Crafting positive/negative patterns and nanopillars of polymer brushes by photocatalytic lithography

We demonstrate a convenient and versatile approach based on the photocatalytic lithography to obtain micro- and nanostructures of polymer brushes. Micro-patterns of polymer brushes are obtained through two ways: by the selective photocatalytic degradation of an initiator, self-assembled on the surface (\u201cpositive\u201d pattern), or by a \u201cnegative\u201d pattern obtained, first, degrading an alkylsiloxane monolayer and, then, refilling it with the initiator. In both cases, the patterned initiator monolayer is eventually amplified into polymer brushes with a controlled radical polymerization protocol (ARGET ATRP). The approach described here mimics the conventional photolithography but is free from the disadvantages associated to this technique (i.e. highly energetic light sources, polymeric resists and on purpose-made photomasks). Moreover, the ability to generate nanometer-sized pillars of polymer brushes using remote photocatalysis coupled with nanosphere lithography is demonstrated. Highly monodisperse silica particles with spherical shape (diameter 3c600\ua0nm) are assembled on the surface to be patterned and used as a mask for remote photocatalysis. Our results confirm the great potentialities of TiO2-photocatalytic lithography for patterning of polymer brushes

Mesoporous silica networks with improved diffusion and interference-rejecting properties for electroanalytical sensing

Mesoporous silica materials characterized by well-ordered microstructure and size- and shape-controlled pores have attracted much attention in the last years. These systems can be used for the development of functional thin films for advanced applications in catalysis and electrocatalysis, sensors and actuators, separation techniques, micro- and nano-electronic engineering [1-2]. In this work, \u201cinsulating\u201d and mesoporous silica films were prepared by spin coating a home-made silica sol on a cleaned ITO glass support. The mesoporosity was controlled by the use of Polystyrene (PS) latex beads with different dimensions (30-60-100 nm) as template. The number of successive multi-layer depositions was varied (1-2-3-5 layers) and after the template removal, stable, homogeneous and reproducible transparent films were obtained, characterized by an interconnected porous structure. The morphological features and the physicochemical and optical properties of the films and/or sol-precursors were studied by DLS, FE-SEM, AFM, UV-vis transmittance spectroscopy and wettability analyses. Moreover, a deep electrochemical characterization was also performed by Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). In particular, the use of two redox mediator probes [(K4Fe(CN)6) and (Ru(NH3)6Cl3)], presenting opposite charge and different diffusional behaviour, allowed the comprehension of the mass transport and charge transfer phenomena, evidencing the effects of spatial confinement and charge selection. In the case of \u201cinsulating\u201d films prepared without the use of PS latexes, we proved an experimental evidence for theoretical models [3] concerning electroinactive layer-modified electrodes, with a scan-rate-dependent variation of the CV shape due to a progressive increase in the diffusion coefficient inside the insulating layer. A complex balance between diverging effects (higher hydrophilicity and insulating behavior effects of silica) when increasing the numbers of layers was also observed [4]. In the case of mesoporous layers, a better electrochemical response of smaller pores and of thicker layers was found, due to two main cooperative phenomena: i) a diffusion modification from fully planar to radial-convergent at the pore-silica interface due to surface porosity; ii) the presence of pores in a hydrophilic matrix which leads to a capillary pull effects, stronger in the case of smaller hydrophilic pores. The easiness of preparation and the interesting properties of these devices pave the way towards their use in many fields, particularly trace electroanalysis in real matrices. In fact, for example, the porous and properly charged network is able to exclude interfering macromolecules (mucin in our case), preventing electrode biofouling and enhancing the performances of the sensor towards dopamine detection. References [1] M. Ogawa, Chem. Rec. 17 (2017) 217-232. [2] A. Walcarius, Chem. Soc. Rev. 42 (2013) 4098-4140. [3] D. Menshykau, R.G. Compton, Langmuir 25 (2009) 2519\u20132529. [4] V. Pifferi, L. Rimoldi, D. Meroni, F. Segrado, G. Soliveri, S. Ardizzone, L. Falciola, Electrochem. Commun. 81 (2017) 102-105

Patterning of polymer brushes made easy using titanium dioxide: direct and remote photocatalytic lithography

Photocatalytic lithography is proved for the realization of micropatterned polymer brushes. Initiator-functionalized titanium dioxide or silicon surfaces are respectively exposed directly to near-UV light through a photomask (direct approach) or through a transparent photoactive TiO2 film (remote approach). Initiator patterns are then amplified as polymer brushes with SI-ATRP. Features down to 10 \u3bcm could be obtained using simple equipment. The process is intrinsically parallel, has high throughput and scalable to wafer size, making it powerful for microfabrication purposes

Preparation of a sepia melanin and poly(ethylene-alt-maleic anhydride) hybrid material as an adsorbent for water purification

Meeting the increasing demand of clean water requires the development of novel efficient adsorbent materials for the removal of organic pollutants. In this context the use of natural, renewable sources is of special relevance and sepia melanin, thanks to its ability to bind a variety of organic and inorganic species, has already attracted interest for water purification. Here we describe the synthesis of a material obtained by the combination of sepia melanin and poly(ethylene-alt-maleic anhydride) (P(E-alt-MA)). Compared to sepia melanin, the resulting hybrid displays a high and fast adsorption efficiency towards methylene blue (a common industrial dye) for a wide pH range (from pH 2 to 12) and under high ionic strength conditions. It is easily recovered after use and can be reused up to three times. Given the wide availability of sepia melanin and P(E-alt-MA), the synthesis of our hybrid is simple and affordable, making it suitable for industrial water purification purposes

ON/OFF switching of silicon wafer electrochemistry by pH-responsive polymer brushes

pH-Switchable electrochemical properties are demonstrated for the first time for native oxide-coated silicon wafer electrodes. Ultrathin and ultrathick pH-responsive poly(methacrylic acid) (PMAA) brushes, obtained by surface-initiated atom transfer radical polymerization, were used to achieve redox gating. PMAA brushes are reversibly switched between their protonated and deprotonated states by alternating acidic and basic pH, which corresponds to a swelling/collapsing behavior. As a result, the electrochemical properties of the PMAA brush-modified silicon electrode are switched "ON" and "OFF" simply by changing pH. The electrochemical properties of the modified electrode were examined by means of cyclic voltammetry and electrochemical impedance spectroscopy both in the absence and presence of ruthenium(iii) hexamine, a well-known cationic redox probe

Self-cleaning properties in engineered sensors for dopamine electroanalytical detection

Fouling and passivation are the major drawbacks for a wide applicability of electroanalytical sensors based on nanomaterials, especially in biomedical and environmental fields. The production of highly engineered devices, designed ad hoc for specific applications, is the key factor in the direction of overcoming the problem and accessing effective sensors. Here, the fine-tuning of the system, composed of a highly ordered distribution of silver nanoparticles between a bottom silica and a top titania layer, confers multifunctional properties to the device for a biomedical complex challenge: dopamine detection. The crucial importance of each component towards a robust and efficient electroanalytical system is studied. The total recovery of the electrode performance after a simple UV-A cleaning step (self-cleaning), due to the photoactive interface and the aging resistance, is deeply investigated

The interplay between pore size and wettability in solid-templated silica films

In recent years, the attention to templated SiO2 nanomaterials is particularly focused to film structures, for several different applications. Beside the use of MCM-41 mesoporous silica types, solid templating agents such as polystyrene (PS) latex have been adopted in order to create a morphologically different porosity network, characterized no more by cylindrical pores, but by spherical and possibly interconnected cavities. In the present work, a silica sol was prepared and deposited on conductive glass in a mixture with a PS latex suspension. A careful adjustment of the preparation procedure was conducted and allowed stable, reproducible and electrochemically performing mesoporous thin films to be synthesized. Especially, the sol composition, the controlled ageing procedure, the right template to silica precursor ratio and the deposition procedure parameters revealed to be pivotal for the obtainment of homogeneous and transparent silica thin films. In this context, the physicochemical properties of the films as well as the SiO2 sol were studied. For example, Dynamic Light Scattering (DLS) analyses allowed the dimensions of the silica nuclei promoting the obtainment of the deposited layers to be quantified as a function of the sol ageing. Both the number of successive deposited layers and the dimension of the template (30, 60, 100 nm) were varied. In this sense, aspects pertaining the morphological features of the silica films were deeply characterized by FE-SEM and AFM analyses. Multi-layered depositions allowed an interconnected porous structure to be created, while the influence of the template diameter affected not only the morphology of the film, but above all the diffusion properties of electrochemically active species to the conductive surface of the substrate. In this regard, the electrochemical properties of the prepared devices were compared to thin films in which no templating agent was adopted, revealing large differences both by Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). Electrochemical results were also interpreted in the light of water contact angle measurements. The wettability of the samples surface revealed to be a crucial parameter for the sensing properties of the films and was found to be in complete agreement with roughness data provided by AFM measurements, according to the Wenzel model. Moreover, the study of the optical properties by UV-vis transmittance spectroscopy revealed nonreflective properties with respect to the pristine substrate, thus opening the path to other possible applications, e.g. in the field of optical devices

Electrochemical characterization of insulating silica-modified electrodes : Transport properties and physicochemical features

The effect of depositing different numbers of insulating layers from a silica sol onto an ITO support was investigated to elucidate the changes occurring to diffusion and transfer mechanisms compared with bare electrodes. The electrochemical studies highlighted unexpected trends, which were discussed with respect to literature models and interpreted in the light of the physicochemical characterization (by FE-SEM, AFM, UV-vis transmittance) and particularly the hydrophilicity of the layers

Apraxia and motor dysfunction in corticobasal syndrome

Background: Corticobasal syndrome (CBS) is characterized by multifaceted motor system dysfunction and cognitive disturbance; distinctive clinical features include limb apraxia and visuospatial dysfunction. Transcranial magnetic stimulation (TMS) has been used to study motor system dysfunction in CBS, but the relationship of TMS parameters to clinical features has not been studied. The present study explored several hypotheses; firstly, that limb apraxia may be partly due to visuospatial impairment in CBS. Secondly, that motor system dysfunction can be demonstrated in CBS, using threshold-tracking TMS, and is linked to limb apraxia. Finally, that atrophy of the primary motor cortex, studied using voxel-based morphometry analysis (VBM), is associated with motor system dysfunction and limb apraxia in CBS.   Methods: Imitation of meaningful and meaningless hand gestures was graded to assess limb apraxia, while cognitive performance was assessed using the Addenbrooke's Cognitive Examination - Revised (ACE-R), with particular emphasis placed on the visuospatial subtask. Patients underwent TMS, to assess cortical function, and VBM.   Results: In total, 17 patients with CBS (7 male, 10 female; mean age 64.4+/2 6.6 years) were studied and compared to 17 matched control subjects. Of the CBS patients, 23.5% had a relatively inexcitable motor cortex, with evidence of cortical dysfunction in the remaining 76.5% patients. Reduced resting motor threshold, and visuospatial performance, correlated with limb apraxia. Patients with a resting motor threshold <50% performed significantly worse on the visuospatial sub-task of the ACE-R than other CBS patients. Cortical function correlated with atrophy of the primary and pre-motor cortices, and the thalamus, while apraxia correlated with atrophy of the pre-motor and parietal cortices.   Conclusions: Cortical dysfunction appears to underlie the core clinical features of CBS, and is associated with atrophy of the primary motor and pre-motor cortices, as well as the thalamus, while apraxia correlates with pre-motor and parietal atrophy

Structure of a Wbl protein and implications for NO sensing by M. tuberculosis

Mycobacterium tuberculosis causes pulmonary tuberculosis (TB) and claims ~1.8 million human lives per annum. Host nitric oxide (NO) is important in controlling TB infection. M. tuberculosis WhiB1 is a NO-responsive Wbl protein (actinobacterial iron-sulfur proteins first identified in the 1970s). Until now, the structure of a Wbl protein has not been available. Here a NMR structural model of WhiB1 reveals that Wbl proteins are four-helix bundles with a core of three α-helices held together by a [4Fe-4S] cluster. The iron-sulfur cluster is required for formation of a complex with the major sigma factor (σA) and reaction with NO disassembles this complex. The WhiB1 structure suggests that loss of the iron-sulfur cluster (by nitrosylation) permits positively charged residues in the C-terminal helix to engage in DNA binding, triggering a major reprogramming of gene expression that includes components of the virulence-critical ESX-1 secretion system