Tackling Performance Challenges in Organic Photovoltaics: An Overview about Compatibilizers

Organic Photovoltaics (OPVs) based on Bulk Heterojunction (BHJ) blends are a mature technology. Having started their intensive development two decades ago, their low cost, processability and flexibility rapidly funneled the interest of the scientific community, searching for new solutions to expand solar photovoltaics market and promote sustainable development. However, their robust implementation is hampered by some issues, concerning the choice of the donor/acceptor materials, the device thermal/photo-stability, and, last but not least, their morphology. Indeed, the morphological profile of BHJs has a strong impact over charge generation, collection, and recombination processes; control o…

Protective Effects of L- and D-Carnosine on R-Crystallin Amyloid Fibril Formation: Implications for Cataract Disease

Mildly denaturing conditions induce bovine ?-crystallin, the major structural lens protein, to self-assemble into fibrillar structures in vitro. The natural dipeptide L-carnosine has been shown to have potential protective and therapeutic significance in many diseases. Carnosine derivatives have been proposed as potent agents for ophthalmic therapies of senile cataracts and diabetic ocular complications. Here we report the inhibitory effect induced by the peptide (L- and D-enantiomeric form) on ?-crystallin fibrillation and the almost complete restoration of the chaperone activity lost after denaturant and/or heat stress. Scanning force microscopy (SFM), thioflavin T, and a turbidimetry ass…

Multi-doped Brookite-Prevalent TiO2 Photocatalyst with Enhanced Activity in the Visible Light

© 2018 Springer Science+Business Media, LLC, part of Springer Nature Abstract: Enabling solar and/or visible light-driven photocatalysis is a crucial step to access innovative applications in environmental science and sustainable energy. Titanium dioxide is the most used photocatalyst because of its low cost and toxicity, however it is also limitedly active under visible light irradiation due to its wide band gap. Among its polymorphs, brookite holds promising optoelectronic properties for visible light photocatalysis, which have to the best of our knowledge been limitedly exploited. Here, a C,S,N-doped brookite-based TiO2has been prepared via a rapid one-pot sol–gel synthesis. Besides subs…

THE SAN VITO WOODEN PULPIT FROM MUSEO DIOCESANO OF PALERMO, ITALY: MULTIDISCIPLINARY APPROACH AND ANALYTICAL TECHNIQUES FOR DATING AND RESTORATION

The aim of the present research is to investigate the constitutive materials and the execution techniques of San Vito wooden pulpit from Museo Diocesano of Palermo (Italy) and to provide helpful information to dating it in addition to technical, historical and artistic evaluations. The pulpit, attributed to unknown artist, belongs to the decorative arts and the most relevant feature is its double dating, in addition to the singular painting technique: it has a linear structure typical of XIXth century and three polychrome and gilded panels probably dated to the end of XVIIth century. This paper describes the application of analytical techniques (imaging diagnostics techniques, Scanning Elec…

Carnosine Inhibits Aβ42Aggregation by Perturbing the H-Bond Network in and around the Central Hydrophobic Cluster

Aggregation of the amyloid-β peptide (Aβ) into fibrillar structures is a hallmark of Alzheimer's disease. Thus, preventing self-assembly of the Aβ peptide is an attractive therapeutic strategy. Here, we used experimental techniques and atomistic simulations to investigate the influence of carnosine, a dipeptide naturally occurring in the brain, on Aβ aggregation. Scanning force microscopy, circular dichroism and thioflavin T fluorescence experiments showed that carnosine does not modify the conformational features of Aβ42 but nonetheless inhibits amyloid growth. Molecular dynamics (MD) simulations indicated that carnosine interacts transiently with monomeric Aβ42 by salt bridges with charge…

Improved Photocatalytic Activity of Polysiloxane TiO2 Composites by Thermally Induced Nanoparticle Bulk Clustering and Dye Adsorption

Fine control of nanoparticle clustering within polymeric matrices can be tuned to enhance the physicochemical properties of the resulting composites, which are governed by the interplay of nanoparticle surface segregation and bulk clustering. To this aim, out-of-equilibrium strategies can be leveraged to program the multiscale organization of such systems. Here, we present experimental results indicating that bulk assembly of highly photoactive clusters of titanium dioxide nanoparticles within an in situ synthesized polysiloxane matrix can be thermally tuned. Remarkably, the controlled nanoparticle clustering results in improved degradation photocatalytic performances of the material under …

Amperometric Biosensor and Front-End Electronics for Remote Glucose Monitoring by Crosslinked PEDOT-Glucose Oxidase

Focusing on the interplay between interface chemistry, electrochemistry, and integrated electronics, we show a novel low-cost and flexible biosensing platform for continuous glucose monitoring. The amperometric biosensing system features a planar three-electrode structure on a plastic substrate, and a wireless near-field communication-powered electronic system performing sensor analog front-end, A/D conversion, digital control, and display tasks. The working electrode is made of electropolymerized poly (3,4-ethylenedioxythiophene) film onto a polyethylene terephthalate/gold electrode followed by immobilization of cross-linked glucose oxidase by glutaraldehyde. The advantages offered by such…

Substrate and atmosphere influence on oxygen p-doped graphene

Abstract The mechanisms responsible for p-type doping of substrate supported monolayer graphene (Gr) by thermal treatments in oxygen ambient have been investigated by micro-Raman spectroscopy, atomic force microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS), considering commonly employed dielectric substrates, such as SiO 2 and Al 2 O 3 thin films grown on Si. While a high p-type doping (∼10 13  cm −2 ) is observed for Gr on SiO 2 , no significant doping is found for Gr samples on the Al 2 O 3 substrate, suggesting a key role of the Gr/SiO 2 interface states in the trapping of oxygen responsible for the Gr p-type doping. Furthermore, we investigated the doping stability of Gr on SiO…

SPM and TOF-SIMS investigation of the physical and chemical modification induced by tip writing of self-assembled monolayers

Abstract The nanoelectrochemical modification of alkyl self-assembled monolayers (SAMs) obtained on hydrogenated silicon surfaces via radical-initiated reactions of 1-octadecene has been investigated. Scanning Probe Microscopy (SPM) showed that the modification of the organic layer occurs by applying either positive or negative biases to the tip at a threshold of about ±5 V. When the bias absolute value was ≤6 V, the height of the monolayer was only faintly modified, whereas a consistent increase in tip/sample friction force was observed, in agreement with the formation of hydrophilic moieties at the organic surface. In addition to the increase of friction, bias absolute values larger than …

Poly(alkoxyphenylene-thienylene) Langmuir-Schäfer thin-films for advanced performance transistors

Solution processed Langmuir-Scha ̈fer and cast thin films of regioregular poly(2,5-dioctyloxy-1,4- phenylene-alt-2,5-thienylene) are investigated as transistor active layers. The study of their field-effect properties evidences that no transistor behavior can be seen with a cast film channel material. This was not surprising considering the twisted conformation of the polymer backbone predicted by various theoretical studies. Strikingly, the Langmuir-Scha ̈fer (LS) thin films exhibit a field-effect mobility of 5 × 10-4 cm2/V‚s, the highest attained so far with an alkoxy-substituted conjugated polymer. Extensive optical, morphological, and structural thin-film characterization supports the a…

On the Interaction between 1D Materials and Living Cells

One-dimensional (1D) materials allow for cutting-edge applications in biology, such as single-cell bioelectronics investigations, stimulation of the cellular membrane or the cytosol, cellular capture, tissue regeneration, antibacterial action, traction force investigation, and cellular lysis among others. The extraordinary development of this research field in the last ten years has been promoted by the possibility to engineer new classes of biointerfaces that integrate 1D materials as tools to trigger reconfigurable stimuli/probes at the sub-cellular resolution, mimicking the in vivo protein fibres organization of the extracellular matrix. After a brief overview of the theoretical models r…

Polychrome wood sculpture depicting The Madonna del Soccorso or della Mazza from the Archdiocese of Palermo: an integrated analytical approach for the restoration

In this study the Madonna del Soccorsoo della Mazza wooden sculpture has been analysed by an interdisciplinary and integrated approach. The polychrome sculpture, dating back to the 18thcentury, comes from the church of the Madonna del Soccorso or della Mazza (1604) situated in Via Maqueda, in Palermo and it was placed on the main recess of the altar. All steps of the conservation project, from the preliminary study to the choice of materials and the restoration procedures have been accompanied and supported by diagnostic and scientific analysis. In order to evaluate the state of conservation of the sculpture and the technique employed to construct the support, computer tomography study was …

Artificial Biosystems by Printing Biology

The continuous progress of printing technologies over the past 20 years has fueled the development of a plethora of applications in materials sciences, flexible electronics, and biotechnologies. More recently, printing methodologies have started up to explore the world of Artificial Biology, offering new paradigms in the direct assembly of Artificial Biosystems (small condensates, compartments, networks, tissues, and organs) by mimicking the result of the evolution of living systems and also by redesigning natural biological systems, taking inspiration from them. This recent progress is reported in terms of a new field here defined as Printing Biology, resulting from the intersection betwee…

Autonomous molecularly crowded confinement in inkjet printed femtoliter-scale aqueous compartments

Natural evolution has chosen the localization of biomolecular processes into crowded sub-cellular femtoliter (fL) scale compartments for organizing complex biological processes. [1] Many synthetic biology platforms with life-like activities have been able to mimic these systems under different compartment sizes regimes. [2] However, the fabrication of crowded compartments down to sub-cellular scales is challenging, mainly because of high surface-volume ratio of these systems, finally compromising the stability of the encapsulated biomolecules. In this regard, we here bridge this gap by showing the possibility to produce femtoliter-scale aqueous droplets using a novel inkjet printing approac…

(E)-2-Cyano-3-(5′-piperidin-1-yl-2,2′-bithien-5-yl)acrylic Acid: A Fluorescent Probe for Detecting Prefibrillar Oligomers

The synthesis of (E)-2-cyano-3-(5′-piperidin-1-yl-2,2′-bithien-5-yl)acrylic acid, a novel amyloid aggregation fluorescent probe, is reported. This new probe is able to monitor soluble oligomeric aggregates after 24 h, at which time Thioflavin T emission, commonly used to monitor amyloid fibril formation, remains unchanged. Atomic force microscopy, native polyacrylamide gel electrophoresis, and dynamic light scattering confirm that the earlier stages of aggregation are prefibrillar oligomeric species not possessing the amyloid structure. This new molecular scaffold expands the toolbox of fluorescent probes for the identification of prefibrillar oligomers, which is needed in studies aimed at …

Mastering the Tools: Natural versus Artificial Vesicles in Nanomedicine

Naturally occurring extracellular vesicles and artificially made vesicles represent important tools in nanomedicine for the efficient delivery of biomolecules and drugs. Since its first appearance in the literature 50 years ago, the research on vesicles is progressing at a fast pace, with the main goal of developing carriers able to protect cargoes from degradation, as well as to deliver them in a time- and space-controlled fashion. While natural occurring vesicles have the advantage of being fully compatible with their host, artificial vesicles can be easily synthetized and functionalized according to the target to reach. Research is striving to merge the advantages of natural and artifici…

Preface

Beta-amyloid monomers are neuroprotective

The 42-aa-long β-amyloid protein—Aβ1-42—is thought to play a central role in the pathogenesis of Alzheimer's disease (AD) (Walsh and Selkoe, 2007). Data from AD brain (Shankar et al., 2008), transgenic APP (amyloid precursor protein)-overexpressing mice (Lesné et al., 2006), and neuronal cultures treated with synthetic Aβ peptides (Lambert et al., 1998) indicate that self-association of Aβ1-42monomers into soluble oligomers is required for neurotoxicity. The function of monomeric Aβ1-42is unknown. The evidence that Aβ1-42is present in the brain and CSF of normal individuals suggests that the peptide is physiologically active (Shoji, 2002). Here we show that synthetic Aβ1-42monomers support …

Scientific studies for the restoration of a wood painting of the Galleria Interdisciplinare Regionale della Sicilia—Palazzo Mirto di Palermo

Abstract The Ritratto muliebre, referring to Venus, is a panel painting, oil on wood, attributed to unknown artist and probably dated to the second half of 16th century, today conserved in the Galleria Interdisciplinare Regionale della Sicilia—Palazzo Mirto of Palermo. The aim of this research was to assess the techniques used to decorate the wooden painting and to verify the state of conservation of the artwork's materials but also to identify the previous treatments. This study was the essential condition to plane and perform the correct restoration. For this reason, an integrated analytical approach based on the use of non-invasive and micro-invasive techniques was used, with the aim to …

ELECTRODEPOSITION OF NOVEL POLY(NAPHTHALENEDIIMIDE-QUATERTHIOPHENE) THIN FILMS AND APPLICATIONS IN PLASTIC OPTOELECTRONICS DEVICES

A novel symmetric naphthalenediimide-quaterthiophene derivative (NDIT4d) has been polymerized on different substrates including glassy carbon and ITO/PET electrodes by means of electrochemical methods. XPS and UV-VIS spectroscopy as well as cyclic voltammetry have been employed for characterizing the thin film chemical features, the band gap and the HOMO and LUMO levels. DFT computational studies were in close agreement with the experimental observables also showing intriguing geometrical effects on the band gap energy values. The comparison of the energy levels locations of the electrodeposited poly(naphthalenediimide-quaterthiophene) derivative (e-PNDIT4) and P3HT thin films transferred b…

On the Relationship between Jetted Inks and Printed Biopatterns:Molecular-Thin Functional Microarrays of Glucose Oxidase

Arrays of circular spots of glucose oxidase have been obtained on functionalized silicon oxide by piezoelectric inkjet printing and the enzymatic activity toward glucose recognition has been monitored. The addition of glycerol to the molecular ink allows to obtain high spot definition and resolution (tens of micrometers wide; one molecule tall), but in spite of its well-known structural stabilizing properties, in dynamic conditions it may lead to increased protein stresses. The jetting voltage and pulse length have been found to be critical factors for both activity retention and pattern definition. High voltages and pulse lengths results in stress effects along with the loss of activity, w…

Trehalose effects on α-crystallin aggregates

alpha-Crystallin in its native state is a large, heterogeneous, low-molecular weight (LMW) aggregate that under certain conditions may progressively became part of insoluble high-molecular weight (HMW) systems. These systems are supposed to play a relevant role in eye lens opacification and vision impairment. In this paper, we report the effects of trehalose on alpha-crystallin aggregates. The role of trehalose in alpha-crystallin stress tolerance, chaperone activity and thermal stability is studied. The results show that trehalose stabilizes the alpha-crystallin native structure, inhibits alpha-crystallin aggregation, and disaggregates preformed LMW systems not affecting its chaperone acti…

Temperature and pressure dependence of quercetin-3-O-palmitate interaction with a model phospholipid membrane: film balance and scanning probe microscopy study

The molecular interaction of quercetin-3-O-palmitate (QP) with dimyristoylphosphatidylcholine (DMPC) has been studied. Film balance measurements of the average molecular area vs QP molar fraction in DMPC/QP mixed monolayers showed that relevant positive deviations from ideality, i.e., a less dense monolayer packing, occurred for a temperature of 10 degrees C, below the critical melting transition temperature of DMPC monolayers T c m approximately equal 20 degrees C), while ideal behavior was observed at 37 degrees C, above this phase transition temperature. The positive deviation observed at low temperatures in the average molecular area increased with the surface pressure. Scanning probe m…

Ethane-Bridged Zinc-Porphyrin Dimers in Langmuir-Shäfer Thin Films: Structural and Spectroscopic Properties

This work reports on the structural and spectroscopic properties of ethane-bridged Zn porphyrin dimers (1) in Langmuir-Scha¨fer (LS) thin films by combining scanning force microscopy (SFM) with film balance, UV-vis absorption, fluorescence, and nanosecond laser flash photolysis measurements. Results show that depending on the surface pressure the Langmuir films of pure 1 can be arranged in two different condensed phases, whereas SFM of the LS films shows characteristic fractal networks constituted by nanoscopic aggregates. The spectral findings agree with a picture in which 1 is apparently present in the anti conformation but aggregated in a sort of H-type structure whose optical features r…

Supra-aggregates of fiber-forming anisotropic molecules.

In this paper, the self-organization of fiber-forming anisotropic molecules is inspected both theoretically and experimentally. In the first part, a theoretical model which extends the de Gennes theory of thin films to assemblies of strongly anisotropic molecules is reported. The model predicts that solid supported thin films made up of fiber-forming discotic molecules can grow with both tangential and radial arrangement of the fibers, respectively leading to the formation of compact and holed supra- aggregates. These last systems form according to the following picture. The tangential growth minimizes the number of unfavorable free ends but introduces elastic strain especially in the centr…

Self-organization and nanostructural control in thin film heterojunctions.

In spite of more than two-decades of studies of molecular self-assembly, the achievement of low cost, easy-to-implement and multi-parameter bottom-up approaches to address the supramolecular morphology in three-dimensional (3D) systems is still missing. In the particular case of molecular thin films, the 3D nanoscale morphology and function are crucial for both fundamental and applied research. Here we show how it is possible to tune the 3D film structure (domain size, branching, etc.) of thin film heterojunctions with nanoscale accuracy together with the modulation of their optoelectronic properties by employing an easy two-step approach. At first we prepared multi-planar heterojunctions w…

Nanostructural depth-profile and field-effect properties of poly(alkoxyphenylene-thienylene) Langmuir-Schäfer thin-films

The correlations between morphological features and field-effect properties of poly(alkoxyphenylene-thiophene) thin Langmuir–Schafer film deposited on differently terminated gate dielectric surfaces, namely bare and methyl functionalized thermal silicon dioxide (t-SiO2), have been systematically studied. The film morphology has been investigated at different film thickness by Scanning Force Microscopy. Films thicker than a few layers show comparable morphology on both dielectric surfaces while differences are seen for the ultra-thin polymer deposit in close proximity to the substrate. Such deposit is notably more heterogeneous on bare t-SiO2, while a more compact and uniform nanogranular st…

Monitoring few molecular binding events in scalable confined aqueous compartments by raster image correlation spectroscopy (CADRICS)

The assembly of scalable liquid compartments for binding assays in array formats constitutes a topic of fundamental importance in life sciences. This challenge can be addressed by mimicking the structure of cellular compartments with biological native conditions. Here, inkjet printing is employed to develop up to hundreds of picoliter aqueous droplet arrays stabilized by oil-confinement with mild surfactants (Tween-20). The aqueous environments constitute specialized compartments in which biomolecules may exploit their function and a wide range of molecular interactions can be quantitatively investigated. Raster Image Correlation Spectroscopy (RICS) is employed to monitor in each compartmen…

Luminometric sub-nanoliter droplet-to-droplet array (LUMDA) and its application to drug screening by phase I metabolism enzymes.

Here we show the fabrication of the Luminometric Sub-nanoliter Droplet-to-droplet Array (LUMDA chip) by inkjet printing. The chip is easy to be implemented and allows for a multiplexed multi-step biochemical assay in sub-nanoliter liquid spots. This concept is here applied to the integral membrane enzyme CYP3A4, i.e. the most relevant enzymatic target for phase I drug metabolism, and to some structurally-related inhibitors.

The zero field self-organization of cobalt/surfactant nanocomposite thin films

Cobalt nanostructures have been prepared by a chemical route based on the Co(II) reduction in the confined space of cobalt bis(2-ethylhexyl)sulfosuccinate (Co(DEHSS)(2)) reverse micelles dispersed in n-heptane. This procedure involves the rapid formation of surfactant softly coated Co nanostructures followed by a slow separation process of the magnetic-field responsive Co/surfactant nanocomposites from the liquid phase. The detailed structure of thin films of the Co/surfactant nanocomposites has been investigated by scanning force microscopy (SFM). The thin films were characterized by different anisotropic features. Micrometric long domains of self-aligned ellipsoidal NPs (tens of nanometer…

The European Young Chemist Award 2018

Young traditions: The 2018 European Young Chemist Award competition was held in Liverpool during the 7th EuCheMS Chemistry Congress continuing the tradition of showcasing and recognizing the excellent research being carried out by young scientists working in the chemical sciences.

Aqueous Processed Biopolymer Interfaces for Single-Cell Microarrays

Single-cell microarrays are emerging tools to unravel intrinsic diversity within complex cell populations, opening up new approaches for the in-depth understanding of highly relevant diseases. However, most of the current methods for their fabrication are based on cumbersome patterning approaches, employing organic solvents and/or expensive materials. Here, we demonstrate an unprecedented green-chemistry strategy to produce single-cell capture biochips onto glass surfaces by all-aqueous inkjet printing. At first, a chitosan film is easily inkjet printed and immobilized onto hydroxyl-rich glass surfaces by electrostatic immobilization. In turn, poly(ethylene glycol) diglycidyl ether is graft…

Biochips for cell biology by combined dip-pen nanolithography and DNA-directed protein immobilization.

A general methodology for patterning of multiple protein ligands with lateral dimensions below those of single cells is described. It employs dip pen nanolithography (DPN) patterning of DNA oligonucleotides which are then used as capture strands for DNA-directed immobilization (DDI) of oligonucleotide-tagged proteins. This study reports the development and optimization of PEG-based liquid ink, used as carrier for the immobilization of alkylamino-labeled DNA oligomers on chemically activated glass surfaces. The resulting DNA arrays have typical spot sizes of 4-5 μm with a pitch of 12 μm micrometer. It is demonstrated that the arrays can be further functionalized with covalent DNA-streptavidi…

Improved performance in flexible organic solar cells by using copolymeric phase-separation modulators

One of the main problems related to the low performance of the organic solar cells (OSCs), concerns the low mobility of the materials constituting the heterojunction. Indeed, the poor charge transport in the active layer is the principal cause of a competition between separation and recombination of the photogenerated carriers. In this regard, a major obstacle to enhance OSCs efficiency is developing strategies to optimize the exciton dissociation and, consequently, the charge collection at the electrodes. Donor and acceptor systems must be well mixed on the length scale of 5 – 20 nm (exciton diffusion length) to meet the criteria for efficient exciton dissociation. In addition, the network…

Investigation of recovery mechanisms in dye sensitized solar cells

Abstract We study the spontaneous recovery phenomenon displayed by solar cells sensitized with a ruthenium complex-based dye N719, which manifests with the increase over the time (from several minutes up to some days) of the short circuit current density J sc and the open circuit voltage V oc , during cell illumination. Under dark conditions the current decreases over time after the application of forward bias voltages. We investigate the effects of temperature and electrolyte composition by means of current–voltage measurements and electrochemical impedance spectroscopy, both under dark and illumination conditions. The main result is that the recovery of the performances depends on the cha…

A supramolecular heteropolyoxopalladate {Pd15} cluster host encapsulating a {Pd2} dinuclear guest: [Pd(II)2⊂{H7Pd(II)15O10(PO4)10}](9-).

A high-nuclearity polyoxopalladate compound, [Pd(II)(2)⊂{H(7)Pd(II)(15)O(10)(PO(4))(10)}](9-) {Pd(II)(17)}, comprising a {Pd(15)} host occupied by a {Pd(2)} guest and the parent pristine "empty" [H(7)Pd(II)(15)O(10)(P(V)O(4))(10)](13-) {Pd(15)} cluster have both been prepared and characterized by single-crystal X-ray crystallography, (31)P NMR, CSI-MS, and XPS. The encapsulated {Pd(2)} has a short Pd(II)-Pd(II) distance within the {Pd(15)} host. Solution studies indicate that the empty host and filled guest complex are in equilibrium with each other, and UV titrations revealed a binding constant of ca. 10(3) for the guest Pd(II) ions, with a binding stoichiometry of almost 2.

Semitransparent Perovskite Solar Cells for Building Integration and Tandem Photovoltaics: Design Strategies and Challenges

Over the past decade, halide perovskite systems have captured widespread attention among researchers since their exceptional photovoltaic (PV) performance was disclosed. The unique combination of optoelectronic properties and solution processability shown by these materials has enabled perovskite solar cells (PSCs) to reach efficiencies higher than 25% at low fabrication costs. Moreover, PSCs display enormous potential for modern unconventional PV applications, since they can be made lightweight, semitransparent (ST), and/or flexible by means of appropriate design strategies. In particular, by enabling transparency and high efficiency simultaneously, ST-PSCs hold great promise for future ve…

Insight into mechanisms of creatinine optical sensing using fluorescein-gold complex

Abstract Creatinine level in biological fluids is a clinically relevant parameter to monitor vital functions and it is well assessed that measuring creatinine levels in the human body can be of great utility to evaluate renal, muscular, or thyroid dysfunctions. The accurate detection of creatinine levels may have a critical role in providing information on health status and represents a tool for the early diagnosis of severe pathologies. Among different methods for creatinine detection that have been introduced and that are evolving with increasing speed, fluorescence-based and colorimetric sensors represent one of the best alternatives, thanks to their affordability, sensitivity and easy r…

Design and synthesis of new trehalose-conjugated pentapeptides as inhibitors of Aβ(1-42) fibrillogenesis and toxicity

Aggregation of the amyloid A? peptide and its accumulation into insoluble deposits (plaques) are believed to be the main cause of neuronal dysfunction associated with Alzheimer's disease (AD); small molecules that can interfere with the A? amyloid fibril formation are therefore of interest for a potential therapeutic strategy. Three new trehalose-conjugated peptides of the well known ?-sheet breaker peptide iA?5p,were synthesized. The disaccharide was covalently attached to different sites of the LPFFD peptide chain, i.e. at the N-terminus, C-terminus or at the Asp side chain. CD spectroscopy in different solvents was used to assess changes in the peptide conformation of these compounds. Th…

Raman Monitoring of Strain Induced Effects in Mechanically Deposited Single Layer Graphene

Graphene is a two dimensional building block for carbon allotropes of many other dimensionality and shows remarkable electronic and optical properties that attract enormous interest. In order to make graphene useful for real technology, a control of its electronic and mechanical properties is a must. In this respect, a crucial step for the use of graphene layers in device fabrication is the deposition onto suitable substrates, understanding the interaction with them. Micromechanical cleavage of graphite has been used to produce high-quality graphene sheets. The aim of this work is to study the strain effects induced in graphene by the deposition process using Raman spectroscopy and scanning…

Semitransparent Design of Planar n-i-p Perovskite Solar Cells using a Cost-Effective, Perovskite-Compatible DMD Structure as the Top Electrode

In recent years, a significant emphasis has been placed on developing multi-functional solar cells that integrate new features such as color and transparency, thereby opening up the possibility of unconventional photovoltaic (PV) applications, including building-integrated PV (BIPV) systems, tandem solar cells, and wearable electronics. In particular, the integration of semitransparent (ST) solar cells into buildings as power-generating windows, facades or other aesthetic architectural elements constitutes one of the most intriguing perspectives [1]. Since silicon-based panels are generally opaque and unaesthetic, there has been a growing research interest in emerging thin-film solar cells …

Programmable Surface Architectures Derived from Hybrid Polyoxometalate-Based Clusters

The exploration of the self-organization of a range of the polyoxometalate-based molecular structures reveals a diverse range of surface patterns and morphologies on solid substrates of technological interest, including methylated and hydroxylated silicon surfaces (namely, SiCH3 and SiOH). By exploiting the interplay between the intrinsic molecular properties and the surface chemistry as well as dynamic spatiotemporal phenomena (e.g., dewetting), we show that these systems can yield 0D, 2D, and 3D architectures via solution deposition at the solid surface, including nanodots, discs, lamellas, porous networks, and layer-by-layer assemblies. In general, we observed that layer-by-layer growth …

Engineering 3D ordered molecular thin films by a nanoscale control

This perspective aims to report on experimental preparation and investigation tools for engineering molecular thin films with a three-dimensional (3D) nanoscale control that is of relevant interest for different emerging applications as well as for the development of calibration standards. Such thin films may be obtained by man-made methods, self-assembly or spatio-temporal self-organization and/or by the combination of these last approaches with external tools. Understanding the main features and the physical-chemistry underlying the related ordering phenomena is in due course and a theoretical framework is under development. In this respect it is of fundamental importance to achieve the a…

Nanostructured molecular surfaces: advances in investigation and patterning tools

This feature article is aimed to showcase advanced soft and radiationless nanotools for the morphological characterization and for the preparation/modification of molecular surfaces, namely solid supported ultrathin films not exceeding 1–2 molecular layers. As to the characterization, the development of dynamic scanning force microscopy in attractive regime is presented as an important progress at least as far as it concerns imaging of nanoscale features of molecular surfaces with minimal probe–sample physical interaction. To date, this tool has been applied only by a few groups in spite of its larger resolution and image quality than the conventional scanning probe methods. As to the prepa…

Inkjet printing methodologies for drug screening

We show for the first time a contactless, low-cost, and rapid drug screening methodology by employing inkjet printing for molecular dispensing in a microarray format. Picoliter drops containing a model substrate (D-glucose)/ inhibitor (D-glucal) couple were accurately dispensed on a single layer consisting of the enzymatic target (glucose oxidase) covalently linked to a functionalized silicon oxide support. A simple colorimetric detection method allowed one to prove the screening capability of the microarray with the possibility to assay with high reproducibility at the single spot level. Measurements of the optical signal as a function of concentration and of time verified the occurrence a…

Assembly of modular asymmetric organic-inorganic polyoxometalate hybrids into anisotropic nanostructures.

Three organic-inorganic hybrid Mn-Anderson polyoxometalates (POMs), with both symmetrical and asymmetrical appended groups, have been synthesized, identified using electrospray mass spectrometry, and isolated using an approach that allows the three AA, BB, and AB compounds to be structurally characterized. Investigation of the self-assembly of the hybrids on hydrophilic surfaces reveals the formation of nanofibres with characteristics that reflect the nature of the substitution of the POM yielding a route to the programmed assembly of anisotropic hybrid nanostructures.

Nonprecious Copper‐Based Transparent Top Electrode via Seed Layer–Assisted Thermal Evaporation for High‐Performance Semitransparent n‐i‐p Perovskite Solar Cells

Semitransparent perovskite solar cells (ST‐PSCs) are highly attractive for applications in building‐integrated photovoltaics as well as in multijunction tandem devices. To fabricate high‐performance ST‐PSCs, suitable transparent top electrodes are strongly needed. Dielectric/metal/dielectric (DMD) multilayer structures have been shown to be promising candidates, though generally based on high‐value metals such as gold or silver, the latter causing also stability issues by reacting with perovskite. Here, a novel DMD transparent electrode based on nonprecious, less‐reactive copper is developed via thermal evaporation and used as a top anode in the fabrication of high‐performance semitranspare…

Enhanced Thin-Film Transistor Performance by Combining 13,6-N-Sulfinylacetamidopentacene with Printed PEDOT:PSS Electrodes

Bottom-contact/bottom-gate organic thin-film transistors (OTFTs) are fabricated using a soluble pentacene precursor (13,6-N-sulfinylacetamidopentacene; SAP) and inkjet printed PEDOT:PSS electrodes on bare SiO2 dielectrics. Saturation mobility, Ion/Ioff ratio, and threshold voltage parameters, respectively, of 0.27 cm2 V−1 s−1, 105, and −4.25 V were measured under ambient conditions after the thermal conversion of SAP to pentacene in 100 μm long channel OTFT devices. The results obtained by the above solution approach are comparable to that of vapor-phase grown pentacene-based OTFTs with photolithographic gold contacts and organic buffer layers and/or inorganic injection layers. The present …

Copper(ii) and zinc(ii) dependent effects on Aβ42 aggregation: a CD, Th-T and SFM study

A? aggregation is a central event in Alzheimer's disease (AD). In vitro evidence indicates that A? aggregation and fibrillogenesis are significantly influenced by the employed experimental conditions. Indeed, although it is widely established that metal ions, such as copper and zinc, have significant effects on the A? aggregation process, their actual role in A? fibrillogenesis is still debated. In this work the effects of a molar excess of zinc(ii) and/or copper(ii) ions on the A?42 aggregation process and the morphology of the resultant aggregates have been compared in samples exhibiting different initial conformations. CD spectroscopy, Th-T-induced fluorescence and Scanning Force Microsc…

Preface

Printing ZnO Inks: From Principles to Devices

Solution-based printing approaches permit digital designs to be converted into physical objects by depositing materials in a layer-by-layer additive fashion from microscale to nanoscale resolution. The extraordinary adaptability of this technology to different inks and substrates has received substantial interest in the recent literature. In such a context, this review specifically focuses on the realization of inks for the deposition of ZnO, a well-known wide bandgap semiconductor inorganic material showing an impressive number of applications in electronic, optoelectronic, and piezoelectric devices. Herein, we present an updated review of the latest advancements on the ink formulations an…

Self-Cleaning ZnO Nanosheets for Piezoelectric Sensors

The design of wearable sensors coupling versatile analytical detection to self-cleaning is a highly desired combination, tackling the need of smart devices in response to the recent virus pandemics. To this aim, this work shows ZnO nanostructures obtained by a mild wet-chemistry approach onto ITO/PET flexible supports, resulting in wearable piezoelectric sensors exhibiting photocatalytic activity. ITO surfaces are treated with 0.5 mM KMnO4 aqueous solution (20 minutes, 90°C); ZnO growth is subsequently carried out by a previously shown wet-chemistry method [1]. SEM analysis shows the presence of a good surface coverage of ZnO nanosheets (NSs) (about 1.5 NSs/μm2) in the case of treated ITO, …

Tailored conjugated polymer Langmuir-Schafer thin films in sensing transistors

Organic Thin Film Transistors (OTFTs) have been fabricated, in a standard bottom gate configuration, with Langmuir-Schäfer (LS) or cast thin films of regioregular poly[1,4-(2,5-dioctyloxyphenylene)-2,5-thiophene], synthesized via an organometallic protocol, as active layers. The transistors electrical characterization has evidenced that LS based devices exhibit better performance level than cast film ones. Appealing perspectives for newly substituted conjugated polymers in OTFT sensing devices are discussed.

Imbibition of Femtoliter-Scale DNA-Rich Aqueous Droplets into Porous Nylon Substrates by Molecular Printing

This work presents the first reported imbibition mechanism of femtoliter (fL)-scale droplets produced by microchannel cantilever spotting (μCS) of DNA molecular inks into porous substrates (hydrophilic nylon). Differently from macroscopic or picoliter droplets, the downscaling to the fL-size leads to an imbibition process controlled by the subtle interplay of evaporation, spreading, viscosity, and capillarity, with gravitational forces being quasi-negligible. In particular, the minimization of droplet evaporation, surface tension, and viscosity allows for a reproducible droplet imbibition process. The dwell time on the nylon surface permits further tuning of the droplet lateral size, in acc…

Superhydrophobic TiO2/Fluorinated Polysiloxane Hybrid Coatings with Controlled Morphology for Solar Photocatalysis

Abstract Technological applications of polysiloxane coatings have been influenced by their intrinsic low surface energy, which increases their water repellence. Accurate control of composition and interfacial properties through the introduction of perfluorinated moieties further lowers the polysiloxane surface energy, while mixing with metal oxide nanoparticles enhances roughness, resulting in a great potential in the development of superhydrophobic materials for photocatalysis. Herein, a series of hydrophobic and superhydrophobic hybrid coatings were prepared by dehydrocoupling and hydrosilylation reactions of polymethylhydrosiloxane with 1H,1H,2H,2H‐perfluorooctyltriethoxysilane and 1,3-d…

Oxidation effects in antiaggregogenic properties of Epigallocatechingallate

Epigallocatechin-gallate (EGCG), the most abundant flavonoid in green tea, has been extensively studied for its potential in the treatment of amyloid related disorders. This molecule was found to modulate abnormal protein self-assembly, reducing resulting cellular toxicity. EGCG is known to suppress or to slow down the aggregation processes of several proteins, thus supporting the idea that general mechanisms regulate its anti-aggregogenic effects and, interestingly, in the oxidised form it demonstrated an higher efficiency in reducing protein aggregation with respect to intact molecule. We here investigate the effects of intact and oxidized EGCG the thermal aggregation pathway of Bovine Se…

An insight into the functionalisation of carbon nanotubes by diazonium chemistry: Towards a controlled decoration

The derivatisation of materials including iron, gold, and carbon by addition of diazonium salts is a reliable process to tune their interfacial interaction with the surrounding media. In this regard, the functionalisation of carbon nanostructures by diazonium chemistry is a versatile strategy to obtain soluble nanomaterials with degrees of functionalisation among the highest ever reported. Starting from these premises we have studied the functionalisation of multi-walled carbon nanotubes by addition of the aryl diazonium salts generated in situ by treatment of 4-methoxyaniline with isopentylnitrite. Following a thorough purification and characterisation protocol (UV-vis, TGA, ATR-IR, cyclic…

Piezoresistive Sensors from Bithiophene-fulleropyrrolidine Bisadducts Thin-Films

The phenomenon of piezoresistivity in materials is based on the separation of conductive domains triggered by mechanical strains, resulting in a variation of the electrical resistance.1 This property is at the core of sensors for wearable electronics, e-skins, human motion detectors and machine learning devices.2 Fundamental requirements include lightness, good transparency, high flexibility and sensitivity to tiny deformations. However, the fabrication of a system integrating all these features is challenging. Herein, we show a semitransparent piezoresistive sensor realized by an electropolymerized bithiophene‐fulleropyrrolidine bisadduct onto ITO/PET3 (see Figure 1a). The good outcome of …

Le indagini scientifiche per lo studio e la conservazione dei beni culturali : un approccio analitico integrato, la conoscenza dei materiali costitutivi e della tecnica esecutiva della Madonna Odigitria di Monreale

The icon Virgin Hodegetria, now in Santa Maria Nuova Cathedral in Monreale near Palermo (Italy), probably dates from the beginning of thirteen century could be considered one of the earliest examples of medieval icon in Sicily. The icon is distinguished from other southern icons by the strong Byzantine matrix and by its size (169x131x3 cm). Since 2015, the icon is part of the Arab-Norman Palermo UNESCO Heritage. This paper will deal with historical and scientific investigations on the icon to better understand the painting materials, the executive technique and to resolve question about on-going restoration in planning a complex conservation project. Examination of the icon was both non-inv…

Polymeric Thin Films for Organic Electronics: Properties and Adaptive Structures

This review deals with the correlation between morphology, structure and performance of organic electronic devices including thin film transistors and solar cells. In particular, we report on solution processed devices going into the role of the 3D supramolecular organization in determining their electronic properties. A selection of case studies from recent literature are reviewed, relying on solution methods for organic thin-film deposition which allow fine control of the supramolecular aggregation of polymers confined at surfaces in nanoscopic layers. A special focus is given to issues exploiting morphological structures stemming from the intrinsic polymeric dynamic adaptation under non-…

Donor–Acceptor Interfaces by Engineered Nanoparticles Assemblies for Enhanced Efficiency in Plastic Planar Heterojunction Solar Cells

Precisely positioning functionalized gold nanoparticles assemblies at planar donor-acceptor interfaces results in 14-fold enhancement of power conversion efficiency in P3HT/PCBM organic solar cells on plastic (ITO/PET) substrates. This result has been achieved by employing naphthalenethiol-capped gold nanoparticles (NT-Au-NPs) produced by laser ablation in liquid and size varied in the 10-30 nm range. Upon surface functionalization with the aromatic thiol, these particles self-assemble in submicrometer aggregates, which give increased light scattering. When these aggregates are deposited in the planar heterojunction between the donor and the acceptor systems, the localized scattering leads …

Tantalum nitride thin film resistors by low temperature reactive sputtering for plastic electronics

This article describes the fabrication and characterisation of tantalum nitride (TaN) thin film for applications in plastic electronics. Thin films of comparable thickness (50-60 nm) have been deposited by RF-magnetron-reactive sputtering at low temperature (100 °C) and their structure and physical (electrical and mechanical) properties have been correlated by using sheet resistance, stress measurements, atomic force microscopy (AFM), XPS, and SIMS. Different film compositions have been obtained by varying the argon to nitrogen flow ratio in the sputtering chamber. XPS showed that 5:1, 2:1 and 1:1 Ar:N 2 ratios gives Ta 2 N, TaN and Ta 3 N 5 phases, respectively. Sheet resistance revealed a…

The European Young Chemists Award 2016

The future is in good hands! The European Young Chemist Award for 2016 was awarded at the 6th EuCheMS Chemistry Congress in Seville. Reflections on the participants and their chemistry from the Convener of the event, Professor Bruno Pignataro, are given in the Guest Editorial.

Carbon nanotubes and organic solar cells

The use of carbon nanotubes in photovoltaics is still challenging due to different issues connected to their synthesis, purification, functionalization, processing and device integration. From this perspective at first we review on selected contributions dealing with the above issues; then we focus on the advantages and limitations of carbon nanotubes for the development of organic solar cells.

Ambipolar MoS2 Transistors by Nanoscale Tailoring of Schottky Barrier Using Oxygen Plasma Functionalization

One of the main challenges to exploit molybdenum disulfide (MoS2) potentialities for the next-generation complementary metal oxide semiconductor (CMOS) technology is the realization of p-type or ambipolar field-effect transistors (FETs). Hole transport in MoS2 FETs is typically hampered by the high Schottky barrier height (SBH) for holes at source/drain contacts, due to the Fermi level pinning close to the conduction band. In this work, we show that the SBH of multilayer MoS2 surface can be tailored at nanoscale using soft O-2 plasma treatments. The morphological, chemical, and electrical modifications of MoS2 surface under different plasma conditions were investigated by several microscopi…

Switching direction of laterally ordered monolayers induced by transfer instability

Langmuir-Blodgett monolayers may show nanoscopic periodic patterns parallel and/or perpendicular to the transfer direction. The experimental findings are interpreted by a nonequilibrium model based on the stability of surfactant concentration and film thickness coupled fluctuations near the meniscus of a surfactant-covered receding thin film. In the high and low transfer speed limits, periodic fluctuations of the fluid subphase thickness, respectively perpendicular and parallel to the transfer, are selected. A qualitative phase diagram shows how transfer speed and film density manage the pattern shape.

ChemInform Abstract: Selecting Speed-Dependent Pathways for a Programmable Nanoscale Texture by Wet Interfaces

The realization of well-defined and ordered structures on the nanoscale is a main issue in nanoscience and nanotechnology, biotechnology and other related fields like plastic or organic electronics. Among the bottom-up approaches, to date, self-assembly (equilibrium aggregates) received a major attention. In spite of this, far from equilibrium conditions allow for the generation of a wider landscape of organized systems depending on the set of control parameters employed. Under an adaptation vision of the structures, here we report some case studies showing how it is possible to programme and control the nanoscale features of ordered super- or supra-aggregates at wet interfaces by modulatin…

Adhesion of liposomes: a quartz crystal microbalance study

Three different systems are presented, exploring the adhesion of liposomes mediated by electrostatic and lipid–protein interactions as well as molecular recognition of ligand receptor pairs. Liposomes are frequently used to gain insight into the complicated processes involving adhesion and subsequent events such as fusion and fission mainly triggered by specific proteins. We combined liposome technology with the quartz crystal microbalance (QCM) technique as a powerful tool to study the hidden interface between the membrane and functionalized surface. Electrostatic attraction and molecular recognition were employed to bind liposomes to the functionalized quartz crystal. The QCM was used to …

Printing Life-Inspired Subcellular Scale Compartments with Autonomous Molecularly Crowded Confinement.

A simple, rapid, and highly controlled platform to prepare life-inspired subcellular scale compartments by inkjet printing has been developed. These compartments consist of fL-scale aqueous droplets (few µm in diameter) incorporating biologically relevant molecular entities with programmed composition and concentration. These droplets are ink-jetted in nL mineral oil drop arrays allowing for lab-on-chip studies by fluorescence microscopy and fluorescence life time imaging. Once formed, fL-droplets are stable for several hours, thus giving the possibility of readily analyze molecular reactions and their kinetics and to verify molecular behavior and intermolecular interactions. Here, this pla…

Preface

Thiophene pyrenyl derivatives for the supramolecular processability of single-walled carbon nanotubes in thin film heterojunction

Abstract A major problem for the use of single-wall carbon nanotubes (SWCNTs) in electronic devices relates to their poor processability. Chemical modification inevitably introduces defects in the nanotube lattice, resulting in a loss of electronic properties. In this contest, we report on a supramolecular approach with the aim of increasing the dispersion of SWCNTs in solution and in organic semiconductor matrices by ensuring the optoelectronic properties. In particular, new pyrenyl derivatives of thiophene have been synthesized and used to improve the solubility of SWCNTs for electron transfer in thin film heterojunction with poly(3-hexylthiophene) (P3HT) as donor system. Photoinduced ele…

Editorial: Young Chemists and the European Young Chemist Award

Symmetric naphthalenediimidequaterthiophenes for electropolymerized electrochromic thin films

A new symmetric naphthalenediimidequaterthiophene (s-NDI2ODT4) was synthesized and exhibited the capability to electropolymerize alone or with EDOT affording polymers with controlled donor/acceptor monomer ratios. s-NDI2ODT4-EDOT-based copolymers showed low band gaps, wide optical absorption ranges extending to the near IR region, tuned electrical properties, thin-film surface morphology and hydrophilicity as well as high coloration efficiency in electrochromic devices.

Printing Biology for Advanced Synthetic Biosystem

Printing technologies represent a powerful tool for the direct micro- and nano- fabrication of biomolecular structures at the interface between life and materials sciences (Arrabito et al., 2012). Their continuous development over the last years has permitted the onset of man-made biosystems with customizable dimensions (from the micron-scale down to the nanometer scale), composition (organic molecules, DNA, proteins, phospholipids), and relevant functions (molecular interactions, drug screening, cellular biointerfaces, cell-like compartments). In this work, we show the possibility to leverage the fabrication of a wide class of solid-supported or liquid-liquid based synthetic compartments b…

Structural and in situ vibrational study of luminescent cluster assembled silicon thin films

A Low Energy Cluster Beam Deposition apparatus is employed to produce cluster assembled silicon thin films (1-500 nm thick) by using a laser vaporization source. The generated clusters are studied since their formation through time of flight mass spectra and the calculated size in the gas phase are compared with those of the deposited aggregates obtained through Dynamic Scanning Force Microscopy. The deposited material is also studied "in situ" by Raman and infrared spectroscopy. The spectra reveal that the as deposited clusters are hydrogenated with negligible amount of oxide. A comparison of the film properties before and after their air exposure shows that the exposition induces a consis…

Sub-Cellular Scale Compartments: Printing Life-Inspired Subcellular Scale Compartments with Autonomous Molecularly Crowded Confinement (Adv. Biosys. 7/2019)

Self-cleaning ZnO/ITO/PET Bending Sensors

The design of multifunctional materials is of pivotal importance for developing wearable biosensors. In particular, the advancement in self-cleaning materials suitable for bending sensors, i.e. devices able to track human body movements for healthcare monitoring [1], has raised much interest in recent pandemic times. Such technology can be facilitated by leveraging piezo-photocatalytic cleaning effects under visible light [2]. Herein, we show a new class of ZnO-based nanosheets (NSs) synthesized in aqueous solution (85 °C, 24 hours) onto seeded or seedless ITO/PET surfaces that couple sensing to photocatalysis. UV-vis and FT-IR spectroscopies show the typical absorption peaks of ZnO. A nano…

Young Chemists: A Source of New Ideas

Young again: A second edition of this special issue has been assembled to honor both the recent participants of the European Young Chemist Award (EYCA) as well as young and emerging scientists from around the world.

Blue light activated photodegradation of biomacromolecules by N-doped titanium dioxide in a chitosan hydrogel matrix

The use of photocatalysis activated by titanium dioxide nanostructured materials is a promising solution for many biomedical applications ranging from drug-free antibacterial to anticancer therapies, as well as for innovative hydrogel-supported phototherapies. This makes the effects of photocatalysis on the structure of biomolecules of a great relevance in order to define the applicability of photocatalytic materials in the biomedical fields. In this work, the effects of nitrogen-doped titanium dioxide (N-TiO2) dispersed in a biocompatible chitosan/PEG hydrogel on myoglobin and bovine serum albumin as target model proteins were investigated. The efficiency of this composite biocompatible ma…

Inkjet printing Ag nanoparticles for SERS hot spots

A novel inkjet printing based approach is developed for the fabrication of a customizable platform on glass substrates allowing for surface enhanced Raman spectroscopy (SERS) detection of analytes up to single hot spots generated by the spontaneous aggregation of Ag nanoparticles (Ag NPs) in pL scale droplets. After drying the printed droplets under ambient conditions, trace amounts of the analyte can be detected by SERS given the proximity to NP hot spots. By employing alizarin (10-5M) as a model system and scaling the ink droplet volume from 1 nL to 10 pL, the absolute quantity of hot spots has been derived in the printed droplets allowing detecting up to a few molecules in proximity to i…

Bending Sensors Based on Thin Films of Semitransparent Bithiophene-Fulleropyrrolidine Bisadducts

In this study, a novel bithiophene‐fulleropyrrolidine bisadducts system (bis‐Th2PC 60 ) was synthesized and electropolymerized by chronoamperometry onto flexible ITO/PET substrates. The resulting semitransparent thin film was characterized by XPS, FT‐IR, cyclic voltammetry and optical techniques, confirming the good outcome of the electropolymerization process. AFM investigations permitted to highlight an inherent disordered granular morphology, in which the grain‐to‐grain separation depends upon the application of bending. The electrical resistance of the thin film was characterized as function of bending (in the range 0°‐90°), showing promising responsivity to low bending angles (10°‐30°)…

Self-Cleaning Bending Sensors Based on Semitransparent ZnO Nanostructured Films

The design of multifunctional nanostructured materials is the key to the development of smart wearable devices. For instance, nanostructures endowed with both piezoelectric and photocatalytic activities could well be the workhorse for solar-light-driven self-cleaning wearable sensors. In this work, a simple strategy for the assembly of a flexible, semitransparent piezophotocatalytic system is demonstrated by leveraging rational wet chemistry synthesis of ZnO-based nanosheets/nanoflowers (NSs/NFs) under basic pH conditions onto flexible ITO/PET supports. A KMnO4 pretreatment before the ZnO synthesis (seeded ZnO) allows for the control of the density, size, and orientation of the NSs/NFs syst…

Selecting speed-dependent pathways for a programmable nanoscale texture by wet interfaces

The realization of well-defined and ordered structures on the nanoscale is a main issue in nanoscience and nanotechnology, biotechnology and other related fields like plastic or organic electronics. Among the bottom-up approaches, to date, self-assembly (equilibrium aggregates) received a major attention. In spite of this, far from equilibrium conditions allow for the generation of a wider landscape of organized systems depending on the set of control parameters employed. Under an adaptation vision of the structures, here we report some case studies showing how it is possible to programme and control the nanoscale features of ordered super- or supra-aggregates at wet interfaces by modulatin…

Aß(25-35) and its C-and/or N-blocked derivatives: copper driven structural features and neurotoxicity

The toxic properties of beta-amyloid protein, Abeta(1-42), the major component of senile plaques in Alzheimer's disease, depend on nucleation-dependent oligomerization and aggregation. In addition, Abeta(1-42) toxicity is favored by the presence of trace metals, which affect the secondary structure of the peptide. A peptide comprising 11 residues within Abeta(1-42) [Abeta(25-35)] aggregates and retains the neurotoxic activity of Abeta(1-42). We have used both Abeta(25-35) and its C-amidated or N-acetylated/C-amidated derivatives to investigate the role of copper(II) in modulating the conformation and aggregation state as well as the neurotoxic properties of amyloid peptides. Electrospray io…

Role of photoactive layer morphology in high fill factor all-polymer bulk heterojunction solar cells

We report on the realization of all-polymer solar cells based on blends of poly(3-hexylthiophene-2,5-diyl) (P3HT) as a donor and poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2)) as an acceptor. High fill factors are demonstrated for the first time in this class of devices suggesting high dissociation efficiency for the bounded electron-hole pairs and balanced electron and hole mobility along the thin films. The use of the high-mobility n-type P(NDI2OD-T2) polymer enables us to overcome one of the problems limiting the efficiency of all-polymer solar cells, resulting in fill factors comparable with those reported for …

Organic Transistors: Supramolecular Order of Solution-Processed Perylenediimide Thin Films: High-Performance Small-Channel n-Type Organic Transistors (Adv. Funct. Mater. 23/2011)

Advances in SPMs for Investigation and Modification of Solid-Supported Monolayers

Improvement in nanotechnology research has been strongly driven by the advancement that nanoscale characterization and manipulation tools made from the beginning. Solidsupported monolayers (SSMs) represent one of the most important systems in nanotechnology. High-quality SSMs may be fabricated at low cost by solution processes employing techniques like self-assembly and Langmuir–Blodgett methods. In the last decade, advances in scanning probe methods provided more and more efficient tools able both to probe with largely improved resolution the morphological features of SSMs and to modify selectively their functional groups. The modified self-assembled monolayers can be used as nanotemplates…

Supramolecular silver polyoxometalate architectures direct the growth of composite semiconducting nanostructures.

Nanosilver on a string: Crystalline silver polyoxovanadate supramolecular architectures are employed as precursors for the synthesis of composite nanowires (see scheme). The nanostructures are composed of semiconducting vanadium oxide which forms wires with high aspect ratios, and are embedded with metallic silver nanoparticles. © 2009 Wiley-VCH Verlag GmbH & Co. KCaA.

Recent advances in upscalable wet methods and ink formulations for printed electronics

This review deals with the use of solution processing approaches for organic electronics with a focus on material ink formulations as well as on their applicability. The solution processing techniques include methods like gravure printing, screen printing and ink-jet printing. Basic principles of each approach are understood and fundamental correlations between material (metals, semiconductors, and dielectrics) ink properties and final device performances can be drawn. Nevertheless, solution processing methods have the potential to evolve as the most promising tools in organic device fabrication techniques and have already been applied successfully in the fields of organic thin film transis…

LANGMUIR-SCHAEFER FILMS OF A NEW CALIX[4]PYRROLE-BASED MACROCYCLE EXHIBITING INDUCED CHIRALITY UPON DIFFERENTIATED BINDING WITH CHIRAL ALCOHOL VAPOURS

Identification of microplastics using 4‐dimethylamino‐4′‐nitrostilbene solvatochromic fluorescence

In this work, we introduce the use of 4-dimethylamino-4'-nitrostilbene (DANS) fluorescent dye for applications in the detection and analysis of microplastics, an impendent source of pollution made of synthetic organic polymers with a size varying from less than 5 mm to nanometer scale. The use of this dye revealed itself as a versatile, fast and sensitive tool for readily discriminate microplastics in water environment. The experimental evidences herein presented demonstrate that DANS efficiently absorbs into a variety of polymers constituting microplastics, and its solvatochromic properties lead to a positive shift of the fluorescence emission spectrum according to the polarity of the poly…

Vertically Aligned Nanowires and Quantum Dots: Promises and Results in Light Energy Harvesting

The synthesis of crystals with a high surface-to-volume ratio is essential for innovative, high-performance electronic devices and sensors. The easiest way to achieve this in integrated devices with electronic circuits is through the synthesis of high-aspect-ratio nanowires aligned vertically to the substrate surface. Such surface structuring is widely employed for the fabrication of photoanodes for solar cells, either combined with semiconducting quantum dots or metal halide perovskites. In this review, we focus on wet chemistry recipes for the growth of vertically aligned nanowires and technologies for their surface functionalization with quantum dots, highlighting the procedures that yie…

DNA-based biosensor on flexible nylon substrate by dip-pen lithography for topoisomerase detection

Dip-pen lithography (DPL) technique has been employed to develop a new flexible biosensor realized on nylon with the aim to detect the activity of human topoisomerase. The sensor is constituted by an ordered array of a DNA substrate on flexible nylon supports that can be exploited as a drug screening platform for anticancer molecules. Here, we demonstrate a rapid protocol that permits to immobilize minute quantities of DNA oligonucleotides by DPL on nylon surfaces. Theoretical and experimental aspects have been investigated to successfully print DNA oligonucleotides by DPL on such a porous and irregular substrate.

Novel benzofulvenes-based polymers: Characterization and employment in flexible electrochromic devices

Benzofulvenes-based monomers have been synthesized for the first time and have been polymerized by means of electrochemical methods onto different electrodic materials. Morphological investigation has been performed by using SEM; electrical and optical properties have been studied by means of both cyclic voltammetry, optical absorption and spectroelectrochemical techniques. Finally, solid state electrochromic devices have been fabricated. They have displayed high optical contrast.

Supramolecular Order of Solution-Processed Perylenediimide Thin Films

N,N ′ -1 H ,1 H -perfl uorobutyl dicyanoperylenecarboxydiimide (PDIF-CN 2 ), a soluble and air stable n-type molecule, undergoes signifi cant reorganization upon thermal annealing after solution deposition on several substrates with different surface energies. Interestingly, this system exhibits an exceptional edge-on orientation regardless of the substrate chemistry. This preferential orientation is rationalized in terms of strong intermolecular interactions between the PDIF-CN 2 molecules. The presence of a pronounced π– π stacking is confi rmed by combining near-edge X-ray absorption fi ne structure spectroscopy (NEXAFS), dynamic scanning force microscopy (SFM) and surface energy measure…

Oil-in-Water fL Droplets by Interfacial Spontaneous Fragmentation and Their Electrical Characterization

Inkjet printing is here employed for the first time as a method to produce femtoliter-scale oil droplets dispersed in water. In particular, picoliter-scale fluorinated oil (FC40) droplets are printed in the presence of perfluoro-1-octanol surfactant at a velocity higher than 5 m/s. Femtoliter-scale oil droplets in water are spontaneously formed through a fragmentation process at the water/air interface using minute amounts of nonionic surfactant (down to 0.003% v/v of Tween 80). This fragmentation occurs by a Plateau-Rayleigh mechanism at a moderately high Weber number (10(1)). A microfluidic chip with integrated microelectrodes allows droplets characterization in terms of number and diamet…

Printing Biology: engineering analytical platforms by molecular inks

Exploring the Interplay Between Ligand Derivatisation and Cation Type in the Assembly of Hybrid Polyoxometalate Mn-Andersons

Herein a library of hybrid Mn-Anderson polyoxometalates anions are presented: 1, [(MnMo6 O18 )((OCH2 )3 -C-(CH2 )7 CHCH2 )2 ](3-) ; compound 2, [(MnMo6 O18 )((OCH2 )3 C-NHCH2 C16 H9 )2 ](3-) ; compound 3, [(MnMo6 O18 )((OCH2 )3 C-(CH2 )7 CHCH2 )1 ((OCH2 )3 C-NHCH2 C16 H9 )1 ](3-) ; compound 4, [(MnMo6 O18 )((OCH2 )3 C-NHC(O)CH2 CHCH2 )2 ](3-) and compounds 5-9, [(MnMo6 O18 )((OCH2 )3 C-NHC(O)(CH2 )x CH3 )2 ]), where x = 4, 10, 12, 14, and 18 respectively. The compounds resulting from the cation exchange of the anions 1-9 to give TBA (a) and DMDOA (b) salts, and additionally for compounds 1, 2 and 3, tetraphenylphosphonium (PPh4 ) (c) salts, are explored at the air/water interface using scan…

La Chimica Europea a Istanbul, al 5° Congresso Euchems

From monolayer to multilayer N-channel polymeric field-effect transistors with precise conformational order

Monolayer field-effect transistors based on a high-mobility n-type polymer are demonstrated. The accurate control of the long-range order by Langmuir-Schafer (LS) deposition yields dense polymer packing exhibiting good injection properties, relevant current on/off ratio and carrier mobility in a staggered configuration. Layer-by-layer LS film transistors of increasing thickness are fabricated and their performance compared to those of spin-coated films.

Enhanced power-conversion efficiency in organic solar cells incorporating copolymeric phase-separation modulators

A new class of copolymers containing oligothiophene moieties with different lengths and fullerene units have been designed and prepared by an easy and inexpensive one-step synthetic approach. The incorporation of small quantities of these copolymers into bulk heterojunction (BHJ) solar cells with donor regioregular polythiophene (P3HT) and an acceptor fullerene derivate (PCBM) results in good control of the phase separation process without further affecting the BHJ optoelectronic properties. Indeed, under thermal annealing these copolymers allow the modulation of the growth of domains whose size depends on the length of the copolymer repetitive units. Domain size on the same length scale as…

Pseudo-Planar Organic Heterojunctions by Sequential Printing of Quasi-Miscible Inks

This work deals with the interfacial mixing mechanism of picoliter (pL)-scale droplets produced by sequential inkjet printing of organic-based inks onto ITO/PET surfaces at a moderately high Weber number (~101). Differently from solution dispensing processes at a high Bond number such as spin coating, the deposition by inkjet printing is strictly controlled by droplet velocity, ink viscosity, and surface tension. In particular, this study considers the interfacial mixing of droplets containing the most investigated donor/acceptor couple for organic solar cells, i.e., poly(3-hexylthiophene) (P3HT) and (6,6)-phenyl-C61-butyric acid methyl ester (PCBM), showing how low-viscosity and low-surfac…

Redox Materials by the Covalent Entrapment of Redox-Active Dirhodium(II,II) Species in a Siloxane Network

Hydrolysis and polycondensation of the coupling agent (aminopropyl)triethoxysilane (APS), axially coordinated to the redox-active complex [Rh 2 (form) 2 (CH 3 COO) 2 -(APS) 2 ], lead to the insertion of redox-active inorganic microdomains into a siloxane network; the new polymers undergo cyclic redox reactions indicating that dirhodium(II,II) centres retain their redox activity even when incorporated into siloxane networks.

SUPERHYDROPHOBIC TIO2-FLUORINATED POLYSILOXANE NANOCOMPOSITES WITH PHOTOCATALYTIC CLEANING ACTIVITY FOR CULTURAL HERITAGE APPLICATIONS

Synergies and compromises between charge and energy transfers in three-component organic solar cells

In this paper, we developed different three-component organic heterojunction structures supported by PET/ITO substrates with the aim to study the possible synergies and/or compromises between charge transfer (CT) and energy transfer (ET) processes in organic solar cells (OSCs). As components, we employed poly(3-hexylthiophene-2,5-diyl) (P3HT; donor), [6,6]-phenyl-C61-butyric acid methyl ester (PCBM; acceptor) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) that is known to give good ET to P3HT. At first, we observed that in a planar heterojunction (PHJ) solar cell, F8BT has to be properly located in between P3HT and PCBM to get a cascade energy level configuration allowing for a b…

Solution Processed Micro- and Nano-Bioarrays for Multiplexed Biosensing

This Feature article reports on solution dispensing methodologies which enable the realization of multiplexed arrays at the micro- and nanoscale for relevant biosensing applications such as drug screening or cellular chips.

Boosting the Performance of One-Step Solution-Processed Perovskite Solar Cells Using a Natural Monoterpene Alcohol as a Green Solvent Additive

The perovskite film is the core of a perovskite solar cell (PSC), and its quality is crucial for the performance of such devices. The morphology, crystallinity, and surface coverage of the perovskite layer greatly affect the power conversion efficiency (PCE), hysteresis, and long-term stability of PSCs. The incorporation of appropriate solvent additives in the perovskite precursor solution is an effective strategy to control the film morphology and reduce the defects and grain boundaries. However, the commonly used solvent additives are environmentally harmful and highly toxic. In this work, α-terpineol (a nontoxic, eco-friendly, and low-cost monoterpene alcohol) is employed for the first t…

Ag nanoparticles agargel nanocomposites for SERS detection of cultural heritage interest pigments

Agarose gel (agargel) composites with commercial and laboratory made silver nanoparticles were prepared by a wet solution method at room temperature. The gel composites were used for pigment extraction and detection by Raman spectroscopy. Red (alizarin) and violet (crystal violet) pigments deposited on paper were extracted by the composites and were investigated by micro-Raman spectroscopy. Evaluation was carried out of the surface-enhanced Raman spectroscopy (SERS) effect induced by the silver nanoparticles embedded in the gel. A kinetic approach as a function of time was used to determine the efficiency of pigments extraction by composites deposition. A non-invasive extraction process of …

Layered Double Hydroxides: A Toolbox for Chemistry and Biology

Layered double hydroxides (LDHs) are an emergent class of biocompatible inorganic lamellar nanomaterials that have attracted significant research interest owing to their high surface-to-volume ratio, the capability to accumulate specific molecules, and the timely release to targets. Their unique properties have been employed for applications in organic catalysis, photocatalysis, sensors, drug delivery, and cell biology. Given the widespread contemporary interest in these topics, time-to-time it urges to review the recent progresses. This review aims to summarize the most recent cutting-edge reports appearing in the last years. It firstly focuses on the application of LDHs as catalysts in re…

SURFACE EFFECTS ON THE GROWTH OF SOLUTION PROCESSED PENTACENE THIN FILMS

13,6-N-Sulfinylacetamidopentacene (SAP) has been transferred on solid substrates both by water-rich environment and organic solvents without altering his chemical structure. Thermal conversion of SAP to pentacene leads to crystals showing similar features of vacuum-sublimated pentacene both in the bulk and thin-film phases. The thin-film phase is strongly affected by the substrate surface properties. Low energy Si-CH3 rich surfaces allow for the formation of compact micrometric crystals following a Volmer-Weber like growth with orientation suitable for field-effect carrier mobility. Screw dislocations along with straight edges are found on these systems as an indication of a loose interlaye…

MATERIALS AND PROCESSING ISSUES FOR THE MANUFACTURING OF INTEGRATED PASSIVE AND ACTIVE DEVICES ON FLEXIBLE SUBSTRATES

Plast_ICs is a Public/Private Laboratory funded by Italian Government aimed to build a novel technological platform for the development of flexible electronics, mainly, but not solely, based on thin inorganic films. Integration of different functions, on single and/or multiple plastic foils, to generate a smart system is the final goal of the project. The building blocks of the platform will be presented, starting from the different plastic substrates characterization, going through the development of active devices, such as thin-film- transistors, and passive devices, like thin-film- resistors, capacitors, inductors. Fully inorganic elementary devices, based on optical patterning and in va…

Ink depletion-free printing of phospholipids micropatches

Organic Thin-Film Transistors with Enhanced Sensing Capabilities

Organic thin-film transistors, used as sensing devices, have been attracting quite a considerable interest lately as they offer advantages such as multi parameter behaviour and possibility to be quite easily molecularly tuned for the detection of specific analytes. Here, a study on the dependences of the devices responses on important parameters such as the active layer thickness and its morphology as well as on the transistor channel length is presented. To introduce the least number of variables the system chosen for this study is quite a simple and well assessed one being based on a thiophene oligomer active layer exposed to 1-butanol vapours.

Self-Organization Pathways and Spatial Heterogeneity in Insulin Amyloid Fibril Formation

At high temperature and low pH, the protein hormone insulin is highly prone to form amyloid fibrils, and for this reason it is widely used as a model system to study fibril formation mechanisms. In this work, we focused on insulin aggregation mechanisms occurring in HCl solutions (pH 1.6) at 60 degrees C. By means of in situ Thioflavin T (ThT) staining, the kinetics profiles were characterized as a function of the protein concentration, and two concurrent aggregation pathways were pointed out, being concentration dependent. In correspondence to these pathways, different morphologies of self-assembled protein molecules were detected by atomic force microscopy images also evidencing the prese…

Organoboron Polymers for Photovoltaic Bulk Heterojunctions

We report on the application of three-coordinate organoboron polymers, inherently strong electron acceptors, in flexible photovoltaic (PV) cells. Poly[(1,4-divinylenephenylene)(2,4,6-triisopropylphenylborane)] (PDB) has been blended with poly(3-hexylthiophene-2,5-diyl) (P3HT) to form a thin film bulk heterojunction (BHJ) on PET/ITO substrates. Morphology may be modulated to give a high percentage of domains (10-20 nm in size) allowing exciton separation. The photoelectric properties of the BHJs in devices with aluminium back electrodes were imaged by light beam induced current (LBIC) and light beam induced voltage (LBIV) techniques. Open circuit voltages, short circuit currents and overall …

On the Interaction of Carbon Nanowires with Noble Metals through a Study of Their Surface-Enhanced Raman Spectra

This paper deals with the interaction of linear carbon chains (polyynes) with silver and gold surfaces in the form of nanometer-sized clusters. Surface-enhanced Raman signals have been detected rev...

Low angle bending detection semi-transparent piezoresistive sensor

We designed, fabricated, and validated a piezoresistive bending sensor, a fundamental component of wearable electronic devices for monitoring human motion. The most diffused opaque carbon-based resistance flex sensors suffer from low detection for small bending angles. The sensor we here present is based on a semi-transparent active material (fulleropyrrolidine bisadducts polymer) and has the remarkable advantage of good electrical properties for low bending angles. The fabrication steps are effective since a pre-patterned ITO/PET surface is functionalized by chronoamperometric deposition, and the silver electrical contacts are inkjet printed. We propose a fitting function of the measured t…

On the trade-off between processability and opto-electronic properties of single wall carbon nanotube derivatives in thin film heterojunctions

A flow functionalization route has been employed to derivatize single wall carbon nanotubes (SWCNTs) by thienylphenyl groups. The SWCNT derivatives in the most soluble fraction have been characterized by thermogravimetric analysis, DLS analysis, DFT calculations, and UV-vis-NIR, microRaman and IR spectroscopies to study the degree of functionalization, the concentration of SWCNTs in solution, the dimension of the aggregates in solutions, the density of defects, and the presence of the thienylphenyl groups. Thin-film heterojunctions made of SWCNT derivatives and poly(3-hexylthiophene) (P3HT) have been prepared by various methods employing the Langmuir–Schaefer technique, spin-coating and the…

CCDC 903781: Experimental Crystal Structure Determination

Related Article: Mali H. Rosnes, Chiara Musumeci, Carine Yvon, Andrew Macdonell,Chullikkattil P. Pradeep, Camillo Sartorio, De-Liang Long,Bruno Pignataro, Leroy Cronin|2013|Small|9|2316|doi:10.1002/smll.201202510

CCDC 903785: Experimental Crystal Structure Determination

Related Article: Mali H. Rosnes, Chiara Musumeci, Carine Yvon, Andrew Macdonell,Chullikkattil P. Pradeep, Camillo Sartorio, De-Liang Long,Bruno Pignataro, Leroy Cronin|2013|Small|9|2316|doi:10.1002/smll.201202510

CCDC 903783: Experimental Crystal Structure Determination

Related Article: Mali H. Rosnes, Chiara Musumeci, Carine Yvon, Andrew Macdonell,Chullikkattil P. Pradeep, Camillo Sartorio, De-Liang Long,Bruno Pignataro, Leroy Cronin|2013|Small|9|2316|doi:10.1002/smll.201202510

CCDC 903782: Experimental Crystal Structure Determination

Related Article: Mali H. Rosnes, Chiara Musumeci, Carine Yvon, Andrew Macdonell,Chullikkattil P. Pradeep, Camillo Sartorio, De-Liang Long,Bruno Pignataro, Leroy Cronin|2013|Small|9|2316|doi:10.1002/smll.201202510

CCDC 903784: Experimental Crystal Structure Determination

Related Article: Mali H. Rosnes, Chiara Musumeci, Carine Yvon, Andrew Macdonell,Chullikkattil P. Pradeep, Camillo Sartorio, De-Liang Long,Bruno Pignataro, Leroy Cronin|2013|Small|9|2316|doi:10.1002/smll.201202510