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Pubblicazioni Scientifiche

Pubblicazioni 2018

Data‐Matrix Technology for Multiparameter Monitoring of Cell Cultures

M. Barbalinardo, D. Gentili, F. Lazzarotto, F. Valle, M. Brucale, M. Melucci, L. Favaretto, M. Zambianchi, A.I. Borrachero-Conejo, E. Saracino, V. Benfenati, D. Natalini, P. Greco, M.G. Di Carlo, G. Foschi, M. Cavallini

Small Methods 2018, 2, 1700377.

Abstract

A data-matrix (DM)-technology approach in cell biology is implemented as an efficient method for the multiparameter monitoring of cell cultures. The pro-posed method takes advantage of the know-how developed for fault tolerance in digital information technology by measuring the amount of errors induced by intervening cells upon checking a DM code placed behind them. It gives continuous access to several quantitative parameters of the observed culture, such as cell coverage, mean size, viability, and transfection efficiency.

 

Fluid Mixing for Low‐Power ‘Digital Microfluidics’ Using Electroactive Molecular Monolayers

Maria Serena Maglione, Stefano Casalini, Stamatis Georgakopoulos, Marianna Barbalinardo, Vitaliy Parkula, Núria Crivillers, Concepció Rovira, Pierpaolo Greco, Marta Mas‐Torrent

Small 2018, 14, 1703344.

Abstract

A switchable electrode, which relies on an indium-tin oxide conductive substrate coated with a self-assembled monolayer terminated with an anth-raquinone group (AQ), is reported as an electrowetting system. AQ electro-chemical features confer the capability of yielding a significant modulation of surface wettability as high as 26° when its redox state is switched. Hence, an array of planar electrodes for droplets actuation is fabricated and integrated in a microfluidic device to perform mixing and dispensing on sub-nanoliter scale. Vehiculation of cells across microfluidic compartments is made pos-sible by taking full advantage of surface electrowetting in culture medium.

 

Pubblicazioni 2017

Asymmetric Injection in Organic Transistors via Direct SAM Functionalization of Source and Drain Electrodes

Thomas Mosciatti, Pierpaolo Greco, Tim Leydecker, Matilde Eredia, Fabio Biscarini, and Paolo Samorì

ACS Omega, 2017, 2 (7), pp 3502–3508.

Abstract

The fabrication of organic optoelectronic devices integrating asymmetric electrodes enables optimal charge injection/extraction at each individual metal/semi-conductor interface. This is key for applications in devices such as solar cells, light-emitting transistors, photodetectors, inverters, and sensors. Here, we describe a new method for the asymmetric functionalization of gold electrodes with different thiolated molecules as a viable route to obtain two electrodes with drastically different work function values. The process involves an ad hoc design of electrode geometry and the use of a polymeric mask to protect one electrode during the first functionalization step. Photoelectron yield ambient spectroscopy and X-ray photoelectron spectrometry were used to characterize the energetic properties and the composition of the asymmetrically functionalized electrodes. Finally, we used poly(3-hexylthiophene)-based organic thin-film transistors to show that the asymmetric electronic response stems from the different electronic  structures of the functionalized electrodes.

 

Pubblicazioni 2016

Optical Input/Electrical Output Memory Elements based on a Liquid Crystalline Azobenzene Polymer

Thomas Mosciatti, Sara Bonacchi, Marco Gobbi, Laura Ferlauto, Fabiola Liscio, Loris Giorgini, Emanuele Orgiu, and Paolo Samorì

ACS Appl. Mater. Interfaces 2016, 8(10), 6563-6569.

Abstract

Responsive polymer materials can change their properties when subjected to external stimuli. In this work, thin films of thermotropic poly(metha)acrylate/azobenzene polymers are explored as active layer in light-programmable, electrically readable memories. The memory effect is based on the reversible modifications of the film morphology induced by the photoisomerization of azobenzene mesogenic groups. When the film is in the liquid crystalline phase, the trans → cis isomerization induces a major surface reorganization on the mesoscopic scale that is characterized by a reduction in the effective thickness of the film. The film conductivity is measured in vertical two-terminal devices in which the polymer is sandwiched between a Au contact and a liquid compliant E-GaIn drop. We demonstrate that the trans → cis isomerization is accompanied by a reversible 100-fold change in the film conductance. In this way, the device can be set in a high- or low-resistance state by light irradiation at different wavelengths. This result paves the way toward the potential use of poly(metha)acrylate/azobenzene polymer films as active layer for optical input/electrical output memory elements.

 

Self-protective action in multicomponent fluorescent self-assembled monolayers

Marianna Barbalinardo, Denis Gentili, Marco Brucale, Francesco Valle, Ilse Manet, Giulia Foschi, Massimo Zambianchi, Manuela Melucci and Massimiliano Cavallini

RSC Adv. 2016, 6, 17106-17109.

Abstract

We report on the fabrication of self-protective self-assembled monolayers constituted by a highly fluorescent component and a linear alkyl chain. We demonstrate the formation of an interpenetrated molecular network in which the alkyl component acts as an ultra-thin protective layer able to effectively shield the functional component from several types of aqueous solution.

 

Pubblicazioni 2015

Additive, modular functionalization of reactive self-assembled monolayers: toward the fabrication of multilevel optical storage media

Denis Gentili, Marianna Barbalinardo, Ilse Manet, Margherita Durso, Marco Brucale, Alessio Mezzi, Manuela Melucci and Massimiliano Cavallini

Nanoscale 2015,7, 7184-7188.

Abstract

We report a novel strategy based on iterative microcontact printing, which provides additive, modular functionalization of reactive SAMs by different functional molecules. We demonstrate that after printing the molecules form an interpenetrating network at the SAM surface preserving their individual properties. We exploited the process by fabricating new optical storage media that consist of a multilevel TAG.

 

Amorphous Aggregation of Amyloid Beta 1-40 Peptide in Confined Space

Giulia Foschi, Cristiano Albonetti, Fabiola Liscio, Silvia Milita, Pierpaolo Greco e Fabio Biscarini

ChemPhysChem 2015, 16(16), 3379-3384.

Abstract

The amorphous aggregation of Aβ1-40 peptide is addressed by using micromolding in capillaries. Both the morphology and the size of the aggregates are modulated by changing the contact angle of the sub-micrometric channel walls. Upon decreasing the hydrophilicity of the channels, the aggregates change their morphology from small aligned drops to discontinuous lines, thereby keeping their amorphous structure. Aβ1-40 fibrils are observed at high contact angles.

 
Human Neuronal SHSY5Y Cells on PVDF:PTrFE Copolymer Thin Films

Ilaria Tonazzini, Eva Bystrenova, Beatrice Chelli, Pierpaolo Greco, Dago De Leeuw and Fabio Biscarini

Adv. Eng. Mater. 2015, 17(7), 1051-1056.

Abstract

Here, we investigate the in vitro biocompatibility of polyvinylidenefluoride (PVDF)–polytrifluoroethylene (PTrFE) copolymer thin films using neuronal cells. The aim is to obtain an optimal capping layer material for hybrid bio-organic electronic transducers based on organic electronic devices, which can be applied for bidirectional communication with the central nervous system. PVDF:PTrFE thin films were grown by spin coating and characterized by AFM. Human neuroblastoma SHSY5Y cells were used as neuronal model and their interaction with PVDF:PTrFE films was investigated in term of cell adhesion, proliferation, differentiation, and cytoskeleton organization. We show that PVDF:PTrFE thin films allowed standard SHSY5Y proliferation and neuronal differentiation, even if with reduced short-term cell adhesion and spreading.

 

Multi-modal sensing in spin crossover compounds

Denis Gentili, Nicola Demitri, Bernhard Schäfer, Fabiola Liscio, Ilaria Bergenti, Giampiero Ruani, Mario Ruben and Massimiliano Cavallini

J. Mater. Chem. C 2015, 3, 7836-7844.

Abstract

We exploited the solvatochromic spin-state switching in a spin crossover (SCO) compound based on the FeII complex and the simultaneous change of spectroscopic properties for selective multimodal sensing of methanol and ethanol. We demonstrate that sensing capabilities are due to the inclusion of methanol or ethanol molecules into the crystalline structure, which tailors simultaneously the transition temperature, colour, birefringence and vibrational modes. We exploited this capability by integrating a neutral compound, switchable at room temperature, into a micrometric TAG sensitive to the colour and birefringence. The system was characterised by optical microscopy, magnetic susceptibility, Raman spectroscopy and X-ray diffraction.

 

Organic Materials for Time–Temperature Integrator Devices

Massimiliano Cavallini and Manuela Melucci

ACS Appl. Mater. Interfaces 2015, 7(31), 16897–16906.

Abstract

Time–temperature integrators (TTIs) are devices capable of recording the thermal history of a system. They have an enormous impact in the food and pharmaceutical industries. TTIs exploit several irreversible thermally activated transitions such as recrystallization, dewetting, smoothening, chemical decomposition, and polymorphic transitions, usually considered drawbacks for many technological applications. The aim of this article is to sensitize research groups working in organic synthesis and surface science toward TTI devices, enlarging the prospects of many new materials. We reviewed the principal applications highlighting the need and criticisms of TTIs, which offer a new opportunity for the development of many materials.

 

Pubblicazioni 2014

Neural cell alignment by patterning gradients of the extracellular matrix protein laminin

Beatrice Chelli, Marianna Barbalinardo, Francesco Valle, Pierpaolo Greco, Eva Bystrenova, Michele Bianchi, Fabio Biscarini

Interface focus 2014, 4(1), 20130041.

Abstract

Anisotropic orientation and accurate positioning of neural cells is achieved by patterning stripes of the extracellular matrix protein laminin on the surface of polystyrene tissue culture dishes by micromoulding in capillaries (MIMICs). Laminin concentration decreases from the entrance of the channels in contact with the reservoir towards the end. Immunofluorescence analysis of laminin shows a decreasing gradient of concentration along the longitudinal direction of the stripes. The explanation is the superposition of diffusion and convection of the solute, the former dominating at length scales near the entrance (characteristic length around 50 μm), the latter further away (length scale in excess of 900 μm). These length scales are independent of the channel width explored from about 15 to 45 μm. Neural cells are randomly seeded and selectively adhere to the pattern, leaving the unpatterned areas depleted even upon 6 days of incubation. Cell alignment was assessed by the orientation of the long axis of the 4′,6-diamidino-2-phenylindole-stained nuclei. Samples on patterned the laminin area exhibit a large orientational order parameter. As control, cells on the unpatterned laminin film exhibit no preferential orientation. This implies that the anisotropy of laminin stripes is an effective chemical stimulus for cell recruiting and alignment.

 

Pubblicazioni 2013

A time-temperature integrator based on fluorescent and polymorphic compounds

Denis Gentili, Margherita Durso, Cristian Bettini, Ilse Manet, Massimo Gazzano, Raffaella Capelli, Michele Muccini, Manuela Melucci & Massimiliano Cavallini

Scientific Reports 2013, 3, Article number: 2581.

Abstract

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.

 

Facile maskless fabrication of organic field effect transistors on biodegradable substrates

Marianna Barbalinardo, Denis Gentili, Marco Brucale, Francesco Valle, Ilse Manet, Giulia Foschi, Massimo Zambianchi, Manuela Melucci and Massimiliano Cavallini

RSC Adv. 2016, 6, 17106-17109.

Abstract

Fabrication of a test pattern with interdigitated gold electrodes (channel length 12 μm) on a biodegradable substrate is achieved by direct laser ablation of a Au film using a high-precision multifunction infrared-laser scan marker. The whole process involves two solvent-free steps: Au film deposition by sublimation followed by maskless ablation. The approach is suited for fast prototyping of a variety of materials. We demonstrate the fabrication of a water-gated organic field effect transistor on the biodegradable poly(lactic-co-glycolic acid) scaffold and its operations in water.

 

Pubblicazioni 2012

Patterned conductive nanostructures from reversible self-assembly of 1D coordination polymer

Denis Gentili, Gonzalo Givaja, Rubén Mas-Ballesté, Mohammad-Reza Azani, Arian Shehu, Francesca Leonardi, Eva Mateo-Martí, Pierpaolo Greco, Félix Zamora and Massimiliano Cavallini

Chem. Sci. 2012, 3, 2047-2051.

Abstract

In this study, the outstanding ability of the coordination polymer [Pt2(nBuCS2)4I]n (nBu = n-butyl) (1) to reversibly self-organize from solution was demonstrated. This feature allowed us to generate highly electrical conductive structures located upon demand on technologically relevant surfaces, by easy-to-handle and low cost micromolding in capillaries (MIMIC) and lithographically controlled wetting (LCW). Electrical characterization reveals a near Ohmic behaviour and a high stability of the stripes (in air). Electrodes produced by the MIMIC technique from a solution of compound 1 demonstrated that this material can be efficiently used as electrodes for organic field-effect transistors (OFETs).

 

Unconventional Multi-Scale Patterning of Titanium Dioxide: A New Tool for the Investigation of Cell–Topography Interactions

Fabio Biscarini, Michele Bianchi,Beatrice Chelli, Francesco Valle, Chiara Dionigi,Eva Bystrenova and Pierpaolo Greco

Adv. Eng. Mater. 2012, 14(5), B208–B215.

Abstract

Titanium dioxide (TiO2) is a biocompatible material with important applications in the field of regenerative medicine. Here we show that a multi-scale hierarchical architecture of TiO2, realized with sub-micrometer polystyrene beads as templating agent patterned by “micromolding in capillaries” (MIMICs), is a viable functional tool for the systematic investigation of cell behavior with respect to a complex topographic texture of the substrate. TiO2 stripes of different width and interconnected porosity whose size ranges from a few hundred to a few tens nanometer, are obtained after thermal treatment of the precursors with concurrent removal of the templating agent. The adhesion and proliferation of two human secondary neural cell lines, i.e., 1321N1 astrocytoma and SH-SY5Y neuroblastoma, on the patterns is statistically assessed with respect to the TiO2 stripe width and porosity. Our results show that cells have a strong preference for TiO2 patterns with respect to glass, the proliferation rate is not affected by cell porosity whereas adhesion is although ligthly, whereas the response of cell density to stripe width is very different in astocytoma cells with respect to neuroblastoma cells.

 

Pubblicazioni 2011

One-step substrate nanofabrication and patterning of nanoparticles by lithographically controlled etching

M Bianchi, D Limones Herrero, F Valle, P Greco, G M Ingo, S Kaciulis, F Biscarini and M Cavallini

Nanotechnology 2011, 22(35), 355301.

Abstract

We propose an integrated top-down and bottom-up approach to single-step nanofabrication of complex nanostructures made of different materials. The process, termed lithographically controlled etching (LCE), starts with a drop of an etching solution cast on the surface to be patterned. By placing a polymeric mold on the substrate, the stamp protrusions come into contact with the surface, thus protecting it, whereas the surface beneath the mold recesses is exposed to a thin layer of etching solution, allowing the surface to be etched. By dispersing nanoparticles into the etching solution, these can be deposited and self-organize in the recesses on the substrate as these are excavated. We demonstrate here the fabrication of complex structures and nanowires 30 nm wide. Moreover, by exploiting capillary forces, it is possible to deposit nanoparticles at precise positions with respect to optically addressable microstructures, thus realizing a multiscale functional pattern.

 

Pubblicazioni 2010

Fabrication of ordered carbon nanotube structures by unconventional lithography

Pierpaolo Greco, Massimo Facchini, Massimiliano Cavallini, Giampiero Ruani, Chiara Dionigi and Fabio Biscarini

Phys. Status Solidi B 2010, 247(4), 877–883.

Abstract

We use stamp-assisted deposition to align single-walled carbon nanotubes (CNTs) starting from a water suspension of CNTs in sodium dodecyl sulphate (SDS) solution. The driving force of the process is the interplay between capillary flow and spatial confinement, which leads CNTs to self-organize into bundles aligned in rows hundreds of micrometres long. Lithographically controlled wetting, where the solution is confined in menisci pinned to the stamp protrusions, yields patterns with feature size as small as single nanotubes. Using micromolding in capillaries instead we fabricate patterns of CNTs lines, with nanometric size, preferentially aligned along the microchannel axis and exhibiting a conductivity of about 100 S/cm.

Stable Non-Covalent Large Area Patterning of Inert Teflon-AF Surface: A New Approach to Multiscale Cell Guidance

Francesco Valle, Beatrice Chelli, Michele Bianchi, Pierpaolo Greco, Eva Bystrenova, Ilaria Tonazzini and Fabio Biscarini

Adv. Eng. Mater. 2010, 12(6), B185–B191.

Abstract

Micro- and nano-patterning of cell adhesion proteins is demonstrated to direct the growth of neural cells, viz. human neuroblastoma SHSY5Y, at precise positions on a strongly antifouling substrate of technolological interest. We adopt a soft-lithographic approach with oxygen plasma modified PDMS stamps to pattern human laminin on Teflon-AF films. These patterns are based on the interplay of capillary forces within the stamp and non-covalent intermolecular and surface interactions. Remarkably, they remain stable for several days upon cell culture conditions. The fabrication of substrates with adjacent antifouling and adhesion-promoting regions allows us to reach absolute spatial control in the positioning of neuroblastoma cells on the Teflon-AF films. This patterning approach of a technologically-relevant substrate can be of interest in tissue engineering and biosensing.

Time−Temperature Integrator Based on the Dewetting of Polyisobutylene Thin Films

Annalisa Calò, Pablo Stoliar, Francesco Cino Matacotta, Massimiliano Cavallini and Fabio Biscarini

Langmuir 2010, 26(8), 5312–5315.

Abstract

This work reports the application of a patterned thin film of polyisobutylene (PIB) irradiated with an electron beam as a time−temperature integrator, i.e., a device that is able to record the thermal history of a product. The device is fabricated by irradiation with an electron beam of regions of a PIB thin film to different doses of electrons. A different dewetting behavior occurs at these regions upon thermal exposure, depending on the dose. The experimental results are quantified by means of a model of dewetting based on nucleation and growth of holes in a strong slippage regime.

Pubblicazioni 2009

Lithographic Alignment of Discotic Liquid Crystals: A New Time–Temperature Integrating Framework

Massimiliano Cavallini,* Annalisa Calò, Pablo Stoliar, Jean Crispin Kengne, Sandrine Martins, Francesco Cino Matacotta, Florence Quist, Gabin Gbabode, Nicolas Dumont, Yves H. Geerts, and Fabio Biscarini*

Adv. Mater. 2009, 21, 4688–4691.

Abstract

Liquid crystals (LCs) are a successful example of how the control of self-assembling [1, 2] and self-organization [3] via chemical design [4] leads to novel applications. These are mostly based on bulk (quasi-) equilibrium properties related to long-range molecular ...

079 Adv. Mater. 2009, 21, 4688-4691

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