Smartphone-Based Sensing of Cortisol by Functionalized Rhodamine Probes.

During a stress condition, the human body synthesizes catecholamine neurotransmitters and specific hormones (called "stress hormones"), the most important of which is cortisol. The monitoring of cortisol levels should be extremely important to control the stress levels, and for this reason, it shows important medical applications. The common analytical methods (HPLC, GC-MS) cannot be used in real life, due to the bulky size of the instruments and the necessity of specialized personnel. Molecular probes solve these problems due to their fast and easy use. The synthesis of new fluorescent rhodamine probes, able to interact by non-covalent interactions with cortisol, the recognition properties in solution as well as in solid state by Strip Test, using a smartphone as detector, are here reported. DFT calculations and FT-IR measurements suggest the formation of supramolecular complexes through hydrogen bonds as main non-covalent interaction. The present study represents one of the first sensor, based on synthetical chemical receptors, able to detect cortisol in a linear range from 1 mM to 1 pM, based on non-covalent molecular recognition and paves the way to the realization of practical point-of-care device for the monitoring of cortisol in real live.

Carbon dots as a versatile tool to monitor insulin aggregation.

The possibility to monitor peptide and protein aggregation is of paramount importance in the so-called conformational diseases, as the understanding of many physiological pathways, as well as pathological processes involved in the development of such diseases, depends very much on the actual possibility to monitor biomolecule oligomeric distribution and aggregation. In this work, we report a novel experimental method to monitor protein aggregation, based on the change of the fluorescent properties of carbon dots upon protein binding. The results obtained in the case of insulin with this newly proposed experimental approach are compared with those obtained with other common experimental techniques normally used for the same purpose (circular dichroism, DLS, PICUP and ThT fluorescence). The greatest advantage of the hereby presented methodology over all the other experimental methods considered is the possibility to monitor the initial stages of insulin aggregation under the different experimental conditions sampled and the absence of possible disturbances and/or molecular probes during the aggregation process.

Direct Measurement of Surfactant-Mediated Picoforces among Nanoparticles in a Quasi-Two-Dimensional Environment.

The lack of methodologies which enable us to measure forces acting between nanomaterials is one of the factors limiting the full comprehension of their behavior and their more effective exploitation in new devices. Here we exploit the irreversible adsorption of surfactant-decorated nanoparticles at the air/water interface to investigate interparticle forces and the effect of the surfactant structure on them. We measured the interparticle repulsive forces as a function of the modulation of the interparticle distance by simultaneously performing compression isotherms and the grazing incidence small-angle X-ray scattering (GISAXS) structural characterization of the monolayers at water-vapor interfaces. Our results demonstrate that the short-range interparticle forces are strongly affected by the presence of the organic ligands, which are shown to be able to influence the interparticle repulsions even when added in micromolar amounts. In particular, we demonstrate the predominant steric nature of short-range forces, which are accounted for in terms of the compression-induced stretched-to-coiled conformational transition of the ligand hydrophobic tail.

Smartphone-Based Dopamine Detection by Fluorescent Supramolecular Sensor.

Supramolecular recognition of dopamine by two quinoxaline cavitands was studied in solution by fluorescence titrations, ESI-MS and ROESY measurements. In addition, the tetraquinoxaline cavitand was dropped onto a siloxane-based polymeric solid support, obtaining a sensor able to detect dopamine in a linear range of concentrations 10 Mm-100 pM, with a detection limit of 1 pM, much lower than the normal concentration values in the common human fluids (plasma, urine and saliva), by using a simple smartphone as detector. This sensor shows also good selectivity for dopamine respect to the other common analytes contained in a saliva sample and can be reused after acid-base cycles, paving the way for the realization of real practical sensor for human dopamine detection.

Revealing Contamination and Sequence of Overlapping Fingerprints by Unsupervised Treatment of a Hyperspectral Secondary Ion Mass Spectrometry Dataset.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been successfully applied for chemical imaging of overlapping fingermarks. The resulting big dataset has been treated by means of an unsupervised machine learning approach based on uniform manifold approximation and projection. The hyperspectral matrix was composed of 49 million pixels associated with 518 peaks. However, the single-pixel spectrum results in a very poor signal intensity, mostly like a barcode. Contrary to what has been reported in the literature recently, we have not applied a crude approach based on binning but a sophisticated machine learning method capable of separating the chemical signals of the two fingerprints from each other and from the substrate in which they were impressed. Moreover, using ToF-SIMS, an extremely surface-sensitive technique, the sequence of deposition of the fingerprints has been determined.

Agile Detection of Chemical Warfare Agents by Machine Vision: a Supramolecular Approach.

The supramolecular detection by image analysis of a simulant chemical warfare agent on a solid device containing a selective molecular sensor based on a BODIPY scaffold is reported. The recognition properties were investigated in solution, demonstrating high affinity (log K 6.60) and sensitivity (LOD 10 ppt). A test strip also confirmed the sensing properties in gas phase. Image analysis of the solid device allows quantitative information about the simulant to be obtained, recovering the sensor almost 5 times and thus confirming the goal of the supramolecular approach.

Supramolecular Sensing of a Chemical Warfare Agents Simulant by Functionalized Carbon Nanoparticles.

Real-time sensing of chemical warfare agents by optical sensors is today a crucial target to prevent terroristic attacks by chemical weapons. Here the synthesis, characterization and detection properties of a new sensor, based on covalently functionalized carbon nanoparticles, are reported. This nanosensor exploits noncovalent interactions, in particular hydrogen bonds, to detect DMMP, a simulant of nerve agents. The nanostructure of the sensor combined with the supramolecular sensing approach leads to high binding constant affinity, high selectivity and the possibility to reuse the sensor.

In situ structure and force characterization of 2D nano-colloids at the air/water interface.

The control of self-assembly and the related interactions among nanoparticles (NPs) at liquid surfaces and interfaces represents a stimulating experimental challenge to fully understand the behaviour of nano-colloids confined in a 2D asymmetric environment, in turn prompting the building of novel NP-based functional monolayers. Here, we first investigate the structural evolution of a model mixed surfactant/NP monolayer as a function of the surfactant/NP bulk ratio finding that, at ratios lower than 20, the adsorption at the air/water interface of surfactant-decorated NPs is dominant. We then employed these 2D nano-colloidal monolayers as model systems for grazing incidence small angle X-ray scattering measurements, performed using synchrotron radiation, while compressing the monolayers in a Langmuir trough. The simultaneous determination of the compression work and the related reduction of the inter-particle distance at the interface enabled, for the first time, the quantitative characterization of the forces acting between adsorbed NPs, as well as their dispersion law with the inter-particle distance. Distinct surfactant reorganization processes are proposed to interpret the measured forces and the characteristic inter-particle distances.

Reactive nanomessengers for artificial chemical communication.

Artificial chemical communication is an emerging field of study driven by the need of exchanging information in delicate environments where standard procedures based on electromagnetic waves cannot be used. A non-synchronized artificial chemical communication system, based on a new modulation technique, namely reaction shift keying (RSK), is presented. The RSK implies that the quenchers are injected into the transmitter, the chemical messenger reacts and a chemically modified messenger travels towards the receiver. Encoding of "0" is obtained by means of the emission of a messenger that reaches the receiver once chemically modified. To encode the value "1", the messenger is not subjected to chemical reaction. Fluorescent carbon nanoparticle molecular messengers that exploit the reaction with Cu(ii) ions for signal modulation were synthesized. A prototypal RSK modulated chemical communication system is developed, from simulations of the communication platform to an operating prototypal system.

Unsupervised Analysis of Big ToF-SIMS Data Sets: a Statistical Pattern Recognition Approach.

We present a new method, fast and low demanding in terms of CPU performances, which is able to extract latent chemical information from ToF-SIMS big data sets, such as those arising from chemical imaging, by working on the unbinned raw data files. The method is able to evaluate the similarity/dissimilarity of very low intensity spectra, such as those arising from a single pixel, in terms of symmetry and asymmetry relationships of the count distribution in the Fourier transform domain. The tests performed so far on model samples show that the method supplies results that, without sacrificing mass or spatial resolution, are equivalent, at least, to those achievable by an experienced ToF-SIMS user by applying PCA techniques.

Driving Coordination Polymer Monolayer Formation by Competitive Reactions at the Air/Water Interface.

We have developed a novel approach enabling us to follow and facilitate the formation of two-dimensional coordination polymer monolayers directly at the air/water interface without the need of complex instrumentation. The method is based on the use of a surface active ligand that, when spread at the air/water interface, progressively undergoes hydrolysis with consequent gradual decrease in surface pressure. Notably, if the aqueous subphase contains metal ions capable of coordinating the ligand, coordination competes with hydrolysis, resulting in a lower surface pressure decrease. As a consequence, the formation of the coordination polymer monolayer can be verified simply by surface pressure measurements. Competition between hydrolysis and coordination was investigated as a function of the main experimental parameters affecting the two reactions, enabling the formation of stable coordination polymer monolayers with controlled density. Finally, the formation of continuous rigid 2D layers was confirmed by compression isotherms and ex situ morphological characterization. This work will simplify the verification of coordination polymer monolayer formation; thus, it will boost the synthesis of novel and innovative 2D materials.

Reactive messengers for digital molecular communication with variable transmitter-receiver distance.

Molecular communication exploits functional molecular systems travelling along fluid media to deliver messages encoded as concentration pulses, e.g. molecular bits. As the bits are naturally broadened by diffusion, limiting the distance along which information can be transferred, by careful design and optimization of the molecular messengers, is required. A new paradigm, exploiting the chemical reactivity of a suitable molecular messenger, has been developed to achieve long range information transfer with variable transmitter-receiver distances. The experimental results and theoretical simulations, carried out by using fluorescent molecules switched by pH-driven hydrolysis, are reported here. In particular, we simulated the information transport process by using numerical solutions of differential equations governing information swapping and we show that by exploiting the reactivity of the chemical messenger, a stable signal at the receiver is maintained within a wide range of distance. This theoretical prediction was fully experimentally verified by using a prototypal molecular communication platform.

Detection of insulin oligomeric forms by a novel surface plasmon resonance-diffusion coefficient based approach.

Insulin is commonly used to treat diabetes and undergoes aggregation at the site of repeated injections in diabetic patients. Moreover, aggregation is also observed during its industrial production and transport and should be avoided to preserve its bioavailability to correctly adjust glucose levels in diabetic patients. However, monitoring the effect of various parameters (pH, protein concentration, metal ions, etc.) on the insulin aggregation and oligomerization state is very challenging. In this work, we have applied a novel Surface Plasmon Resonance (SPR)-based experimental approach to insulin solutions at various experimental conditions, monitoring how its diffusion coefficient is affected by pH and the presence of metal ions (copper and zinc) with unprecedented sensitivity, precision, and reproducibility. The reported SPR method, hereby applied to a protein for the first time, besides giving insight into the insulin oligomerization and aggregation phenomena, proved to be very robust for determining the diffusion coefficient of any biomolecule. A theoretical background is given together with the software description, specially designed to fit the experimental data. This new way of applying SPR represents an innovation in the bio-sensing field and expanding the potentiality of commonly used SPR instruments well over the canonical investigation of biomolecular interactions.

Chitosan-based films grafted with citrus waste-derived antifungal agents: An innovative and sustainable approach to enhance post-harvest preservation of citrus fruit.

This paper reports the synthesis, characterization, and properties of chitosan films (CHI) grafted with a natural antifungal agent with the aim of developing active films of natural origin to prevent post-harvest losses of citrus fruit. The antifungal agent was prepared by fermentation using lemon peel (AntiFun-LM), a citrus waste, and grafted on chitosan using different coupling agents (CHI/AntiFun-LM). Bioactive films were prepared by solvent casting. FTIR-ATR and ToF-SIMS analyses provided compelling evidence of the successful grafting process. TGA-DSC demonstrated that the films are stable after grafting. SEM studies showed the continuous and compact surface of the films. WCA measurements proved that CHI/AntiFun-LM films are more hydrophilic than CHI films. Moreover, the CHI/AntiFun-LM films showed stronger UV shielding effect when compared to CHI. The biological evaluation demonstrated that CHI/AntiFun-LM films gained considerable antifungal properties against most fungi responsible for post-harvest decay. Cytotoxicity tests showed that CHI/AntiFun-LM films did not cause any toxic effect against L929 fibroblasts. This study highlights the great potential of chemical grafting of antifungal agents produced from citrus waste to chitosan and preparation of natural-based films to act as a powerful alternative in post-harvest protection of citrus fruit in a perspective of circular economy.

Time-of-flight SIMS investigation of peptides containing cell penetrating sequences.

Surface functionalization with biological molecules, such as peptides or proteins, is a very promising method for developing new biomaterials with many potential applications. However, due to their chemical complexity, the characterization of biological materials is often a very challenging task. In this context, time-of-flight secondary ion mass spectrometry is a very helpful characterization tool due to its ability to provide very detailed spatially resolved chemical information of the topmost layer. The peculiar emission/ion formation mechanisms involved in ToF-SIMS analysis often do not allow the detection of the molecular ion of proteins and peptides, providing a rich fragmentation pattern, which is difficult to be related to the surface composition using a univariate approach, due to the relevant number of peaks in the SIMS spectra of peptides and proteins and the slight differences in intensities between different samples. Therefore, we used multivariate analysis to extract the information contained in the ToF-SIMS spectra of four peptides with high amino acid sequence similarity along the peptide chain. The reference peptide (TAT1) is a 12-unit sequence of six amino acids (GRKKRRQRRRPS). The other three peptides have been obtained by inserting a bAla-H dipeptide (carnosine) in three different positions inside the TAT1 chain, namely, GRKKRRQRRRPS-bAla-H (TAT1-Car), bAla-HGRKKRRQRRRPS (Car-TAT1), and GRKKRRQ-bAla-H-RRRPS (T-Car-T). We show that these peptides can be distinguished by ToF-SIMS combined with multivariate data analysis.

Modulating Polymer Ultrathin Film Crystalline Fraction and Orientation with Nanoscale Curvature.

We investigated the effect of nanoscale curvature on the structure of thermally equilibrated poly-3-hexylthiophene (P3HT) ultrathin films. The curvature-induced effects were investigated with synchrotron grazing incidence X-ray diffraction (GIXRD) and atomic force microscopy (AFM). Our results demonstrate that nanoscale curvature reduces the polymer crystalline fraction and the crystal length. The first effect is strongest for the lowest curvature and results in a decrease in the out-of-plane thickness of the polymer crystals. On the other hand, the crystal in-plane length decreases with the increase in substrate curvature. Finally, the semi-quantitative analysis of crystal anisotropy shows a marked dependence on the substrate curvature characterized by a minimum at curvatures between 0.00851 nm-1 and 0.0140 nm-1. The results are discussed in terms of a curvature-dependent polymer fraction, which fills the interstices between neighboring particles and cannot crystallize due to extreme space confinement. This fraction, whose thickness is highest at the lowest curvatures, inhibits the crystal nucleation and the out-of-plane crystal growth. Moreover, because of the adhesion to the curved portion of the substrates, crystals adopt a random orientation. By increasing the substrate curvature, the amorphous fraction is reduced, leading to polymer films with higher crystallinity. Finally, when the thickness of the film exceeds the particle diameter, the curvature no longer affects the crystal orientation, which, similarly to the flat case, is predominantly edge on.

Comprehensive step-by-step procedure to setup a molecular communication through liquid experiment.

Molecular communication allows information to be exchanged in environments where electromagnetic waves are prohibited. It employs the exchange of information particles travelling through fluids. The transmitter releases several chemical messengers inside the communication channel, encoding the message it intends to send in an appropriate way. These messengers will be propagated in the communication channel according to the laws that determine their movement in the environment, until they reach the receiver, which then captures their presence and decodes their content. To set up an experiment of molecular communication through liquid, the following are required:•The simulation of the experiment by means of numerical resolution of the differential equations governing the process, in order to select the proper modulation technique.•The synthesis of the carbon nanoparticles to serve as the information nanoparticles.•The arrangement of the bench prototype for the experiments.

Fluorescence sensing by carbon nanoparticles.

Sensing is one of the most important fields in which chemists, engineers and other scientists are involved to realize sensoristic devices that can detect different analytes, both chemicals and biologicals. In this context, fluorescence sensing paves the way for the realization of smart sensoristic devices due to the possibility to detect the target analyte via a change in colour or emission. Recently (since 2006), carbon nanoparticles, which are a "new class" of nanostructures based on carbon atoms, have been widely used in sensing applications due to their intriguing optical properties. The scientific literature on this topic started from 2006 and a progressive increase in the corresponding number of publications has been observed. This review summarises the application of carbon nanoparticles in the sensing field, focusing on chemical and ion sensing.

A super absorbent polymer containing copper to control Plenodomus tracheiphilus the causative agent of mal secco disease of lemon.

The aim of this study was to determine the effectiveness of a Super absorbent polymer (SAP) containing copper (SAP-Cu) in controlling mal secco disease (MSD) of lemon caused by the fungus Plenodomus tracheiphilus. Super absorbent polymer containing copper was characterized by atomic absorption spectrometry (AAS) and UV-VIS spectroscopy. In vitro tests were performed to determine the inhibitory effects of SAP-Cu against the pathogen on both potato-dextrose-agar medium and naturally infected lemon cuttings. Super absorbent polymer was able to absorb up to about 200 and 30 times its weight of ionized water and copper (II) sulfate solution (Cu2+ ions at the concentration 236 mM), respectively. The distribution of copper released on twigs after 24 h of contact with SAP-Cu was determined by secondary ion mass spectrometry with time-of-flight analyzer (ToF-SIMS). Super absorbent polymer containing copper significantly inhibited the viability of P. tracheiphilus in lemon twigs. Overall, the results of this study showed that the SAP could be a suitable carrier of antifungal compounds.

Carbon dots surface chemistry drives fluorescent properties: New tools to distinguish isobaric peptides.

The possibility to design rational carbon dots surface functionalization for specific analytical and bioanalytical applications is hindered by the lack of a full knowledge of the surface chemical features driving fluorescent properties. In this model study, we have synthesized four different peptides, three of which are isobaric and not distinguishable by common MSMS experiments. After having characterized the peptides conformations by CD analyses, we have covalently bonded all four peptides to carbon dots by using different experimental procedures, which produce different functional groups on the carbon dots surface. The peptide orientations obtained on the differently functionalized surface of the nanoparticles were different and produced different fluorescent responses. The reported results indicate the possibility to design amino and carboxyl enriched surface carbon dots to answer specific chemical requirements, paving the way for the use of these nanoparticles as a versatile and useful new chemical and biochemical tool.