enhanced uptake by fibroblasts, opening new perspectives for cellular internalization.

Leaf surfaces and neolithization - the case of Arundo donax L.

Arundo donax L. (Arundinoideae subfamily, Poaceae family) is a sub-tropical and temperate climate reed that grows in arid and semi-arid environmental conditions, from eastern China to the Mediterranean basin, suggesting potential adaptations at the epicuticular level. A thorough physical-chemical examination of the adaxial and abaxial surfaces of A. donax leaf was performed herein in an attempt to track such chemophenetic adaptations. This sort of approach is of the utmost importance for the current debate about the hypothetical invasiveness of this species in the Mediterranean basin versus its natural colonization along the Plio-Pleistocene period. We concluded that the leaf surfaces contain, apart from stomata, prickles, and long, thin trichomes, and silicon-rich tetralobate phytolits. Chemically, the dominating elements in the leaf ashes are oxygen and potassium; minor amounts of calcium, silicon, magnesium, phosphorous, sulphur, and chlorine were also detected. In both surfaces the epicuticular waxes (whose density is higher in the adaxial surface than in the abaxial surface) form randomly orientated platelets, with irregular shape and variable size, and aggregated rodlets with variable diameter around the stomata. In the case of green mature leaves, the dominating organic compounds of the epicuticular waxes of both surfaces are triterpenoids. Both surfaces feature identical hydrophobic behaviour, and exhibit the same total transmittance, total reflectance, and absorption of incident light. The above findings suggest easy growth of the plant, remarkable epidermic robustness of the leaf, and control of water loss. These chemophenetic characteristics and human influence support a neolithization process of this species along the Mediterranean basin.

Erratum: Development of Poly(l-Lactic Acid)-Based Bending Actuators. Polymers 2020, 12, 1187.

The authors wish to make a change to their published paper [...].

Bombyx mori silk/titania/gold hybrid materials for photocatalytic water splitting: combining renewable raw materials with clean fuels.

The synthesis, structure, and photocatalytic water splitting performance of two new titania (TiO2)/gold(Au)/Bombyx mori silk hybrid materials are reported. All materials are monoliths with diameters of up to ca. 4.5 cm. The materials are macroscopically homogeneous and porous with surface areas between 170 and 210 m2/g. The diameter of the TiO2 nanoparticles (NPs) - mainly anatase with a minor fraction of brookite - and the Au NPs are on the order of 5 and 7-18 nm, respectively. Addition of poly(ethylene oxide) to the reaction mixture enables pore size tuning, thus providing access to different materials with different photocatalytic activities. Water splitting experiments using a sunlight simulator and a Xe lamp show that the new hybrid materials are effective water splitting catalysts and produce up to 30 mmol of hydrogen per 24 h. Overall the article demonstrates that the combination of a renewable and robust scaffold such as B. mori silk with a photoactive material provides a promising approach to new monolithic photocatalysts that can easily be recycled and show great potential for application in lightweight devices for green fuel production.

Chitosan membranes containing micro or nano-size bioactive glass particles: evolution of biomineralization followed by in situ dynamic mechanical analysis.

A new family of biodegradable polymer/bioactive glass (BG) composite materials has emerged based on the availability of nano-sized bioactive particles. Such novel biocomposites can have enhanced performance, in terms of mechanical properties and bioactivity, and they can be designed to be used in bone regeneration approaches. In this work, membranes of chitosan (CTS) and chitosan with bioactive glass (BG) both micron and nano sized particles (CTS/µBG, CTS/nBG, respectively) were prepared by solvent casting. Microstructural and mechanical properties were evaluated in order to compare the effects of the incorporation of micro (µBG) and nano (nBG) particles in the chitosan matrix. In vitro bioactivity tests were performed to characterize the apatite layer that is formed on the surface of the material after being immersed in simulated body fluid (SBF). The biomineralization process on the biomaterials was also followed using non-conventional dynamic mechanical analysis (DMA), both online and offline. In such DMA experiments, the change in the storage modulus, E', and the loss factor, tan δ, were measured as a function of the immersion time in SBF. The results demonstrated that CTS/nBG membranes possess enhanced mechanical properties and higher bioactivity in comparison with the CTS/µBG membranes. Such results suggest the potential of nBG for the development of bioactive composites for bone regeneration applications.

Self-structuring of lamellar bridged silsesquioxanes with long side spacers.

Diurea cross-linked bridged silsesquioxanes (BSs) C(10)C(n)C(10) derived from organosilane precursors, including decylene chains as side spacers and alkylene chains with variable length as central spacers (EtO)(3)Si-(CH(2))(10)-Y-(CH(2))(n)-Y-(CH(2))(10)-Si(OEt)(3) (n = 7, 9-12; Y = urea group and Et = ethyl), have been synthesized through the combination of self-directed assembly and an acid-catalyzed sol-gel route involving the addition of dimethylsulfoxide (DMSO) and a large excess of water. This new family of hybrids has enabled us to conclude that the length of the side spacers plays a unique role in the structuring of alkylene-based BSs, although their morphology remains unaffected. All the samples adopt a lamellar structure. While the alkylene chains are totally disordered in the case of the C(10)C(7)C(10) sample, a variable proportion of all-trans and gauche conformers exists in the materials with longer central spacers. The highest degree of structuring occurs for n = 9. The inclusion of decylene instead of propylene chains as side spacers leads to the formation of a stronger hydrogen-bonded urea-urea array as evidenced by two dimensional correlation Fourier transform infrared spectroscopic analysis. The emission spectra and emission quantum yields of the C(10)C(n)C(10) materials are similar to those reported for diurea cross-linked alkylene-based BSs incorporating propylene chains as side spacers and prepared under different experimental conditions. The emission of the C(10)C(n)C(10) hybrids is ascribed to the overlap of two distinct components that occur within the urea cross-linkages and within the siliceous nanodomains. Time-resolved photoluminescence spectroscopy has provided evidence that the average distance between the siliceous domains and the urea cross-links is similar in the C(10)C(n)C(10) BSs and in oxyethylene-based hybrid analogues incorporating propylene chains as side spacers (diureasils), an indication that the longer side chains in the former materials adopt gauche conformations. It has also allowed us to demonstrate for the first time that the emission features of the urea-related component of the emission of alkylene-based BSs depend critically on the length of the side spacers.

Lanthanide-containing light-emitting organic-inorganic hybrids: a bet on the future.

Interest in lanthanide-containing organic-inorganic hybrids has grown considerably during the last decade, with the concomitant fabrication of materials with tunable attributes offering modulated properties. The potential of these materials relies on exploiting the synergy between the intrinsic characteristics of sol-gel derived hosts (highly controlled purity, versatile shaping and patterning, excellent optical quality, easy control of the refractive index, photosensitivity, encapsulation of large amounts of isolated emitting centers protected by the host) and the luminescence features of trivalent lanthanide ions (high luminescence quantum yield, narrow bandwidth, long-lived emission, large Stokes shifts, ligand-dependent luminescence sensitization). Promising applications may be envisaged, such as light-emitting devices, active waveguides in the visible and near-IR spectral regions, active coatings, and bio-medical actuators and sensors, opening up exciting directions in materials science and related technologies with significant implications in the integration, miniaturization, and multifunctionalization of devices. This review provides an overview of the latest advances in Ln(3+)-containing siloxane-based hybrids, with emphasis on the different possible synthetic strategies, photoluminescence features, empirical determination.