Microplastics determination and quantification in two benthic filter feeders Sabella spallanzanii, Polychaeta and Paraleucilla magna, Porifera.

Plastic pollution is a worldwide problem especially in the marine environment. Plastic items once fragmented into microplastics (MPs), can be captured by different marine species. Benthic filter feeders like sponges and polychaetas, due to their trophic strategy, are highly exposed to MPs pollution. Herein a simple but effective method to digest the fan worm Sabella spallanzanii and the calcareous sponge Paraleucilla magna is presented: a solution with KOH and H2O2 was able to remove quantitatively (more than 98 %) the organic matter in 3 h while an acid treatment dissolved most of spicules and chaetes in less than 30 min. MPs were easily identified both microscopically and spectroscopically on filters. Quantification in animals collected from the same environment showed that, on average, sponges accumulate fewer MPs than polychaetes (66 ± 31 and 117 ± 46 particles/g dry weight, respectively). The plastic recovery of the method was validated using three different approaches (spiking of standard PS microspheres, of common-use plastic objects, and of microplastics already weathered in marine environment). This procedure can make it easier and cost-effective to process biota in monitoring studies, providing information about bioindicator/bioremediation species.

Insights into Plastic Degradation Processes in Marine Environment by X-ray Photoelectron Spectroscopy Study.

The present study employs X-ray photoelectron spectroscopy (XPS) to analyze plastic samples subjected to degradation processes with the aim to gain insight on the relevant chemical processes and disclose fragmentation mechanisms. Two model plastics, namely polystyrene (PS) and polyethylene (PE), are selected and analyzed before and after artificial UV radiation-triggered weathering, under simulated environmental hydrodynamic conditions, in fresh and marine water for different time intervals. The object of the study is to identify and quantify chemical groups possibly evidencing the occurrence of hydrolysis and oxidation reactions, which are the basis of degradation processes in the environment, determining macroplastic fragmentation. Artificially weathered plastic samples are analyzed also by Raman and FT-IR spectroscopy. Changes in surface chemistry with weathering are revealed by XPS, involving the increase in chemical moieties (hydroxyl, carbonyl, and carboxyl functionalities) which can be correlated with the degradation processes responsible for macroplastic fragmentation. On the other hand, the absence of significant modifications upon plastics weathering evidenced by Raman and FT-IR spectroscopy confirms the importance of investigating plastics surface, which represents the very first part of the materials exposed to degradation agents, thus revealing the power of XPS studies for this purpose. The XPS data on experimentally weathered particles are compared with ones obtained on microplastics collected from real marine environment for investigating the occurring degradation processes.

Cellulose-Based Hydrogels for Wastewater Treatment: A Focus on Metal Ions Removal.

The rapid worldwide industrial growth in recent years has made water contamination by heavy metals a problem that requires an immediate solution. Several strategies have been proposed for the decontamination of wastewater in terms of heavy metal ions. Among these, methods utilizing adsorbent materials are preferred due to their cost-effectiveness, simplicity, effectiveness, and scalability for treating large volumes of contaminated water. In this context, heavy metal removal by hydrogels based on naturally occurring polymers is an attractive approach for industrial wastewater remediation as they offer significant advantages, such as an optimal safety profile, good biodegradability, and simple and low-cost procedures for their preparation. Hydrogels have the ability to absorb significant volumes of water, allowing for the effective removal of the dissolved pollutants. Furthermore, they can undergo surface chemical modifications which can further improve their ability to retain different environmental pollutants. This review aims to summarize recent advances in the application of hydrogels in the treatment of heavy metal-contaminated wastewater, particularly focusing on hydrogels based on cellulose and cellulose derivatives. The reported studies highlight how the adsorption properties of these materials can be widely modified, with a wide range of adsorption capacity for different heavy metal ions varying between 2.3 and 2240 mg/g. The possibility of developing new hydrogels with improved sorption performances is also discussed in the review, with the aim of improving their effective application in real scenarios, indicating future directions in the field.

Green Synthesis of a Molecularly Imprinted Polymer Based on a Novel Thiophene-Derivative for Electrochemical Sensing.

An environmentally friendly and sustainable approach was adopted to produce a molecularly imprinted polymer (MIP) via electropolymerization, with remarkable electrochemical sensing properties, tested in tyrosine (tyr) detection. The 2,2'-bis(2,2'-bithiophene-5-yl)-3,3'-bithianaphtene (BT2-T4) was chosen as functional monomer and MIP electrosynthesis was carried out via cyclic voltammetry on low-volume (20 µL) screen-printed carbon electrodes (C-SPE) in ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ((BMIM) TFSI). An easy and rapid washing treatment allowed us to obtain the resulting MIP film, directly used for tyr electrochemical detection, carried out amperometrically. The sensor showed a linear response in the concentration range of 15-200 µM, with LOD of 1.04 µM, LOQ of 3.17 µM and good performance in selectivity, stability, and reproducibility. Tyrosine amperometric detection was also carried out in human plasma, resulting in a satisfactory recovery estimation. The work represents the first use of BT2-T4 as a functional monomer for the production of a molecularly imprinted polymer, with a green approach afforded by using a few microliters of a room temperature ionic liquid as an alternative to common organic solvents on screen-printed carbon electrodes, resulting in a valuable system that meets the green chemistry guidelines, which is today an essential criterion in both research and application field.

Correction: An impedimetric sensor based on molecularly imprinted nanoparticles for the determination of trypsin in artificial matrices - towards point-of-care diagnostics.

Correction for 'An impedimetric sensor based on molecularly imprinted nanoparticles for the determination of trypsin in artificial matrices - towards point-of-care diagnostics' by Sabrina Di Masi et al., Anal. Methods, 2024, 16, 742-750, https://doi.org/10.1039/D3AY01762A.

Rational Design of a Portable Chemometric-Assisted Voltammetric Sensor Based on Ion-Imprinted Polymeric Film for Co(II) Determination in Water.

Herein, chemometric-assisted synthesis of electrochemical sensors based on electropolymerised ion-imprinted polymeric (e-IIP) films was explored. Co(II)-IIPs sensors were prepared by performing electropolymerisation procedures of polymerisation mixtures comprising varying concentrations of an electroactive o-aminophenol (o-AP) monomer and Co(II) ions, respectively, according to the Taguchi L9 experimental design, exploiting the simultaneous evaluation of other controlled parameters during electrosynthesis. Each e-IIP developed from Taguchi runs was compared with the respective non-imprinted polymer (NIP) films and fitted according to Langmuir-Freudlich isotherms. Distinctive patterns of low and high-affinity films were screened based on the qualities and properties of the developed IIPs in terms of binding kinetics (KD), imprinting factor, and the heterogeneity index of produced cavities. These results can provide a generic protocol for chemometric-assisted synthesis of e-IIPs based on poly-o-AP, providing highly stable, reproducible, and high-affinity imprinted polymeric films for monitoring purposes.

An impedimetric sensor based on molecularly imprinted nanoparticles for the determination of trypsin in artificial matrices - towards point-of-care diagnostics.

A high-performance impedimetric sensing platform was designed to detect proteins by employing molecularly imprinted polymeric nanoparticles (nanoMIPs) as selective receptors. This was achieved via the combination of the nanoMIPs with a self-assembled thioctic acid (SAM-TA) monolayer onto screen-printed gold electrodes, providing stable covalent attachment of the selective binder to the transducer. Taguchi design has been modelled to achieve the optimal level of sensor fabrication parameters and to maximise the immobilisation of nanoMIPs and their response (e.g. the response of imprinted polymers compared with the non-imprinted control). The developed sensor was tested towards a range of concentrations of trypsin dissolved in ammonium acetate (pH = 6) and showed promising applicability in artificial saliva, with a recovery percentage between 103 and 107%.

Optimisation of electrochemical sensors based on molecularly imprinted polymers: from OFAT to machine learning.

Molecularly imprinted polymers (MIPs) rely on synthetic engineered materials able to selectively bind and intimately recognise a target molecule through its size and functionalities. The way in which MIPs interact with their targets, and the magnitude of this interaction, is closely linked to the chemical properties derived during the polymerisation stages, which tailor them to their specific target. Hence, MIPs are in-deep studied in terms of their sensitivity and cross-reactivity, further being used for monitoring purposes of analytes in complex analytical samples. As MIPs are involved in sensor development within different approaches, a systematic optimisation and rational data-driven sensing is fundamental to obtaining a best-performant MIP sensor. In addition, the closer integration of MIPs in sensor development requires that the inner properties of the materials in terms of sensitivity and selectivity are maintained in the presence of competitive molecules, which focus is currently opened. Identifying computational models capable of predicting and reporting the best-performant configuration of electrochemical sensors based on MIPs is of immense importance. The application of chemometrics using design of experiments (DoE) is nowadays increasingly adopted during optimisation problems, which largely reduce the number of experimental trials. These approaches, together with the emergent machine learning (ML) tool in sensor data processing, represent the future trend in design and management of point-of-care configurations based on MIP sensing. This review provides an overview on the recent application of chemometrics tools in optimisation problems during development and analytical assessment of electrochemical sensors based on MIP receptors. A comprehensive discussion is first presented to cover the recent advancements on response surface methodologies (RSM) in optimisation studies of MIPs design. Therefore, the recent advent of machine learning in sensor data processing will be focused on MIPs development and analytical detection in sensors.

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 µM. 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%.

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.

Particle uptake by filter-feeding macrofoulers from the Mar Grande of Taranto (Mediterranean Sea, Italy): potential as microplastic pollution bioremediators.

Microplastics (MPs) are a serious threat to the marine environment affecting ecosystem functioning and biodiversity. There is a vast literature about the uptake of MPs at different trophic levels, mainly focused on ecotoxicological effects in commercially relevant species. Little is still known about possible strategies to face MP pollution. Bioremediation is recently gaining attention in this framework. The clearance rate and particle retention of Sabella spallanzanii, Mytilus galloprovincialis, Phallusia mammillata, Paraleucilla magna at three MP concentrations (C1: 1.4 · 101 p/L; C2: 1.4 · 102 p/L; C3: 1.4 · 103 p/L) were investigated to test their potential as MP remover. Digestion protocol removed 98 % of tissues simplifying the MP quantification. P. magna clearance rate decreased with increasing concentration while P. mammillata showed no significant variations. S. spallanzanii and M. galloprovincialis instead exhibited the highest values of clearance rate. Yet, unlike mussels, S. spallanzanii can inhibit particle return to the surrounding water storing them in the tube, resulting to be the best candidate for bioremediation purposes.

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.

An insight into polyscopoletin electrosynthesis by a quality-by-design approach.

Scopoletin (SP) as a functional monomer for electropolymerization has recently been investigated in the context of molecularly imprinted polymers for biosensing applications. Herein we describe an in-depth analysis of the mechanisms involved in the electropolymerization of SP toward the optimization of the experimental conditions for applications in sensor studies. PolySP films have been in situ synthesized on a standard glassy carbon electrodes by varying three independent experimental parameters, and the output of the analysis has been evaluated in terms of the resulting electroactive area and surface coverage. A quality-by-design approach including design-of-experiments principles and response surface methodology produced unbiased observations on the most relevant parameters to be controlled during the electropolymerization of SP. By combining the output of electroactive area and surface overage, we highlighted a strong dependence on the monomer concentration and scan rate. Thus, an appropriate selection of these two parameters should be sought to have an optimal electropolymerization process, leading to uniform films and homogeneous surface behavior. This study shows that the application of multi-factorial analysis in a comprehensive design of experiments allows the systematic study of polymer electrosynthesis. Therefore, this research is expected to guide further efforts in the electropolymerization of several functional monomers. Supplementary Information: The online version contains supplementary material available at 10.1007/s10853-022-07349-8.

Redox Profiling of Selected Apulian Red Wines in a Single Minute.

Wine is a complex bioproduct whose chemical composition is highly variable across production regions. In order to shed light on affordable ways to promote the characterization of wines and explore the physicochemical basis of their antioxidant capacity, this work reported on the quick and easy redox profiling of selected red wines from Apulia, Italy. Therefore, an affordable and quickly performed semiempirical quantum chemistry approach, i.e., the extended Hückel method, was used to compute the bandgaps of the main phytochemical markers attributed to red wines. The findings of these calculations were then compared to an electroanalytical investigation in the form of cyclic and square-wave voltammetry, and the electric current of the redox profiles was used as the input dataset for principal component analysis. Results showcased that the semiempirical quantum chemistry calculations allowed the correlation of the bandgaps to the observed faradaic signals upon voltammetry; thereby, also providing insights on their antioxidant appeal by highlighting the feasibility of charge-transfer processes at low electric potentials. Furthermore, the principal component analysis showed that the electric current dataset gathered in a time span of 55 s allowed the appropriate separation of the samples, which hints at the possible use of quick voltammetric assays as fingerprinting tools.

Electrochemical sensing of macromolecules based on molecularly imprinted polymers: challenges, successful strategies, and opportunities.

Looking at the literature focused on molecularly imprinted polymers (MIPs) for protein, it soon becomes apparent that a remarkable increase in scientific interest and exploration of new applications has been recorded in the last several years, from 42 documents in 2011 to 128 just 10 years later, in 2021 (Scopus, December 2021). Such a rapid threefold increase in the number of works in this field is evidence that the imprinting of macromolecules no longer represents a distant dream of optimistic imprinters, as it was perceived until only a few years ago, but is rapidly becoming an ever more promising and reliable technology, due to the significant achievements in the field. The present critical review aims to summarize some of them, evidencing the aspects that have contributed to the success of the most widely used strategies in the field. At the same time, limitations and drawbacks of less frequently used approaches are critically discussed. Particular focus is given to the use of a MIP for protein in the assembly of electrochemical sensors. Sensor design indeed represents one of the most active application fields of imprinting technology, with electrochemical MIP sensors providing the broadest spectrum of protein analytes among the different sensor configurations.

HPLC-MS/MS method applied to an untargeted metabolomics approach for the diagnosis of "olive quick decline syndrome".

Olive quick decline syndrome (OQDS) is a disorder associated with bacterial infections caused by Xylella fastidiosa subsp. pauca ST53 in olive trees. Metabolic profile changes occurring in infected olive trees are still poorly investigated, but have the potential to unravel reliable biomarkers to be exploited for early diagnosis of infections. In this study, an untargeted metabolomic method using high-performance liquid chromatography coupled to quadrupole-time-of-flight high-resolution mass spectrometry (HPLC-ESI-Q-TOF-MS) was used to detect differences in samples (leaves) from healthy (Ctrl) and infected (Xf) olive trees. Both unsupervised and supervised data analysis clearly differentiated the groups. Different metabolites have been identified as potential specific biomarkers, and their characterization strongly suggests that metabolism of flavonoids and long-chain fatty acids is perturbed in Xf samples. In particular, a decrease in the defence capabilities of the host after Xf infection is proposed because of a significant dysregulation of some metabolites belonging to flavonoid family. Moreover, oleic acid is confirmed as a putative diffusible signal factor (DSF). This study provides new insights into the host-pathogen interactions and confirms LC-HRMS-based metabolomics as a powerful approach for disease-associated biomarkers discovery in plants.

Polydopamine-Coated Alginate Microgels: Process Optimization and In Vitro Validation.

In the last decade, alginate-based microgels have gained relevant interest as three-dimensional analogues of extracellular matrix, being able to support cell growth and functions. In this study, core-shell microgels were fabricated by self-polymerization of dopamine (DA) molecules under mild oxidation and in situ precipitation of polydopamine (PDA) onto alginate microbeads, processed by electro fluid dynamic atomization. Morphological (optical, SEM) and chemical analyses (ATR-FTIR, XPS) confirmed the presence of PDA macromolecules, distributed onto the microgel surface. Nanoindentation tests also indicated that the PDA coating can influence the biomechanical properties of the microgel surfaces-i.e., σmaxALG = 0.45 mN vs. σmaxALG@PDA = 0.30 mN-thus improving the interface with hMSCs as confirmed by in vitro tests; in particular, protein adsorption and viability tests show a significant increase in adhesion and cell proliferation, strictly related to the presence of PDA. Hence, we concluded that PDA coating contributes to the formation of a friendly interface able to efficiently support cells' activities. In this perspective, core-shell microgels may be suggested as a novel symmetric 3D model to study in vitro cell interactions.

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.

Optimization of a new multi-reagent procedure for quantitative mussel digestion in microplastic analysis.

Over the last few years, different digestion protocols have been proposed to extract microplastics from mussels, an important product from aquaculture and a relevant economic resource, always scrutinized as a potential pollutant concentrator. In this study, a full factorial experimental design technique has been employed to achieve efficiency in removing biological materials while maximizing the recoveries of five common microplastics (polyethylene, polystyrene, polyethylene terephthalate, polypropylene and polyamide). A robust setpoint was calculated, 2.5% potassium hydroxide at 60 °C for 3 h with 5% hydrogen peroxide and 2.7% of methanol, permitting the quantitative digestion of mussel tissues and recovery of microplastics. These experimental conditions were successfully used to digest whole mussels bought from a local market, which possess high levels of microplastic contamination (41 items/g dry weight). The results highlight the importance of optimizing protocols to develop robust, easy to use and cheap quantitative approaches for analysing microplastic accumulation in edible organisms.

Enzyme-Mimics Molecularly Imprinted Polymers Based on Metal Complexes: Electropolymerization and Electrocatalytic Application.

The development of an electrosynthesized molecularly imprinted polymer (MIP) based on a metal complex is here reported as an effective strategy for combining advantages coming from metal-ion coordination and catalytic capabilities of metallic centers with ones deriving from electropolymerization. Metal ion coordination combines the flexibility of noncovalent imprinting approaches with the strength and specificity of covalent ones representing an attractive binding mechanism in MIP design for the recognition of a vast array of analytes. In addition, such a MIP possesses catalytic properties other than recognition capability, which is not so common in MIP field. On the other hand, electropolymerization represents a highly successful way of easily anchoring MIP-based sensing layers to the transducer surface. Procedures for MIP electrosynthesis as well as for its analytical application in electrocatalytic sensing are described.