Designing Ionic Ir(III) Cyclometalated Complexes as Photocatalysts for Light Assisted ATRP of MMA. A Combined Experimental and Mechanistic Study.

A new family of ionic Ir(III) cyclometalated complexes with general formula [Ir(CN)2(NN)][Br], was designed and prepared to be assessed as photocalysts for the visible light assisted ATRP polymerization of MMA. To this purpose, our design strategy involved both: i) the decoration of the cyclometalating (CN) and the ancillary (NN) ligands with various electron withdrawing and/or electron donor substituents and, ii) the use of Br- as the counter anion for these cationic Ir(III) species. After an extensive screening in which the [Ir(CN)2(NN)][Br]-type compounds were compared to the model neutral complex fac-[Ir(ppy)3], the "fully" amino-substituted ion pairs abbreviated as [10][Br] and [11][Br], exhibited the best photocatalytic performances under irradiation with CFL lamps. It is worth noting that the outcomes of transient absorption spectroscopy (TAS) experiments combined with theoretical DFT calculations, enlightened the role played by the Ir(III) complexes in the mechanism of the photoATRP process, and suggested the rationalization of the different performances that were highlighted by our Ir(III) catalyst in the visible light assisted photopolymerization of MMA.

Bio-Based PA11/Graphene Nanocomposites Prepared by In Situ Polymerization.

Bio-based polyamide 11 (PA11)-graphene nanocomposites with different filler concentrations (0.25, 0.5, 0.75, 1.5 and 3 wt%) were prepared by In Situ polymerization starting from a water dispersed suspension of graphene nanoplatelets. The effects of the incorporation of the filler were studied in terms of molecular, morphological, thermal and dynamic mechanical properties of the final materials. During the crystallization process from the melt, the filler induces a notable nucleating effect even if the crystal growth rate tends to decrease. The glass transition temperature tends to shift to higher temperatures indicating a decrement of the molecular mobility. Thermal stability is enhanced confirming a good filler dispersion into the matrix. Mechanical reinforcement, investigated by means of a dynamic mechanical thermal analyzer was also highlighted. It was observed that a graphene concentration of 0.75 wt% induces the highest final performances.

Facile and Bioinspired Approach from Gallic Acid for the Synthesis of Biobased Flame Retardant Coatings of Basalt Fibers.

A sustainable, bioinspired approach to functionalize basalt fibers with an innovative gallic acid (GA)-iron phenyl phosphonate complex (BF-GA-FeP), for the purpose of improving the flame retardancy in composite materials, is developed. BFs were at first pretreated with O3, obtaining surface free hydroxyl groups that allowed the subsequent covalent immobilization of biosourced GA units on the fiber through ester linkages. Phenolic -OH groups of the GA units were then exploited for the complexation of iron phenyl phosphonate, resulting in the target-complex-coated BF fiber (BF-GA-FeP). Microwave plasma atomic emission spectroscopy and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy analyses of BF-GA-FeP highlighted an increase in iron content, modification of fiber morphology, and occurrence of phosphorus, respectively. BFs, modified with a low amount of the developed complex, were used to reinforce a poly(lactic acid) (PLA) matrix in the production of a biocomposite (PLA/BF-FeP). PLA/BF-FeP showed a higher thermal stability than neat PLA and PLA reinforced with untreated BFs (PLA/BF), as confirmed by thermogravimetric analysis. The cone calorimeter test highlighted several advantages for PLA/BF-FeP, including a prolonged time to ignition, a reduced time to flame out, an 8% decrease in the peak heat release rate, and a 15% reduced fire propagating index compared to PLA/BF.

Valorization of Agro-Wastes as Fillers in PLA-Based Biocomposites for Increasing Sustainability in Fused Deposition Modeling Additive Manufacturing.

The use of wheat middlings (WM) and rice husks (RH) as biofillers for mixing with poly(lactic acid) (PLA) matrix to produce new 3D-printable biocomposites was assessed. Filaments containing 10 and 20 wt.% agro-waste-derived biofillers were manufactured and, for the sake of comparison, filaments of neat PLA were also produced. The obtained filaments were characterized via thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), showing potential for further application in additive manufacturing processing. Three-dimensionally printed specimens were thus produced and characterized via: DSC, also evaluating the specific heat capacity (CP) of specific 3D-printed specimens; dynamic mechanical analysis (DMA), also applied for determining the coefficient of linear thermal expansion (CLTE) measured on 3D-printed specimens in two different directions (X and Y); and tensile tests. The latter testing campaign was carried out along three printing directions (X, Y, and Z axes) to test the intrinsic biocomposite features (X-printed samples) as well as interbead and interlayer adhesion (Y- and Z-printed specimens, respectively). All samples demonstrated acceptable properties. The inclusion of a cost-free natural material leads to a strong reduction of the whole material cost. Implementing this new class of composite material to an additive manufacturing technique can significantly reduce the environmental impact of 3D-printed products.

Water-Resistant Photo-Crosslinked PEO/PEGDA Electrospun Nanofibers for Application in Catalysis.

Catalysts are used for producing the vast majority of chemical products. Usually, catalytic membranes are inorganic. However, when dealing with reactions conducted at low temperatures, such as in the production of fine chemicals, polymeric catalytic membranes are preferred due to a more competitive cost and easier tunability compared to inorganic ones. In the present work, nanofibrous mats made of poly(ethylene oxide), PEO, and poly(ethylene glycol) diacrylate, PEGDA, blends with the Au/Pd catalyst are proposed as catalytic membranes for water phase and low-temperature reactions. While PEO is a water-soluble polymer, its blending with PEGDA can be exploited to make the overall PEO/PEGDA blend nanofibers water-resistant upon photo-crosslinking. Thus, after the optimization of the blend solution (PEO molecular weight, PEO/PEGDA ratio, photoinitiator amount), electrospinning process, and UV irradiation time, the resulting nanofibrous mat is able to maintain the nanostructure in water. The addition of the Au6/Pd1 catalyst (supported on TiO2) in the PEO/PEGDA blend allows the production of a catalytic nanofibrous membrane. The reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP), taken as a water phase model reaction, demonstrates the potential usage of PEO-based membranes in catalysis.

(Meth)acrylate-Free Three-Dimensional Printing of Bio-Derived Photocurable Resins with Terpene- and Itaconic Acid-Derived Poly(ester-thioether)s.

Vat photopolymerization, a very efficient and precise object manufacturing technique, still strongly relies on the use of acrylate- and methacrylate-based formulations because of their low cost and high reactivity. However, the environmental impact of using fossil fuel-based, volatile, and toxic (meth)acrylic acid derivatives is driving the scientific community toward the development of alternatives that can match the mechanical performance and three-dimensional (3D) printing processability of traditional photocurable mixtures but are made from environmentally friendly building blocks. Herein, itaconic acid is polymerized with polyols derived from naturally occurring terpenes to produce photocurable poly(ester-thioether)s. The formulation of such polymers using itaconic acid-based reactive diluents allows the preparation of a series of (meth)acrylate-free photocurable resins, which can be 3D printed into solid objects. Extensive analysis has been conducted on the properties of photocured polymers including their thermal, thermomechanical, and mechanical characteristics. The findings suggest that these materials exhibit properties comparable to those of traditional alternatives that are created using harmful and toxic blends. Notably, the photocured polymers are composed of biobased constituents ranging from 75 to 90 wt %, which is among the highest values ever recorded for vat photopolymerization applications.

New Application Field of Polyethylene Oxide: PEO Nanofibers as Epoxy Toughener for Effective CFRP Delamination Resistance Improvement.

Delamination is the most severe weakness affecting all composite materials with a laminar structure. Nanofibrous mat interleaving is a smart way to increase the interlaminar fracture toughness: the use of thermoplastic polymers, such as poly(ε-caprolactone) and polyamides (Nylons), as nonwovens is common and well established. Here, electrospun polyethylene oxide (PEO) nanofibers are proposed as reinforcing layers for hindering delamination in epoxy-based carbon fiber-reinforced polymer (CFRP) laminates. While PEO nanofibers are well known and successfully applied in medicine and healthcare, to date, their use as composite tougheners is undiscovered, resulting in the first investigation in this application field. The PEO-modified CFRP laminate shows a significant improvement in the interlaminar fracture toughness under Mode I loading: +60% and +221% in G I,C and G I,R, respectively. The high matrix toughening is confirmed by the crack path analysis, showing multiple crack planes, and by the delamination surfaces, revealing that extensive phase separation phenomena occur. Under Mode II loading, the G II enhancement is almost 20%. Despite a widespread phase separation occurring upon composite curing, washings in water do not affect the surface delamination morphology, suggesting a sufficient humidity resistance of the PEO-modified laminate. Moreover, it almost maintains both the original stiffness and glass transition temperature (T g), as assessed via three-point bending and dynamic mechanical analysis tests. The achieved results pave the way for using PEO nanofibrous membranes as a new effective solution for hindering delamination in epoxy-based composite laminates.

Self-Assembled NBR/Nomex Nanofibers as Lightweight Rubbery Nonwovens for Hindering Delamination in Epoxy CFRPs.

Still today, concerns regarding delamination limit the widespread use of high-performance composite laminates, such as carbon fiber-reinforced polymers (CFRPs), to replace metals. Nanofibrous mat interleaving is a well-established approach to reduce delamination. However, nanomodifications may strongly affect other laminate thermomechanical properties, especially if achieved by integrating soft materials. Here, this limitation is entirely avoided by using rubbery nitrile butadiene rubber (NBR)/Nomex mixed nanofibers: neither laminate stiffness nor glass-transition temperature (Tg) lowering occurs upon CFRP nanomodification. Stable noncrosslinked nanofibers with up to 60% wt of NBR were produced via single-needle electrospinning, which were then morphologically, thermally, spectroscopically, and mechanically characterized. NBR and Nomex disposition in the nanofiber was investigated via selective removal of the sole rubber fraction, revealing the formation of particular self-assembled structures resembling quasi-core-shell nanofibers or fibril-like hierarchical structures, depending on the applied electrospinning conditions (1.10 and 0.20 mL/h, respectively). Mode I and Mode II loading tests show a significant improvement of the interlaminar fracture toughness of rubbery nanofiber-modified CFRPs, especially GI (up to +180%), while GII enhancement is less pronounced but still significant (+40% in the best case). The two nanofibrous morphologies (quasi-core-shell and fibril-like ones) improve the delamination resistance differently, also suggesting that the way the rubber is located in the nanofibers plays a role in the toughening action. The quasi-core-shell nanofiber morphology provides the best reinforcing action, besides the highest productivity. By contrast, pure Nomex nanofibers dramatically worsen the interlaminar fracture toughness (up to -70% in GI), acting as a release film. The achieved delamination resistance improvements, combined with the retention of both the original laminate stiffness and Tg, pave the way to the extensive and reliable application of NBR/Nomex rubbery nanofibrous mats in composite laminates.

Rubber-enhanced polyamide nanofibers for a significant improvement of CFRP interlaminar fracture toughness.

Nanofibrous mats provide substantial delamination hindering in composite laminates, especially if the polymer (as rubbers) can directly toughen the composite resin. Here, the well-known Nylon 66 nanofibers were impregnated with Nitrile Butadiene Rubber (NBR) for producing rubber/thermoplastic membranes for hampering the delamination of epoxy Carbon Fiber Reinforced Polymers (CFRPs). The starting polyamide mats were electrospun using two different solvent systems, and their effect on the mat's thermal and mechanical properties was investigated, as well as the laminate Mode I delamination resistance via Double Cantilever Beam (DCB) tests. Plain Nylon 66 mats electrospun from formic acid/chloroform perform better than the ones obtained from a solvent system containing trifluoroacetic acid, showing up to + 64% vs + 53% in interlaminar fracture toughness (GI), respectively. The effect of NBR coating benefits both nanofiber types, significantly raising the GI. The best results are obtained when interleaving medium-thickness and lightweight mats (20 µm, 9-10 g/m2) with 70-80 wt% of loaded rubber, achieving up to + 180% in GI. The work demonstrates the ability of NBR at improving the delamination hindering of common polyamide nonwovens, paving the way to the use of NBR-coated Nylon 66 nanofibers as effective interleaves for GI enhancement and overall composite safety improvement.

Is Graphene Always Effective in Reinforcing Composites? The Case of Highly Graphene-Modified Thermoplastic Nanofibers and Their Unfortunate Application in CFRP Laminates.

Graphene (G) can effectively enhance polymers' and polymer composites' electric, thermal, and mechanical properties. Nanofibrous mats have been demonstrated to significantly increase the interlaminar fracture toughness of composite laminates, hindering delamination and, consequently, making such materials safer and more sustainable thanks to increased service life. In the present paper, poly(ethylene oxide) (PEO), polycaprolactone (PCL), and Nylon 66 nanofibers, plain or reinforced with G, were integrated into epoxy-matrix Carbon Fiber Reinforced Polymers (CFRPs) to evaluate the effect of polymers and polymers + G on the laminate mechanical properties. The main aim of this work is to compare the reinforcing action of the different nanofibers (polyether, polyester, and polyamide) and to disclose the effect of G addition. The polymers were chosen considering their thermal properties and, consequently, their mechanism of action against delamination. PEO and PCL, displaying a low melting temperature, melt, and mix during the curing cycle, act via matrix toughening; in this context, they are also used as tools to deploy G specifically in the interlaminar region when melting and mixing with epoxy resin. The high extent of modification stems from an attempt to deploy it in the interlaminar layer, thus diluting further in the resin. In contrast, Nylon 66 does not melt and maintain the nanostructure, allowing laminate toughening via nanofiber bridging. The flexural properties of the nanomodifed CFRPs were determined via a three-point bending (3PB) test, while delamination behavior in Mode I and Mode II was carried out using Double Cantilever Beam (DCB) and End-Notched Flexture (ENF) tests, respectively. The lack of a positive contribution of G in this context is an interesting point to raise in the field of nanoreinforced CFRP.

Keratin/Polylactic acid/graphene oxide composite nanofibers for drug delivery.

In this work keratin/poly(lactic acid) (PLA) 50/50 wt blend nanofibers with different loadings of graphene-oxide (GO) were prepared by electrospinning and tested as delivery systems of Rhodamine Blue (RhB), selected as a model of a drug. The effect of GO on the electrospinnability and drug release mechanism and kinetics was investigated. Rheological measurements carried out on the blend solutions revealed unsatisfactory compatibility between keratin and PLA under quiet condition. Accordingly, poor interfacial adhesion between the two phases was observed by SEM analysis of a film prepared by solution casting. On the contrary, keratin chains seem to rearrange under the flux conditions of the electrospinning process thus promoting better interfacial interactions between the two polymers, thereby enhancing their miscibility, which resulted in homogeneous and defect-free nanofibers. The loading of GO into the keratin/PLA solution contributes to increase its viscosity, its shear thinning behavior, and its conductivity. Accordingly, thinner and more homogeneous nanofibers resulted from solutions with a relatively high conductivity coupled with a pronounced shear thinning behavior. FTIR and DSC analyses have underlined, that while the PLA/GO interfacial interactions significantly compete with the PLA/keratin ones, there are no significant effects of GO on the structural organization of keratin in blend with the PLA. However, GO offers several advantages from the application point of view by slightly improving the mechanical properties of the electrospun mats and by slowing down the release of the model drug through the reduction of the matrix swelling.

Rubbery-Modified CFRPs with Improved Mode I Fracture Toughness: Effect of Nanofibrous Mat Grammage and Positioning on Tanδ Behaviour.

Carbon Fiber Reinforced Polymers (CFRPs) are widely used where high mechanical performance and lightweight are required. However, they suffer from delamination and low damping, severely affecting laminate reliability during the service life of components. CFRP laminates modified by rubbery nanofibers interleaving is a recently introduced way to increase material damping and to improve delamination resistance. In this work, nitrile butadiene rubber/poly(ε-caprolactone) (NBR/PCL) blend rubbery nanofibrous mats with 60 wt% NBR were produced in three different mat grammages (5, 10 and 20 g/m2) via single-needle electrospinning and integrated into epoxy CFRP laminates. The investigation demonstrated that both mat grammage and positioning affect CFRP tanδ behaviour, evaluated by dynamic mechanical analysis (DMA) tests, as well as the number of nano-modified interleaves. Double cantilever beam (DCB) tests were carried out to assess the mat grammage effect on the interlaminar fracture toughness. Results show an outstanding improvement of GI,R for all the tested reinforced laminates regardless of the mat grammage (from +140% to +238%), while the effect on GI,C is more dependent on it (up to +140%). The obtained results disclose the great capability of NBR/PCL rubbery nanofibrous mats at improving CFRP damping and interlaminar fracture toughness. Moreover, CFRP damping can be tailored by choosing the number and positioning of the nano-modified interleaves, besides choosing the mat grammage.

Bio-Based Furan-Polyesters/Graphene Nanocomposites Prepared by In Situ Polymerization.

In situ intercalative polymerization has been investigated as a strategic way to obtain poly(propylene 2,5-furandicarboxylate) (PPF) and poly(hexamethylene 2,5-furandicarboxylate) (PHF) nanocomposites with different graphene types and amounts. Graphene (G) has been dispersed in surfactant stabilized water suspensions. The loading range in composites was 0.25-0.75 wt %. For the highest composition, a different type of graphene (XT500) dispersed in 1,3 propanediol, containing a 6% of oxidized graphene and without surfactant has been also tested. The results showed that the amorphous PPF is able to crystallize during heating scan in DSC and graphene seems to affect such capability: G hinders the polymer chains in reaching an ordered state, showing even more depressed cold crystallization and melting. On the contrary, such hindering effect is absent with XT500, which rather induces the opposite. Concerning the thermal stability, no improvement has been induced by graphene, even if the onset degradation temperatures remain high for all the materials. A moderate enhancement in mechanical properties is observed in PPF composite with XT500, and especially in PHF composite, where a significative increase of 10-20% in storage modulus E' is maintained in almost all the temperature range. Such an increase is also reflected in a slightly higher heat distortion temperature. These preliminary results can be useful in order to further address the field of application of furan-based polyesters; in particular, they could be promising as packaging materials.

Coral micro- and macro-morphological skeletal properties in response to life-long acclimatization at CO2 vents in Papua New Guinea.

This study investigates the effects of long-term exposure to OA on skeletal parameters of four tropical zooxanthellate corals naturally living at CO2 seeps and adjacent control sites from two locations (Dobu and Upa Upasina) in the Papua New Guinea underwater volcanic vent system. The seeps are characterized by seawater pH values ranging from 8.0 to about 7.7. The skeletal porosity of Galaxea fascicularis, Acropora millepora, massive Porites, and Pocillopora damicornis was higher (up to ~ 40%, depending on the species) at the seep sites compared to the control sites. Pocillopora damicornis also showed a decrease of micro-density (up to ~ 7%). Thus, further investigations conducted on this species showed an increase of the volume fraction of the larger pores (up to ~ 7%), a decrease of the intraskeletal organic matrix content (up to ~ 15%), and an increase of the intraskeletal water content (up to ~ 59%) at the seep sites. The organic matrix related strain and crystallite size did not vary between seep and control sites. This multi-species study showed a common phenotypic response among different zooxanthellate corals subjected to the same environmental pressures, leading to the development of a more porous skeletal phenotype under OA.

Synthesis and chiroptical properties of chiral azoaromatic dendrimers with a C3-symmetrical core.

New chiral azoaromatic dendrimeric systems have been synthesized starting from 1,3,5-benzenetricarbonyl trichloride as the core molecule. The simultaneous presence of the (S)-3-hydroxy pyrrolidinyl ring as the optically active moiety and the azobenzene donor-acceptor conjugated system as the photochromic group with permanent dipole moment, makes these systems potentially interesting as materials for advanced applications in nanotechnologies. All the compounds obtained have been characterized with particular attention to the effects induced by changing the electron-withdrawing group in the chromophoric moiety and to their optical activity. A strong nonlinear enhancement of chiroptical properties related to the number of chiral units linked to the symmetrical core is observed in these derivatives, which indicates the presence of conformationally chiral substructures.

Adenine as Epoxy Resin Hardener for Sustainable Composites Production with Recycled Carbon Fibers and Cellulosic Fibers.

In this work, Adenine is proposed, for the first time, as a cross-linker for epoxy resins. Adenine is an amino-substituted purine with heterocyclic aromatic structure showing both proton donors, and hydrogen bonding ability. DSC studies show that adenine is able to positively cross-link a biobased DGEBA-like commercial epoxy precursor with good thermal performance and a reaction mechanism based on a 1H NMR investigation has been proposed. The use of such a formulation to produce composite with recycled short carbon fibers (and virgin ones for the sake of comparison), as well as jute and linen natural fibers as sustainable reinforcements, leads to materials with high compaction and fiber content. The curing cycle was optimized for both carbon fiber and natural fiber reinforced materials, with the aim to achieve the better final properties. All composites produced display good thermal and mechanical properties with glass transition in the range of HT resins (Tg > 150 °C, E' =26 GPa) for the carbon fiber-based composites. The natural fiber-based composites display slightly lower performance that is nonetheless good compared with standard composite performance (Tg about 115-120 °C, E' = 7-9 GPa). The present results thus pave the way to the application of adenine as hardener system for composites production.

Pebax® 2533/Graphene Oxide Nanocomposite Membranes for Carbon Capture.

In this work, the behavior of new GO-based mixed matrix membranes was tested in view of their use as CO2-selective membrane in post combustion carbon capture applications. In particular, the new materials were obtained by mixing of Pebax® 2533 copolymer with different types of graphene oxide (GO). Pebax® 2533 has indeed lower selectivity, but higher permeability than Pebax® 1657, which is more commonly used for membranes, and it could therefore benefit from the addition of GO, which is endowed with very high selectivity of CO2 with respect to nitrogen. The mixed matrix membranes were obtained by adding different amounts of GO, from 0.02 to 1% by weight, to the commercial block copolymers. Porous graphene oxide (PGO) and GO functionalized with polyetheramine (PEAGO) were also considered in composites produced with similar procedure, with a loading of 0.02%wt. The obtained films were then characterized by using SEM, DSC, XPS analysis and permeability experiments. In particular, permeation tests with pure CO2 and N2 at 35°C and 1 bar of upstream pressure were conducted for the different materials to evaluate their separation performance. It has been discovered that adding these GO-based nanofillers to Pebax® 2533 matrix does not improve the ideal selectivity of the material, but it allows to increase CO2 permeability when a low filler content, not higher than 0.02 wt%, is considered. Among the different types of GO, then, porous GO seems the most promising as it shows CO2 permeability in the order of 400 barrer (with an increase of about 10% with respect to the unloaded block copolymer), obtained without reducing the CO2/N2 selectivity of the materials, which remained in the order of 25.

New examples of Ru(II)-tetrazolato complexes as thiocyanate-free sensitizers for dye-sensitized solar cells.

A set of three new Ru(ii) polypyridyl complexes decorated with 5-aryl tetrazolato ligands (R-CN4)-, (D series, namely D1, D3 and D4), is presented herein. Whereas complex D1 represents the pyrazinyl tetrazolato analogue of a previously reported Ru(ii) complex (D2) with the general formula cis-[(dcbpy)2Ru(N^N)]+, in which dcbpy is 2,2'-bipyridine-4,4'-dicarboxylic acid and N^N is the chelating 2-pyridyl tetrazolato anion, the design of the unprecedented Ru(ii) species D3 and D4 relied upon a completely different architecture. More specifically, the molecular structure of thiocyanate-based species cis-[(dcbpy)2Ru(NCS)2], that is typically found in benchmark Ru(ii) dyes for dye sensitized solar cell (DSSCs), was modified with the replacement of two of the -NCS ligands in favour of the introduction of 5-aryl tetrazolato anions, such as the deprotonated form of 5-(4-bromophenyl)-1H-tetrazole, for complex D3 and 5-(4-cyanophenyl)-1H-tetrazole in the case of complex D4. To streamline the behavior of the D series of Ru(ii) complexes as photosensitizers for DSSCs, an in-depth analysis of the excited state properties of D1, D3 and D4 was performed through TDDFT calculations and TDAS (nanosecond transient difference absorption spectroscopy). The obtained results highlight a trend that was confirmed once D1, D3 and D4 were tested as photosensitizers for DSSC under different conditions. Along the series of the Ru(ii) complexes, the neutrally charged species D3 and D4 displayed the best photovoltaic performances.

Polyvinylamine Membranes Containing Graphene-Based Nanofillers for Carbon Capture Applications.

In the present study, the separation performance of new self-standing polyvinylamine (PVAm) membranes loaded with few-layer graphene (G) and graphene oxide (GO) was evaluated, in view of their use in carbon capture applications. PVAm, provided by BASF as commercial product named LupaminTM, was purified obtaining PVAm films with two degrees of purification: Low Grade (PVAm-LG) and High Grade (PVAm-HG). These two-grade purified PVAm were loaded with 3 wt% of graphene and graphene oxide to improve mechanical stability: indeed, pristine tested materials proved to be brittle when dry, while highly susceptible to swelling in humid conditions. Purification performances were assessed through FTIR-ATR spectroscopy, DSC and TGA analysis, which were carried out to characterize the pristine polymer and its nanocomposites. In addition, the membranes' fracture surfaces were observed through SEM analysis to evaluate the degree of dispersion. Water sorption and gas permeation tests were performed at 35 °C at different relative humidity (RH), ranging from 50% to 95%. Overall, composite membranes showed improved mechanical stability at high humidity, and higher glass transition temperature (Tg) with respect to neat PVAm. Ideal CO2/N2 selectivity up to 80 was measured, paired with a CO2 permeability of 70 Barrer. The membranes' increased mechanical stability against swelling, even at high RH, without the need of any crosslinking, represents an interesting result in view of possible further development of new types of facilitated transport composite membranes.

Supramolecular chirality and reversible chiroptical switching in new chiral liquid-crystal azopolymers.

The synthesis of chiral liquid-crystalline polymers of well-controlled structure (linear and three-armed star-shaped) with distinct average chain lengths and low polydispersity was achieved by atom transfer radical polymerisation (ATRP) of a new optically active monomer (S)-4-[6-(2-methacryloyloxypropanoyloxy)hexyloxy)]-4'-ethoxyazobenzene [(S)-ML6A], containing the L-lactic residue of one absolute configuration in the side-chain. All the obtained polymeric samples, characterised by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and polarised optical microscopy (POM), exhibit a smectic A(1/2) (fully interdigitated) liquid-crystalline phase and high cleaning points, with transition temperatures dependent on the average polymerisation degree and the macromolecular structure. The chirality originated at the molecular level by the asymmetric functionality of the L-lactic acid residue provides the polymers, in the smectic phase, of highly homogeneous conformations with a prevailing chirality related to the presence of H-aggregates having conformational dissymmetry of one prevailing screw-sense. By irradiating with circularly polarised light (CPL), it is possible to photomodulate the chiroptical properties of these intrinsically chiral polymeric thin films. Upon irradiation with left-handed CPL (l-CPL), the circular dichroism (CD) spectra of the films show enhancement of ellipticity and a net inversion of sign. The effect is reversible and the mirror image of the CD spectrum can be restored by pumping with right-handed CPL radiation (r-CPL). The results show the ability of l-CPL to invert the supramolecular chirality of the materials and demonstrate the essential role of azoaromatic aggregates.