An Ideal Spin Filter: Long-Range, High-Spin Selectivity in Chiral Helicoidal 3-Dimensional Metal Organic Frameworks.

An enantiopure, conductive, and paramagnetic crystalline 3-D metal-organic framework (MOF), based on Dy(III) and the l-tartrate chiral ligand, is proved to behave as an almost ideal electron spin filtering material at room temperature, transmitting one spin component only, leading to a spin polarization (SP) power close to 100% in the ±2 V range, which is conserved over a long spatial range, larger than 1 µm in some cases. This impressive spin polarization capacity of this class of nanostructured materials is measured by means of magnetically polarized conductive atomic force microscopy and is attributed to the Chirality-Induced Spin Selectivity (CISS) effect of the material arising from a multidimensional helicity pattern, the inherited chirality of the organic motive, and the enhancing influence of Dy(III) ions on the CISS effect, with large spin-orbit coupling values. Our results represent the first example of a MOF-based and CISS-effect-mediated spin filtering material that shows a nearly perfect SP. These striking results obtained with our robust and easy-to-synthesize chiral MOFs constitute an important step forward in to improve the performance of spin filtering materials for spintronic device fabrication.

Degradability of cross-linked polyurethanes based on synthetic polyhydroxybutyrate and modified with polylactide.

In many areas of application of conventional non-degradable cross-linked polyurethanes (PUR), there is a need for their degradation under the influence of specific environmental factors. It is practiced by incorporation of sensitive to degradation compounds (usually of natural origin) into the polyurethane structure, or by mixing them with polyurethanes. Cross-linked polyurethanes (with 10 and 30%wt amount of synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) in soft segments) and their physical blends with poly([d,l]-lactide) (PDLLA) were investigated and then degraded under hydrolytic (phosphate buffer solution) and oxidative (CoCl2/H2O2) conditions. The rate of degradation was monitored by changes of samples mass, morphology of surface and their thermal properties. Despite the small weight losses of samples, the changes of thermal properties of polymers and topography of their surface indicated that they were susceptible to gradual degradation under oxidative and hydrolytic conditions. Blends of PDLLA and polyurethane with 30 wt% of R,S-PHB in soft segments and PUR/PDLLA blends absorbed more water and degraded faster than polyurethane with low amount of R,S-PHB.

Optically active multilayer films based on chitosan and an azopolymer.

The layer-by-layer technique has been widely adopted for the fabrication of nanostructures with tailored properties. In this work, photoactive multilayer films consisting of alternating layers of chitosan and an azopolymer were developed by this method. Taking into account that pH is the factor controlling the charge of weak polyelectrolytes, the influence of this parameter on the structure and properties of the multilayer films was evaluated. Thus, different films were prepared by varying pH conditions as well as bilayer number. The morphology and properties of the films were analyzed by diverse advanced techniques, such as ultraviolet-visible spectroscopy, X-ray diffraction, and atomic force microscopy equipped with PeakForce QNM (Quantitative Nanomechanical Property Mapping). It was found that the thickness, roughness and elastic modulus of the developed multilayer films increased with the decrease of the chitosan solution pH and the increase of the bilayer number. Furthermore, induced birefringence measurements revealed that a higher level of photo-orientation was attained with the decrease of pH and the increase of bilayer number.

Selective confinement of oleylamine capped Au nanoparticles in self-assembled PS-b-PEO diblock copolymer templates.

Amphiphilic polystyrene-block-polyethylene oxide (PS-b-PEO) block copolymers (BCPs) have been demonstrated to be effective in directing organization of colloidal Au nanoparticles (NPs). Au NPs have been incorporated into the polymer and the different chemical affinity between the NP surface and the two blocks of the BCP has been used as a driving force of the assembling procedure. The morphology of the nanocomposites, prepared and fabricated as thin films, has been investigated by means of atomic force and scanning electron microscopies as a function of the NP content and BCP molecular weight. NPs have been effectively dispersed in PS-b-PEO hosts at any investigated content (up to 17 wt%) and a clear effect of the BCP properties on the final nanocomposite morphology has been highlighted. Finally, electrostatic force microscopy has demonstrated the conductive properties of the nanocomposite films, showing that the embedded Au NPs effectively convey their conductive properties to the film. The overall investigation has confirmed the selective confinement of the as-prepared surfactant-coated metal NPs in the PS block of PS-b-PEO, thus proposing a very simple and prompt assembling tool for nanopatterning, potentially suitable for optoelectronic, sensing and catalysis applications.

Lewy bodies under atomic force microscope.

Lewy bodies are the hallmark of Parkinson disease and their sophisticated analysis will undoubtedly elucidate the pathogenic process. They have been studied by using different microscopic tools. The authors have used atomic force microscopy (AFM) to study the ultramicrotom cut postmortem brain tissue of Parkinson disease patients. Under the same preparation conditions, they have found aggregated fibrillary nanostructures in Lewy bodies, as well as a loss of connections between neurons located in other parts of the substantia nigra. Although these results are preliminary and descriptive in nature, this paper reports the application of a novel and intriguing technique. Further studies including the study of cortical LB and Lewy neurites will be needed to determine the full potential of AFM in the study of the pathogenesis of cell death in Parkinson disease and other synucleinopathies.

Thermally-Activated Shape Memory Behavior of Biodegradable Blends Based on Plasticized PLA and Thermoplastic Starch.

Biodegradable blends based on plasticized poly(lactic acid) PLA and thermoplastic starch (TPS) have been obtained. The influence of the PLA plasticizer as a compatibility agent has been studied by using two different plasticizers such as neat oligomeric lactic acid (OLA) and functionalized with maleic acid (mOLA). In particular, the morphological, thermal, and mechanical properties have been studied as well as the shape memory ability of the melt-processed materials. Therefore, the influence of the interaction between different plasticizers and the PLA matrix as well as the compatibility between the two polymeric phases on the thermally-activated shape memory properties have been studied. It is very interesting to use the same additive able to act as both plasticizer and compatibilizer, decreasing the glass transition temperature of PLA to a temperature close to the physiological one, obtaining a material suitable for potential biomedical applications. In particular, we obtain that OLA-plasticized blend (oPLA/TPS) show very good thermally-activated capability at 45 °C and 50% deformation, while the blend obtained by using maleic OLA (moPLA/TPS) did not show shape memory behavior at 45 °C and 50% deformation. This fact is due to their morphological changes and the loss of two well-distinguished phases, one acting as fixed phase and the other one acting as switching phase to typically obtain shape memory response. Therefore, the thermally-activated shape memory results show that it is very important to make a balance between plasticizer and compatibilizer, considering the need of two well-established phases to obtain shape memory response.

Functionalisation of CdSe semiconductor nanoparticles with polystyrene brushes by radical polimerization.

CdSe nanoparticles with polystyrene (PS) brushes are obtained by "grafting through" technique starting from solely aqueously synthesized nanoparticles. Mercaptoethanol (ME) capped nanoparticles are used to achieve double bond functional groups on the surface by condensation reaction with methacryloxypropyltrimethoxysilane (MPS). PS polymerization starts from these double bonds. Spectroscopic, diffraction and thermal techniques are used to characterize the nanoparticles. Infrared spectroscopy shows the formation of robust bonding between CdSe nanoparticles and the organic ligand, as well as the presence of the functional double bond on the surface of nanoparticles. Thermal analysis reveals changes in thermal properties of PS, as thermal stability of PS in the functionalised nanoparticles is improved. UV-vis and fluorescence measurements show that PS-CdSe nanoparticles exhibit good optical properties and transmission electron microscope (TEM) micrographs shows good level of dispersion of CdSe nanoparticles in a PS matrix.

Compatibility of Sustainable Mater-Bi/poly(ε-caprolactone)/cellulose Biocomposites as a Function of Filler Modification.

Despite their popularity and multiplicity of applications, wood-polymer composites (WPCs) still have to overcome particular issues related to their processing and properties. The main aspect is the compatibility with plant-based materials which affects the overall performance of the material. It can be enhanced by strengthening the interfacial adhesion resulting from physical and/or chemical interactions between the matrix and filler, which requires introducing a compatibilizer or a proper modification of one or both phases. Herein, the impact of cellulose filler modifications with varying contents (1-10 wt%) of hexamethylene diisocyanate (HDI) on the compatibility of Mater-Bi/poly(ε-caprolactone) (PCL)-based biocomposites was evaluated. An analysis of surface wettability revealed that the filler modification reduced the hydrophilicity gap between phases, suggesting compatibility enhancement. It was later confirmed via microscopic observation (scanning electron microscopy (SEM) and atomic force microscopy (AFM)), which pointed to the finer dispersion of modified particles and enhanced quality of the interface. The rheological analysis confirmed increased system homogeneity by the reduction in complex viscosity. In contrast, thermogravimetric analysis (TGA) indicated the efficient modification of filler and the presence of the chemical interactions at the interface by the shift of thermal decomposition onset and the changes in the degradation course.

The Evolution and Future Trends of Unsaturated Polyester Biocomposites: A Bibliometric Analysis.

Unsaturated polyester resin (UPR) is one of the first commercialized polymer matrices for composites reinforced with glass fibers, but has remained popular to this day. To reduce their environmental impact, natural fibers have been used as reinforcements. Researchers all over the world are still interested in these composites, and numerous papers have been published in the last four decades. Using bibliometric analysis, this work provides compiled, structured, and relevant information about the evolution and current state of these materials. This first study on UPR biocomposites based on bibliometric analysis examined 531 published papers identified in the Scopus database from 1982 to July 2022. An analysis of the most active states, leading institutions, and leading authors is followed by the identification of key areas such as the most common natural fibers used as reinforcements, fiber treatments, and composite design parameters such as processing techniques; recently, composite testing; and technological applications. The findings emphasize the importance of staying active in this global field and provide information on novel promising topics for future research.

Nanostructuring Biobased Epoxy Resin with PEO-PPO-PEO Block Copolymer.

A biobased diglycidyl ether of vanillin (DGEVA) epoxy resin was nanostructured by poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (PEO-PPO-PEO) triblock copolymer. Due to the miscibility/immiscibility properties of the triblock copolymer in DGEVA resin, different morphologies were obtained depending on the triblock copolymer amount. A hexagonally packed cylinder morphology was kept until reaching 30 wt% of PEO-PPO-PEO content, while a more complex three-phase morphology was obtained for 50 wt%, in which large worm-like PPO domains appear surrounded by two different phases, one of them rich in PEO and another phase rich in cured DGEVA. UV-vis measurements show that the transmittance is reduced with the increase in triblock copolymer content, especially at 50 wt%, probably due to the presence of PEO crystals detected by calorimetry.

GTR/Thermoplastics Blends: How Do Interfacial Interactions Govern Processing and Physico-Mechanical Properties?

In this work, GTR/thermoplastics blends (in ratio 50/50 and 75/25 wt.%) were prepared by melt-compounding in an internal mixer. During research, trans-polyoctenamer rubber (TOR), ethylene-vinyl acetate copolymer (EVA), ethylene-octene copolymer (EOC), and linear low-density polyethylene (LLDPE), were used in their thermoplastic phase. Microstructure and processing-performance property interrelationships of the studied materials were investigated by: atomic force microscopy (AFM), scanning electron microscopy (SEM), rubber process analyzer (RPA), Mooney viscometer, plastometer, gas chromatography with mass spectrometry, differential scanning calorimetry (DSC), tensile tests and swelling behavior. In blends of thermoplastics with a high content of GTR (50 and 75 wt.%), the thermoplastic modifier type had a significant impact on the processing behavior and microstructure of blends. In terms of the physico-mechanical properties, the GTR/thermoplastics ratio affected elongation at break, hardness, and density, while its effect on tensile strength was negligible. DSC analysis showed that thermoplastics, as modifiers of GTR, should be considered as binders and not plasticizers, as reflected in the almost constant glass-transition temperature of the blends. RPA measurements indicated higher values of G* and η* for GTR-rich blends. SEM showed a rubber-like interfacial break, while AFM confirmed interfacial contact between GTR and thermoplastics.

Semi-paracrystallinity in semi-conducting polymers.

Precise determination of structural organization of semi-conducting polymers is of paramount importance for the further development of these materials in organic electronic technologies. Yet, prior characterization of some of the best-performing materials for transistor and photovoltaic applications, which are based on polymers with rigid backbones, often resulted in conundrums in which X-ray scattering and microscopy yielded seemingly contradicting results. Here we solve the paradox by introducing a new structural model, i.e., semi-paracrystalline organization. The model establishes that the microstructure of these materials relies on a dense array of small paracrystalline domains embedded in a more disordered matrix. Thus, the overall structural order relies on two parameters: the novel concept of degree of paracrystallinity (i.e., paracrystalline volume/mass fraction, introduced here for the first time) and the lattice distortion parameter of paracrystalline domains (g-parameter from X-ray scattering). Structural parameters of the model are correlated with long-range charge carrier transport, revealing that charge transport in semi-paracrystalline materials is particularly sensitive to the interconnection of paracrystalline domains.

Bio-Based Polyurethane Networks Derived from Liquefied Sawdust.

The utilization of forestry waste resources in the production of polyurethane resins is a promising green alternative to the use of unsustainable resources. Liquefaction of wood-based biomass gives polyols with properties depending on the reagents used. In this article, the liquefaction of forestry wastes, including sawdust, in solvents such as glycerol and polyethylene glycol was investigated. The liquefaction process was carried out at temperatures of 120, 150, and 170 °C. The resulting bio-polyols were analyzed for process efficiency, hydroxyl number, water content, viscosity, and structural features using the Fourier transform infrared spectroscopy (FTIR). The optimum liquefaction temperature was 150 °C and the time of 6 h. Comprehensive analysis of polyol properties shows high biomass conversion and hydroxyl number in the range of 238-815 mg KOH/g. This may indicate that bio-polyols may be used as a potential substitute for petrochemical polyols. During polyurethane synthesis, materials with more than 80 wt% of bio-polyol were obtained. The materials were obtained by a one-step method by hot-pressing for 15 min at 100 °C and a pressure of 5 MPa with an NCO:OH ratio of 1:1 and 1.2:1. Dynamical-mechanical analysis (DMA) showed a high modulus of elasticity in the range of 62-839 MPa which depends on the reaction conditions.

Morphology, Thermo-Mechanical Properties and Biodegradibility of PCL/PLA Blends Reactively Compatibilized by Different Organic Peroxides.

Reactive blending is a promising approach for the sustainable development of bio-based polymer blends and composites, which currently is gaining more and more attention. In this paper, biodegradable blends based on poly(ε-caprolactone) (PCL) and poly(lactic acid) (PLA) were prepared via reactive blending performed in an internal mixer. The PCL and PLA content varied in a ratio of 70/30 and 55/45. Reactive modification of PCL/PLA via liquid organic peroxides (OP) including 0.5 wt.% of tert-butyl cumyl peroxide (BU), 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane (HX), and tert-butyl peroxybenzoate (PB) is reported. The materials were characterized by rotational rheometer, atomic force microscopy (AFM), thermogravimetry (TGA), differential scanning calorimetry (DSC), tensile tests and biodegradability tests. It was found that the application of peroxides improves the miscibility between PCL and PLA resulted in enhanced mechanical properties and more uniform morphology. Moreover, it was observed that the biodegradation rate of PCL/PLA blends reactively compatibilized was lower comparing to unmodified samples and strongly dependent on the blend ratio and peroxide structure. The presented results confirmed that reactive blending supported by organic peroxide is a promising approach for tailoring novel biodegradable polymeric systems with controllable biodegradation rates.

Degradability of Polyurethanes and Their Blends with Polylactide, Chitosan and Starch.

One of the methods of making traditional polymers more environmentally friendly is to modify them with natural materials or their biodegradable, synthetic equivalents. It was assumed that blends with polylactide (PLA), polysaccharides: chitosan (Ch) and starch (St) of branched polyurethane (PUR) based on synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) would degrade faster in the processes of hydrolysis and oxidation than pure PUR. For the sake of simplicity in the publication, all three modifiers: commercial PLA, Ch created by chemical modification of chitin and St are called bioadditives. The samples were incubated in a hydrolytic and oxidizing environment for 36 weeks and 11 weeks, respectively. The degradation process was assessed by observation of the chemical structure as well as the change in the mass of the samples, their molecular weight, surface morphology and thermal properties. It was found that the PUR samples with the highest amount of R,S-PHB and the lowest amount of polycaprolactone triol (PCLtriol) were degraded the most. Moreover, blending with St had the greatest impact on the susceptibility to degradation of PUR. However, the rate of weight loss of the samples was low, and after 36 weeks of incubation in the hydrolytic solution, it did not exceed 7% by weight. The weight loss of Ch and PLA blends was even smaller. However, a significant reduction in molecular weight, changes in morphology and changes in thermal properties indicated that the degradation of the samples should occur quickly after this time. Therefore, when using these polyurethanes and their blends, it should be taken into account that they should decompose slowly in their initial life. In summary, this process can be modified by changing the amount of R,S-PHB, the degree of cross-linking, and the type and amount of second blend component added (bioadditives).

Sequential Crystallization and Multicrystalline Morphology in PE-b-PEO-b-PCL-b-PLLA Tetrablock Quarterpolymers.

We investigate for the first time the morphology and crystallization of two novel tetrablock quarterpolymers of polyethylene (PE), poly(ethylene oxide) (PEO), poly(ε-caprolactone) (PCL), and poly(l-lactide) (PLLA) with four potentially crystallizable blocks: PE18 7.1 -b-PEO37 15.1 -b-PCL26 10.4 -b-PLLA19 7.6 (Q1) and PE29 9.5 -b-PEO26 8.8 -b-PCL23 7.6 -b-PLLA22 7.3 (Q2) (superscripts give number average molecular weights in kg/mol, and subscripts give the composition in wt %). Their synthesis was performed by a combination of polyhomologation (C1 polymerization) and ring-opening polymerization techniques using a ″catalyst-switch″ strategy, either ″organocatalyst/metal catalyst switch″ (Q1 sample, 96% isotactic tetrads) or ″organocatalyst/organocatalyst switch″ (Q2 sample, 84% isotactic tetrads). Their corresponding precursors-triblock terpolymers PE-b-PEO-b-PCL, diblock copolymers PE-b-PEO, and PE homopolymers-were also studied. Cooling and heating rates from the melt at 20 °C/min were employed for most experiments: differential scanning calorimetry (DSC), polarized light optical microscopy (PLOM), in situ small-angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS), and atomic force microscopy (AFM). The direct comparison of the results obtained with these different techniques allows the precise identification of the crystallization sequence of the blocks upon cooling from the melt. SAXS indicated that Q1 is melt miscible, while Q2 is weakly segregated in the melt but breaks out during crystallization. According to WAXS and DSC results, the blocks follow a sequence as they crystallize: PLLA first, then PE, then PCL, and finally PEO in the case of the Q1 quarterpolymer; in Q2, the PLLA block is not able to crystallize due to its low isotacticity. Although the temperatures at which the PEO and PCL blocks and the PE and PLLA blocks crystallize overlap, the analysis of the intensity changes measured by WAXS and PLOM experiments allows identifying each of the crystallization processes. The quarterpolymer Q1 remarkably self-assembles during crystallization into tetracrystalline banded spherulites, where four types of different lamellae coexist. Nanostructural features arising upon sequential crystallization are found to have a relevant impact on the mechanical properties. Nanoindentation measurements show that storage modulus and hardness of the Q1 quarterpolymer significantly deviate from those of the stiff PE and PLLA blocks, approaching typical values of compliant PEO and PCL. Results are mainly attributed to the low crystallinity of the PE and PLLA blocks. Moreover, the Q2 copolymer exhibits inferior mechanical properties than Q1, and this can be related to the PE block within Q1 that has thinner crystal lamellae according to its much lower melting point.

Cost-Effectively 3D-Printed Rigid and Versatile Interpenetrating Polymer Networks.

Versatile acrylate-epoxy hybrid formulations are becoming widespread in photo/thermal dual-processing scenarios, especially in 3D printing applications. Usually, parts are printed in a stereolithography or digital light processing (DLP) 3D printer, after which a thermal treatment would bestow the final material with superior mechanical properties. We report the successful formulation of such a hybrid system, consisting of a commercial 3D printing acrylate resin modified by an epoxy-anhydride mixture. In the final polymeric network, we observed segregation of an epoxy-rich phase as nano-domains, similar to what was observed in a previous work. However, in the current work, we show the effectiveness of a coupling agent added to the formulation to mitigate this segregation for when such phase separation is undesired. The hybrid materials showed significant improvement of Young's modulus over the neat acrylate. Once the flexible, partially-cured material was printed with a minimal number of layers, it could be molded into a complex form and thermally cured. Temporary shapes were readily programmable on this final material, with easy shape recovery under mild temperatures. Inspired by repairable 3D printed materials described recently, we manufactured a large object by printing its two halves, and then joined them covalently at the thermal cure stage with an apparently seamless union.

Conductive behavior of high TiO2 nanoparticle content of inorganic/organic nanostructured composites.

Amphiphilic polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers with different block ratios were used as templates for the incorporation of a high content of titanium dioxide nanoparticles using the sol-gel method. Confinement of the inorganic part in the PEO block of the block copolymer allows the generation of nanostructured systems with a high nanoparticle content. As successfully demonstrated using tunneling atomic force microscopy, the investigated systems maintained the conductive properties of the TiO(2) nanoparticles. The obtained results confirmed that with increasing TiO(2) nanoparticle content, the local current value increased up to 15 pA, and this conductivity value strongly depended on the amount of the PEO block in the block copolymer template. Moreover, the results indicated that control of the ratio between the sol-gel and the PEO block allows the design of well-dispersed, conductive inorganic/organic hybrids with high inorganic content. These materials can provide attractive strategies in the field of dye-sensitized solar cells.

Conductive properties of switchable photoluminescence thermosetting systems based on liquid crystals.

Conductive properties of different thermosetting materials modified with nematic 4'-(hexyl)-4-biphenyl-carbonitrile (HBC) liquid crystal and rutile TiO(2) nanoparticles were successfully studied by means of tunneling atomic force miscroscopy (TUNA). Taking into account the liquid crystal state of the HBC at room temperature, depending on both the HBC content and the presence of TiO(2) nanoparticles, designed materials showed different TUNA currents passed through the sample. The addition of TiO(2) nanoparticles into the systems multiply the detected current if compared to the thermosetting systems without TiO(2) nanoparticles and simultaneously stabilized the current passed through the sample, making the process reversible since the absolute current values were almost the same applying both negative and positive voltage. Moreover, thermosetting systems modified with liquid crystals with and without TiO(2) nanoparticles are photoluminescence switchable materials as a function of temperature gradient during repeatable heating/cooling cycle. Conductive properties of switchable photoluminescence thermosetting systems based on liquid crystals can allow them to find potential application in the field of photoresponsive devices, with a high contrast ratio between transparent and opaque states.

Predicted Studies of Branched and Cross-Linked Polyurethanes Based on Polyhydroxybutyrate with Polycaprolactone Triol in Soft Segments.

The number of cross-links in the non-linear polyurethane structure is the basic factor affecting its properties. Selected properties of aliphatic polyurethanes with soft segments made of different amounts of polycaprolactonetriol, polycaprolactonediol and synthetic, telechelic poly([R,S]-3-hydroxybutyrate) were determined. On the basis of changes in polyurethane properties, the correlation between these properties and the construction of soft segments was found. The structure of polyurethanes, their morphology, hydrophilicity, thermal and mechanical properties were examined. These properties were changed linearly up to 15% content of polycaprolactonetriol in soft segments. A further increase in the amount of triol causes that these properties are mainly determined by the high number of cross-links.