Vapor‐Phase Synthesis of Molecularly Imprinted Polymers on Nanostructured Materials at Room‐Temperature

Molecularly imprinted polymers (MIPs) have recently emerged as robust and versatile artificial receptors. MIP synthesis is carried out in liquid phase and optimized on planar surfaces. Application of MIPs to nanostructured materials is challenging due to diffusion-limited transport of monomers within the nanomaterial recesses, especially when the aspect ratio is >10. Here, the room temperature vapor-phase synthesis of MIPs in nanostructured materials is reported. The vapor phase synthesis leverages a >1000-fold increase in the diffusion coefficient of monomers in vapor phase, compared to liquid phase, to relax diffusion-limited transport and enable the controlled synthesis of MIPs also in nanostructures with high aspect ratio. As proof-of-concept application, pyrrole is used as the functional monomer thanks to its large exploitation in MIP preparation; nanostructured porous silicon oxide (PSiO2) is chosen to assess the vapor-phase deposition of PPy-based MIP in nanostructures with aspect ratio >100; human hemoglobin (HHb) is selected as the target molecule for the preparation of a MIP-based PSiO2 optical sensor. High sensitivity and selectivity, low detection limit, high stability and reusability are achieved in label-free optical detection of HHb, also in human plasma and artificial serum. The proposed vapor-phase synthesis of MIPs is immediately transferable to other nanomaterials, transducers, and proteins

Carbon Black Functionalized with Naturally Occurring Compounds in Water Phase for Electrochemical Sensing of Antioxidant Compounds

A new sustainable route to nanodispersed and functionalized carbon black in water phase (W-CB) is proposed. The sonochemical strategy exploits ultrasounds to disaggregate the CB, while two selected functional naturally derived compounds, sodium cholate (SC) and rosmarinic acid (RA), act as stabilizing agents ensuring dispersibility in water adhering onto the CB nanoparticles' surface. Strategically, the CB-RA compound is used to drive the AuNPs self-assembling at room temperature, resulting in a CB surface that is nanodecorated; further, this is achieved without the need for additional reagents. Electrochemical sensors based on the proposed nanomaterials are realized and characterized both morphologically and electrochemically. The W-CBs' electroanalytical potential is proved in the anodic and cathodic window using caffeic acid (CF) and hydroquinone (HQ), two antioxidant compounds that are significant for food and the environment. For both antioxidants, repeatable (RSD <= 3.3%; n = 10) and reproducible (RSD <= 3.8%; n = 3) electroanalysis results were obtained, achieving nanomolar detection limits (CF: 29 nM; HQ: 44 nM). CF and HQ are successfully determined in food and environmental samples (recoveries 97-113%), and also in the presence of other phenolic classes and HQ structural isomers. The water dispersibility of the proposed materials can be an opportunity for (bio) sensor fabrication and sustainable device realization

Nanozymes based on octahedral platinum nanocrystals with {111} surface facets: glucose oxidase mimicking activity in electrochemical sensors

The ability of shape-controlled octahedral Pt nanoparticles to act as nanozyme mimicking glucose oxidase enzyme is reported. Extended {111} particle surface facets coupled with a size comparable to natural enzymes and easy-to-remove citrate coating give high affinity for glucose, comparable to the enzyme as proven by the steady-state kinetics of glucose electrooxidation. The easy and thorough removal of the citrate coating, demonstrated by X-ray photoelectron spectroscopy analysis, allows a highly stable deposition of the nanozymes on the electrode. The glucose electrochemical detection (at -0.2 V vs SCE) shows a linear response between 0.36 and 17 mM with a limit of detection of 110 mu M. A good reproducibility has been achieved, with an average relative standard deviation (RSD) value of 9.1% (n = 3). Similarly, a low intra-sensor variability has been observed, with a RSD of 6.6% (n = 3). Moreover, the sensor shows a long-term stability with reproducible performances for at least 2 months (RSD: 7.8%). Tests in saliva samples show the applicability of Pt nanozymes to commercial systems for non-invasive monitoring of hyperglycemia in saliva, with recoveries ranging from 92 to 98%

Humic acid coated magnetic particles as highly efficient heterogeneous photo-Fenton materials for wastewater treatments

Abstract Heterogeneous photo-Fenton reaction with iron-based magnetic materials has been proposed as an alternative to the homogeneous Fenton process to remove contaminants of emerging concern (CECs) because of the low cost, facile recovery and reuse. The iron-based material is not only a reservoir to maintain an effective concentration of iron in solution, but it also activates H2O2 at the surface. Magnetic particles (MPs) coated with different amount of humic acid (HA), prepared by co-precipitation method under anoxic and oxygenated conditions were synthesized. Their features were characterized by different techniques (XPS, XRD, TGA, SEM and FTIR). The ability of those materials to promote Fenton and photo-Fenton-like processes was investigated using 4-chlorophenol as standard substrate. The HA coating increased the catalyst efficiency, both in the dark and under irradiation, showing the best performance at pH below 4 under simulated sunlight. The iron speciation at the MPs surface had a paramount role in the H2O2 (photo)activation, although the processes promoted by the released iron in solution were not negligible on the overall degradation process. It was demonstrated a role of the surface defectivity to promote faster degradations as a consequence of not only a faster photodissolution, but also a higher heterogeneous reactivity promoted by defective sites. The best performing MPs/HA showed high efficiency for the abatement of CECs, namely Carbamazepine, Ibuprofen, Bisphenol A and 5-Tolylbenzotriazole also in real wastewater. The obtained results demonstrated the potential application of the heterogeneous (photo)-Fenton process activated by these inexpensive and environmental friendly materials in advanced wastewater treatments

An Insight into Chemistry and Structure of Colloidal 2D-WS2 Nanoflakes: Combined XPS and XRD Study

The surface and structural characterization techniques of three atom-thick bi-dimensional 2D-WS2 colloidal nanocrystals cross the limit of bulk investigation, offering the possibility of simultaneous phase identification, structural-to-morphological evaluation, and surface chemical description. In the present study, we report a rational understanding based on X-ray photoelectron spectroscopy (XPS) and structural inspection of two kinds of dimensionally controllable 2D-WS2 colloidal nanoflakes (NFLs) generated with a surfactant assisted non-hydrolytic route. The qualitative and quantitative determination of 1T’ and 2H phases based on W 4f XPS signal components, together with the presence of two kinds of sulfur ions, S22− and S2−, based on S 2p signal and related to the formation of WS2 and WOxSy in a mixed oxygen-sulfur environment, are carefully reported and discussed for both nanocrystals breeds. The XPS results are used as an input for detailed X-ray Diffraction (XRD) analysis allowing for a clear discrimination of NFLs crystal habit, and an estimation of the exact number of atomic monolayers composing the 2D-WS2 nanocrystalline samples

A comparison of EIS and QCM nanoMIP-based sensors for morphine

In this work we have compared two different sensing platforms for the detection of morphine as an example of a low molecular weight target analyte. For this, molecularly imprinted polymer nanoparticles (NanoMIP), synthesized with an affinity towards morphine, were attached to an electrochemical impedance spectroscopy (EIS) and a quartz crystal microbalance (QCM) sensor. Assay design, sensors fabrication, analyte sensitivity and specificity were performed using similar methods. The results showed that the EIS sensor achieved a limit of detection (LOD) of 0.11 ng·mL−1, which is three orders of magnitude lower than the 0.19 µg·mL−1 achieved using the QCM sensor. Both the EIS and the QCM sensors were found to be able to specifically detect morphine in a direct assay format. However, the QCM method required conjugation of gold nanoparticles (AuNPs) to the small analyte (morphine) to amplify the signal and achieve a LOD in the µg·mL−1 range. Conversely, the EIS sensor method was labor-intensive and required extensive data handling and processing, resulting in longer analysis times (~30–40 min). In addition, whereas the QCM enables visualization of the binding events between the target molecule and the sensor in real-time, the EIS method does not allow such a feature and measurements are taken post-binding. The work also highlighted the advantages of using QCM as an automated, rapid and multiplex sensor compared to the much simpler EIS platform used in this work, though, the QCM method will require sample preparation, especially when a sensitive (ng·mL−1) detection of a small analyte is needed

Basaltic material in the main belt: a tale of two (or more) parent bodies?

The majority of basaltic objects in the main belt are dynamically connected to Vesta, the largest differentiated asteroid known. Others, due to their current orbital parameters, cannot be easily dynamically linked to Vesta. This is particularly true for all the basaltic asteroids located beyond 2.5 au, where lies the 3:1 mean motion resonance with Jupiter. In order to investigate the presence of other V-type asteroids in the middle and outer main belt (MOVs) we started an observational campaign to spectroscopically characterize in the visible range MOV candidates. We observed 18 basaltic candidates from TNG and ESO-NTT between 2015 and 2016. We derived spectral parameters using the same approach adopted in our recent statistical analysis and we compared our data with orbital parameters to look for possible clusters of MOVs in the main belt, symptomatic for a new basaltic family. Our analysis seemed to point out that MOVs show different spectral parameters respect to other basaltic bodies in the main belt, which could account for a diverse mineralogy than Vesta; moreover, some of them belong to the Eos family, suggesting the possibility of another basaltic progenitor. This could have strong repercussions on the temperature gradient present in the early Solar system, and on our current understanding of differentiation processes. <P /

Investigating the composition of Potentially Hazardous Asteroids with the NEO-SURFACE survey

There is a high degree of diversity among the physical properties of the Potentially Hazardous asteroids (PHAs). For these objects, the physical characterization is essential to define a successful mitigation mission, therefore ground-based surveys like NEO-SURFACE could provide a fundamental contribution. Our analysis suggest a prevalence of silicate S-types in the PHA population, which could be due in principle to the high efficiency of the transport mechanisms in the inner main belt, or to an observational bias due to the fact that S-types are brighter. <P /

Humoral and cellular immune response elicited by mRNA vaccination against SARS-CoV-2 in people living with HIV (PLWH) receiving antiretroviral therapy (ART) according with current CD4 T-lymphocyte count

BACKGROUND: Data on SARS-CoV-2 vaccine immunogenicity in PLWH are currently limited. Aim of the study was to investigate immunogenicity according to current CD4 T-cell count. METHODS: PLWH on ART attending a SARS-CoV-2 vaccination program, were included in a prospective immunogenicity evaluation after receiving BNT162b2 or mRNA-1273. Participants were stratified by current CD4 T-cell count (poor CD4 recovery, PCDR: 500/mm^{3}). RBD-binding IgG, SARS-CoV-2 neutralizing antibodies (nAbs) and IFN-γ release were measured. As control group, HIV-negative healthcare workers (HCWs) were used. FINDINGS: Among 166 PLWH after 1 month from the second dose, detectable RBD-binding IgG were elicited in 86.7% of PCDR, 100% of ICDR, 98.7% of HCDR, and a neutralizing titre ≥1:10 elicited in 70.0%, 88.2% and 93.1%, respectively. Compared to HCDR, all immune response parameters were significantly lower in PCDR. After adjusting for confounders, current CD4 T-cell 500 cell/mm^{3} and HIV-negative controls. A decreased RBD-binding antibody response than HCWs was also observed in PLWH with CD4 T-cell 200-500/mm^{3}, whereas immune response elicited in PLWH with a CD4 T-cell >500/mm^{}3 was comparable to HIV-negative population