•Development of the first detailed pyrolysis database for sheep and camel wool.•Interpretation of the pyrolysis profiles of the keratin proteins in wool.•Characterization of wool samples and ...historical threads by Double Shot Py-GC/MS and EGA/MS.•Evaluation of the relevant parameters affecting wool degradation.
Wool has been the most widely used textile fiber in Europe since the Iron Age. It was largely employed to weave fabrics and clothes, and also for artistic purposes such as producing tapestries. This kind of artworks is among the most fragile of our heritage and is often in bad preservation conditions. Thus, the knowledge on the degradation processes of wool fibers is crucial for conservation issues.
In the present study, we tested the potentialities of Pyrolysis coupled with Gas Chromatography and Mass Spectrometry (Py-GC/MS) and Evolved Gas Analysis coupled to Mass Spectrometry (EGA/MS) for the characterization of woolen reference samples, also subjected to artificial ageing, and of historical and archeological samples. The reference sheep wool yarns were prepared with different mordants and dyes, and have been analyzed both after storage in the dark for three years after preparation, and artificially aged for different time intervals and at different relative humidity values. We created a detailed pyrolysis database, evidencing the phenomena occurring with ageing and including camel wool for comparison. The ageing process undergone by the proteinaceous fraction of wool has also been investigated through monitoring specific fragment ions in the EGA profiles. The relevant parameters affecting the degradation process identified in this study match those assessed in previous investigations by different and complementary techniques, thus validating our approach. We proved that the novel approach based on EGA/MS is suitable for quickly assessing the conservation conditions of the woolen yarns and represents an advantage with respect to more time-consuming and complex methods, such as GC/MS or High Performance Liquid Chromatography (HPLC).
The environmental threat represented by tire and road wear particles (TRWPs) has highlighted the need for effective analytical strategies for their detection and quantitation in different matrices. ...To date, however, there is little consensus in the literature on how to obtain reliable data on TRWPs in environmental samples, which chemical marker should be used, and how analytical results can be correlated with the amount of particulate. This review compares the analytical strategies described in the literature from a critical point of view and outlines the most crucial aspects, giving an overview of the current knowledge and discussing the analytical challenges that need to be addressed. The literature highlights the critical role played by the selection of detection and quantitation markers, the variations in the formulation of the tires, the environmental degradation pathways of TRWPs components, and the effects of the sample matrix and composition on the analytical response.
•TRWPs have only recently been identified as a potential environmental threat.•Reliable analytical strategies for detection and quantitation of TRWPs in the environment are crucial.•Determination of TRWPs relies on elemental analyses or mass spectrometry-based techniques.•Literature survey highlights need for standardized protocols for detection and quantitation of TRWPs.•Quantitation of TRWPs is limited by choice of marker and correlation between amount and instrumental output.
Plastic film mulching and use of wastewaters for irrigation have been common agricultural practices for over half a century in Tunisia, especially in arid regions, resulting in the undesired creation ...of a pathway for microplastics (MPs) to enter farmland soil. In order to assess the extent and characteristics of soil contamination by MPs in the Moknine province, an area of intensive agricultural practices, 16 farmland soil samples were collected and characterized. The total concentration of targeted MPs was 50–880 items/kg; among them, the most common MPs type being polypropylene (PP), mainly occurring as white/transparent fibers with small size (cross section <0.3 mm). SEM images of MPs surfaces revealed multiple features related to environmental exposure and degradation. ATR-FTIR spectroscopy and pyrolysis-GC/MS analyses enabled the accurate identification of MPs separated from the embedding soil micro- and macro-aggregates. Finally, contamination of the polymeric microparticles with a broad range of metals was found by ICP-MS analysis, suggesting that MPs can be vectors for transporting heavy metals in the soil and indicators of soil contamination as a result of mismanagement of industrial wastewaters.
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•Microplastics (MPs) were isolated from intensive farming soils of Tunisia.•The concentration of MPs in the soils investigated ranged from 50 to 880 items/kg.•Synthetic textile fibers shorter than 1 mm were the dominant MPs types.•The greenhouse and plastic mulch have been identified as possible MPs point source.•DSC and Py-GC/MS technique offer a promising option in the field of MPs analysis.
Textile fibers have represented an important resource for mankind throughout all human history. In fact, ancient cultures employed them not just to produce clothes, but also for expressing their ...habits and traditions. Based on the chemical composition, textile fibers are classified as natural, artificial, and synthetic. The analysis of textile fibers can be very challenging, so it is crucial to find new analytical tools capable of identifying them and studying their behavior in the environment. The collected information can be transferred in many different fields, such as the industrial sector, forensic science, environmental science, and heritage science. In the present study, the capability of Pyrolysis coupled to Gas Chromatography and Mass Spectrometry (Py-GC/MS), and Evolved Gas Analysis coupled to Mass Spectrometry (EGA-MS) to discriminate textile fibers was tested. The first part of the study was addressed to the analysis of pure samples to build a detailed database by highlighting the main differences in the chromatographic profiles. Then, three textile blends of known composition were investigated, and the results compared with those acquired by Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy (ATR-FTIR). Eventually, the information obtained from the reference materials was exploited for the study of textile samples collected from the stage costumes of the lyrical opera ‘I Puritani’ directed by Franco Zeffirelli in 1961. The EGA-MS and Py-GC/MS results, integrated with those obtained by optical microscopy, allowed us to deepen the characterization of the historical samples.
•Evolved Gas Analysis coupled to Mass Spectrometry was tested to discriminate textile fibers.•Pyrolysis - Gas Chromatography/Mass Spectrometry was tested to discriminate textile fibers.•A database for natural, artificial, and synthetic fibers was built up, including mixtures.•The performances of the method were compared with results obtained by ATR-FTIR•The method was applied to characterize samples collected from the stage costumes from 1961.
Biodegradable polymers are proposed as a potential solution to environmental problems related to plastic pollution. Potential benefits have been suggested in applications such as agricultural ...mulching and fishing gear, where there can be considerable difficulty recovering products from the environment at the end of their service life. Biodegradation is a complex process influenced by both the properties of the material and the receiving environment in which it needs to biodegrade. Assessing the degradation process necessitates the chemical composition (i.e. polymer and additives) of biodegradable products to be characterised by reliable analytical methods. Pyrolysis coupled to Gas Chromatography and Mass Spectrometry (Py-GC-MS) and Evolved Gas Analysis coupled to Mass Spectrometry (EGA-MS) are emerging techniques to characterise plastic materials, providing a greater sensitivity and resolution when compared to more widely used spectroscopic techniques (FTIR and Raman). In this work, we have applied a systematic approach combining EGA-MS and multi-shot Py-GC-MS for the thermoanalytical investigation of 5 biodegradable polymers and 5 biodegradable-labelled commercial products. We identified thermal degradation profiles, main m/z ions and pyrolysis markers for the polymers PBAT, PBS, PBHV and two types of PLA. We applied the obtained information to investigate the composition of 4 mulch films and 1 fishing net. EGA-MS was fundamental to optimise single or multi shot pyrolysis acquisition, allowing an optimal Py-GC-MS separation and identification of the pyrolysis products. PLA and PBAT were detected in three mulch films, with the addition of starch in a film labelled as Mater-Bi and in one of unknown composition. Online silylation was crucial for detecting polysaccharides in a composite film containing hemp fibres. The presence of butylene, succinate, adipate and terephthalate units was highlighted analysing a fishing net made of a newly developed PBSAT resin. Finally, Py-GC-MS was effective in identifying the presence of additives such as 1,6-diisocyanato-hexane (chain extender) and di(3-butenyl) ester of sebacic acid derived from the plasticizer dibutyl sebacate.
•EGA-MS was applied to study the thermal behaviour of biodegradable polymers.•Py-GC-MS was applied to investigate the composition of biodegradable samples.•A database of PBAT, PBS, PHBV, and PLA reference polymers was developed.•The method was used to characterise biodegradable commercial products.
A significant area of study and upgrading for increasing sensitivity and general performances of matrix-assisted laser-desorption ionization (MALDI) mass spectrometry (MS) is related to matrix ...design. Several efforts have been made to address the challenge of low-mass-region interference-free for metabolomics analysis and specifically for lipidomics. To this aim, rationally designed matrices as 4-chloro-α-cyanocinnamic acid (ClCCA) were introduced and reported to provide enhanced analytical performances. We have taken this rational design one step further by developing and optimizing new MALDI matrices with a range of modifications on the CHCA core, involving different functionalities and substituents. Of particular interest was the understanding of the electron-withdrawing (e.g., nitro-) or donating (e.g., methoxy-) effects along with the extent of conjugation on the ionization efficiency. In the present work, ten matrices were designed on a reasonable basis, synthesized, and characterized by NMR and UV spectroscopies and laser desorption ionization. With the assistance of these putative MALDI matrices, samples containing phospholipids (PL), and neutral di-/tri-acylglycerols (DAG, TAG) were investigated using milk, fish, blood, and human plasma extracts. In comparison with CHCA and ClCCA, four of them, viz. (2E,4E)-2-cyano-5-(4-methoxyphenyl)penta-2,4-dienoic acid (
), (2E,4E)-2-cyano-5-(4-nitrophenyl)penta-2,4-dienoic acid (
), (E)-2-cyano-3-(6-methoxynaphthalen-2-yl)acrylic acid (
) and (E)-2-cyano-3-(naphthalen-2-yl)acrylic acid (
) displayed good to even excellent performances as MALDI matrices in terms of ionization capability, interference-free spectra, S/N ratio, and reproducibility. Especially compound
(cyano naphthyl acrylic acid, CNAA) was the election matrix for PL analysis and matrix
(cyano nitrophenyl dienoic acid, CNDA) for neutral lipids such as DAG and TAG in positive ion mode.
The effectiveness of a synthesized matrix, α-cyano-5-phenyl-2,4-pentadienic acid (CPPA), for protein analysis by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry ...(MALDI-TOF MS) in complex samples such as foodstuff and bacterial extracts, is demonstrated. Ultraviolet (UV) absorption along with laser desorption/ionization mass spectrometry (LDI-MS) experiments were systematically conducted in positive ion mode under standard Nd:YLF laser excitation with the aim of characterizing the matrix in terms of wavelength absorption and proton affinity. Besides, the results for standard proteins revealed that CPPA significantly enhanced the protein signals, reduced the spot-to-spot variability and increased the spot homogeneity. The CPPA matrix was successful employed to investigate intact microorganisms, milk and seed extracts for protein profiling. Compared to conventional matrices such as sinapinic acid (SA), α-cyano-4-hydroxycinnamic acid (CHCA) and 4-chloro-α-cyanocinnamic acid (CClCA), CPPA exhibited better signal-to-noise (S/N) ratios and a uniform response for most examined proteins occurring in milk, hazelnut and in intact bacterial cells of
. These findings not only provide a reactive proton transfer MALDI matrix with excellent reproducibility and sensitivity, but also contribute to extending the battery of useful matrices for intact protein analysis.
Background
Long‐term daily use of aspirin reduces incidence and mortality due to colorectal cancer (CRC). This study aimed to analyze the effect of aspirin on the tumor microenvironment, systemic ...immunity, and on the healthy mucosa surrounding cancer.
Methods
Patients with a diagnosis of CRC operated on from 2015 to 2019 were retrospectively analyzed (METACCRE cohort). Expression of mRNA of immune surveillance‐related genes (PD‐L1, CD80, CD86, HLA I, and HLA II) in CRC primary cells treated with aspirin were extracted from Gene Expression Omnibus–deposited public database (GSE76583). The experiment was replicated in cell lines. The mucosal immune microenvironment of a subgroup of patients participating in the IMMUNOREACT1 (ClinicalTrials.gov NCT04915326) project was analyzed with immunohistochemistry and flow cytometry.
Results
In the METACCRE Cohort, 12% of 238 patients analyzed were aspirin users. Nodal metastasis was significantly less frequent (p = .008) and tumor‐infiltrating lymphocyte infiltration was higher (p = .02) among aspirin users. In the CRC primary cells and selected cell lines, CD80 mRNA expression was increased following aspirin treatment (p = .001). In the healthy mucosa surrounding rectal cancer, the ratio of CD8/CD3 and epithelial cells expressing CD80 was higher in aspirin users (p = .027 and p = .034, respectively).
Conclusions
These data suggested that regular aspirin use may have an active role in enhancing immunosurveillance against CRC.
In patients with colorectal cancer, nodal metastasis was significantly less frequent, and tumor‐infiltrating lymphocytes were higher among aspirin users. In the colorectal cancer primary cells and selected cell lines, CD80 mRNA expression was increased following aspirin treatment. In the healthy mucosa surrounding rectal cancer, the ratio of CD8/CD3 and epithelial cells expressing CD80 was higher in aspirin users.
We explored the significance of the L-Arginine/asymmetric dimethylarginine (L-Arg/ADMA) ratio as a biomarker of endothelial dysfunction in stroke patients. To this aim, we evaluated the correlation, ...in terms of severity, between the degree of endothelial dysfunction (by L-Arg/ADMA ratio), the methylene tetrahydrofolate reductase (MTHFR) genotype, and the interatrial septum (IAS) phenotype in subject with a history of stroke.
L-Arg, ADMA, and MTHFR genotypes were evaluated; the IAS phenotype was assessed by transesophageal echocardiography. Patients were grouped according to the severity of IAS defects and the residual enzymatic activity of MTHFR-mutated variants, and values of L-Arg/ADMA ratio were measured in each subgroup. Of 57 patients, 10 had a septum integrum (SI), 38 a patent foramen ovale (PFO), and 9 an ostium secundum (OS). The L-Arg/ADMA ratio differed across septum phenotypes (
≤ 0.01), and was higher in SI than in PFO or OS patients (
≤ 0.05,
≤ 0.01, respectively). In the PFO subgroup a negative correlation was found between the L-Arg/ADMA ratio and PFO tunnel length/height ratio (
≤ 0.05; r = - 0.37; R
= 0.14). Interestingly, the L-Arg/ADMA ratio varied across MTHFR genotypes (
≤ 0.0001) and was lower in subgroups carrying the most impaired enzyme with respect to patients carrying the conservative MTHFR (
≤ 0.0001,
≤ 0.05, respectively). Consistently, OS patients carried the most dysfunctional MTHFR genotypes, whereas SI patients the least ones.
A low L-Arg/ADMA ratio correlates with impaired activity of MTHFR and with the jeopardized IAS phenotype along a severity spectrum encompassing OS, PFO with long/tight tunnel, PFO with short/large tunnel, and SI. This infers that genetic MTHFR defects may underlie endothelial dysfunction-related IAS abnormalities, and predispose to a cryptogenic stroke. Our findings emphasize the role of the L-Arg/ADMA ratio as a reliable marker of stroke susceptibility in carriers of IAS abnormalities, and suggest its potential use both as a diagnostic tool and as a decision aid for therapy.
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