Light-powered micro- and nanomotors based on photocatalytic semiconductors convert light into mechanical energy, allowing self-propulsion and various functions. Despite recent progress, the ongoing quest to enhance their speed remains crucial, as it holds the potential for further accelerating mass transfer-limited chemical reactions and physical processes. This study focuses on multilayered MXene-derived metal-TiO2 micromotors with different metal materials to investigate the impact of electronic properties of the metal-semiconductor junction, such as energy band bending and built-in electric field, on self-propulsion. By asymmetrically depositing Au or Ag layers on thermally annealed Ti3C2Tx MXene microparticles using sputtering, Janus structures are formed with Schottky junctions at the metal-semiconductor interface. Under UV light irradiation, Au-TiO2 micromotors show higher self-propulsion velocities due to the stronger built-in electric field, enabling efficient photogenerated charge carrier separation within the semiconductor and higher hole accumulation beneath the Au layer. On the contrary, in 0.1 wt % H2O2, Ag-TiO2 micromotors reach higher velocities both in the presence and absence of UV light irradiation, owing to the superior catalytic properties of Ag in H2O2 decomposition. Due to the widespread use of plastics and polymers, and the consequent occurrence of nano/microplastics and polymeric waste in water, Au-TiO2 micromotors were applied in water remediation to break down polyethylene glycol (PEG) chains, which were used as a model for polymeric pollutants in water. These findings reveal the interplay between electronic properties and catalytic activity in metal-semiconductor junctions, offering insights into the future design of powerful light-driven micro- and nanomotors with promising implications for water treatment and photocatalysis applications.

Mixed matrix membranes (MMMs) are emerging as a promising technology for gas separation. These materials are composites made by blending a polymer with a porous filler that exhibits exceptional adsorption properties, such as a covalent organic framework or a metal-organic framework (MOF). Due to their composition, MMMs are considered next-generation membranes, since they combine the processability advantages of the polymer with the enhanced separation properties of the filler.[1] Understanding the separation properties of the composites requires characterizing the structural and dynamic properties of both filler and membrane at the atomic level, as well as understanding how they are altered in the composite. This knowledge is crucial for the design of novel materials with improved separation properties. Solid State NMR (SSNMR) is widely recognized as one of the most powerful techniques for characterizing the structural and dynamic properties of MOFs, composite materials, and their adsorbates at the atomic scale.[2,3] This is primarily due to the possibility to detect different nuclear observables (chemical shifts and anisotropic line shapes, dipolar couplings, nuclear relaxation times, etc.) that are highly sensitive to local structure and dynamics. In this study, multinuclear SSNMR is used to investigate three different perfluorinated MOFs with high affinity for CO2,[4,5,6] gas separation membranes obtained from the commercial polymer Hyflon, and their corresponding MMMs. 13C, 19F and 1H high-resolution SSNMR spectra and longitudinal relaxation times are analyzed to unravel structural and dynamic properties of the MOFs and the membrane and how they change in the MMMs. Acknowledgements The authors thank the Italian Ministry of University and Research through the Project PRIN 2020 doMino (ref. 2020P9KBKZ) References [1] J. Dechnik, et al. Angew. Chem. Int Ed. 2017, 56, 9292-9310. [2] B. E. G. Lucier, S. Chen, Y. Huang Acc. Chem. Res. 2018, 51, 319-330. [3] B. Reif, et al. Nat. Rev. Methods Primers 2021, 1, 2. [4] R. D'Amato, et al. ACS Sustainable Chem. Eng. 2019, 7, 394-402. [5] M. Cavallo, et al. J. Mater. Chem. A. 2023, 11, 5568-5583. [6] D. Morelli Venturi, et al. Mol. Syst. Des. Eng., 2023,8, 586-590

Over the last years, metal organic frameworks (MOFs), porous membranes, and MOF-based mixed matrix membranes (MMMs) have gained a lot of interest in the research community as promising materials for gas separation [1,2]. MOFs are organic/inorganic materials constituted of metal oxide clusters linked by organic ligands. Their gas separation properties can be finely tuned by combining different metals and linkers, as well as adopting post-synthetic modification procedures. MMMs, comprised of polymeric matrices and MOF fillers, are considered next-generation membranes for gas separation because they combine the benefits of the polymer processability with the enhanced separation properties of the filler. The physico-chemical properties of both the MOF and the polymer, as well as their interactions in the composite, play a key role in obtaining MMMs with enhanced separation performances. It is thus important to unravel these properties at the molecular level to understand the structure-property relationships and to guide the design of optimized materials for gas separation. Solid-state Nuclear Magnetic Resonance (SSNMR) spectroscopy has established itself as one of the most powerful techniques to characterize structural and dynamic properties of MOFs, polymeric membranes, and MMMs at the atomic scale, as well as to gain insight into the interaction with gases [3-7]. In fact, high-resolution SSNMR spectra provide information on local structure and spatial proximity between nuclei. Moreover, other nuclear observables (e.g. nuclear relaxation times and anisotropic line shapes) give unique possibilities for the study of molecular dynamics. In this work, SSNMR is applied to investigate structural and dynamic properties of perfluorinated MOFs with high affinity towards CO2 [8], membranes, and MMMs. Multinuclear high-resolution SSNMR experiments are carried out to study the structural properties of each material and their changes upon gas adsorption. MAS and static 13C SSNMR experiments are also applied to investigate the interaction of CO2 with MOFs and membranes. Acknowledgements: MUR is acknowledged through the Project PRIN 2020 doMino (ref. 2020P9KBKZ).

Porous materials have attracted considerable scientific and technological interest due to their critical applications in many fields, such as membrane-based gas separation, building materials, adsorption and storage, catalysis, ion exchange, nanotechnology, etc. From a chemical and structural point of view, the definition of "porous materials" encompasses a wide variety of systems, including inorganic, hybrid organic-inorganic, and polymeric materials. Solid state NMR spectroscopy (ssNMR) has been showing its tremendous potential to clarify the often-intricate behavior of this class of materials at a molecular and nanometric level. Indeed, it provides a wide variety of tools, relying on the observation of different nuclei and the measurement of different spectral and relaxation properties, which can reveal information on structural and dynamic features on wide spatial and time scales, respectively [1,2]. This lecture will cover a selection of ssNMR studies aimed at unravelling these features, and especially the dynamic aspects, on different classes of porous materials. In particular, the case studies presented will concern microporous polymers for solid-state gas separation and ion-exchange membranes, 1D coordination polymers devised to sequester volatile organic compounds, Ce-based metal organic frameworks with potential applications in the field of CO2 capture, and Mg- and Ca-based cement pastes. The main focus will be put on the detailed description of motional processes of polymeric chains and organic ligands and on the interactions and dynamic behavior of adsorbed water and other guest molecules. It will be shown how, depending on the type of material, on the available nuclei, on the desired detail of the information, and on the time scale of the motion, different experimental approaches can be used, combined with different analyses of the nuclear parameters measured in terms of suitable theoretical models. The experiments employed include static and Magic Angle Spinning as well as high- and low-field techniques, and in particular they rely on: 1H and 19F on-resonance FID analysis; 1H, 19F and 13C spin-lattice relaxation times in the laboratory frame and of 1H spin-lattice relaxation times in the rotating frame; 13C chemical shift anisotropy; 2H quadrupolar interaction. References [1] K. Mu?ller, and M. Geppi Solid State NMR: Principles, Methods, and Applications, Wiley ed. (2021). [2] S. Li et al. Adv. Mater. 32, 2002879 (2020).

The application and use of environmentally friendly components in rubber compound formulation is one of the most challenging goals of the tire industry. Specifically, tires are composed of elastomeric materials, obtained through the vulcanization of one or more polymers in the presence of curing agents and many other components, such as inorganic fillers, stabilizers, oils and resins. In particular, resins play a crucial role for the improvement of the rheological behaviour of the elastomeric compound, as well as the mechanical properties of the final product, such as rolling resistance and wet traction. However a significant issue of standard resins used for tire production is their fossil hydrocarbon source and the related environmental impact. Because of this, there is a strong interest in the development of more sustainable and renewable resins which fulfil specific requirements without altering the applicative properties of the final product. In order to achieve this goal, it is fundamental to investigate what happens at the molecular level between polymer and resin and to relate it with the macroscopic behaviour and performances of the final material [1]. In this context, we characterized both cured and uncured styrene-butadiene based compounds, containing three different resins, one of which of vegetal origin, by means of low-field time-domain and high-resolution solid-state NMR (SSNMR) techniques, which proved to be key to study resin/polymer interactions and miscibility, as well as the effect of resins on the overall dynamics of polymer chains. In particular, 1H time-domain experiments allowed us to measure 1H spin-lattice relaxation times in the laboratory (T1) and in the rotating frame (T1?), as well as 1H spin-spin relaxation times (T2), which are sensitive to molecular and mobility differences in heterogeneous materials, as they depend on the modulation of 1H-1H dipolar couplings by molecular motions. Moreover, 1H T1 and T1? relaxation times measured at different temperatures allowed us to investigate the effect of resin on polymer chain dynamics. Complementary structural information on each ingredient of the compounds were obtained by 13C high-resolution SSNMR [2,3,4]. The results obtained by combining time-domain and high-resolution techniques provided useful information regarding both polymer-resin interactions and mixing degree, gaining insights into the structure-property relationship, which is helpful for the design of rubber compounds and the rationalization of their macroscopic behaviour. References [1] B. Rodgers, W. Waddell, Chapter 9-The Science of Rubber Compounding. In The Science and Technology of Rubber, 4th ed., 417-471 (2013) [2] K. Saalwachter, Rubber Chemistry and Technology, 85, 350-386 (2012) [3] K. Mu?ller, and M. Geppi Solid State NMR: Principles, Methods, and Applications, (2021) [4] M. Pierigé, F. Nerli, F. Nardelli, L. Calucci, M. Cettolin, L. Giannini, M. Geppi, and F. Martini Appl. Sci. 13, 1939 (2023)

The use of traditional biocidal products in cultural heritage has suffered a slowdown due to the risks related to human health and the environment. Thus, many studies have been carried out with the aim of testing innovative and environmentally friendly alternatives. In this framework, this review attempts to provide an overview of some novel potential products with biocidal action, tested to counteract the process of degradation of paper and stone materials due to microbial activity, keeping in mind the sustainability criteria. In particular, we have focused our attention on the testing of nanotechnologies, essential oils, DES (deep eutectic solvents) with low toxicity, and colloidal substances for conservation purposes.

Core-shell architecture provides unique features to microparticles (MPs) by accurately selecting the employed materials. MPs with a mesogenic core and a metallic shell of gold nanoparticles (NPs) have been realized. The core is obtained by UV induced polymerization of reactive mesogens droplets in a chloroauric acid aqueous solution, whilst gold nanoparticles precipitation happens at the same time, covering the MPs surface. The MPs optical properties are modified by the gold shell, in the Bragg onion resonator condition when a chiral core is utilized, improving the laser emission stability compared to the MPs without shell. The proposed strategy, due to both the method and the versatility of the materials, suggests a new route to realize microdevices with wide control in term of intensity, polarization, generation [1]. The development of efficient micromachines is a challenge for applied and fundamental research. Light is a worthy mean to remotely displace micro-objects by inducing forces and torques. Rotational dynamics of core-shell MPs having ellipsoidal shape and nematic core is studied, and in particular a peculiar synchronous spin-orbital motion when the MPs are irradiated by a simple Gaussian beam. The observed effects originate from the coupling of the metallic NPs' optical response and the core anisotropies. The rotation performances strongly improve when trapping wavelength lie inside the plasmonic resonance range. In that case, spin kinetic energy achieves values two orders of magnitude larger than the one obtained from the bare MPs. The proposed approach bears important insights for design optimization in the MPs light driven motion, giving benefits to applications in microfluidics, microrheology, and micromachining that imply rotational dynamics [2]. References [1] N. Pellizzi, A. Mazzulla, P. Pagliusi, G. Cipparrone. "Core-shell chiral polymericmetallic particles obtained in a single step by concurrent light induced processes". Journal of Colloid and Interface Science (606):113, 2022. [2] N. Pellizzi, A. Mazzulla, P. Pagliusi, G. Cipparrone. "Plasmon-enhanced rotational dynamics of anisotropic core-shell polymeric-metallic microparticles". Photonics Research Journal, (10):2734, 2022.

Core-shell architecture provides unique features to microparticles (MPs) by accurately selecting the employed materials. MPs with a mesogenic core and a metallic shell of gold nanoparticles (NPs) have been realized. The core is obtained by UV induced polymerization of reactive mesogens droplets in a chloroauric acid aqueous solution, whilst gold nanoparticles precipitation happens at the same time, covering the MPs surface. The MPs optical properties are modified by the gold shell, in the Bragg onion resonator condition when a chiral core is utilized, improving the laser emission stability compared to the MPs without shell. The proposed strategy, due to both the method and the versatility of the materials, suggests a new route to realize microdevices with wide control in term of intensity, polarization, generation [1]. The development of efficient micromachines is a challenge for applied and fundamental research. Light is a worthy mean to remotely displace micro-objects by inducing forces and torques. Rotational dynamics of core-shell MPs having ellipsoidal shape and nematic core is studied, and in particular a peculiar synchronous spin-orbital motion when the MPs are irradiated by a simple Gaussian beam. The observed effects originate from the coupling of the metallic NPs' optical response and the core anisotropies. The rotation performances strongly improve when trapping wavelength lie inside the plasmonic resonance range. In that case, spin kinetic energy achieves values two orders of magnitude larger than the one obtained from the bare MPs. The proposed approach bears important insights for design optimization in the MPs light driven motion, giving benefits to applications in microfluidics, microrheology, and micromachining that imply rotational dynamics [2]. [1] N. Pellizzi, A. Mazzulla, P. Pagliusi, G. Cipparrone, "Core-shell chiral polymeric-metallic particles obtained in a single step by concurrent light induced processes", Journal of Colloid and Interface Science 606:Part 1, 113-123 (2022) [2] N. Pellizzi, A. Mazzulla, P. Pagliusi, G. Cipparrone, "Plasmon-enhanced rotational dynamics of anisotropic core-shell polymeric-metallic microparticles", Photonics Research Journal, 10:12, 2734-2742 (2022).

A series of poly(ether sulfone) random copolymers at various loading of diphenolic acid (DPA) units were synthesized and subjected to a comprehensive kinetics degradation study to assess their thermal behaviour. Poly(ether sulfones) were synthesized from different amounts of 4,4?dihydroxydiphenylsulfone, DPA and stoichiometric quantity of 4,4?-dichlorodiphenyl sulfone by nucleophilic aromatic displacement. The apparent activation energy (E) of degradation for the prepared compounds was determined by using a kinetics literature method, discussed and compared with each other and with those obtained in the past for similar polymers. The comprehensive thermal stability evaluation was completed with the assessment of the initial decomposition temperature of the prepared copolymer, showing a good thermal performance but, in the meantime, suggesting caution as regards the percentage of functionalization setting the limit beyond which a deterioration of the physical properties of the copolymers at 30% of pendant carboxylic acid groups was observed.

The development of efficient and cost-effective micromachines is a challenge for applied and fundamental science, given their wide fields of usage. Light is a suitable tool to move small objects in a noncontact way, given its capabilities in exerting forces and torques. However, when complex manipulation is required, micro-objects with proper architecture could play a specific role. Here we report on the rotational dynamics of core-shell particles, with a polymeric nematic core of ellipsoidal shape capped by Au nanoparticles. They undergo a peculiar synchronous spinning and orbital motion when irradiated by a simple Gaussian beam, which originates from the coupling of the metallic nanoparticles' optical response and the core anisotropies. The rotation capabilities are strongly enhanced when the trapping wavelength lies in the plasmonic resonance region: indeed, the spin kinetic energy reaches values two orders of magnitude larger than the one of bare microparticles. The proposed strategy brings important insights into optimizing the design of light controlled micro-objects and might benefit applications in microfluidics, microrheology, and micromachining involving rotational dynamics.

Experimental studies in recent years highlight the presence of an increasingly high quantity of microplastics worldwide [1]. The "resin pellets" represent a significant share among the first generation microplastics in the millimeter range (from 1 to 5 mm). They disperse in the environment, even unintentionally, during transport, storage and processing and recent studies show that their content varies from 3% to about 30% of all microplastics surveyed on beaches [2]. A three-years experiment was carried out on a simulated beach and in marine water in Santa Teresa Bay (Gulf of La Spezia, Italy). In detail, special cages have been installed on the underwater observatory, LabMARE coastal station [3], placed at ten meters deep. The submarine station is equipped with a sensor for monitoring environmental parameters, recording data every 10 min. The experiment, aimed at investigating the behavior of plastic items and HDPE, PP, PLA and PBAT pellets, began on March 3, 2020 and is still ongoing. Here, the comparison between the properties of the raw pellets and those placed in the two different environments after six months, is discussed. Through chemical, spectroscopic and thermal analyses (GPC, SEM, FTIR-ATR, DSC, TGA) of granules, variations in color, surface morphology, chemical composition, thermal properties and molecular weight, and polydispersity of materials are analysed to show the different influences of environmental conditions. Acknowledgement: The authors thank the Italian Istituto Zooprofilattico Sperimentale del Piemonte, Liguria e Valle d'Aosta for some of the materials useful for the setup of the experiment, DLTM for the availability of LabMARE coastal underwater platform, Dr. Andrea Bordone and Dr. Giancarlo Raiteri (ENEA) for the temperature data of the seawater, and Dipartimento Polizia di Stato--Centro Nautico Sommozzatori of La Spezia (Italy) for the precious support in sampling activities. The authors also thank the Win on Waste group at Area della Ricerca CNR of Pisa (WoW, https://wow.area.pi.cnr.it/). References: [1] L. Peng, D. Fu, Sci. Total Environ, 698, 134254, 2020. [2] S. Merlino, M. Locritani, G. Bernardi, C. Como, S. Legnaioli, V. Palleschi, M. Abbate, Water, 12, 3389, 2020. [3] https://www.dltm.it/it/news/685-alla-spezia-un-laboratorio-sottomarino-costiero-per-testare-nuove-tecnologie-4.html

EnjoiPol comprises several interesting research activities in the framework of the development and characterization of hybrid polymeric nanomaterials. The mission is to develop concrete solutions to the modern environmental challenges such as the pollution of natural water supplies, marine environment, and soil due to the presence of emerging contaminants such as microplastics, pesticides and fertilizers, heavy metals and drugs. Specifically, EnjoiPol research activities concern: a)chemical and structural characterization of plastics and microplastics present in marine environment and soil; in particular, the study of their interaction with organic and inorganic contaminants and their adsorption/release behaviour in the media.1 Part of the work is devoted to the valorisation of plastic debris collected from the sea, obtaining biofuel by means of pyrolysis treatment; b)formulation and study of innovative nano-systems coated with chitosan or alginate, for the realization of safe nano-fertilisers with low environmental impact;2 c)synthesis of acrylic and vinyl hydrogels/cryogels, properly functionalised for the selective removal of organic and inorganic contaminants from water. Specifically, we focused our attention on the sequestration of heavy metals3, drugs and pesticides4, by using chelation and molecular imprinting strategies. Hybrid organic/inorganic nanomaterials have been designed and synthesised, by combining the polyacrylates with organic photoactive units. The final hybrid nano-systems can perform selective removal and photodegradation of the contaminants at the polymer/water interface until mineralization.5 The patented polymer materials are currently involved in the industrial scale up activities, as well as the technology transfer process, including business study and marketing analysis; d)formulation and characterization of new bio-based polymer nanocomposites for the realization of rigid and sustainable packaging. Study of the degradation induced by UV light irradiation and by exposure to marine environment.6 Acknowledgements: the authors really thank all the people and institution involved in the projects Papillion, Clean, Antìbio, Samothrace, CrioPura References [1]. Submitted: Chemosphere [2]. Leonardi M., Caruso M.G., Carroccio S.C., Boninelli S., Curcuruto G., Zimbone M., Allegra M., Torrisi B., Ferlito F., Miritello M.; Smart nanocomposites of chitosan/alginate nanoparticles loaded with copper oxide as alternative nanofertilizers; Environ. Sci.: Nano, 2021, 8, 174187. [3]. Brevetto e CEJ 2020 [4]. Zagni C., Dattilo S., Mecca T., Gugliuzzo C., Scamporrino A. A., Privitera V., Puglisi R., Carroccio S. C.; Single and dual polymeric sponges for emerging pollutants removal, European Polymer Journal, 2022, 179, 111556

We report on lasing from a new organic mixture, in which a high resolution one dimensional reflection hologram is recorded via blue laser light irradiation at ? = 457.9 nm. The mixture is made by a photo-sensitized acrylate (di-pentaerythrithol-penta/hexa-acrylate) blended with halo-alkanes (1-bromo-hexane and 1-bromo-butane).The halo-alkanes mixture is selected on the basis of its ability to originate phase-separation from the acrylate during the photo-polymerization process and for its relatively low refractive index value. This last property allows the achievement of a good dielectric contrast between polymer-rich and haloalkane-rich layers constituting a one dimensional grating. The recorded structures show a narrow reflection peak and a 40% value diffraction efficiency. The addition of a small percentage (10 M) of a fluorescent molecule (9-[2-(Ethoxycarbonyl)phenyl]-N-ethyl-6-(ethylamino)-2,7-dimethyl-3H-xanthen-3-iminium chloride) allows lasing when the structure is optically pumped with a pulsed laser. The reflected grating peak (? = 563 nm) is indeeed tuned to fall inside the emission band of the fluorescent molecule. The periodic grating selects and amplifies only a very narrow band of frequencies which represent our laser radiation.

We report on the optical characterization of very high-efficiency and high-resolution holographic volume phase transmission gratings. The gratings are recorded in a new photo-polymerizable mixture made by epoxy-resin and multi-acrylate. The epoxy-resin used is known to make tenacious acrylate-based films. The holographic mixture contains two photo-initiators, the synergic effect of which enables a reliable photo-polymerization process in the visible region of the electromagnetic spectrum. The recorded holograms are mechanically stable, show long-term temporal stability and very high values of diffraction efficiency, coupled with good angular selectivity due to a relatively narrow band of wavelengths. We measured the intensity of the transmitted beam and calculated the intensity of the diffracted beam at different wavelengths, deriving the refractive index modulation and the grating pitch by fitting the experimental data with a slightly modified theoretical approach. These kind of mixtures can be used in several fields of application, such as chemical or bio-sensors, high resolution optical sensors, high-density optical data storage, encryption and security.

The shelf life of a food products is the time during which food remains safe under defined storage conditions, maintaining the desired sensory, chemical, physical and biological characteristics in compliance with the label declaration [1]. Many physical factors could influence the shelf life like temperature changes, light exposure, gases transmission, humidity changes as well as contamination with microorganism and spores. Packaging plays a critical role in extending the shelf life of food products, preventing or reducing the environmental interactions. Recent EU regulations promoted a growing interest in bio-based materials production for replacement of the traditional petro-plastics, limiting the accumulation problem and reducing the environmental pollution. NMR spectroscopy represents a valid approach to evaluate the effects of packaging on the shelf life of foods and possible chemical contamination. [2]. Moreover, NMR spectroscopy has already demonstrated its pivotal role in metabolomics [3,4] allowing to monitor in a single experiment different classes of chemical compounds, and its capabilities in microstructural characterization of packaging materials. In this study the analyses of polar and organic extracts of seasoned zucchini stored at 4°C for 35 days, in plastic and compostable trays, performed by NMR in combination with chemometrics, are reported.

The needle phobia includes the fear for all the medical procedures involving injections and the use of syringes. In some cases, the fear of needles is so great even before the indentation, inducing a serious of psychological complication and causing difficulties with managing strong emotion and sensation. The design and development of technological solutions that could overcome this problem is very interesting from a social and industrial point of view. In this paper, we focus on the fabrication of polymeric micro-needles as a user-driven device able to hinder needle-phobia for drug-delivery and sensing purposes. We focus on the fabrication of polymeric needle that in case of use for children appear as a friendly solution, we will focus on the fabrication of a sort of patch that could be easily applied avoiding all the invasive procedures usually involved in case of conventional syringes. We are confident that the children- driven device could open to application also for adults or elderly people involved by the needle phobia or more in general exhausted of the conventional therapies.

Lezione a scopo divulgativo presso la Scuola di Scienze Matematiche, Fisiche e Naturali, nell'ambito di UNITE, l'Università della Terza Età dell'Università degli Studi di Genova.

Polycyclic hydrocarbons with nonzero radical character have attracted enormous interest as potential active media for organic electronics and spintronics. In this context, indenofluorenes are an intriguing class of formally antiaromatic, biradical materials with a radical character that depends on the connectivity of their six- and five-membered rings. Synthesis of indenofluorene polymers and related compounds, first achieved in the early '90s with the production of ladder-type chains, represents a major step toward incorporation of these systems into devices. However, solution-based synthetic protocols require bulky protecting groups to stabilize the most reactive sites and, at the same time, to improve solubility and processability of such compounds. The preparation of various pristine - that is, unprotected--indenofluorene polymers has recently become possible via the on-surface synthesis approach, where the resulting nanostructures are supported and efficiently stabilized by the underlying substrate in ultrahigh vacuum conditions. Here, an overview of these recent works is given, with a focus on synthetic challenges, structural details and electronic properties.

The advantages of additive manufactured scaffolds, as custom-shaped structures with a completely interconnected and accessible pore network from the micro- to the macroscale, are nowadays well established in tissue engineering. Pore volume and architecture can be designed in a controlled fashion, resulting in a modulation of scaffold's mechanical properties and in an optimal nutrient perfusion determinant for cell survival. However, the success of an engineered tissue architecture is often linked to its surface properties as well. The aim of this study was to create a family of polymeric pastes comprised of poly(ethylene oxide therephthalate)/poly(butylene terephthalate) (PEOT/PBT) microspheres and of a second biocompatible polymeric phase acting as a binder. By combining microspheres with additive manufacturing technologies, we produced 3D scaffolds possessing a tailorable surface roughness, which resulted in improved cell adhesion and increased metabolic activity. Furthermore, these scaffolds may offer the potential to act as drug delivery systems to steer tissue regeneration.

Mixed-matrix membranes (MMMs) are membranes that are composed of polymers embedded with inorganic particles. By combining the polymers with the inorganic fillers, improvements can be made to the permeability compared to the pure polymer membranes due to new pathways for gas transport. However, the fillers, such as hyper cross-linked polymers (HCP), can also help to reduce the physical aging of the MMMs composed of a glassy polymer matrix. Here we report the synthesis of two novel HCP fillers, based on the Friedel-Crafts reaction between a tetraphenyl methane monomer and a bromomethyl benzene monomer. According to the temperature and the solvent used during the reaction (dichloromethane (DCM) or dichloroethane (DCE)), two different particle sizes have been obtained, 498 nm with DCM and 120 nm with DCE. The change in the reaction process also induces a change in the surface area and pore volumes. Several MMMs have been developed with PIM-1 as matrix and HCPs as fillers at 3% and 10wt % loading. Their permeation performances have been studied over the course of two years in order to explore physical aging effects over time. Without filler, PIM-1 exhibits the classical aging behavior of polymers of intrinsic microporosity, namely, a progressive decline in gas permeation, up to 90% for CO permeability. On the contrary, with HCPs, the physical aging at longer terms in PIM-1 is moderated with a decrease of 60% for CO permeability.C spin-lattice relaxation times (T1) indicates that this slowdown is related to the interactions between HCPs and PIM-1.