Simple Sol-Gel Protein Stabilization toward Rainbow and White Lighting Devices.

Fluorescent proteins (FPs) are heralded as a paradigm of sustainable materials for photonics/optoelectronics. However, their stabilization under non-physiological environments and/or harsh operation conditions is the major challenge. Among the FP-stabilization methods, classical sol-gel is the most effective, but less versatile, as most of the proteins/enzymes are easily degraded due to the need of multi-step processes, surfactants, and mixed water/organic solvents in extreme pH. Herein, sol-gel chemistry with archetypal FPs (mGreenLantern; mCherry) is revisited, simplifying the method by one-pot, surfactant-free, and aqueous media (phosphate buffer saline pH = 7.4). The synthesis mechanism involves the direct reaction of the carboxylic groups at the FP surface with the silica precursor, generating a positively charged FP intermediate that acts as a seed for the formation of size-controlled mesoporous FP@SiO2 nanoparticles. Green-/red-emissive (single-FP component) and dual-emissive (multi-FPs component; kinetic studies not required) FP@SiO2 are prepared without affecting the FP photoluminescence and stabilities (>6 months) under dry storage and organic solvent suspensions. Finally, FP@SiO2 color filters are applied to rainbow and white bio-hybrid light-emitting diodes featuring up to 15-fold enhanced stabilities without reducing luminous efficacy compared to references with native FPs. Overall, an easy, versatile, and effective FP-stabilization method is demonstrated in FP@SiO2 toward sustainable protein lighting.

Influence of microbial biomass content on biodegradation and mechanical properties of poly(3-hydroxybutyrate) composites.

Biodegradation rates and mechanical properties of poly(3-hydroxybutyrate) (PHB) composites with green algae and cyanobacteria were investigated for the first time. To the authors knowledge, the addition of microbial biomass led to the biggest observed effect on biodegradation so far. The composites with microbial biomass showed an acceleration of the biodegradation rate and a higher cumulative biodegradation within 132 days compared to PHB or the biomass alone. In order to determine the causes for the faster biodegradation, the molecular weight, the crystallinity, the water uptake, the microbial biomass composition and scanning electron microscope images were assessed. The molecular weight of the PHB in the composites was lower than that of pure PHB while the crystallinity and microbial biomass composition were the same for all samples. A direct correlation of water uptake and crystallinity with biodegradation rate could not be observed. While the degradation of molecular weight of PHB during sample preparation contributed to the improvement of biodegradation, the main reason was attributed to biostimulation by the added biomass. The resulting enhancement of the biodegradation rate appears to be unique in the field of polymer biodegradation. The tensile strength was lowered, elongation at break remained constant and Young's modulus was increased compared to pure PHB.

Synthesis and Characterization of Functional Cellulose-Ether-Based PCL- and PLA-Grafts-Copolymers.

The use of biodegradable materials such as cellulose and polyesters can be extended through the combination, as well as modification, of these biopolymers. By controlling the molecular structure and composition of copolymers of these components, it should also be possible to tailor their material properties. We hereby report on the synthesis and characterization of cellulose-based graft copolymers with a precise molecular composition and copolymer architecture. To prepare such materials, we initially modified cellulose through the regioselective protection of the 6-OH group using trityl chloride. The 6-O protected compound was then alkylated, and deprotection at the 6-OH group provided the desired 2,3-di-O-alkyl cellulose compounds that were used as macroinitiators for ring opening polymerization. Regioselective modification was hereby necessary to obtain compounds with an exact molecular composition. Ring opening polymerization, catalyzed by Sn(Oct)2, at the primary 6-OH group of the cellulose macroinitiator, using L-lactide or ε-caprolactone, resulted in graft copolymers with the desired functionalization pattern. The materials were characterized using Fourier-transform infrared spectroscopy, 1H- and 13C- nuclear magnetic resonance spectroscopy, size exclusion chromatography as well as X-ray diffraction, and differential scanning calorimetry. PCL-based copolymers exhibited distinct melting point as well as a crystalline phase of up to 47%, while copolymers with PLA segments were highly amorphous, showing a broad amorphous reflex in the XRD spectra, and no melting or crystallization points were discernible using differential scanning calorimetry.

Biocompatible Optical Fibers Made of Regenerated Cellulose and Recombinant Cellulose-Binding Spider Silk.

The fabrication of green optical waveguides based on cellulose and spider silk might allow the processing of novel biocompatible materials. Regenerated cellulose fibers are used as the core and recombinantly produced spider silk proteins eADF4(C16) as the cladding material. A detected delamination between core and cladding could be circumvented by using a modified spider silk protein with a cellulose-binding domain-enduring permanent adhesion between the cellulose core and the spider silk cladding. The applied spider silk materials were characterized optically, and the theoretical maximum data rate was determined. The results show optical waveguide structures promising for medical applications, for example, in the future.

Fabrication of Cellulose-Based Biopolymer Optical Fibers and Their Theoretical Attenuation Limit.

Currently, almost all polymer optical materials are derived from fossil resources with known consequences for the environment. In this work, a processing route to obtain cellulose-based biopolymer optical fibers is presented. For this purpose, the optical properties such as the transmission and the refractive index dispersion of regenerated cellulose, cellulose diacetate, cellulose acetate propionate, and cellulose acetate butyrate were determined from planar films. Cellulose fibers were produced using a simple wet-spinning setup. They were examined pure and also coated with the cellulose derivatives to obtain core-cladding-structured optical fibers. The cellulose-based optical fibers exhibit minimum attenuations between 56 and 82 dB m-1 at around 860 nm. The ultimate transmission loss limit of the cellulose-based optical fibers was simulated to characterize the attenuation progression. By reducing extrinsic losses, cellulose-based biopolymer optical fibers could attain theoretical attenuation minima of 84.6 × 10-3 dB m-1 (507 nm), 320 × 10-3 dB m-1 (674 nm), and 745.2 × 10-3 dB m-1 (837 nm) and might substitute fossil-based polymer optical fibers in the future.

Determining paracrystallinity in mixed-tacticity polyhydroxybutyrates.

Recently, the authors reported on the development of crystallinity in mixed-tacticity polyhydroxybutyrates. Comparable values reported in the literature vary depending on the manner of determination, the discrepancies being partially attributable to scattering from paracrystalline portions of the material. These portions can be qualified by peak profile fitting or quantified by allocation of scattered X-ray intensities. However, the latter requires a good quality of the former, which in turn must additionally account for peak broadening inherent in the measurement setup, and due to limited crystallite sizes and the possible presence of microstrain. Since broadening due to microstrain and paracrystalline order both scale with scattering vector, they are easily confounded. In this work, a method to directionally discern these two influences on the peak shape in a Rietveld refinement is presented. Allocating intensities to amorphous, bulk and paracrystalline portions with changing tactic disturbance provided internal validations of the obtained directional numbers. In addition, the correlation between obtained thermal factors and Young's moduli, determined in earlier work, is discussed.

Light-diffractive patterning of Porphyridium purpureum.

Light guidance is a convenient and versatile way to control the positions of phototactic microorganisms. However, the illumination strategies require adaption to the respective organism. We report on the generation of structures composed of the gliding and exopolysaccharide-secreting algae Porphyridium purpureum via their photomovement. Light patterns from a two-dimensional computer-generated hologram were projected onto inoculated agar plates. The obtained pixelated algae patterns were evaluated with regard to the illuminated intensity, contrast and pixel size. Upper and lower thresholds for algae accumulation were determined, allowing to enhance future manipulation of phototactic microorganisms.

Biobased chiral semi-crystalline or amorphous high-performance polyamides and their scalable stereoselective synthesis.

The use of renewable feedstock is one of the twelve key principles of sustainable chemistry. Unfortunately, bio-based compounds often suffer from high production cost and low performance. To fully tap the potential of natural compounds it is important to utilize their functionalities that could make them superior compared to fossil-based resources. Here we show the conversion of (+)-3-carene, a by-product of the cellulose industry into ε-lactams from which polyamides. The lactams are selectively prepared in two diastereomeric configurations, leading to semi-crystalline or amorphous, transparent polymers that can compete with the thermal properties of commercial high-performance polyamides. Copolyamides with caprolactam and laurolactam exhibit an increased glass transition and amorphicity compared to the homopolyamides, potentially broadening the scope of standard polyamides. A four-step one-vessel monomer synthesis, applying chemo-enzymatic catalysis for the initial oxidation step, is established. The great potential of the polyamides is outlined.

A Perspective on Bio-Mediated Material Structuring.

Bioinspiration, biomorphy, biomimicry, biomimetics, bionics, and biotemplating are terms used to describe the fabrication of materials or, more generally, systems to solve technological problems by abstracting, emulating, using, or transferring structures from biological paradigms. Herein, a brief overview of how the different terminologies are being typically applied is provided. It is proposed that there is a rich field of research that can be expanded by utilizing various novel approaches for the guidance of living organisms for "bio-mediated" material structuring purposes. As examples of contact-based or contact-free guidance, such as substrate patterning, the application of light, magnetic fields, or chemical gradients, potentially interesting methods of creating hierarchically structured monolithic engineering materials, using live patterned biomass, biofilms, or extracellular substances as scaffolds, are presented. The potential advantages of such materials are discussed, and examples of live self-patterning of materials are given.

Passive and active mechanical properties of biotemplated ceramics revisited.

Living nature and human technology apply different principles to create hard, strong and tough materials. In this review, we compare and discuss prominent aspects of these alternative strategies, and demonstrate for selected examples that nanoscale-precision biotemplating is able to produce uncommon mechanical properties as well as actuating behavior, resembling to some extent the properties of the original natural templates. We present and discuss mechanical testing data showing for the first time that nanometer-precision biotemplating can lead to porous ceramic materials with deformation characteristics commonly associated with either biological or highly advanced technical materials. We also review recent findings on the relation between hierarchical structuring and humidity-induced directional motion. Finally, we discuss to which extent the observed behavior is in agreement with previous results and theories on the mechanical properties of multiscale hierarchical materials, as well as studies of highly disperse technical materials, together with an outlook for further lines of investigation.

Moisture-Driven Ceramic Bilayer Actuators from a Biotemplating Approach.

The former ovuliferous scales of biotemplated cones of Pinus nigra show moisture-driven actuation similar to their biological templates, demonstrating a facile route to obtain ceramic moisture-sensitive bilayer actuators. Based on comparative analysis of their hierarchical nanometer-precision replica structures, using, e.g., spatially resolved small-angle X-ray scattering, the origin of the actuation is explained.

Enhancement of the antimicrobial properties of orthorhombic molybdenum trioxide by thermal induced fracturing of the hydrates.

The oxides of the transition metal molybdenum exhibit excellent antimicrobial properties. We present the preparation of molybdenum trioxide dihydrate (MoO3 × 2H2O) by an acidification method and demonstrate the thermal phase development and morphological evolution during and after calcination from 25 °C to 600 °C. The thermal dehydration of the material was found to proceed in two steps. Microbiological roll-on tests using Staphylococcus aureus, Escherichia coli and Pseudomonas aeruginosa were performed and exceptional antimicrobial activities were determined for anhydrous samples with orthorhombic lattice symmetry and a large specific surface area. The increase in the specific surface area is due to crack formation and to the loss of the hydrate water after calcination at 300 °C. The results support the proposed antimicrobial mechanism for transition metal oxides, which based on a local acidity increase as a consequence of the augmented specific surface area.

Transparent cellulose sheets as synthesis matrices for inorganic functional particles.

Transparent cellulose sheets were prepared through tape-casting a solution of cellulose. Flexible, luminescent sheets were produced by adding europium trichloride to the casting solution and treating the sheets with an aqueous solution of ammonium fluoride. Scanning electron micrographs of the resulting sheets showed europium trifluoride particles with diameters from 200nm to 500nm. These were found by transmission electron microscopy to be agglomerates of crystallites in the size range of 10-20nm. The structure of supercritically dried sheets was further assessed by small-angle X-ray scattering and suggests a preferred orientation of slightly elongated pores of roughly 12nm in diameter. Evaluation of the emission characteristics of the sheets showed the band pattern between 580nm and 700nm typical for Eu3+ phosphors. Our developed process is a versatile tool for the fabrication of transparent cellulose structures with different shapes and various embedded functional particles.