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.

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.

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.

Contact Resistance in Ambipolar Organic Field-Effect Transistors Measured by Confocal Photoluminescence Electro-Modulation Microscopy.

Although it is theoretically expected that all organic semiconductors support ambipolar charge transport, most organic transistors either transport holes or electrons effectively. Single-layer ambipolar organic field-effect transistors enable the investigation of different mechanisms in hole and electron transport in a single device since the device architecture provides a controllable planar pn-junction within the transistor channel. However, a direct comparison of the injection barriers and of the channel conductivities between electrons and holes within the same device cannot be measured by standard electrical characterization. This article introduces a novel approach for determining threshold gate voltages for the onset of the ambipolar regime from the position of the pn-junction observed by photoluminescence electro-modulation (PLEM) microscopy. Indeed, the threshold gate voltage in the ambipolar bias regime considers a vanishing channel length, thus correlating the contact resistance. PLEM microscopy is a valuable tool to directly compare the contact and channel resistances for both carrier types in the same device. The reported results demonstrate that designing the metal/organic-semiconductor interfaces by aligning the bulk metal Fermi levels to the highest occupied molecular orbital or lowest unoccupied molecular orbital levels of the organic semiconductors is a too simplistic approach for optimizing the charge-injection process in organic field-effect devices.

Graphene Oxide Promotes Site-Selective Allylic Alkylation of Thiophenes with Alcohols.

The graphene oxide (GO) assisted allylic alkylation of thiophenes with alcohols is presented. Mild reaction conditions and a low GO loading enabled the isolation of a range of densely functionalized thienyl and bithienyl compounds in moderate to high yields (up to 90%). The cooperative action of the Brønsted acidity, epoxide moieties, and π-surface of the 2D-promoter is highlighted as crucial in the reaction course of the present Friedel-Crafts-type protocol.

A time-temperature integrator based on fluorescent and polymorphic compounds.

Despite the variety of functional properties of molecular materials, which make them of interest for a number of technologies, their tendency to form inhomogeneous aggregates in thin films and to self-organize in polymorphs are considered drawbacks for practical applications. Here, we report on the use of polymorphic molecular fluorescent thin films as time temperature integrators, a class of devices that monitor the thermal history of a product. The device is fabricated by patterning the fluorescent model compound thieno(bis)imide-oligothiophene. The fluorescence colour of the pattern changes as a consequence of an irreversible phase variation driven by temperature, and reveals the temperature at which the pattern was exposed. The experimental results are quantitatively analysed in the range 20-200°C and interpreted considering a polymorph recrystallization in the thin film. Noteworthy, the reported method is of general validity and can be extended to every compound featuring irreversible temperature-dependent change of fluorescence.

π-Core tailoring for new high performance thieno(bis)imide based n-type molecular semiconductors.

The synthesis and characterization of two thieno(bis)imide based n-type semiconductors with electron mobilities of up to 0.3 cm(2) V(-1) s(-1) are described. The relationships between the electronic features of the π-inner core and the functional properties of the new materials are also discussed.

Live-cell-permeant thiophene fluorophores and cell-mediated formation of fluorescent fibrils.

In our search for thiophene fluorophores that can overcome the limits of currently available organic dyes in live-cell staining, we synthesized biocompatible dithienothiophene-S,S-dioxide derivatives (DTTOs) that were spontaneously taken up by live mouse embryonic fibroblasts and HeLa cells. Upon treatment with DTTOs, the cells secreted nanostructured fluorescent fibrils, while cell viability remained unaltered. Comparison with the behavior of other cell-permeant, newly synthesized thiophene fluorophores showed that the formation of fluorescent fibrils was peculiar to DTTO dyes. Laser scanning confocal microscopy of the fluorescent fibrils showed that most of them were characterized by helical supramolecular organization. Electrophoretic analysis and theoretical calculations suggested that the DTTOs were selectively recognized by the HyPro component of procollagen polypeptide chains and incorporated through the formation of multiple H-bondings.

Testing oligothiophene fluorophores under physiological conditions. Preparation and optical characterization of the conjugates of bovine serum albumin with oligothiophene N-hydroxysuccinimidyl esters.

Bovine serum albumin (BSA) was reacted with linear and newly synthesized branched oligothiophene N-hydroxysuccinimidyl ester fluorophores (TSEs) in moderately basic carbonate buffer solution. Optically stable BSA-TSE conjugates were obtained with a degree of labeling depending on experimental conditions. Conjugates with high fluorophore to BSA ratios (F/BSA = 8) displayed fluorescence quantum yields in the range of 10-30% in water at pH = 7.2, comparable to the quantum yield (25%) of the BSA-FITC conjugate prepared under the same conditions and with the same degree of labeling.

Oligothiophene molecular beacons.

Oligomers of thiophene are widely studied compounds for their electronic and optoelectronic properties. Despite their strong fluorescence, their use as markers for biomolecules, especially for oligonucleotides (ONs), is still largely unexplored. Here, we describe the synthesis of a series of ON molecular beacons employing different oligothiophenes as fluorescent probes and discuss their fluorescence emissions in comparative experiments with and without dabcyl as a quencher, in their hairpin and linear conformations, and as duplexes after hybridization with a complementary target.