Self-Standing 3D-Printed PEGDA-PANIs Electroconductive Hydrogel Composites for pH Monitoring.

Additive manufacturing (AM), or 3D printing processes, is introducing new possibilities in electronic, biomedical, sensor-designing, and wearable technologies. In this context, the present work focuses on the development of flexible 3D-printed polyethylene glycol diacrylate (PEGDA)- sulfonated polyaniline (PANIs) electrically conductive hydrogels (ECHs) for pH-monitoring applications. PEGDA platforms are 3D printed by a stereolithography (SLA) approach. Here, we report the successful realization of PEGDA-PANIs electroconductive hydrogel (ECH) composites produced by an in situ chemical oxidative co-polymerization of aniline (ANI) and aniline 2-sulfonic acid (ANIs) monomers at a 1:1 equimolar ratio in acidic medium. The morphological and functional properties of PEGDA-PANIs are compared to those of PEGDA-PANI composites by coupling SEM, swelling degree, I-V, and electro-chemo-mechanical analyses. The differences are discussed as a function of morphological, structural, and charge transfer/transport properties of the respective PANIs and PANI filler. Our investigation showed that the electrochemical activity of PANIs allows for the exploitation of the PEGDA-PANIs composite as an electrode material for pH monitoring in a linear range compatible with that of most biofluids. This feature, combined with the superior electromechanical behavior, swelling capacity, and water retention properties, makes PEGDA-PANIs hydrogel a promising active material for developing advanced biomedical, soft tissue, and biocompatible electronic applications.

Nanodiamond Influence on the Nucleation and Growth of YBCO Superconducting Film Deposited by Metal-Organic Decomposition.

It was recently shown that the introduction of nanodiamond (ND) into a superconducting metal-organic deposited YBa2Cu3O7-δ (YBCO) film produces an increase in critical current density in self-field conditions (B = 0 T). Such improvement appears to be due to the formation of denser and smoother films than the samples deposited without ND. This paper presents the work done to understand the role of ND during YBCO nucleation and growth. A detailed study on YBCO+ND films quenched at different temperatures of the crystallization process was carried out. Results showed that the reaction responsible for YBCO production appeared effectively affected by ND. In particular, ND stabilizes one of the YBCO precursors, BaF2(1-x)Ox, whose conversion into YBCO requires a prolonged time. Therefore, the YBCO nucleation is slowed down by ND and begins when the experimental conditions favor both thermodynamically and kinetically the formation of YBCO along the c-axis. This effect has important implications because the growth of a highly epitaxial c-axis YBCO film enables excellent superconducting performance.

A Sustainable Hydroxypropyl Cellulose-Nanodiamond Composite for Flexible Electronic Applications.

Designing fully green materials for flexible electronics is an urgent need due to the growing awareness of an environmental crisis. With the aim of developing a sustainable, printable, and biocompatible material to be exploited in flexible electronics, the rheological, structural and charge transport properties of water-based hydroxypropyl cellulose (HPC)-detonation nanodiamond (DND) viscous dispersions are investigated. A rheological investigation disclosed that the presence of the DND affects the orientation and entanglement of cellulose chains in the aqueous medium. In line with rheological analyses, the NMR diffusion experiments pointed out that the presence of DND modifies the hydrodynamic behavior of the cellulose molecules. Despite the increased rigidity of the system, the presence of DND slightly enhances the ionic conductivity of the dispersion, suggesting a modification in the charge transport properties of the material. The electrochemical analyses, performed through Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS), revealed that the HPC-DND system is remarkably stable in the explored voltage range (-0.1 to +0.4 V) and characterized by a lowered bulk resistance with respect to HPC. Such features, coupled with the printability and filmability of the material, represent good requirements for the exploitation of such systems in flexible electronic applications.

Single-walled carbon nanotubes protect photosynthetic reactions in Chlamydomonas reinhardtii against photoinhibition.

Single-walled carbon nanotubes (SWCNTs) are among the most exploited carbon allotropes in nanosensing, bioengineering, and photobiological applications, however, the interactions of nanotubes with the photosynthetic process and structures are still poorly understood. We found that SWCNTs are not toxic to the photosynthetic apparatus of the model unicellular alga Chlamydomonas reinhardtii and demonstrate that this carbon nanomaterial can protect algal photosynthesis against photoinhibition. The results show that the inherent phytotoxicity of the nanotubes may be overcome by an intentional selection of nanomaterial characteristics. A low concentration (2 µg mL-1) of well-dispersed, purified and small SWCNTs did not alter the growth and pigment accumulation of the cultures. Indeed, under the photoinhibitory conditions of our experiments, SWCNT-enriched samples were characterized by a lower rate of PSII inactivation, reduced excitation pressure in PSII, a higher rate of photosynthetic electron transport, and an increased non-photochemical quenching in comparison with the controls. In addition, SWCNTs change the distribution of energy between the photosystems in favour of PSII (state 1). The underlying mechanism of this action is not yet understood but possibly, electrons or energy can be exchanged between the redox active nanotubes and photosynthetic components, and probably other redox active intra-chloroplast constituents. Alternatively, nanotubes may promote the formation of an NPQ conformation of PSII. Our results provided evidence for such electron/energy transfer from photosynthetic structures toward the nanotubes. The discovered photoprotective effects can potentially be used in photobiotechnology to maintain the photosynthetic activity of microorganisms under unfavourable conditions.

Mapping Single Walled Carbon Nanotubes in Photosynthetic Algae by Single-Cell Confocal Raman Microscopy.

Carbon nanotubes (CNTs) are among the most exploited carbon allotropes in the emerging technologies of molecular sensing and bioengineering. However, the advancement of algal nanobiotechnology and nanobionics is hindered by the lack of methods for the straightforward visualization of the CNTs inside the cell. Herein, we present a handy and label-free experimental strategy based on visible Raman microscopy to assess the internalization of single-walled carbon nanotubes (SWCNTs) using the model photosynthetic alga Chlamydomonas reinhardtii as a recipient. The relationship between the properties of SWCNTs and their biological behavior was demonstrated, along with the occurrence of excitation energy transfer from the excited chlorophyll molecules to the SWCNTs. The non-radiative deactivation of the chlorophyll excitation promoted by the SWCNTs enables the recording of Raman signals originating from cellular compounds located near the nanotubes, such as carotenoids, polyphosphates, and starch. Furthermore, the outcome of this study unveils the possibility to exploit SWCNTs as spectroscopic probes in photosynthetic and non-photosynthetic systems where the fluorescence background hinders the acquisition of Raman scattering signals.

The Integration of Metagenomics and Chemical Physical Techniques Biodecoded the Buried Traces of the Biodeteriogens of Parchment Purple Spots.

Ancient parchments record an immense part of our cultural heritage, having been used as the main written support material for centuries. Parchment easily undergoes biodeterioration, whose main signs are the so-called purple spots, which often lead to detachment of the superficial written layer. Up to recent years, several studies have been analyzing damaged parchments from different world's archives, trying to trace back the culprit of the purple spots. However, standard cultivation and early molecular techniques have been demonstrated to be unsuccessful, leading the parchment damage issue remaining unsolved for many years. Nowadays, some studies have explored the parchment biodeterioration dynamics by adopting a multidisciplinary approach combining standard microbiological methods with high-throughput molecular, chemical and physical techniques. This approach allowed an unprecedented level of knowledge on the complex dynamics of parchment biodeterioration. This mini review discusses the application of the combination of basic and high-throughput techniques to study historical parchments, highlighting the strengths and weaknesses of this approach. In particular, it focuses on how metagenomics has been paramount for the unequivocal identification of the microbial main actors of parchment biodeterioration and their dynamics, but also on how metagenomics may suffer the distortion inflict by the historical perspective on the analysis of ancient specimens. As a whole, this mini review aims to describe the scenario of information on parchment biodeterioration obtained so far by using the integration of metagenomic with recent chemical (Raman spectroscopy) and physical (Light Transmission Analysis) approaches, which might have key implications in the preservation of many ancient documents.

The Stain of the Original Salt: Red Heats on Chrome Tanned Leathers and Purple Spots on Ancient Parchments Are Two Sides of the Same Ecological Coin.

Animal hides are one of man's earliest and mostly used materials; many rawhide products, primarily leather, have for centuries been used for several purposes. The peculiar mechanical properties of leather depend on the hide composition, a dense collagen feltwork. Unfortunately, due to their proteic composition, rawhides may undergo microbial attack and biodeterioration. Over centuries, different processes and treatments (brining, vegetal or chrome tanning, tawing, etc.) were set up to face the biological attack and modify/stabilise the hide's mechanical properties. Nevertheless, even present-day rawhides are subjected to biological colonisation, and traces of this colonisation are clearly shown in Chrome(III) tanned leathers (in the wet blue stage), with obvious economic damages. The colonisation traces on tanned leathers consist of isolated or coalescent red patches, known as red heat deterioration. Parchments are rawhide products, too; they derive from another manufacturing procedure. Even parchments undergo microbial attack; the parchment biodeterioration seems comparable to leather red heat deterioration and is known as purple spots. Recently, an ecological succession model explained the process of historical parchment purple spot deterioration; the haloarchaea Halobacterium salinarum is the pioneer organism triggering this attack. The marine salt used to prevent rawhide rotting is the carrier of haloarchaea colonisers (Migliore et al., 2019). The aim of this study was to investigate the dynamics of biodeterioration on Chrome(III) tanned leathers and its effects on the stability/integrity of collagen structure. To this end, standard cultivation methods were integrated with three updated technologies, Next-Generation Sequencing (NGS), Raman spectroscopy, and Light Transmitted Analysis (LTA). A bioinformatic comparison between chrome tanned leather vs. historical parchment colonisers was performed to evaluate if leather and parchment share common culprits; furthermore, the effect of the biodeterioration on the physical properties of the hide product was evaluated.

Three ancient documents solve the jigsaw of the parchment purple spot deterioration and validate the microbial succession model.

The preservation of cultural heritage is one of the major challenges of today's society. Parchments, a semi-solid matrix of collagen produced from animal skin, are a significant part of the cultural heritage, being used as writing material since ancient times. Due to their animal origin, parchments easily undergo biodeterioration: the most common biological damage is characterized by isolated or coalescent purple spots, that often lead to the detachment of the superficial layer and the consequent loss of written content. Although many parchments with purple spot biodegradative features were studied, no common causative agent had been identified so far. In a previous study a successional model has been proposed, basing on the multidisciplinary analysis of damaged versus undamaged samples from a moderately damaged document. Although no specific sequences were observed, the results pointed to Halobacterium salinarum as the starting actor of the succession. In this study, to further investigate this topic, three dramatically damaged parchments were analysed; belonging to a collection archived as Faldone Patrizi A 19, and dated back XVI-XVII century A.D. With the same multidisciplinary approach, the Next Generation Sequencing (NGS, Illumina platform) revealed DNA sequences belonging to Halobacterium salinarum; the RAMAN spectroscopy identified the pigment within the purple spots as haloarchaeal bacterioruberin and bacteriorhodopsine, and the LTA technique quantified the extremely damaged collagen structures through the entire parchments, due to the biological attack to the parchment frame structures. These results allowed to propose a model of the progressive degradation pattern of the parchment collagen. Overall, these data validate a multi-phase microbial succession model. This demonstration is pivotal to possible new restoration strategies, important for a huge number of ancient documents.

Purple spot damage dynamics investigated by an integrated approach on a 1244 A.D. parchment roll from the Secret Vatican Archive.

Ancient parchments are commonly attacked by microbes, producing purple spots and detachment of the superficial layer. Neither standard cultivation nor molecular methods (DGGE) solved the issue: causative agents and colonization model are still unknown. To identify the putative causal agents, we describe the 16 S rRNA gene analysis (454-pyrosequencing) of the microbial communities colonizing a damaged parchment roll dated 1244 A.D. (A.A. Arm. I-XVIII 3328, Vatican Secret Archives). The taxa in damaged or undamaged areas of the same document were different. In the purple spots, marine halotolerant Gammaproteobacteria, mainly Vibrio, were found; these microorganisms are rare or absent in the undamaged areas. Ubiquitous and environmental microorganisms were observed in samples from both damaged and undamaged areas. Pseudonocardiales were the most common, representing the main colonizers of undamaged areas. We hypothesize a successional model of biodeterioration, based on metagenomic data and spectroscopic analysis of pigments, which help to relate the damage to a microbial agent. Furthermore, a new method (Light Transmitted Analysis) was utilized to evaluate the kind and entity of the damage to native collagen. These data give a significant advance to the knowledge in the field and open new perspectives to remediation activity on a huge amount of ancient document.

Structural and morphological peculiarities of hybrid Au/nanodiamond engineered nanostructures.

Nanostructured Au nano-platelets have been synthesized from an Au(III) complex by growth process triggered by nanodiamond (ND). An electroless synthetic route has been used to obtain 2D Au/ND architectures, where individual nanodiamond particles are intimately embedded into face-centered cubic Au platelets. The combined use of high resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED), was able to reveal the unusual organization of these hybrid nanoparticles, ascertaining the existence of preferential crystallographic orientations for both nanocrystalline species and highlighting their mutual locations. Detailed information on the sample microstructure have been gathered by fast Fourier transform (FFT) and inverse fast Fourier transform (IFFT) of HR-TEM images, allowing us to figure out the role of Au defects, able to anchor ND crystallites and to provide specific sites for heteroepitaxial Au growth. Aggregates constituted by coupled ND and Au, represent interesting systems conjugating the best optoelectronics and plasmonics properties of the two different materials. In order to promote realistically the applications of such outstanding Au/ND materials, the cooperative mechanisms at the basis of material synthesis and their influence on the details of the hybrid nanostructures have to be deeply understood.

Graphene Meets Microbubbles: A Superior Contrast Agent for Photoacoustic Imaging.

Coupling graphene with a soft polymer surface offers the possibility to build hybrid constructs with new electrical, optical, and mechanical properties. However, the low reactivity of graphene is a hurdle in the synthesis of such systems which is often bypassed by oxidizing its carbon planar structure. However, the defects introduced with this process jeopardize the properties of graphene. In this paper we present a different approach, applicable to many different polymer surfaces, which uses surfactant assisted ultrasonication to exfoliate, and simultaneously suspend, graphene in water in its intact form. Tethering pristine graphene sheets to the surfaces is accomplished by using suitable reactive functional groups of the surfactant scaffold. We focused on applying this approach to the fabrication of a hybrid system, made of pristine graphene tethered to poly(vinyl alcohol) based microbubbles (PVA MBs), designed for enhancing photoacoustic signals. Photoacoustic imaging (PAI) is a powerful preclinical diagnostic tool which provides real time images at a resolution of 40 µm. The leap toward clinical imaging has so far been hindered by the limited tissues penetration of near-infrared (NIR) pulsed laser radiation. Many academic and industrial research laboratories have met this challenge by designing devices, each with pros and cons, to enhance the photoacoustic (PA) signal. The major advantages of the hybrid graphene/PVA MBs construct, however, are (i) the preservation of graphene properties, (ii) biocompatibility, a consequence of the robust anchoring of pristine graphene to the bioinert surface of the PVA bubble, and (iii) a very good enhancement in a NIR spectral region of the PA signal, which does not overlap with the signals of PA active endogenous molecules such as hemoglobin.

Hydrogen Adsorption Properties of Carbon Nanotubes and Platinum Nanoparticles from a New Ammonium-Ethylimidazolium Chloroplatinate Salt.

Self-supporting membranes built entirely of carbon nanotubes have been prepared by wet methods and characterized by Raman spectroscopy. The membranes are used as supports for the electrodeposition of Pt nanoparticles without the use of additional additives and/or stabilizers. The Pt precursor is an ad hoc synthesized ammonium-ethylimidazolium chloroplatinate(IV) salt, [NH3 (CH2 )2 MIM)][PtCl6 ]. The Pt complex was characterized using NMR spectroscopy, XRD, ESI-MS, and FTIR spectroscopy. The interaction between the Pt-carbon nanotubes nanocomposites and hydrogen is analyzed using electrochemical and quartz microbalance measurements under near-ambient conditions. The contribution of the Pt phase to the hydrogen adsorption on nanotube is found and explained by a kinetic model that takes into account a spillover event. Such a phenomenon may be exploited conveniently for catalysis and electrocatalysis applications in which the hybrid systems could act as a hydrogen transfer agent in specific hydrogenation reactions.

Nanodiamonds coupled with 5,7-dimethoxycoumarin, a plant bioactive metabolite, interfere with the mitotic process in B16F10 cells altering the actin organization.

For the first time, we coupled reduced detonation nanodiamonds (NDs) with a plant secondary metabolite, citropten (5,7-dimethoxycoumarin), and demonstrated how this complex was able to reduce B16F10 tumor cell growth more effectively than treatment with the pure molecule. These results encouraged us to find out the specific mechanism underlying this phenomenon. Internalization kinetics and quantification of citropten in cells after treatment with its pure or ND-conjugated form were measured, and it was revealed that the coupling between NDs and citropten was essential for the biological properties of the complex. We showed that the adduct was not able to induce apoptosis, senescence, or differentiation, but it determined cell cycle arrest, morphological changes, and alteration of mRNA levels of the cytoskeletal-related genes. The identification of metaphasic nuclei and irregular disposition of ß-actin in the cell cytoplasm supported the hypothesis that citropten conjugated with NDs showed antimitotic properties in B16F10 cells. This work can be considered a pioneering piece of research that could promote and support the biomedical use of plant drug-functionalized NDs in cancer therapy.

Potential of carbon nanotubes in algal biotechnology.

A critical mass of knowledge is emerging on the interactions between plant cells and engineered nanomaterials, revealing the potential of plant nanobiotechnology to promote and support novel solutions for the development of a competitive bioeconomy. This knowledge can foster the adoption of new methodological strategies to empower the large-scale production of biomass from commercially important microalgae. The present review focuses on the potential of carbon nanotubes (CNTs) to enhance photosynthetic performance of microalgae by (i) widening the spectral region available for the energy conversion reactions and (ii) increasing the tolerance of microalgae towards unfavourable conditions occurring in mass production. To this end, current understanding on the mechanisms of uptake and localization of CNTs in plant cells is discussed. The available ecotoxicological data were used in an attempt to assess the feasibility of CNT-based applications in algal biotechnology, by critically correlating the experimental conditions with the observed adverse effects. Furthermore, main structural and physicochemical properties of single- and multi-walled CNTs and common approaches for the functionalization and characterization of CNTs in biological environment are presented. Here, we explore the potential that nanotechnology can offer to enhance functions of algae, paving the way for a more efficient use of photosynthetic algal systems in the sustainable production of energy, biomass and high-value compounds.

Nanodiamonds for field emission: state of the art.

The aim of this review is to highlight the recent advances and the main remaining challenges related to the issue of electron field emission (FE) from nanodiamonds. The roadmap for FE vacuum microelectronic devices envisages that nanodiamonds could become very important in a short time. The intrinsic properties of the nanodiamond materials indeed meet many of the requirements of cutting-edge technologies and further benefits can be obtained by tailored improvements of processing methodologies. The current strategies used to modulate the morphological and structural features of diamond to produce highly performing emitting systems are reported and discussed. The focus is on the current understanding of the FE process from nanodiamond-based materials and on the major concepts used to improve their performance. A short survey of non-conventional microsized cold cathodes based on nanodiamonds is also reported.

"Soft" confinement of graphene in hydrogel matrixes.

Graphene plays as protagonist among the newly discovered carbon nanomaterials on the laboratory bench. Confinement of graphene, combined with enhanced exchange properties within aqueous environment, is key for the development of biosensors, biomedicine devices, and water remediation applications. Such confinement is possible using hydrogels as soft matrixes. Many entrapment methods focused on the modification of the graphene structure. In this paper, however, we address a confinement method that leaves unchanged the graphene structure, although intimately participating in the buildup of a network of polyvinyl alcohol (PVA) chains. PVA is a polymer known as biomaterial for its hydrophilicity, biocompatibility, and chemical versatility. A robust hybrid PVA-graphene construct was obtained starting from a surfactant-assisted sonication of an aqueous dispersion of graphite. Stable graphene sheets suspension was photopolymerized in a methacryloyl-grafted PVA, using the vinyl moiety present on the surfactant scaffold. This method can allow the incorporation in the polymer network of oligomers of N-(isopropylacrylammide), p(NiPAAm). These chains display in aqueous solution a low critical solution temperature, LCST, around 33 °C and trigger a volume phase transition when incorporated in a hydrophilic network around the physiological temperature. Raman analysis was used to characterize the state of hydrogel embedded graphene single sheets. Evidence for an intimate interaction of graphene sheets and polymer matrix was collected. Release of the anticancer drug doxorubicin showed the active role of the graphene/PVA/p(NiPAAm) construct in the drug delivery.

Nanodiamonds coupled with plant bioactive metabolites: a nanotech approach for cancer therapy.

Nanodiamond application in biotechnological and medical fields is nowadays in continuous progress. In fact, biocompatibility, reduced dimensions and high surface chemical interaction are specific features that make nanodiamonds perfect intracellular carriers of bioactive compounds. By confocal microscopy, we confirmed that nanodiamonds were able to penetrate in cell cytoplasm but we also demonstrated how they remained embedded in nuclear membrane just exposing some little portions into nuclear area, definitively clarifying this topic. In this work, for the first time, nanodiamonds were conjugated with plant secondary metabolites, ciproten and quercetin. Moreover, since drug-loading on nanoparticles was strongly conditioned by their chemical surface, different types of nanodiamonds (oxidized, wet chemical reduced and plasma reduced) were synthesized in this work and then functionalized with plant compounds. We found that ciproten and quercetin antiproliferative effects, on human (HeLa) and murine (B16F10) tumor cells, were improved after nanodiamond conjugation. Moreover, plant molecules highly reduced their in vitro pro-oxidant, cytotoxic and pro-apoptotic activity when associated with nanodiamond. We are led to suppose that natural drug-nanodiamond adducts would act at cellular level by different molecular mechanisms with respect to plant metabolite pure forms. Finally, our results showed that chemical and structural modifications of nanodiamond surfaces influenced the bioactivity of transported drugs. According to all these evidences, this work can be considered as a promotional research to favor the use of bioactive plant molecules associated with nanodiamonds for therapeutic purposes.

Nanocarbon surfaces for biomedicine.

The distinctive physicochemical, mechanical and electrical properties of carbon nanostructures are currently gaining the interest of researchers working in bioengineering and biomedical fields. Carbon nanotubes, carbon dendrimers, graphenic platelets and nanodiamonds are deeply studied aiming at their application in several areas of biology and medicine.   Here we provide a summary of the carbon nanomaterials prepared in our labs and of the fabrication techniques used to produce several biomedical utilities, from scaffolds for tissue growth to cargos for drug delivery and to biosensors.