Plinio Innocenzi

University of Sassari | UNISS · Dipartimento di Chimica e Farmacia

The COVID‐19 pandemic profoundly changes the perception of the impact of viral diseases on society and the consequent need to develop new and more effective technologies in vaccines and antivirals. Thus, research in the field of antivirals has received a new and strong impetus by considering new approaches and innovative methodologies. One example...

Smart devices, such as soft robots, artificial organs, and soft actuators, require materials that adapt their morphologies and properties in response to their environment. These materials can be obtained through the composition of different types of materials that exhibit different responses to environmental stimuli, arranged in a rational spatial...

Carbon dots (C‐dots) obtained from D‐glucose have attracted great interest because of their properties and as a model for understanding the synthesis process and the origin of photoluminescence in carbon‐based nanostructures. Synthesising C‐dots under hydrothermal conditions has become one of the most common methods for their preparation. Understan...

The scientific community is actively engaged in the development of innovative nanomaterials with broad‐spectrum virucidal properties, particularly those capable of producing reactive oxygen species (ROS), to combat upcoming pandemics effectively. The generation of ROS capable of inhibiting viral activity on high‐touch surfaces can prove an effectiv...

Alcohol and water photooxidation reactions are employed in concert with optical spectroscopy analyses to demonstrate the occurrence of multiple and distinctive charge-transfer (CT) mechanisms in the environmental photocatalyst MIL-125(Ti). The contribution of ligand-to-metal CT (LMCT) mechanisms increases at wavelengths lower than 320 nm while that...

In the present Account, we report the recent progress of our research group on experimental and theoretical studies of defects in 2D and 0D hexagonal boron nitride. The studies of the effect of defects in boron-based structures have been also extended to boron oxide glasses. Engineering the different types of defects in h-BN is paramount because ma...

The emergence of SARS-CoV-2 variants requires close monitoring to prevent the reoc-currence of a new pandemic in the near future. The Omicron variant, in particular, is one of the fastest-spreading viruses, showing a high ability to infect people and evade neutralization by anti-bodies elicited upon infection or vaccination. Therefore, the search f...

The phosphorescence of boric acid (BA, H3BO3) at room temperature is a puzzling phenomenon subject to controversial interpretations although the role of structural defects has not yet been considered. Heat treatments of boric acid cause its transformation into the metaboric phase and amorphous boron oxide (B2O3). The structural changes after therma...

This book opens a new window to understanding the important role music played in the Renaissance. It was a means of popular and court entertainment and a tool for displaying the magnificence and power achieved by the lords of the time. Leonardo da Vinci, despite not being very well known for this skill, was one of the most famous improvisers and pe...

The first studies on sol–gel processing have been very much focused on the possibility of obtaining bulk gels and through these glasses from a low temperature route. With the time this first idea has been almost abandoned and sol-gel inorganic chemistry has become something different. Nowadays it is an almost ubiquitous process in nano-chemistry to...

The design of functional coatings for touchscreens and haptic interfaces is of paramount importance for smartphones, tablets, and computers. Among the functional properties, the ability to suppress or eliminate fingerprints from specific surfaces is one of the most critical. We produced photoactivated anti-fingerprint coatings by embedding 2D-SnSe2...

Carbon dots (C-dots) are a large family of nanomaterials characterized by an intense photoluminescence. The origin of the emission is multifaceted and is dependent on a number of factors, including structure, surface, and composition. The term "carbon dots" is quite broad and encompasses a wide range of carbon nanostructures. The multiple propertie...

Designing the architecture of l-lysine-based polymeric structures is a highly challenging task that requires careful control of the amino acid reactive groups. Conventional processes to obtain branched polylysine need several steps and the addition of specific catalysts. In the present work, to gain a better understanding and control of the formati...

The synthesis of ordered mesoporous films via self-assembly represents one of the main accomplishments in nanoscience. In fact, controlling the complex chemical-physical phenomena that govern the process triggered by the solvent's fast evaporation during film deposition has represented a challenging task. Several years after the first articles on t...

L-lysine is an essential amino acid whose peculiar optical properties in aqueous solutions are still in search of a comprehensive explanation. In crystalline form L-lysine does not emit, but when in an aqueous solution, as the concentration increases, emits in the blue. The origin of such fluorescence is not yet clear. In the present article, we ha...

The origin of fluorescence in carbon dots (C-dots) is still a puzzling phenomenon. The emission is, in most of the cases, due to molecular fluorophores formed in situ during the synthesis. The carbonization during C-dots processing does not allow, however, a fine control of the properties and makes finding the source of the fluorescence a challengi...

Thermal polymerization of glycine, the simplest amino acid bearing only one alfa carbon atom, is not an efficient process in mild conditions. Hydrothermal processing of glycine produces only small peptides, up to 4 units on average, with only a fraction of glycine that reacts. In the present work, we have used boric acid as a catalyst to promote th...

Heterostructures formed by anatase nanotitania and bidimensional semiconducting materials are expected to become the next-generation photocatalytic materials with an extended operating range and higher performances. The capability of fabricating optically transparent photocatalytic thin films is also a highly demanded technological issue, and incre...

Bioimaging supported by nanoparticles requires low cost, highly emissive and photostable systems with low cytotoxicity. Carbon dots (C-dots) offer a possible solution, even if controlling their properties is not always straightforward, not to mention their potentially simple synthesis and the fact that they do not exhibit long-term photostability i...

The outbreak of the Covid-19 pandemic due to the SARS-CoV-2 coronavirus has accelerated the search for innovative antivirals with possibly broad-spectrum efficacy. One of the possible strategies is to inhibit the replication of the virus by preventing or limiting its entry into the cells. Nanomaterials derived from lysine, an essential amino acid c...

Graphene-enhanced Raman scattering (GERS) produces enhancement of the Raman signal, which is based on chemical rather than electromagnetic mechanism such as in the surface-enhanced Raman scattering. Graphene oxide, amino- and guanidine-functionalized graphene oxide, exfoliated graphene, and commercial graphene nanoplatelets have been used to invest...

This first chapter introduces the models and theories necessary for a basic understanding of mesoporous materials self-assembly. The self-assembly process that drives the formation of an organized mesoporous structure depends on several chemical-physical processes that must be properly designed and governed. In particular, the interaction between t...

Self-assembled materials can be obtained of different compositions; however, due to the specific characteristics of silicon chemistry, silica-based mesostructured materials are among the most intriguing and exciting to study. Therefore, this short volume is dedicated to the silica self-assembly, and in this chapter, we will briefly summarize the fu...

This chapter is dedicated to describing self-assembly during the deposition of a thin silica film. It is a very complex process that can be well controlled through an accurate design of the process parameters. The solvent’s evaporation in the precursor sol induces self-organization through the changes of the chemical-physical variables of the syste...

One of the most important challenges to be faced in the self-assembly of mesoporous films is the control of the organization on a dimensional scale that extends beyond the micron. Furthermore, defects of different types can form during the self-assembly process, similarly to what is observed in crystalline structures. Defect control is critical bec...

Mesoporous materials are defined in general terms by their pore dimension which falls in the 2–10 nm range (Beck and Vartuli in Curr. Opin. Solid State Mater. Sci. 1:76–87, 1996 [1]; Beck et al. in J. Am. Chem. Soc. 114:10834–10843, 1992 [2]). This porosity is coupled with a very high surface area that could be as large as 1000 m² g⁻¹.

The characterization of the EISA process by time-resolved and in-situ techniques such as SAXS and ellipsoporosimetry (Boissiere et al. in Langmuir 21:12362–12371, 2005 1), has allowed to follow in real time the disorder to order transition in thin mesoporous films during the deposition process. The techniques have shown how the system evolves from...

This book introduces the fascinating world of self-assembly in mesoporous ordered silica films. Beginning from a single droplet, it guides the reader, in a step-by-step learning process, how to obtain and control ordered porous mesophases in thin films by varying only the precursor chemistry and the process. It explains, in great detail, how order...

Fabrication of hydrophobic thin films from a liquid phase is a hot topic with critical technological issues. Interest in the production of hydrophobic surfaces is growing steadily due to their wide applications in several industrial fields. Thin films from liquid phases can be deposited on different types of surfaces using a wide variety of techniq...

The coronavirus pandemic (COVID-19) had spread rapidly since December 2019, when it was first identified in Wuhan, China. As of April 2021, more than 130 million cases have been confirmed, with more than 3 million deaths, making it one of the deadliest pandemics in history. Different approaches must be put in place to confront a new pandemic: commu...

The polycondensation of amino acids can originate complex polymers that display fascinating structural and optical properties. Thermally induced amidation of l-lysine allows forming a branched polymer without the support of any catalyst. The polycondensation is completed at 240–250 °C; at higher temperatures, the amino acid degrades. The obtained p...

Nitrite ions pose a severe problem to human health justifying the need for fast and reliable detection of their presence in freshwater. Here we report a method to detect nitrite by photoluminescence of amino-rich carbon dots (C-dots). The dots are synthesized from p-phenylenediamine through a solvothermal treatment in ethanol. When nitrites ions ar...

Hexagonal boron nitride (h-BN) is one of the most attractive 2D materials due to its remarkable properties. Combining h-BN with other components (e.g. graphene, carbonitride, semiconductors) to form heterostructures opens new perspectives to developing advanced functional devices. In this review, we have highlighted the state-of-the-art in h-BN het...

Hexagonal boron nitride (h-BN) nanodots of 10 nm have been synthesized via top-down route from bulk powders. A combination of ultrasonic and thermal treatments in phosphoric acid has been used to achieve edge etching and size reduction to the nanoscale. A new emission in the ultraviolet region, correlated to a characteristic infrared-active vibrati...

Hexagonal boron nitride (h-BN) nanodots of 10 nm have been synthesized via top-down route from bulk powders. A combination of ultrasonic and thermal treatments in phosphoric acid has been used to achieve edge etching and size reduction to the nanoscale. A new emission in the ultraviolet region, correlated to a characteristic infrared-active vibrati...

Exposure to styrene is a major safety concern in the fibreglass processing industry. This compound is classified by the International Agency for Research on Cancer as a possible human carcinogen. Several types of analytical equipment exist for detecting volatile organic compounds (VOCs) in the atmosphere; however, most of them operate ex-situ or do...

The fabrication of optically active heterostructures in the shape of mesostructured thin films is a highly challenging task. It requires an integrated process to allow in one-step incorporating the two-dimensional materials within the mesoporous ordered host without disrupting the pore organization. Hexagonal boron nitride (BN) nanosheets have been...

Molecular structures of siloxane materials should be highly controlled for achieving advanced functionalities. However, it is still difficult to precisely control the structure of siloxane materials by the sol–gel processing. In the present study, we focused on the silanol groups in the intermediate oligomers and resultant siloxane materials as a k...

Functionalization of boron nitride (BN) materials with hydroxyls has attracted great attention to accomplish better performances at micro- and nanoscale. BN surface hydroxylation, in fact, induces a change in properties and allows expanding the fields of application. In this review, we have summarized the state-of-the-art in developing hydroxylated...

Carbonized polymer dots (CPDs), a peculiar type of carbon dots, show extremely high quantum yields, making them very attractive nanostructures for application in optics and biophotonics. The origin of the strong photoluminescence of CPDs resides in a complicated interplay of several radiative mechanisms. To understand the correlation between CPD pr...

Carbon dots (CDs) are highly-emissive nanoparticles obtained through fast and cheap syntheses. The understanding of CDs’ luminescence, however, is still far from being comprehensive. The intense photoluminescence can have different origins: molecular mechanisms, oxidation of polyaromatic graphene-like layers, and core-shell interactions of carbonac...

In recent years, carbon dots (CDs) have attracted considerable attention for their potential application in photonics and optoelectronics. One of the main limitations in realizing efficient and reliable solid-state devices is the aggregation-caused quenching effect. At a short distance, the mutual interaction among nanoparticles enhances the non-ra...

The development of functional optoelectronic applications based on hexagonal boron nitride nanosheets (h-BNNs) relies on controlling the structural defects. The fluorescent emission, in particular, has been observed to depend on vacancies and substitutional defects. In the present work, few-layer h-BNNs have been obtained by sonication-assisted liq...

The origin of carbon-dots (C-dots) fluorescence and its correlation with the dots structure still lack a comprehensive model. In particular, the core-shell model does not always fit with the experimental results, which, in some cases, suggest a molecular origin of the fluorescence. To gain a better insight, we have studied the response of molecular...

The appearance of new and lethal viruses and their potential threat urgently requires innovative antiviral systems. In addition to the most common and proven pharmacological methods, nanomaterials can represent alternative resources to fight viruses at different stages of infection, by a selective action or in a broad spectrum. A fundamental requir...

Investigating and understanding in detail the sol-to-gel transition in inorganic and hybrid systems is a very challenging task. The transition is a critical phenomenon that can only be described with statistical but not thermodynamic models. Graphic schemes, therefore, cannot easily represent such a complicated process. The sol-to-gel transition ha...

Citrazinic acid (CZA) is a weakly fluorescent molecular compound whose optical properties are dependent on aggregation states and chemical environment. This molecule and its derivatives have been recently identified as the source of the intense blue emission of carbon dots obtained from citric acid with a nitrogen source, such as ammonia or urea. C...

Dual-tethered nanosystems which combine different properties at the nanoscale represent a new fascinating frontier of research. In the present work, we present an example of dual nanosystem designed to enhance the radical scavenging performances. Fulleropyrrolidine has been bonded to cerium oxide nanoparticles (nanoceria) to form a dual tethered sy...

Leonardo’s machine designs are an extraordinary testimony to the technologies developed during the Renaissance. Leonardo’s Codices contain a repertoire of machines of all types and for different uses. Many of these projects are shown by Leonardo with extreme attention to details and a sophisticated level of technical representation. Leonardo also a...

Highly fluorescent blue and green-emitting carbon dots have been designed to be integrated into sol-gel processing of hybrid organic-inorganic materials through surface modification with an organosilane, 3-(aminopropyl)triethoxysilane (APTES). The carbon dots have been synthesised using citric acid and urea as precursors; the intense fluorescence e...

Understanding the luminescence of carbon dots is a highly challenging task because of the complex reactions involved in the synthesis process. Several by-products form at different reaction stages and become possible sources of emission. Citrazinic acid and its derivatives, in particular, have been identified as intermediates that give rise to blue...

Despite the potential applications in several technological fields, 2D materials are at their early stages. Among them, boron nitride-based systems are still far from having been comprehensively studied. The possibilities of practical applications extend to very varied fields, from mechanics to optics. However, from careful observation of the exper...

The discovery of graphene has paved the way for intense research into 2D materials which is expected to have a tremendous impact on our knowledge of material properties in small dimensions. Among other materials, boron nitride (BN) nanomaterials have shown remarkable features with the possibility of being used in a large variety of devices. Photoni...

Microporous organic-inorganic hybrid silica films have been designed as active platforms to realise a styrene gas sensor. The microporous film has been synthesized by using tetraethylorthosilicate and phenyltriethoxysilane as precursors and a triblock copolymer (Pluronic F127) as a template for the pores. Multilayer films have been employed to incr...

Bottom-up synthesis of fluorescent boron-nitride based dots is a challenging task because an accurate design of the structure-properties relationship is, in general, difficult to achieve. Incorporation of the dots into a solid-state matrix is also another important target to develop light-emitting devices. Two-colour fluorescent boron oxynitride na...

Thermal decomposition of citric acid is one of the most common synthesis methods for fluorescent carbon dots; the reaction pathway is, however, quite complex and the details are still far from being understood. For instance, several intermediates form during the process and they also give rise to fluorescent species. In the present work, the format...

Thermal decomposition of citric acid is one of the most common syntheses of fluorescent C-dots; the reaction pathway is, however, quite complex and the details are still far from being understood. For instance, several intermediates form during the process and they also give rise to fluorescent species. In the present work, the formation of fluores...

The sol to gel transition in inorganic systems is a process highly dependent on the synthesis conditions. The chemistry of silicon alkoxides, in particular, is very difficult to handle because so many different species can form from the very beginning of the process and a small change of the synthesis parameters is immediately reflected on the hydr...

The sol to gel transition in a bulk gel is a macroscopic event which can be followed using different analytical methods, and even if an accurate determination of the gelation time is always a difficult task, it is possible to obtain reliable measures especially by a combination of several techniques. The liquid phase of the gel remains, even after...

The transformation of an inorganic sol into a gel is a complex process which involves several reactions. Hydrolysis and condensation govern the process, but several parameters, such as the pH, the catalyst, the concentration of the precursor, and the temperature, are some of the variables that affect the formation of the final gel and the sol to ge...

Giving a clear and widely accepted definition in chemistry and physics is always a pretty difficult task, especially because the frontier of science is continuously moving. Time is a good friend for science because knowledge accumulates and allows getting a wider and deeper understanding of nature; however, it is also more complicated organizing wh...

This chapter is dedicated to the methods and techniques which have been used to assess and measure the sol to gel transition and the gel point. The rheological methods have been the first to be applied even if the change in viscosity is not a reliable way to define the gel point. The viscosity gives, however, direct information on the change of the...

The sol to gel transition is a critical phenomenon which is observed in systems of different nature and composition. Several theories using different mathematical approaches have been developed with the main purpose of predicting the gel point. These models have been applied to systems which grow in a stochastic way and to different practical probl...

Sol-gel processing is a highly versatile method and allows obtaining a large variety of materials of different composition such as oxides, mixed oxides, and hybrid organic-inorganic materials. The chemistry of the process largely depends on the choice of precursors. Inorganic salts, metal alkoxides, and organosilanes are some of the most common com...

Raman spectroscopy is one of the most sensitive analytical techniques with the possibility of reaching single molecule detection through the surface-enhanced Raman scattering (SERS). Mesoporous materials, which exhibit an organized porosity in the 2–10 nm range, represent an advanced platform for developing SERS-based systems and devices for multip...

After a lifetime of wandering around Italy, Leonardo made his way to France in the autumn of 1516, accompanied by his servant Battista, and his beloved pupils Francesco Melzi and Salai. He was tired and sick and likely knew that this might be his final journey. Leonardo brought with him some of his most famous paintings, the Gioconda (Mona Lisa) an...

One of the best preserved treasures of the Veneranda Biblioteca Ambrosiana (The Ambrosian Library) in Milan, one of the oldest libraries in the world, is an incredible collection of 1110 folios written by Leonardo da Vinci. They form the so-called Codex Atlanticus. It is the largest surviving collection of notes from Leonardo and has a complicated...

On folio 1058v of the Codex Atlanticus, Leonardo traced a small drawing which has garnered much attention despite its size. It is not very flashy in the context of the page but strikes a contemporary observer at first sight. It is a rough sketch of a man hanging from a pyramidal object seemingly made of cloth (Fig. 4.1).

During the Renaissance, engineering techniques for shipbuilding were of enormous civilian and military interest. At the time, ships were still powered by traditional systems of sails and oars, but new possibilities started to be proposed. These were mostly exploratory in nature and would only come to fruition centuries later, with the emergence of...

The dream of a machine able to remain indefinitely in motion without any external energy source—i.e., the possibility of perpetual motion—is one of those die-hard ideas that still haunts the imagination of many amateur inventors. The history of the search for perpetual motion is full of frustrating attempts, failures, and reattempts in spite of the...

As we saw in the previous chapter, Leonardo developed a very special affection for the geometry of solids which guided him into a fascinating exploration of new forms. This work was not only driven by intellectual curiosity but was also inspired by the need to couple function and form in the design of his innovative machines, such as the “automobil...

The Renaissance engineers devoted special attention to a particular kind of war instrument: the war chariots. The result of their efforts is an impressive list of mobile systems for warfare: scythed chariots, wagons loaded with soldiers, armored vehicles with protection from external attacks, mobile towers built to break through defensive walls, an...

The close relationship between art and science is a distinctive feature of the Renaissance, and, as we have observed again and again, Leonardo represents one of the highest points of this synthesis. The scientific knowledge that he obtained via his studies became a fundamental instrument also for his work as an artist and vice versa. As discussed i...

Among the most famous images of Leonardo, next to the paintings of the Mona Lisa and the Last Supper, we can certainly place the Vitruvian Man, a figure that perfectly represents the Renaissance ideal of man as the measure of all things and the center of creation. Few other images have so captured the popular imagination to become a global icon and...

Leonardo was an affable and gentle person, and during the course of his whole life, he was surrounded by the affection of his many pupils and friends. In Milan, as we have seen in the previous chapter, he enjoyed something akin to brotherhood with Giacomo Andrea, and he also had a very special friendship with the Tuscan mathematician Luca Pacioli w...

The artist-engineers of the Renaissance, including Leonardo, had a special passion, even obsession, for the natural element of water. They dedicated a lot of time to hydraulic studies and to designing innovative machines using water as the driving force. This attraction to water should not come as a surprise. After all, aside from animal power, wat...

To indicate the inability to achieve an enterprise or the futility of some theoretical disquisitions, a range of idiomatic expressions are frequently used in our daily conversation, such as discussing “how many angels can stand on the point of a pin” This saying comes from the long disputes of medieval scholars about angelology, which now appear of...

Leonardo da Vinci dedicated a full page, folio 33r in the Manuscript B, to illustrating a strange type of gun whose invention he attributed to Archimedes (c. 287 BC–212 BC). Leonardo described system’s working in detail and accompanied the note with two drawings, one showing the instrument’s operation (Fig. 15.1) and the other presenting a design f...

Measuring time as accurately as possible has always represented a significant technological challenge. Rather simple time measurement systems had been developed since antiquity, such as hourglasses, sundials, and water clocks, but it was only with the advent of the first mechanical systems in the late Middle Ages that the way would be paved for the...