Opportunity of Patterning in Chemistry.

Patterning offers an efficient way to quantitatively enhance and enlarge material properties and functionalities, offering unprecedented opportunities for innovation in various scientific domains. By precisely controlling the spatial arrangement of materials at the micro- and nanoscale, patterning enables the exploitation of inherent material properties in novel ways. In addition, it generates new properties, leading to the development of advanced devices and applications. This article highlights the significant contributions of spatially controlled patterning in chemistry, particularly in generating new functional properties and devices, discussing some representative articles. Examples include the use of unconventional patterning techniques for surface functionalization, as well as the application of spatial confinement in improving material properties and controlling crystallization processes. Furthermore, the discussion extends to creating new devices, such as optical storage media and sensors, through spatial organization of materials.

Cellulose acetate membranes loaded with combinations of tetraphenylporphyrin, graphene oxide and Pluronic F-127 as responsive materials with antibacterial photodynamic activity.

The development of polymeric fabrics with photoinduced antibacterial activity is important for different emerging applications, ranging from materials for medical and clinical practices to disinfection of objects for public use. In this work we prepared a series of cellulose acetate membranes, by means of phase inversion technique, introducing different additives in the starting polymeric solution. The loading of 5,10,15,20-tetraphenylporphyrin (TPP), a known photosensitizer, was considered to impart antibacterial photodynamic properties to the produced membranes. Besides, the addition of a surfactant (Pluronic F-127) allowed to modify the morphology of the membranes whereas the use of graphene oxide (GO) enabled further photo-activated antibacterial activity. The three additives were tested in various concentrations and in different combinations in order to carefully explore the effects of their mixing on the final photophysical and photodynamic properties. A complete structural/morphologycal characterization of the produced membranes has been performed, together with a detailed photophysical study of the TPP-containing samples, including absorption and emission features, excited state lifetime, singlet oxygen production, and confocal analysis. Their antibacterial activity has been assessed in vitro against S. aureus and E. coli, and the results demonstrated excellent bacterial inactivation for the membranes containing a combination of the three additives, revealing also a non-innocent role of the membrane porous structure in the final antibacterial capacity.

Native Silicon Oxide Properties Determined by Doping.

The physico-chemical properties of native oxide layers, spontaneously forming on crystalline Si wafers in air, can be strictly correlated to the dopant type and doping level. In particular, our investigations focused on oxide layers formed upon air exposure in a clean room after Si wafer production, with dopant concentration levels from ≈1013 to ≈1019 cm-3. In order to determine these correlations, we studied the surface, the oxide bulk, and its interface with Si. The surface was investigated using the contact angle, thermal desorption, and atomic force microscopy measurements which provided information on surface energy, cleanliness, and morphology, respectively. Thickness was measured with ellipsometry and chemical composition with X-ray photoemission spectroscopy. Electrostatic charges within the oxide layer and at the Si interface were studied with Kelvin probe microscopy. Some properties such as thickness, showed an abrupt change, while others, including silanol concentration and Si intermediate-oxidation states, presented maxima at a critical doping concentration of ≈2.1 × 1015 cm-3. Additionally, two electrostatic contributions were found to originate from silanols present on the surface and the net charge distributed within the oxide layer. Lastly, surface roughness was also found to depend upon dopant concentration, showing a minimum at the same critical dopant concentration. These findings were reproduced for oxide layers regrown in a clean room after chemical etching of the native ones.

Osteoporosis and Celiac Disease: Updates and Hidden Pitfalls.

Celiac disease (CD) is an autoimmune disorder caused by gluten ingestion in genetically predisposed individuals. In addition to the typical gastrointestinal symptoms (e.g., diarrhea, bloating, and chronic abdominal pain), CD may also present with a broad spectrum of manifestations, including low bone mineral density (BMD) and osteoporosis. The etiopathology of bone lesions in CD is multifactorial and other conditions, rather than mineral and vitamin D malabsorption, may affect skeletal health, especially those related to the endocrine system. Here, we describe CD-induced osteoporosis in an attempt to enlighten new and less-known aspects, such as the influence of the intestinal microbiome and sex-related differences on bone health. This review describes the role of CD in the development of skeletal alterations to provide physicians with an updated overview on this debated topic and to improve the management of osteoporosis in CD.

Impact of Female Gender in Inflammatory Bowel Diseases: A Narrative Review.

Inflammatory bowel diseases show a gender bias, as reported for several other immune-mediated diseases. Female-specific differences influence disease presentation and activity, leading to a different progression between males and females. Women show a genetic predisposition to develop inflammatory bowel disease related to the X chromosome. Female hormone fluctuation influences gastrointestinal symptoms, pain perception, and the state of active disease at the time of conception could negatively affect the pregnancy. Women with inflammatory bowel disease report a worse quality of life, higher psychological distress, and reduced sexual activity than male patients. This narrative review aims to resume the current knowledge of female-related features in clinical manifestations, development, and therapy, as well as sexual and psychological implications related to inflammatory bowel disease. The final attempt is to provide gastroenterologists with a roadmap of female-specific differences, to improve patients' diagnosis, management, and treatment.

Polymorph Separation by Ordered Patterning.

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

Reversible assembly of nanoparticles: theory, strategies and computational simulations.

The significant advances in synthesis and functionalization have enabled the preparation of high-quality nanoparticles that have found a plethora of successful applications. The unique physicochemical properties of nanoparticles can be manipulated through the control of size, shape, composition, and surface chemistry, but their technological application possibilities can be further expanded by exploiting the properties that emerge from their assembly. The ability to control the assembly of nanoparticles not only is required for many real technological applications, but allows the combination of the intrinsic properties of nanoparticles and opens the way to the exploitation of their complex interplay, giving access to collective properties. Significant advances and knowledge gained over the past few decades on nanoparticle assembly have made it possible to implement a growing number of strategies for reversible assembly of nanoparticles. In addition to being of interest for basic studies, such advances further broaden the range of applications and the possibility of developing innovative devices using nanoparticles. This review focuses on the reversible assembly of nanoparticles and includes the theoretical aspects related to the concept of reversibility, an up-to-date assessment of the experimental approaches applied to this field and the advanced computational schemes that offer key insights into the assembly mechanisms. We aim to provide readers with a comprehensive guide to address the challenges in assembling reversible nanoparticles and promote their applications.

Atomic Vacancies in Transition Metal Dichalcogenides: Properties, Fabrication, and Limits.

Structural defects, such as heteroatoms or atomic vacancies, are always present in materials and significantly affect their physical properties, in both positive or unwanted ways. Interestingly, defects generate an impressive range of functionalities in many materials, such as catalysis, electrical and thermal conductivity tuning, thermoelectricity, enhanced ion storage, magnetism, and others. These properties enable the use of defective materials in a great variety of technological applications. Here we review the principal properties generated by atomic vacancies in 2D compounds and thin films of transition metal dichalcogenides and the most consolidated methods for their formation and engineering. Eventually, we critically analysed the most important advantages, the limits and the current open challenges.

Surface properties modulate protein corona formation and determine cellular uptake and cytotoxicity of silver nanoparticles.

Nanoparticles (NPs) have been studied for biomedical applications, ranging from prevention, diagnosis and treatment of diseases. However, the lack of the basic understanding of how NPs interact with the biological environment has severely limited their delivery efficiency to the target tissue and clinical translation. Here, we show the effective regulation of the surface properties of NPs, by controlling the surface ligand density, and their effect on serum protein adsorption, cellular uptake and cytotoxicity. The surface properties of NPs are tuned through the controlled replacement of native ligands, which favor protein adsorption, with ligands capable of increasing protein adsorption resistance. The extent and composition of the protein layer adsorbed on NPs are strongly correlated to the degree of ligands replaced on their surface and, while BSA is the most abundant protein detected, ApoE is the one whose amount is most affected by surface properties. On increasing the protein resistance, cellular uptake and cytotoxicity in mouse embryonic fibroblasts of NPs are drastically reduced, but the surface coating has no effect on the process by which NPs mainly induce cell death. Overall, this study reveals that the tuning of the surface properties of NPs allows us to regulate their biological outcomes by controlling their ability to adsorb serum proteins.

Evaluation of Long-Lasting Antibacterial Properties and Cytotoxic Behavior of Functionalized Silver-Nanocellulose Composite.

Materials possessing long-term antibacterial behavior and high cytotoxicity are of extreme interest in several applications, from biomedical devices to food packaging. Furthermore, for the safeguard of the human health and the environment, it is also stringent keeping in mind the need to gather good functional performances with the development of ecofriendly materials and processes. In this study, we propose a green fabrication method for the synthesis of silver nanoparticles supported on oxidized nanocellulose (ONCs), acting as both template and reducing agent. The complete structural and morphological characterization shows that well-dispersed and crystalline Ag nanoparticles of about 10-20 nm were obtained in the cellulose matrix. The antibacterial properties of Ag-nanocomposites (Ag-ONCs) were evaluated through specific Agar diffusion tests against E. coli bacteria, and the results clearly demonstrate that Ag-ONCs possess high long-lasting antibacterial behavior, retained up to 85% growth bacteria inhibition, even after 30 days of incubation. Finally, cell viability assays reveal that Ag-ONCs show a significant cytotoxicity in mouse embryonic fibroblasts.

Organic Electrochemical Transistors for Real-Time Monitoring of In Vitro Silver Nanoparticle Toxicity.

Nanomaterials are being widely used in medical applications and consumer products such as cosmetics, fabrics, and food packaging, although their impact on health and the environment is yet to be understood. Strategies enabling reliable and reproducible safety assessment of nanomaterials are needed because predicting their toxic effects is challenging as there is no simple correlation between their properties and the interaction with living systems. Here, the real-time monitoring of toxic effects induced by nanoparticles on cells using organic electrochemical transistors (OECTs) is reported. Noteworthy, OECTs are able to assess the coating-dependent toxicity of nanoparticles on both barrier and non-barrier tissue cells and, moreover, to monitor the cell health status as a function of exposure time, allowing useful insight on the interaction processes between nanomaterials and cells. These results demonstrate that OECTs are effective devices for real-time cell monitoring and in vitro assessment of nanomaterial toxicity.

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

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

Combined wet lithography and fractional precipitation as a tool for fabrication of spatially controlled nanostructures of poly(3-hexylthiophene) ordered aggregates.

Herein, we propose an easy and practical method for the fabrication of highly ordered supramolecular structures. The proposed approach combines fractional precipitation and wet lithography, to obtain a spatially-defined pattern of submicrometric structures with a high molecular order of poly(3-hexylthiophene). The process is demonstrated by XRD, confocal and time-resolved spectroscopy and by the performance of an effective field effect transistor.

Thermodynamically versus Kinetically Controlled Self-Assembly of a Naphthalenediimide-Thiophene Derivative: From Crystalline, Fluorescent, n-Type Semiconducting 1D Needles to Nanofibers.

The control over aggregation pathways is a key requirement for present and future technologies, as it can provide access to a variety of sophisticated structures with unique functional properties. In this work, we demonstrate an unprecedented control over the supramolecular self-assembly of a semiconductive material, based on a naphthalenediimide core functionalized with phenyl-thiophene moieties at the imide termini, by trapping the molecules into different arrangements depending on the crystallization conditions. The control of the solvent evaporation rate enables the growth of highly elaborated hierarchical self-assembled structures: either in an energy-minimum thermodynamic state when the solvent is slowly evaporated forming needle-shaped crystals (polymorph α) or in a local energy-minimum state when the solvent is rapidly evaporated leading to the formation of nanofibers (polymorph ß). The exceptional persistence of the kinetically trapped ß form allowed the study and comparison of its characteristics with that of the stable α form, revealing the importance of molecular aggregation geometry in functional properties. Intriguingly, we found that compared to the thermodynamically stable α phase, characterized by a J-type aggregation, the ß phase exhibits (i) an unusual strong blue shift of the emission from the charge-transfer state responsible for the solid-state luminescent enhancement, (ii) a higher work function with a "rigid shift" of the electronic levels, as shown by Kelvin probe force microscopy and cyclic voltammetry measurements, and (iii) a superior field-effect transistor mobility in agreement with an H-type aggregation as indicated by X-ray analysis and theoretical calculations.

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

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

AC parallel local oxidation of silicon.

Here, we present a suitable advancement of parallel local oxidation nanolithography, demonstrating its feasibility in alternate current mode (AC-PLON). For demonstration, we fabricated model structures consisting of an array of parallel nanostripes of electrochemical SiO x with a controlled roughness. Besides, we proved the repeatability of AC-PLON and its integrability with conventional parallel local oxidation nanolithography.

Protein Corona Mediated Uptake and Cytotoxicity of Silver Nanoparticles in Mouse Embryonic Fibroblast.

Medical applications of nanoparticles (NPs) require understanding of their interactions with living systems in order to control their physiological response, such as cellular uptake and cytotoxicity. When NPs are exposed to biological fluids, the adsorption of extracellular proteins on the surface of NPs, creating the so-called protein corona, can critically affect their interactions with cells. Here, the effect of surface coating of silver nanoparticles (AgNPs) on the adsorption of serum proteins (SPs) and its consequence on cellular uptake and cytotoxicity in mouse embryonic fibroblasts are shown. In particular, citrate-capped AgNPs are internalized by cells and show a time- and dose-dependent toxicity, while the passivation of the NP surface with an oligo(ethylene glycol) (OEG)-alkanethiol drastically reduces their uptake and cytotoxicity. The exposure to growth media containing SPs reveals that citrate-capped AgNPs are promptly coated and stabilized by proteins, while the AgNPs resulting from capping with the OEG-alkanethiol are more resistant to adsorption of proteins onto their surface. Using NIH-3T3 cultured in serum-free, the key role of the adsorption of SPs onto surface of NPs is shown as only AgNPs with a preformed protein corona can be internalized by the cells and, consequently, carry out their inherent cytotoxic activity.

Opposite Surface and Bulk Solvatochromic Effects in a Molecular Spin-Crossover Compound Revealed by Ambient Pressure X-ray Absorption Spectroscopy.

We investigate the solvatochromic effect of a Fe-based spin-crossover (SCO) compound via ambient pressure soft X-ray absorption spectroscopy (AP-XAS) and atomic force microscopy (AFM). AP-XAS provides the direct evidence of the spin configuration for the Fe(II) 3d states of the SCO material upon in situ exposure to specific gas or vapor mixtures; concurrent changes in nanoscale topography and mechanical characteristics are revealed via AFM imaging and AFM-based force spectroscopy, respectively. We find that exposing the SCO material to gaseous helium promotes an effective decrease of the transition temperature of its surface layers, while the exposure to methanol vapor causes opposite surfacial and bulk solvatochromic effects. Surfacial solvatochromism is accompanied by a dramatic reduction of the surface layers stiffness. We propose a rationalization of the observed effects based on interfacial dehydration and solvation phenomena.

Integration of organic electrochemical transistors and immuno-affinity membranes for label-free detection of interleukin-6 in the physiological concentration range through antibody-antigen recognition.

We demonstrate the label-free and selective detection of interleukin-6 (IL-6), a key cell-signaling molecule in biology and medicine, by integrating an OECT with an immuno-affinity regenerated cellulose membrane. The objective of the membrane is to increase the local concentration of IL-6 at the sensing electrode and, thereby, enhance the device response for concentrations falling within the physiological concentration range of cytokines. The OECT gate electrode is functionalized with an oligo(ethylene glycol)-terminated self-assembled alkanethiolate monolayer (SAM) for both the immobilization of anti IL-6 antibodies and the inhibition of non-specific biomolecule binding. The OECT gate/electrolyte interface is exploited for the selective detection of IL-6 through the monitoring of antigen-antibody binding events occurring at the gate electrode.

Spatial control of chirality in supramolecular aggregates.

Chirality is one of the most intriguing properties of matter related to a molecule's lack of mirror symmetry. The transmission of chirality from the molecular level up to the macroscopic scale has major implications in life sciences but it is also relevant for many chemical applications ranging from catalysis to spintronic. These technological applications require an accurate control of morphology, homogeneity and chiral handedness of thin films and nanostructures. We demonstrate a simple approach to specifically transfer chirality to the model supramolecular system of J aggregates of the protonated form of tetrakis(4-sulfonatophenyl)-porphyrin by utilizing a soft lithography technique. This approach successfully allows the fabrication of an ordered distribution of sub-micrometric structures in precise and controllable positions with programmed chirality, providing a fundamental breakthrough toward the exploitation of chiral supramolecular aggregates in technological applications, such as sensors, non-linear optics and spintronic.