Aptapaper─An Aptamer-Functionalized Glass Fiber Paper Platform for Rapid Upconcentration and Detection of Small Molecules.

We tested a paper-based platform ("Aptapaper") for the upconcentration and analysis of small molecules from complex matrices for two well-characterized aptamers, quinine and serotonin binding aptamers (QBA and SBA, respectively). After incubating the aptapaper under conditions that ensure correct aptamer folding, the aptapaper was used to upconcentrate target analytes from complex matrices. Aptapaper was rinsed, dried, and the target analyte was detected immediately or up to 4 days later by paper spray ionization coupled to high-resolution mass spectrometry (PS-MS). The minimum concentrations detectable were 81 pg/mL and 1.8 ng/mL for quinine and serotonin, respectively, from 100 mM AmAc or water. Complementary characterization of the QBA aptapaper system was performed using an orthogonal fluorescence microscopy method. Random adsorption was analyte-specific and observed for quinine, but not serotonin. This aptapaper approach is a semiquantitative (10-20% RSD) platform for upconcentration of small metabolites by mass spectrometry.

The fiscal response to the Italian COVID-19 crisis: A counterfactual analysis.

The COVID-19 pandemic is an unprecedented worldwide event with a massive impact on the economic system. The first Western country that had to face the COVID-19 crisis was Italy, which therefore represents a natural "case study." By using the microdata and granular policy information available at the Italian Ministry of Economy and Finance, this paper provides a macroeconomic quantitative assessment of the initial emergency fiscal measures introduced in 2020 and an analysis of the impact of the COVID-19 shock during the lockdown. We find that emergency measures avoided an additional fall of GDP of about 4.4% in 2020. The impact of public interventions on the dynamics of investments is particularly significant.

Molecular Perturbation Effects in AFM-Based Tip-Enhanced Raman Spectroscopy: Contact versus Tapping Mode.

Tip-enhanced Raman spectroscopy (TERS) is a powerful tool for nondestructive and label-free surface chemical characterization at nanometer length scales. However, despite being considered nondestructive, the interaction of the TERS probe used in the analysis can alter the molecular organization of the sample. In this study, we investigate the role of the atomic force microscopy (AFM) feedback (contact mode and tapping mode) on molecular perturbation in TERS analysis of soft samples using a self-assembled monolayer (SAM) of 2-chloro-4-nitrobenzene-1-thiol (Cl-NBT) as a test sample. Surprisingly, the tapping mode shows a consistently higher TERS signal resulting from a minimal perturbation of the Cl-NBT SAM compared to the contact mode. This study provides novel insights into the choice of the correct AFM-TERS operation mode for nanoscale chemical analysis of soft and delicate samples and is expected to expedite the growing application of TERS in this area.

Grape water: reclaim and valorization of a by-product from the industrial cryoconcentration of grape (Vitis vinifera) must.

BACKGROUND: The term 'grape (Vitis vinifera) water' refers to a by-product from the cryoconcentration of must that, if not reclaimed, would be considered as wastewater. In this study, the nutraceutical potential of waters reclaimed from the cryoconcentration of Grillo and Moscato musts was evaluated. RESULTS: Both waters showed physicochemical parameters in agreement with Italian regulation for drinking water, and interesting levels of F- (3.02-8.02 mg L-1 ) and SO4 - (52.85-49.34 mg L-1 ). Inorganic elements, including Mg (5.54-7.78 mg L-1 ), K (47.12-59.87 mg L-1 ), Fe (219.09-205.32 µg L-1 ), and Zn (189.65-127.30 µg L-1 ), and phenolic contents <35 mg GAE L-1 contributed to determine moderate antioxidant activities. Considering fatty acid composition, oleic and linoleic acids predominated, being higher in Moscato than Grillo samples (64.42% versus 58.22%, and 5.42% versus 6.07%). Grape waters displayed also rich aroma profiles, including mainly esters, alcohols and terpenoids. The latter components (i.e. linalool and α-terpineol) were more abundant in Moscato than in Grillo (13% versus 8%). Interestingly, some minor volatiles, characterized the vine of provenance (e.g. benzaldehyde and 3-methylbutylacetate in Moscato). All grape waters showed also a considerable fraction of ethyl lactate, six-carbon compounds and acetates, reflecting the proximity of samples to the grapes of origin. CONCLUSION: In a growing scenario of environmental decay and resource depletion, results from this study support an innovative and profitable waste recycling strategy for the wine industry. © 2020 Society of Chemical Industry.

A Multi-screening Evaluation of the Nutritional and Nutraceutical Potential of the Mediterranean Jellyfish Pelagia noctiluca.

The phylum Cnidaria is one of the most important contributors in providing abundance of bio- and chemodiversity. In this study, a comprehensive chemical investigation on the nutritional and nutraceutical properties of Mediterranean jellyfish Pelagia noctiluca was carried out. Also, compositional differences between male and female organisms, as well as between their main anatomical parts, namely bell and oral arms, were explored in an attempt to select the best potential sources of nutrients and/or nutraceuticals from jellyfish. With the exception of higher energy densities and total phenolic contents observed in females than males, no statistically significant differences related to the specimen's sex were highlighted for the other compound classes. Rather, the distribution of the investigated chemical classes varied depending on the jellyfish's body parts. In fact, crude proteins were more abundant in oral arms than bells; saturated fatty acids were more concentrated in bells than oral arms, whereas polyunsaturated fatty acids were distributed in the exact opposite way. On the other hand, major elements and trace elements demonstrated an opposite behavior, being the latter most accumulated in oral arms than bells. Additionally, important nutraceuticals, such as eicosapentaenoic and docosahexaenoic acids, and antioxidant minerals, were determined. Overall, obtained data suggest the potential employment of the Mediterranean P. noctiluca for the development of natural aquafeed and food supplements.

Organic contamination of Italian and Tunisian culinary herbs and spices.

Contaminants belonging to various classes, as polychlorobiphenyls, polycyclic aromatic hydrocarbons, organochlorine pesticides, organophosphorous pesticides, pyrethroid insecticides, fungicides, herbicides, synergists, carbamates, acaricides and insect growth regulators were simultaneously analysed by GC-MS/MS in 118 Italian and Tunisian culinary herbs and spices. The results obtained in Italian samples shown that laurel samples were the most contaminated with the presence of 15 residues on 140, whereas in rosemary (max value of 35 ng/g for cis-chlorfenyvinphos) and oregano (max value of 118.16 ng/g for ethion) some occasional residues can be observed, but always lower than the maximum residue levels; all the others samples shown no contamination. Among Tunisian samples, only rosemary contains a notably high content of pollutants exceeded the EU maximum residue limits (i.e., alachlor and phosalone with level of 359.2 and 43.3 ng/g, respectively), while oregano was determined to be free of contaminant residues. Considering the comparison among the different organic pollutants in Italian and Tunisian spices and herbs evaluated and the differences observed in this study a harmonization of regulation on contaminant residues in herbs and spices for human consumption should be needed, considering their increased use in diet and cooking.

New Insights into the Culture Method and Antibacterial Potential of Gracilaria gracilis.

Enormous marine biodiversity offers an endless reservoir of chemicals for many applications. In this scenario, the extraction of seaweeds represents an interesting source of compounds displaying antimicrobial activity. In particular, among the different red algae, Gracilaria gracilis plays an important role due to the presence of important bioactives in its composition. In spite of these features, an efficient culture system is still absent. In the present study, a novel algal culture method was developed and compared to another more common cultural practice, widely reported in literature. A higher efficiency of the new method, both for daily growth rate and biomass, was assessed. Furthermore, the growth inhibitory activity of five extracts, obtained using ethanol, methanol, acetone, chloroform or diethyl ether as a solvent, from the cultured G. gracilis was tested against Gram-positive and Gram-negative pathogens. Algal extracts exhibited a considerable inhibitory activity against B. subtilis strains, while a slight inhibition was observed against V. fischeri. The different extracts showed significant differences in bacterial growth inhibition, with the highest activity that was recorded for the ethanol extract, followed by that of methanol. Based on the chemical characterization, these findings could be related to the antimicrobial activity played by the combination of total carbohydrates and polyphenols, which were determined at high levels in ethanol and methanol extracts, as well as by the highest number and levels of single polyphenols. Conversely, the lower growth inhibitory activities found in chloroform and diethyl ether extracts could be related to the isolation of minor lipid classes (e.g., neutral and medium polar lipids) composed by fatty acids, such as stearic, oleic and arachidonic acids, typically characterized by antimicrobial activity. In consideration of the results obtained, the present study has a double implication, involving both the field of cultural practices and the exploitation of natural sources for the isolation of antimicrobial agents useful both in pharmaceutical and food applications.

Toxic inorganic pollutants in foods from agricultural producing areas of Southern Italy: Level and risk assessment.

This study focused on the inorganic environmental contaminants in specific food products which form part of the food chain of the population residing in the area of Southern Italy (Gela) where there is a high mortality rate linked to tumor diseases and congenital malformations. Determination of toxic metals was performed by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The toxicological data for every toxic element has been applied to evaluate the risk for the consumer by calculating the amount of potentially toxic element that would ingest an average of 60kg weight individual adult. The analysis of the investigated samples shows a high level of metal contamination which can be linked both to the polluted water and air. The obtained results give us an idea about the agricultural products contamination and possible exposure of local people through the food chain.

Traceability of Opuntia ficus-indica L. Miller by ICP-MS multi-element profile and chemometric approach.

BACKGROUND: Opuntia ficus-indica L. Miller fruits, particularly 'Ficodindia dell'Etna' of Biancavilla (POD), 'Fico d'india tradizionale di Roccapalumba' with protected brand and samples from an experimental field in Pezzolo (Sicily) were analyzed by inductively coupled plasma mass spectrometry in order to determine the multi-element profile. A multivariate chemometric approach, specifically principal component analysis (PCA), was applied to individuate how mineral elements may represent a marker of geographic origin, which would be useful for traceability. RESULTS: PCA has allowed us to verify that the geographical origin of prickly pear fruits is significantly influenced by trace element content, and the results found in Biancavilla PDO samples were linked to the geological composition of this volcanic areas. It was observed that two principal components accounted for 72.03% of the total variance in the data and, in more detail, PC1 explains 45.51% and PC2 26.52%, respectively. CONCLUSION: This study demonstrated that PCA is an integrated tool for the traceability of food products and, at the same time, a useful method of authentication of typical local fruits such as prickly pear. © 2017 Society of Chemical Industry.

Toxicological analysis of metals content in agro-food wastes as possible supplement in animal feed.

The agro-food surplus is considered the most abundant renewable resource, interesting for the economic and environmental impact, with a possible employment in different productive fields such as supplement in animal feed. For a safe and effective enhancement of agro-food wastes it is needed a toxicological analysis before of their employment, to avoid potential risks to animals, humans and environment. The purpose of this study was to evaluate the metals content (Cu, Fe, Zn, Mg, Na, K, Ca, Mn, Se, Zn, Co, Ni, V, Sb, Mo, Cr and Pb, Cd, As, Ba), in agro-food wastes through ICP-MS analysis. The results obtained showed the presence of metals analysed with a significant content of essential micro and macro-elements; with regard to toxic metals, only strawberries and fennel samples showed Pb levels above the MRL. These data confirm, from the toxicological point of view, a possible and safe reuse of the most of all agro-food wastes, as raw material at low cost and rich of essential nutrients and particularly as supplement in animal feed.

Nanoscale chemical analysis of 2D molecular materials using tip-enhanced Raman spectroscopy.

Two-dimensional (2D) molecular materials have attracted immense attention due to their unique properties, promising a wide range of exciting applications. To understand the structure-property relationship of these low-dimensional materials, sensitive analytical tools capable of providing structural and chemical characterisation at the nanoscale are required. However, most conventional analytical techniques fail to meet this challenge, especially in a label-free and non-destructive manner under ambient conditions. In the last two decades, tip-enhanced Raman spectroscopy (TERS) has emerged as a powerful analytical technique for nanoscale chemical characterisation by combining the high spatial resolution of scanning probe microscopy and the chemical sensitivity and specificity of surface-enhanced Raman spectroscopy. In this review article, we provide an overview of the application of TERS for nanoscale chemical analysis of 2D molecular materials, including 2D polymers, biomimetic lipid membranes, biological cell membranes, and 2D reactive systems. The progress in the structural and chemical characterisation of these 2D materials is demonstrated with key examples from our as well as other laboratories. We highlight the unique information that TERS can provide as well as point out the common pitfalls in experimental work and data interpretation and the possible ways of averting them.

Effect of Filtration Process on Oxidative Stability and Minor Compounds of the Cold-Pressed Hempseed Oil during Storage.

Cold-pressed hempseed oil (HO) has been increasingly exploited in the human diet for its excellent nutritional and healthy properties. However, it has a high content of polyunsaturated fatty acids (PUFAs) and chlorophylls, which inevitably accelerate its oxidative deterioration, especially in the presence of light. In this scenario, the filtration technology may ameliorate the oxidative stability of the oil, with positive effects on its nutritional quality and shelf life. Therefore, in this study, the oxidative stability and minor compounds of non-filtered and filtered HO (NF-HO and F-HO) were monitored over 12 weeks of storage in transparent glass bottles. F-HO showed a better hydrolytic and oxidative status than NF-HO during storage. As a result, F-HO also displayed better preservation of total MUFAs and PUFAs in the autoxidation process. Filtration consistently reduced chlorophylls, thus causing a variation in the natural color of HO. Accordingly, F-HO not only revealed an increased resistance to photooxidation but it was also suitable for storage in clear bottles within 12 weeks. F-HO predictably showed lower carotenoids, tocopherols, polyphenols, and squalene compared to NF-HO. However, filtration appeared to play a "protective role" toward these antioxidants, which had lower degradation rates in F-HO than NF-HO for 12 weeks. Interestingly, the element profile of HO was not affected by filtration and remained stable during the study period. Overall, this study may be of practical use to both producers and marketers of cold-pressed HO.

Effect of Dietary Enrichment with Flaxseed, Vitamin E and Selenium, and of Market Class on the Broiler Breast Meat-Part 1: Nutritional and Functional Traits.

The effect of dietary enrichment with flaxseed, selenium and vitamin E, and market class on the nutritional and functional value of breast meat was evaluated. A completely randomized block design was set up, where the experimental unit (n = 6000 birds) received conventional or enriched diet and was slaughtered at 37 (light class), 47 (medium class), or 57 (heavy class) days of life. Hence, functional and standard Pectoralis major muscles from every market class were analyzed for FA composition, inorganic elements and vitamin E. Lipid metabolism indices and health lipid indicators were assessed along with the nutritional value. A multiple linear model revealed that in breasts, the dietary treatment significantly influenced (p < 0.05) the FA profile, lipid metabolism and health lipid indices, while the slaughtering weight was related (p < 0.05) to most of elements (e.g., Na, Mg, K, Mn, and Se) and vitamin E. The interdependence of the two factors had strong relations (p < 0.05) with total PUFAs, including linolenic acid, desaturase activities, health lipid indices, trace essential elements and vitamin E. Consequently, enriched meat from heavy chickens showed the best functional and nutritional traits. Overall, the study pointed out that both market class and dietary manipulation are two relevant factors to consider for producing breast meat with higher nutritional and functional value.

Probing coke formation during the methanol-to-hydrocarbon reaction on zeolite ZSM-5 catalyst at the nanoscale using tip-enhanced fluorescence microscopy.

The deactivation mechanism of the widely used zeolite ZSM-5 catalysts remains unclear to date due to the lack of analytical techniques with sufficient sensitivity and/or spatial resolution. Herein, a combination of hyperspectral confocal fluorescence microscopy (CFM) and tip-enhanced fluorescence (TEFL) microscopy is used to study the formation of different coke (precursor) species involved in the deactivation of zeolite ZSM-5 during the methanol-to-hydrocarbon (MTH) reaction. CFM submicron-scale imaging shows a preferential formation of graphite-like coke species at the edges of zeolite ZSM-5 crystals within 10 min of the MTH reaction (i.e., working catalyst), whilst the amount of graphite-like coke species uniformly increased over the entire zeolite ZSM-5 surface after 90 min (i.e., deactivated catalyst). Furthermore, TEFL nanoscale imaging with ∼35 nm spatial resolution revealed that formation of coke species on the zeolite ZSM-5 surface is non-uniform and a relatively larger amount of coke is formed at the crystal steps, indicating a higher initial catalytic activity.

Mineral content and physico-chemical parameters of honey from North regions of Algeria.

Honey is accepted as food and medicine by all generations both ancient and modern. In this study the concentrations of K, Mg, Na, Zn, Fe, Mn, Cu, Cr, Ni, Se, As, Pb, Cd, Sb, Ti, V, Co, Hg and the determination of some physico-chemical parameters in 29 multifloral honeys collected from different North regions of Algeria: Algiers, Bouria, Ghardaïa, Laghouat, M'sila, Naâma, Tlemcen and El Bayadth during year 2018 were carried out. All minerals were determined by ICP-OES/MS and Hg by DMA-80. The most abundant minerals decreased in the following order: K, Na, Mg, Fe, Zn. Lead content exceeded the Codex Alimentarius and the European Union in all honey samples analysed, Cd and As levels were lower than the limits fixed by the European legislation and the regulations of the Codex Alimentarius. The Recommended Dietary Allowance values and benchmark levels were employed to assess the honey quality and safety.

Effect of Dietary Enrichment with Flaxseed, Vitamin E and Selenium, and of Market Class on the Broiler Breast Meat-Part 2: Technological and Sensorial Traits.

The influence of diet enrichment with flaxseed, selenium and vitamin E, and market class on breast meat was investigated in terms of technological and sensorial quality of breast meat. A randomized complete block design with an experimental unit of n = 6000 broilers receiving a standard or enriched diet, and slaughtered at 37 (light class), 47 (medium class), or 57 (heavy class) days of life, was developed. Then, enriched and standard breast muscles from every market class were studied for their technological and sensorial traits­both at 24 h post-mortem and after one month of frozen storage­by a statistical multiple linear model. Redness and yellowness of muscles significantly (p < 0.05) increased and decreased with increasing market age. Moreover, the yellowness significantly (p < 0.05) raised after frozen storage. However, obtained data were always indicative of a normal meat color. The water holding capacity improved following fed enrichment and significantly (p < 0.05) worsened after frozen storage. For the sensory analysis, juiciness and chewing rest of meat resulted significantly (p < 0.05) improved with increasing slaughtering age and diet enrichment, as well as their mutual interaction, while they deteriorated after frozen storage. Overall, fresh and enriched muscles from heavy broilers had the best technological and sensorial traits, thus, confirming that market size and diet should be highly considered to obtain breast meat with greater consumer acceptance.

Comprehensive Chemical Characterization of Chia (Salvia hispanica L.) Seed Oil with a Focus on Minor Lipid Components.

A comprehensive chemical characterization of different lipid components, namely fatty acid composition after derivatization in fatty acid methyl esters (FAMEs), triacylglycerols (TAGs), phospholipids (PLs), free fatty acids (FFAs), sterols, carotenoids, tocopherols, and polyphenols in Chia seed oil, obtained by Soxhlet extraction, was reported. Reversed phase liquid chromatography (RP-LC) coupled to UV and mass spectrometry (MS) detectors was employed for carotenoids, polyphenols, and TAGs determination; normal phase-LC in combination with fluorescence detector (FLD) was used for tocopherols analysis; PL and FFA fractions were investigated after a rapid solid phase extraction followed by RP-LC-MS and NanoLC coupled to electron ionization (EI) MS, respectively. Furthermore, gas chromatography (GC)-flame ionization (FID) and MS detectors were used for FAMEs and sterols analysis. Results demonstrated a significant content of bioactive compounds, such as the antioxidant tocopherols (22.88 µg mL-1), and a very high content of essential fatty acids (81.39%), namely α-linolenic (62.16%) and linoleic (19.23%) acids. In addition, for the best of authors knowledge, FFA profile, as well as some carotenoid classes has been elucidated for the first time. The importance of free fatty acids in vegetable matrices is related to the fact that they can be readily involved in metabolic processes or biosynthetic pathways of the plant itself. For a fast and reliable determination of this chemical class, a very innovative and sensitive NanoLC-EI-MS analytical determination was applied.

Monitoring Cannabinoids and the Safety of the Trace Element Profile of Light Cannabis sativa L. from Different Varieties and Geographical Origin.

Non-intoxicating Cannabis sativa L. (i.e., hemp) is increasingly used for industrial, cosmetic and food applications. Despite the fact that the EU has not yet established a regulatory framework on hazardous compounds (i.e., toxic inorganic elements), the monitoring of cannabis products is of paramount importance to safeguard consumers, also in view of the species propensity to accumulate toxic metals from the environment. The aim of this work was to assess the compliance with Law n. 242/2016 and the safety of hemp inflorescences from different varieties and Italian regions by monitoring the main cannabinoids and trace elements. All samples complied with the Italian law due to a THC content <0.6% counterbalanced by high CBD levels. However, inflorescences grown in Apulia and Lombardy, and from Finola and Tiborzallasi varieties accumulated higher Cu, Co, Cr, Ni and Pb contents than products from other producing areas (i.e., Sicily and Latium) and varieties (i.e., Antal, Futura75, Kompolti and Carmagnola), being moreover above the limits set by the US Pharmacopeia. A principal component analysis confirmed that trace elements, including toxic metals, were mainly affected by the geographical origin more than the botanical variety. Overall, this study highlights the need to continuously monitor hemp products and establish the earliest related regulatory frameworks.

Organic pollutants in marine samples from Tunisian coast: Occurrence and associated human health risks.

140 contaminants belonging to various classes (organochlorine and organophosphorus pesticides, pyrethroid insecticides, carbamates, fungicides, acaricides, herbicides, synergists, insect growth regulators, polychlorobiphenyls, polycyclic aromatic hydrocarbons) were simultaneously analysed by GC-MS/MS in marine sediments, aquatic plant leaves and fish tissues samples. A total of 260 samples from five stations along the coast of Tunisia were evaluated. The results highlight that only 28 residues (12 polychlorobiphenyls, 8 organochlorine pesticides, 7 polycyclic aromatic hydrocarbons and triphenyl phosphate) were detected at levels higher than relative LOQ values. The amounts in sediment samples were compared with Sediment Quality Guidelines (SQGs) showing that the values are acceptable and no toxic effect is expected on aquatic organisms. A little variation of contaminant residues in sediment samples among coastal stations was recorded. Namely, with respect to almost all polychlorobiphenyls and organochlorine pesticides, higher values were recorder in summer. With respect to almost all polycyclic aromatic hydrocarbons, higher values were recorder in autumn. Aquatic plant leaves showed a residue accumulation higher than that of other compartments of marine system. The data about fish samples (Sparus aurata and Sarpa salpa, the two most frequently caught fish species at five sites on the central coast of Tunisia) do not pose direct hazard to human health because values were lower than protection limits.

Physicochemical, Nutritional, Microbiological, and Sensory Qualities of Chicken Burgers Reformulated with Mediterranean Plant Ingredients and Health-Promoting Compounds.

The quality of chicken burgers reformulated by the partial replacement of meat by Mediterranean plant ingredients and enriched with peculiar amounts of n-3 PUFAs, Mg, Fe, Se, and folic acid, was evaluated in comparison to conventional chicken burgers. Specifically, two types of burger were developed, namely the "Sicilian burger"-based on cherry tomato and rosemary-and the "Mediterranean burger"-with basil leaves and thyme essential oil-every recipe being differentially functionalized according to the nutritional requirements of consumers, such as children, pregnant women and elderly. Mediterranean ingredients were responsible for different pH, color, and cooking loss between conventional and functional burgers. Except for n-3 PUFAs resulting poorly fortified, the functionalization with Mg, Fe, Se, and vitamin B9 was successful in all products. Considering the target consumer categories, the daily consumption of the functional burger may assure an intake of Mg, Fe, and Se equal, respectively, to 37.31-59.90%, 17.76-46.81%, and 27.20-50.05%, and a cover of vitamin B9 of 31.98-48.31% of the relative population reference intakes. Fortified products kept a good microbiological quality during 5 days of refrigerated storage, and, according to the sensorial descriptive analysis and the hedonic test, they showed a higher acceptability than conventional burgers.