Selective ion transport in large-area graphene oxide membrane filters driven by the ionic radius and electrostatic interactions.

Filters made of graphene oxide (GO) are promising for purification of water and selective sieving of specific ions; while some results indicate the ionic radius as the discriminating factor in the sieving efficiency, the exact mechanism of sieving is still under debate. Furthermore, most of the reported GO filters are planar coatings with a simple geometry and an area much smaller than commercial water filters. Here, we show selective transport of different ions across GO coatings deposited on standard hollow fiber filters with an area >10 times larger than typical filters reported. Thanks to the fabrication procedure, we obtained a uniform coating on such complex geometry with no cracks or holes. Monovalent ions like Na+ and K+ can be transported through these filters by applying a low electric voltage, while divalent ions are blocked. By combining transport and adsorption measurements with molecular dynamics simulations and spectroscopic characterization, we unravel the ion sieving mechanism and demonstrate that it is mainly due to the interactions of the ions with the carboxylate groups present on the GO surface at neutral pH.

Graphene Oxide-Arginine Composites: Efficient Dual Function Materials for Integrated CO2 Capture and Conversion.

The "on-demand" capture and utilization of CO2 is effectively realized with a readily accessible dual function organic composite. The covalent and controlled derivatization of graphene oxide (GO) surface with naturally occurring arginine led to a "smart" material capable of capturing (chemisorption) CO2 from high-purity flue-gas as well as low-concentration streams (i. e. direct air capture) and concomitant chemical activation toward the incorporation into cyclic carbonates. The overall integrated CO2 capture and conversion (ICCC) strategy has been fully elucidated mechanistically via dedicated computational, spectroscopic and thermal analyses.

Spin-dependent charge transmission through chiral 2T3N self-assembled monolayer on Au.

A gold surface is functionalized by chemisorption of the enantiopure N,N'-bis-[2,2';5',2″]tert-thiophene-5-yl methylcyclohexane-1,2-diamine (2T3N), a chiral oligothiophene derivative, via overnight incubation in a 2T3N ethanol solution. The Au|2T3N interface is characterized by x-ray photoelectron circular dichroism and comparing x-ray photoemission spectroscopy and electro-desorption results. Charge transmission at the Au|2T3N| solution interface is characterized by recording the cyclic voltammetry of the Fe(III)/Fe(II) reversible redox couple, finding a charge transfer rate constant, k°, variation from 1 × 10-1 to 3.3 × 10-2 cm s-1, when comparing the bare Au and the Au|2T3N interfaces, respectively. The "anomalous" high value of k° found for the chiral Au|2T3N interface can be rationalized on the basis of the chiral-induced spin selectivity effect, as further proved by magnetic-conductive atomic force microscopy measurements at room temperature. A spin polarization of about 30% is found.

Chemical Tailoring of ß-Cyclodextrin-Graphene Oxide for Enhanced Per- and Polyfluoroalkyl Substances (PFAS) Adsorption from Drinking Water.

We report on the synthesis of ß-cyclodextrin (ßCD) modified graphene oxide (GO) nanosheets, having different sized alkyl linkers (GO-Cn -ßCD) and their exploitation as sorbent of per- and polyfluoroalkyl substances (PFAS) from drinking water. ßCD were functionalized with a pending amino group, and the resulting precursors grafted to GO nanosheets by epoxide ring opening reaction. Loading of ßCD units in the range 12 %-36 % was estimated by combined XPS and elemental analysis. Adsorption tests on perfluorobutanoic acid (PFBA), a particularly persistent PFAS selected as case study, revealed a strong influence of the alkyl linker length on the adsorption efficiency, with the hexyl linker derivative GO-C6 -ßCD outperforming both pristine GO and granular activated carbon (GAC), the standard sorbent benchmark. Molecular dynamic simulations ascribed this evidence to the favorable orientation of the ßCD unit on the surface of GO which enables a strong contaminant molecules retention.

Recyclable GO-Arginine Hybrids for CO2 Fixation into Cyclic Carbonates.

New covalently modified GO-guanidine materials have been realized in a gram-scale synthesis and purified by an innovative microfiltration. The use of these composites in the fixation of CO2 into cyclic carbonates is demonstrated. Mild operating conditions, high yields (up to 85 %), wide scope (15 examples) and recoverability/reusability (up to 5 cycles) of the material account for the efficiency of the protocol. Dedicated control experiments shed light on the activation modes exerted by GO-l-arginine during the ring-opening/closing synthetic sequence.

Polymorph Separation by Ordered Patterning.

We herein address the problem of polymorph selection by introducing a general and straightforward concept based on their ordering. We demonstrated the concept by the ordered patterning of four compounds capable of forming different polymorphs when deposited on technologically relevant surfaces. Our approach exploits the fact that, when the growth of a crystalline material is confined within sufficiently small cavities, only one of the possible polymorphs is generated. We verify our method by utilizing several model compounds to fabricate micrometric "logic patterns" in which each of the printed pixels is easily identifiable as comprising only one polymorph and can be individually accessed for further operations.

Facile high-yield synthesis and purification of lysine-modified graphene oxide for enhanced drinking water purification.

Lysine-covalently modified graphene oxide (GO-Lys) was prepared by an innovative procedure. Lysine brushes promote enhanced adsorption of bisphenol A, benzophenone-4 and carbamazepine contaminants from tap water, with a removal capacity beyond the state of the art.

Study and application of graphene oxide in the synthesis of 2,3-disubstituted quinolines via a Povarov multicomponent reaction and subsequent oxidation.

The carbocatalyzed synthesis of 2,3-disubstituted quinolines is disclosed. This process involved a three-component Povarov reaction of anilines, aldehydes and electron-enriched enol ethers, which gave the substrate for the subsequent oxidation. Graphene oxide (GO) was exploited as a heterogeneous, metal-free and sustainable catalyst for both transformations. The multicomponent reaction proceeded under simple and mild reaction conditions, exhibited good functional group tolerance, and could be easily scaled up to the gram level. A selection of tetrahydroquinolines obtained was subsequently aromatized to quinolines. The multistep synthesis could also be performed as a one-pot procedure. Investigation of the real active sites of GO was carried out by performing control experiments and a by full characterization of the carbon material by X-ray photoelectron spectroscopy (XPS) and solid-state nuclear magnetic resonance (ssNMR).

Visible-Light Assisted Covalent Surface Functionalization of Reduced Graphene Oxide Nanosheets with Arylazo Sulfones.

We present an environmentally benign methodology for the covalent functionalization (arylation) of reduced graphene oxide (rGO) nanosheets with arylazo sulfones. A variety of tagged aryl units were conveniently accommodated at the rGO surface via visible-light irradiation of suspensions of carbon nanostructured materials in aqueous media. Mild reaction conditions, absence of photosensitizers, functional group tolerance and high atomic fractions (XPS analysis) represent some of the salient features characterizing the present methodology. Control experiments for the mechanistic elucidation (Raman analysis) and chemical nanomanipulation of the tagged rGO surfaces are also reported.

Scalable synthesis and purification of functionalized graphene nanosheets for water remediation.

Microwave (MW) accelerated synthesis combined with microfiltration (MF) on commercial hollow fiber modules enables fast and scalable preparation of highly pure modified graphene oxide nanosheets. The MW-MF procedure is demonstrated on polyethylenimine (PEI) modified GO, and the so-obtained GOPEI is used for simultaneous removal of arsenic and lead from water.

Core-shell graphene oxide-polymer hollow fibers as water filters with enhanced performance and selectivity.

Commercial hollow fiber filters for micro- and ultrafiltration are based on size exclusion and do not allow the removal of small molecules such as antibiotics. Here, we demonstrate that a graphene oxide (GO) layer can be firmly immobilized either inside or outside polyethersulfone-polyvinylpyrrolidone hollow fiber (Versatile PES®, hereafter PES) modules and that the resulting core-shell fibers inherits the microfiltration ability of the pristine PES fibers and the adsorption selectivity of GO. GO nanosheets were deposited on the fiber surface by filtration of a GO suspension through a PES cartridge (cut-off 0.1-0.2 µm), then fixed by thermal annealing at 80 °C, rendering the GO coating stably fixed and unsoluble. The filtration cut-off, retention selectivity and efficiency of the resulting inner and outer modified hollow fibers (HF-GO) were tested by performing filtration on water and bovine plasma spiked with bovine serum albumin (BSA, 66 kDa, ≈15 nm size), monodisperse polystyrene nanoparticles (52 nm and 303 nm sizes), with two quinolonic antibiotics (ciprofloxacin and ofloxacin) and rhodamine B (RhB). These tests showed that the microfiltration capability of PES was retained by HF-GO, and in addition the GO coating can capture the molecular contaminants while letting through BSA and smaller polystyrene nanoparticles. Combined XRD, molecular modelling and adsorption experiments show that the separation mechanism does not rely only on physical size exclusion, but involves intercalation of solute molecules between the GO layers.

Glial Interfaces: Advanced Materials and Devices to Uncover the Role of Astroglial Cells in Brain Function and Dysfunction.

Research over the past four decades has highlighted the importance of certain brain cells, called glial cells, and has moved the neurocentric vision of structure, function, and pathology of the nervous system toward a more holistic perspective. In this view, the demand for technologies that are able to target and both selectively monitor and control glial cells is emerging as a challenge across neuroscience, engineering, chemistry, and material science. Frequently neglected or marginally considered as a barrier to be overcome between neural implants and neuronal targets, glial cells, and in particular astrocytes, are increasingly considered as active players in determining the outcomes of device implantation. This review provides a concise overview not only of the previously established but also of the emerging physiological and pathological roles of astrocytes. It also critically discusses the most recent advances in biomaterial interfaces and devices that interact with glial cells and thus have enabled scientists to reach unprecedented insights into the role of astroglial cells in brain function and dysfunction. This work proposes glial interfaces and glial engineering as multidisciplinary fields that have the potential to enable significant advancement of knowledge surrounding cognitive function and acute and chronic neuropathologies.

On the Nature of Charge-Injecting Contacts in Organic Field-Effect Transistors.

Organic field-effect transistors (OFETs) are key enabling devices for plastic electronics technology, which has a potentially disruptive impact on a variety of application fields, such as health, safety, and communication. Despite the tremendous advancements in understanding the OFET working mechanisms and device performance, further insights into the complex correlation between the nature of the charge-injecting contacts and the electrical characteristics of devices are still necessary. Here, an in-depth study of the metal-organic interfaces that provides a direct correlation to the performance of OFET devices is reported. The combination of synchrotron X-ray spectroscopy, atomic force microscopy, electron microscopy, and theoretical simulations on two selected electron transport organic semiconductors with tailored chemical structures allows us to gain insights into the nature of the injecting contacts. This multiple analysis repeated at the different stages of contact formation provides a clear picture on the synergy between organic/metal interactions, interfacial morphology, and structural organization of the electrode. The simultaneous synchrotron X-ray experiments and electrical measurements of OFETs in operando uncovers how the nature of the charge-injecting contacts has a direct impact on the injection potential of OFETs.

Allylic and Allenylic Dearomatization of Indoles Promoted by Graphene Oxide by Covalent Grafting Activation Mode.

The site-selective allylative and allenylative dearomatization of indoles with alcohols was performed under carbocatalytic regime in the presence of graphene oxide (GO, 10 wt % loading) as the promoter. Metal-free conditions, absence of stoichiometric additive, environmentally friendly conditions (H2 O/CH3 CN, 55 °C, 6 h), broad substrate scope (33 examples, yield up to 92 %) and excellent site- and stereoselectivity characterize the present methodology. Moreover, a covalent activation model exerted by GO functionalities was corroborated by spectroscopic, experimental and computational evidences. Recovering and regeneration of the GO catalyst through simple acidic treatment was also documented.

Control of polymorphism in thiophene derivatives by sublimation-aided nanostructuring.

Here we applied a novel concept of "sublimation-aided nanostructuring" to control the polymorphism of a model material. The process exploits fractional precipitation as a tool for crystallisation in confinement using a templating agent that sublimes away from the system at the end of the process.

Graphene oxide-polysulfone filters for tap water purification, obtained by fast microwave oven treatment.

The availability of clean, pure water is a major challenge for the future of our society. 2-Dimensional nanosheets of GO seem promising as nanoporous adsorbent or filters for water purification; however, their processing in macroscopic filters is challenging, and their cost vs. standard polymer filters is too high. Here, we describe a novel approach to combine graphene oxide (GO) sheets with commercial polysulfone (PSU) membranes for improved removal of organic contaminants from water. The adsorption physics of contaminants on the PSU-GO composite follows Langmuir and Brunauer-Emmett-Teller (BET) models, with partial swelling and intercalation of molecules in between the GO layers. Such a mechanism, well-known in layered clays, has not been reported previously for graphene or GO. Our approach requires minimal amounts of GO, deposited directly on the surface of the polymer, followed by stabilization using microwaves or heat. The purification efficiency of the PSU-GO composites is significantly improved vs. benchmark commercial PSU, as demonstrated by the removal of two model contaminants, rhodamine B and ofloxacin. The excellent stability of the composite is confirmed by extensive (100 hours) filtration tests in commercial water cartridges.

Polydopamine Nanoparticle-Coated Polysulfone Porous Granules as Adsorbents for Water Remediation.

Water purification technologies possibly based on eco-sustainable, low cost, and multifunctional materials are being intensively pursued to resolve the current water scarcity and pollution. In this scenario, polysulfone hollow porous granules (PS-HPGs) prepared from scraps of the industrial production of polysulfone hollow fiber membranes were recently introduced as adsorbents and filtration materials for water and air treatment. Here, we report the functionalization of PS-HPGs with polydopamine (PD) nanoparticles for the preparation of a new versatile and efficient adsorbent material, namely, PSPD-HPGs. The in situ growth of PD under mild alkaline oxidative polymerization allowed us to stably graft PD on polysulfone granules. Enhanced removal efficiency of ofloxacin, an antibiotic drug, with an improvement up to 70% with respect to the pristine PS-HPGs, and removal of Zn(II) and Ni(II) were also observed after PD modification. Remarkably, removal of Cu(II) ions with an efficiency up to 80% was observed for PSPD-HPGs, whereas no adsorption was found for the PD-free precursor. Collectively, these data show that modification with a biocompatible polymer such as PD provides a simple and valuable tool to enlarge the field of application of polysulfone hollow granules for water remediation from both organic and metal cation contaminants.

Polymorphism as an additional functionality of materials for technological applications at surfaces and interfaces.

Polymorphism is a widespread phenomenon occurring in many solid materials having important effects in many scientific disciplines. Since molecular packing can determine the functional properties of materials but is often difficult to control, polymorphism has usually been considered a drawback for technological applications. Thanks to advances in its control over the past few years, polymorphism is now often considered more as an opportunity because it allows a much wider range of functionality in, for example, a solid molecular material, where a corresponding packing type can be selected or even promoted. This tutorial review introduces the reader to the most representative progress in applications of polymorphism as an additional functionality of materials especially in its current promise for technological applications. In addition, it examines the most powerful strategies to control and fully exploit the intrinsic properties of polymorphism and transitions between its various metastable states, through fine-tuning of molecular packing in a reproducible manner. The aim is to create awareness about polymorphism as a novel enabling technology rather than as a problem.

Immobilization of Perylene-3,4,9,10-Tetracarboxylic Dianhydride on Hollow Polysulfone Fibers: Primary Amine Coupling and Fluorescence Reporting.

The fluorescent dye perylene-3,4,9,10-tetracarboxylic dianhydride (PBA) was immobilized onto polysulfone hollow fibers by means of a wet coating procedure. After immobilization, PBA was able to react with primary amines through a double anhydride ring opening reaction. The in situ amine coupling was further revealed by fluorescence analysis. Both emission (534 nm →538 nm) and fluorescence lifetime changes (2.7 ns →3.3 ns) of the dye are a useful tool to detect and visualize the occurrence of the reaction. The successful implementation of amine coupling with a reporting function on polysulfone fibers holds great interest for biomedical applications.