Upcycling of Agricultural Waste Stream to High-Molecular-Weight Bio-based Poly(ethylene 2,5-furanoate).

Invited for this issue's cover is the group of Dr. Adina Anghelescu-Hakala at the VTT Technical Research Centre of Finland. The image shows that high-molecular-weight poly(ethylene 2,5-furanoate) (PEF) polymer can be produced from furan dicarboxylic acid (FDCA) or its esters as bio-based alternative to replace fossil-based poly(ethylene terephthalate) (PET). The Research Article itself is available at 10.1002/cssc.202301551.

Innovations in hydrogel-based manufacturing: A comprehensive review of direct ink writing technique for biomedical applications.

Direct ink writing (DIW) stands as a pioneering additive manufacturing technique that holds transformative potential in the field of hydrogel fabrication. This innovative approach allows for the precise deposition of hydrogel inks layer by layer, creating complex three-dimensional structures with tailored shapes, sizes, and functionalities. By harnessing the versatility of hydrogels, DIW opens up possibilities for applications spanning from tissue engineering to soft robotics and wearable devices. This comprehensive review investigates DIW as applied to hydrogels and its multifaceted applications. The paper introduces a diverse range of printing techniques while providing a thorough exploration of DIW for hydrogel-based printing. The investigation aims to explain the progress made, challenges faced, and potential trajectories that lie ahead for DIW in hydrogel-based manufacturing. The fundamental principles underlying DIW are carefully examined, specifically focusing on rheological attributes and printing parameters, prompting a comprehensive survey of the wide variety of hydrogel materials. These encompass both natural and synthetic variations, all of which can be effectively harnessed for this purpose. Furthermore, the review explores the latest applications of DIW for hydrogels in biomedical areas, with a primary focus on tissue engineering, wound dressing, and drug delivery systems. The document not only consolidates the existing state of DIW within the context of hydrogel-based manufacturing but also charts potential avenues for further research and innovative breakthroughs.

Upcycling of Agricultural Waste Stream to High-Molecular-Weight Bio-based Poly(ethylene 2,5-furanoate).

Orange peel and sugar beet pulp contain large quantities of pectin, which can be turned via galactaric acid into furan dicarboxylic acid (FDCA) and its esters. In this work, we show the polymerisation of these FDCA esters into high-molecular-weight, 70-100 kg/mol, poly(ethylene 2,5-furanoate) (PEF). PEF is an emerging bio-based alternative for poly(ethylene terephthalate) (PET), widely used in for example packaging applications. Closing the loop, we also demonstrated and confirmed that PEF can be hydrolysed by enzymes, which are known to hydrolyse PET, back into FDCA for convenient recycling and recovery of monomers.

Production of 2,5-Furandicarboxylic Acid Methyl Esters from Pectin-Based Aldaric Acid: from Laboratory to Bench Scale.

2,5-Furandicarboxylic acid (FDCA) is one of the most attractive emerging renewable monomers, which has gained interest especially in polyester applications, such as the production of polyethylene furanoate (PEF). Recently, the attention has shifted towards FDCA esters due to their better solubility as well as the easier purification and polymerisation compared to FDCA. In our previous work, we reported the synthesis of FDCA butyl esters by dehydration of aldaric acids as stable intermediates. Here, we present the synthesis of FDCA methyl esters in high yields from pectin-based galactaric acid using a solid acid catalyst. The process enables high substrate concentrations (up to 20 wt %) giving up to 50 mol % FDCA methyl esters with total furancarboxylates yields of up to 90 mol %. The synthesis was successfully scaled up from gram-scale to kilogram-scale in batch reactors showing the feasibility of the process. The stability of the catalyst was tested in re-use experiments. Purification of the crude product by vacuum distillation and precipitation gave furan-2,5-dimethylcarboxylate with a 98 % purity.

Dual functional quaternary chitosans with thermoresponsive behavior: structure-activity relationships in antibacterial activity and biocompatibility.

Cationically modified chitosan derivatives exhibit a range of appealing characteristics, with a particular emphasis on their antimicrobial potential across a broad spectrum of biomedical applications. This study aimed to delve deeper into quaternary chitosan (QC) derivatives. Through the synthesis of both homogeneously and heterogeneously dual-quaternized chitosan (DQC), utilizing AETMAC ([2-(acryloyloxy)ethyl]-trimethylammonium chloride) and GTMAC (glycidyl trimethylammonium chloride), a permanent charge was established, spanning a wide pH range. We assessed structural differences, the type of quaternary functional group, molecular weight (Mw), and charge density. Intriguingly, an upper critical solution temperature (UCST) behavior was observed in AETMAC-functionalized QC. To our knowledge, it is a novel discovery in cationically functionalized chitosan. These materials demonstrated excellent antimicrobial efficacy against model test organisms E. coli and P. syringae. Furthermore, we detected concentration-dependent cytotoxicity in NIH-3T3 fibroblasts. Striking a balance between antimicrobial activity and cytotoxicity becomes a crucial factor in application feasibility. AETMAC-functionalized chitosan emerges as the top performer in terms of overall antibacterial effectiveness, possibly owing to factors like molecular weight, charge characteristics, and variations in the quaternary linker. Quaternary chitosan derivatives, with their excellent antibacterial attributes, hold significant promise as antibacterial or sanitizing agents, as well as across a broad spectrum of biomedical and environmental contexts.

pH-Responsive Near-Infrared Emitting Gold Nanoclusters.

Near-infrared (NIR) fluorophores with pH-responsive properties suggest merits in biological analyses. This work establishes a general and effective method to obtain pH-responsive NIR emissive gold nanoclusters by introducing aliphatic tertiary amine (TA) groups into the ligands. Computational study suggests that the pH-responsive NIR emission is associated with electronic structure change upon protonation and deprotonation of TA groups. Photo-induced electron transfer between deprotonated TA groups and the surface Au-S motifs of gold nanoclusters can disrupt the radiative transitions and thereby decrease the photoluminescence intensity in basic environments (pH=7-11). By contrast, protonated TA groups curb the electron transfer and restore the photoluminescence intensity in acidic environments (pH=4-7). The pH-responsive NIR-emitting gold nanoclusters serve as a specific and sensitive probe for the lysosomes in the cells, offering non-invasive emissions without interferences from intracellular autofluorescence.

Ionic Liquid Containing Block Copolymer Dielectrics: Designing for High-Frequency Capacitance, Low-Voltage Operation, and Fast Switching Speeds.

Polymerized ionic liquids (PILs) are a potential solution to the large-scale production of low-power consuming organic thin-film transistors (OTFTs). When used as the device gating medium in OTFTs, PILs experience a double-layer capacitance that enables thickness independent, low-voltage operation. PIL microstructure, polymer composition, and choice of anion have all been reported to have an effect on device performance, but a better structure property relationship is still required. A library of 27 well-defined, poly(styrene)-b-poly(1-(4-vinylbenzyl)-3-butylimidazolium-random-poly(ethylene glycol) methyl ether methacrylate) (poly(S)-b-poly(VBBI+[X]-r-PEGMA)) block copolymers, with varying PEGMA/VBBI+ ratios and three different mobile anions (where X = TFSI-, PF6 - or BF4 -), were synthesized, characterized and integrated into OTFTs. The fraction of VBBI+ in the poly(VBBI+[X]-r-PEGMA) block ranged from to 100 mol % and led to glass transition temperatures (T g) between -7 and 55 °C for that block. When VBBI+ composition was equal or above 50 mol %, the block copolymer self-assembled into well-ordered domains with sizes between 22 and 52 nm, depending on the composition and choice of anion. The block copolymers double-layer capacitance (C DL) and ionic conductivity (σ) were found to correlate to the polymer self-assembly and the T g of the poly(VBBI+[X]-r-PEGMA) block. Finally, the block copolymers were integrated into OTFTs as the gating medium that led to n-type devices with threshold voltages of 0.5-1.5 V while maintaining good electron mobilities. We also found that the greater the σ of the PIL, the greater the OTFT operating frequency could reach. However, we also found that C DL is not strictly proportional to OTFT output currents.

Multiscale Hierarchical Surface Patterns by Coupling Optical Patterning and Thermal Shrinkage.

Herein, a simple hierarchical surface patterning method is presented by effectively combining buckling instability and azopolymer-based surface relief grating inscription. In this technique, submicron patterns are achieved using azopolymers, whereas the microscale patterns are fabricated by subsequent thermal shrinkage. The wetting characterization of various topographically patterned surfaces confirms that the method permits tuning of contact angles and choosing between isotropic and anisotropic wetting. Altogether, this method allows efficient fabrication of hierarchical surfaces over several length scales in relatively large areas, overcoming some limitations of fabricating multiscale roughness in lithography and also methods of creating merely random patterns, such as black silicon processing or wet etching of metals. The demonstrated fine-tuning of the surface patterns may be useful in optimizing surface-related material properties, such as wetting and adhesion, producing substrates that are of potential interest in mechanobiology and tissue engineering.

Polyzwitterions with LCST Side Chains: Tunable Self-Assembly.

Manipulation of self-assembly behavior of copolymers via environmental change is attractive in the fabrication of smart polymeric materials. We present tunable self-assembly behavior of graft copolymers, poly(sulfobetaine methacrylate)-graft-poly[oligo(ethylene glycol) methyl ether methacrylate)-co-di(ethylene glycol) methyl ether methacrylate] (PSBM-g-P(OEGMA-co-DEGMA)). Upon heating the aqueous solutions, the graft copolymers undergo a transition from micelles with PSBM cores to unimers (i.e., individual macromolecules) and then to reversed micelles with P(OEGMA-co-DEGMA) cores, thus demonstrating the tunability of the self-assembling through temperature change. In the presence of salt the temperature response of PSBM is eliminated, and the structure of the micelles with the P(OEGMA-co-DEGMA) core changes. Moreover, for the graft copolymer with long side chains, micelles with aggregation number ∼ 2 were formed with a PSBM core at low temperature, which is ascribed to the steric effect of the P(OEGMA-co-DEGMA) shell.

Boron nitride nanotubes as vehicles for intracellular delivery of fluorescent drugs and probes.

AIM: To evaluate the response of cells to boron nitride nanotubes (BNNTs) carrying fluorescent probes or drugs in their inner channel by assessment of the cellular localization of the fluorescent cargo, evaluation of the in vitro release and biological activity of a drug (curcumin) loaded in BNNTs. METHODS: Cells treated with curcumin-loaded BNNTs and stimulated with lipopolysaccharide were assessed for nitric oxide release and stimulation of IL-6 and TNF-α. The cellular trafficking of two cell-permeant dyes and a non-cell-permeant dye loaded within BNNTs was imaged. RESULTS: BNNTs loaded with up to 13 wt% fluorophores were internalized by cells and controlled release of curcumin triggered cellular pathways associated with the known anti-inflammatory effects of the drug. CONCLUSION: The overall findings indicate that BNNTs can function as nanocarriers of biologically relevant probes/drugs allowing one to examine/control their local intracellular localization and biochemical effects, leading the way to applications as intracellular nanosensors.

Cell-specific optoporation with near-infrared ultrafast laser and functionalized gold nanoparticles.

Selective targeting of diseased cells can increase therapeutic efficacy and limit off-target adverse effects. We developed a new tool to selectively perforate living cells with functionalized gold nanoparticles (AuNPs) and near-infrared (NIR) femtosecond (fs) laser. The receptor CD44 strongly expressed by cancer stem cells was used as a model for selective targeting. Citrate-capped AuNPs (100 nm in diameter) functionalized with 0.01 orthopyridyl-disulfide-poly(ethylene glycol) (5 kDa)-N-hydroxysuccinimide (OPSS-PEG-NHS) conjugated to monoclonal antibodies per nm(2) and 5 µM HS-PEG (5 kDa) were colloidally stable in cell culture medium containing serum proteins. These AuNPs attached mostly as single particles 115 times more to targeted CD44(+) MDA-MB-231 and CD44(+) ARPE-19 cells than to non-targeted CD44(-) 661W cells. Optimally functionalized AuNPs enhanced the fs laser (800 nm, 80-100 mJ cm(-2) at 250 Hz or 60-80 mJ cm(-2) at 500 Hz) to selectively perforate targeted cells without affecting surrounding non-targeted cells in co-culture. This novel highly versatile treatment paradigm can be adapted to target and perforate other cell populations by adapting to desired biomarkers. Since living biological tissues absorb energy very weakly in the NIR range, the developed non-invasive tool may provide a safe, cost-effective clinically relevant approach to ablate pathologically deregulated cells and limit complications associated with surgical interventions.

Toxicity of two types of silver nanoparticles to aquatic crustaceans Daphnia magna and Thamnocephalus platyurus.

Although silver nanoparticles (NPs) are increasingly used in various consumer products and produced in industrial scale, information on harmful effects of nanosilver to environmentally relevant organisms is still scarce. This paper studies the adverse effects of silver NPs to two aquatic crustaceans, Daphnia magna and Thamnocephalus platyurus. For that, silver NPs were synthesized where Ag is covalently attached to poly(vinylpyrrolidone) (PVP). In parallel, the toxicity of collargol (protein-coated nanosilver) and AgNO3 was analyzed. Both types of silver NPs were highly toxic to both crustaceans: the EC50 values in artificial freshwater were 15-17 ppb for D. magna and 20-27 ppb for T. platyurus. The natural water (five different waters with dissolved organic carbon from 5 to 35 mg C/L were studied) mitigated the toxic effect of studied silver compounds up to 8-fold compared with artificial freshwater. The toxicity of silver NPs in all test media was up to 10-fold lower than that of soluble silver salt, AgNO3. The pattern of the toxic response of both crustacean species to the silver compounds was almost similar in artificial freshwater and in natural waters. The chronic 21-day toxicity of silver NPs to D. magna in natural water was at the part-per-billion level, and adult mortality was more sensitive toxicity test endpoint than the reproduction (the number of offspring per adult).

Interfacial and fluorescence studies on stereoblock poly(N-isopropylacryl amide)s.

Aqueous solution and water-air interfacial properties of associative thermally responsive A-B-A stereoblock poly(N-isopropylacryl amide), PNIPAM, polymers were studied and compared to atactic PNIPAM. The A-B-A polymers consist of atactic PNIPAM as a hydrophilic block (either A or B) and a water-insoluble block of isotactic PNIPAM. The surface tensions of aqueous PNIPAM solutions were measured as a function of both temperature and concentration. The isotactic blocks did not have an effect on the surface activity of the solutions. Rheological measurements on the water-air interface showed that the aggregated PNIPAMs containing isotactic blocks increased the elasticity of the surface significantly as compared to the atactic reference upon heating. Two fluorescence probes, pyrene and (4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (4HP), added to the aqueous polymer solutions were concluded to reside in surroundings with lower polarity and increased microviscosity in cases when the polymers contained isotactic blocks, as compared to ordinary atactic polymers.