Portable NIR spectroscopy: the route to green analytical chemistry.

There is a growing interest for cost-effective and nondestructive analytical techniques in both research and application fields. The growing approach by near-infrared spectroscopy (NIRs) pushes to develop handheld devices devoted to be easily applied for in situ determinations. Consequently, portable NIR spectrometers actually result definitively recognized as powerful instruments, able to perform nondestructive, online, or in situ analyses, and useful tools characterized by increasingly smaller size, lower cost, higher robustness, easy-to-use by operator, portable and with ergonomic profile. Chemometrics play a fundamental role to obtain useful and meaningful results from NIR spectra. In this review, portable NIRs applications, published in the period 2019-2022, have been selected to indicate starting references. These publications have been chosen among the many examples of the most recent applications to demonstrate the potential of this analytical approach which, not having the need for extraction processes or any other pre-treatment of the sample under examination, can be considered the "true green analytical chemistry" which allows the analysis where the sample to be characterized is located. In the case of industrial processes or plant or animal samples, it is even possible to follow the variation or evolution of fundamental parameters over time. Publications of specific applications in this field continuously appear in the literature, often in unfamiliar journal or in dedicated special issues. This review aims to give starting references, sometimes not easy to be found.

Early detection of emerging street drugs by near infrared spectroscopy and chemometrics.

Near-infrared spectroscopy (NIRs) is spreading as the tool of choice for fast and non-destructive analysis and detection of different compounds in complex matrices. This paper investigated the feasibility of using near infrared (NIR) spectroscopy coupled to chemometrics calibration to detect new psychoactive substances in street samples. The capabilities of this approach in forensic chemistry were assessed in the determination of new molecules appeared in the illicit market and often claimed to contain "non-illegal" compounds, although exhibiting important psychoactive effects. The study focused on synthetic molecules belonging to the classes of synthetic cannabinoids and phenethylamines. The approach was validated comparing results with officials methods and has been successfully applied for "in site" determination of illicit drugs in confiscated real samples, in cooperation with the Scientific Investigation Department (Carabinieri-RIS) of Rome. The achieved results allow to consider NIR spectroscopy analysis followed by chemometrics as a fast, cost-effective and useful tool for the preliminary determination of new psychoactive substances in forensic science.

Effects of hydrogen sulfide (H2S) on mesenteric perfusion in experimental induced intestinal ischemia in a porcine model.

INTRODUCTION: Insufficient mesenteric perfusion is a dramatic complication in critically ill patients. Hydrogen sulfide, a newly recognized endogenous gaseous mediator, acts as an intestinal vasoactive agent and seems to protect against mesenteric ischemic damage. We investigated whether sodium hydrogen sulfide, a hydrogen sulfide donor, can improve mesenteric perfusion in an experimental model of pigs, both in physiological and ischemic conditions. METHODS: The study was conducted at Careggi University Hospital (Florence, IT). Fourteen male domestic pigs (≈10 Kg) were anesthetized and mechanically ventilated. Animals were randomized in control and ischemia groups. Mesenteric ischemia was induced with a positive end-expiratory pressure of 15 cmH2O. After mini-laparotomy, each animal received incremental doses of sodium hydrogen sulfide every 20 minutes. Perfusion of both the jejunal mucosa and sternal skin were measured by laser Doppler flowmeter, and systemic hemodynamic parameters were monitored. RESULTS: In the control group, sodium hydrogen sulfide was able to significantly improve the mesenteric perfusion, showing a 50% increase from the baseline blood flow. In the ischemia group, NaHS-induced a two-fold increase of the mesenteric post-ischemic perfusion with a recovery up to 70% of pre- positive end-expiratory pressure mesenteric blood flow. Sodium hydrogen sulfide did not directly or indirectly (by blood flow redistribution) affect the sternal skin microcirculation, heart rates, or mean arterial pressure, suggesting a tissue-specific micro-vascular action. CONCLUSIONS: In a porcine model, we observed a mesenteric perfusion recovery mediated by administration of hydrogen sulfide donor without affecting general hemodynamic.

Monitoring heavy metal pollution by aquatic plants: a systematic study of copper uptake.

INTRODUCTION: The copper bioaccumulation by the floating Lemna minor and by the completely submerged Ranunculus tricophyllus as a function of exposure time and copper concentration was studied, with the aim of proposing these species as environmental biosensors of the water pollution. RESULTS: The results show that both these aquatic angiosperms are good indicators of copper pollution because the copper uptake is the only function of metal concentration (water pollution). CONCLUSION: Uptake behavior is reported as a function of the time and concentration, based on the results of a 3-year study. Kinetic evaluations are proposed.

A role for transient receptor potential vanilloid 4 in tonicity-induced neurogenic inflammation.

BACKGROUND AND PURPOSE: Changes in extracellular fluid osmolarity, which occur after tissue damage and disease, cause inflammation and maintain chronic inflammatory states by unknown mechanisms. Here, we investigated whether the osmosensitive channel, transient receptor potential vanilloid 4 (TRPV4), mediates inflammation to hypotonic stimuli by a neurogenic mechanism. EXPERIMENTAL APPROACH: TRPV4 was localized in dorsal root ganglia (DRG) by immunofluorescence. The effects of TRPV4 agonists on release of pro-inflammatory neuropeptides from peripheral tissues and on inflammation were examined. KEY RESULTS: Immunoreactive TRPV4 was detected in DRG neurones innervating the mouse hindpaw, where it was co-expressed in some neurones with CGRP and substance P, mediators of neurogenic inflammation. Hypotonic solutions and 4alpha-phorbol 12,13-didecanoate, which activate TRPV4, stimulated neuropeptide release in urinary bladder and airways, sites of neurogenic inflammation. Intraplantar injection of hypotonic solutions and 4alpha-phorbol 12,13-didecanoate caused oedema and granulocyte recruitment. These effects were inhibited by a desensitizing dose of the neurotoxin capsaicin, antagonists of CGRP and substance P receptors, and TRPV4 gene knockdown or deletion. In contrast, antagonism of neuropeptide receptors and disruption of TRPV4 did not prevent this oedema. TRPV4 gene knockdown or deletion also markedly reduced oedema and granulocyte infiltration induced by intraplantar injection of formalin. CONCLUSIONS AND IMPLICATIONS: Activation of TRPV4 stimulates neuropeptide release from afferent nerves and induces neurogenic inflammation. This mechanism may mediate the generation and maintenance of inflammation after injury and during diseases, in which there are changes in extracellular osmolarity. Antagonism of TRPV4 may offer a therapeutic approach for inflammatory hyperalgesia and chronic inflammation.

Ultrastructure and lectin cytochemistry of secretory cells in lingual glands of the Japanese quail (Coturnix coturnix japonica).

In the present study, as continuation of our previous research, Japanese quail (Coturnix coturnix japonica) lingual glands were investigated by means of transmission electron microscopy (TEM) to understand the cytoarchitecture and the subcellular sugar distribution within the different secretory structures. Indeed, glycosidic residues were visualized by applying an indirect technique of binding and the terminal sialoglycoconjugate sequences were characterized by employing sialidase digestion combined with lectin affinity. The ultrastructural analysis revealed an unusual cytoarchitecture of the caudal portion of anterior lingual gland that was composed of both secretory cells, filled with granules, and non-secretory cells, filled with mitochondria. Conversely, the posterior lingual gland was composed of secretory units of lingual glands only containing mucous cells filled with secretory granules with a variable morphology, including bipartite features characterized by an electron-lucent matrix and one or more electron-dense areas. Actual findings further supported that the quail lingual glands produce sialoglycoconjugates characterized by a heterogeneous composition. In conclusion, the cytological characteristics and the carbohydrate composition of quail lingual glands suggest that, analogously to mammal salivary glands, avian lingual glands could also be involved in several functions that can be correlated with the occurrence of sialic acids.

Involvement of p53 in phthalate effects on mouse and rat osteoblasts.

The role of two estrogen-mimicking compounds in regulating osteoblast activities were examined. Previously, our attention was focused on benzyl butyl phthalate (BBP) and di-n-butyl phthalate (DBP) since previous works showed that they enter the cytoplasm, bioaccumulate, modify actin cytoarchitecture and exert mitogenic effects involving microfilament disruption, and nuclear actin and lamin A regulation in Py1a rat osteoblasts. In this study we showed that BBP and DBP cause DNA base lesions both in MT3T3-E1 osteoblasts and in mouse primary calvarial osteoblasts (COBs). In addition, treatment with the above effectors caused an increase of p53 and phospho-p53 (ser-15 and ser-20) as well as an increase of apoptotic proteins with consequent decrease of cell viability. Moreover, treatment with phthalates did not modified p53 and phospho-p53 expression in Py1a rat osteoblasts. It is of relevance that in p53 knockdown mouse osteoblasts a proliferative effect of phthalates, similar to that observed in rat Py1a osteoblasts, was found. In conclusion, our data demonstrated that phthalates induce osteoblast apoptosis, which is, at least in part, mediated by p53 activation, suggesting that the proliferative effects could be due to p53 missing activation or p53 mutation.

Cough sensors. II. Transient receptor potential membrane receptors on cough sensors.

The transient receptor potential (TRP) family of channels is represented by at least six members in primary sensory neurons. These include the TRP vanilloid subtypes 1 (TRPV1), 2, 3, and 4, the cold and menthol receptor TRPM8, and TRPA1. Much interest has been directed to the study of the TRPV1, because capsaicin has been instrumental in discovering the unique role of a subset of primary sensory neurons in causing nociceptive responses, in activating reflex pathways including cough, and in producing neurogenic inflammation. TRPV1 is now regarded as an integrator of diverse sensory modalities because it undergoes marked plasticity and sensitization through a variety of mechanisms, including activation of G-protein-coupled or tyrosine kinase receptors. Evidence in experimental animals and in patients with airway diseases indicates a marked hypersensitivity to cough induced by TRPV1 agonists. Recent studies with newly developed high-affinity and selective TRPV1 antagonists have revealed that TRPV1 inhibition reduces cough induced by citric acid or antigen challenge.

Analysis of protease-activated receptor-1 and -2 in human scar formation.

Protease-activated receptor (PAR)-1 and PAR-2 are reported to contribute to the fibrotic process in a number of organs, including lung, liver, pancreas, and kidney. The aim of this study was to localize expression and biological activity of PAR-1 and PAR-2 in normal and pathological cutaneous scars. First, we investigated the immunohistochemical expression of PAR-1 and PAR-2 proteins in a series of human normal scars (NS, n = 10), hypertrophic scars (HS, n = 10), and keloids (K, n = 10). Expression of PAR-1 and PAR-2 was observed in all types of scar. Specifically, in HS and K, diffuse PAR-1 and PAR-2 positivity was found in dermal cellular areas composed of myofibroblasts, while no or minor staining was observed in the scattered fibroblasts embedded in abundant extracellular matrix in the context of the more collagenous nodules, irrespective of the type of scar. The hyperplastic epidermis overlying K was also found to be strongly PAR-1 and PAR-2 positive, whilst in most NS and HS the epidermis was faintly to moderately stained. Second, ribonuclease protection assay on paraffin-embedded specimens showed overexpression of PAR-1 and PAR-2 mRNA in K compared to NS and HS. Third, cultured human fibroblasts exposed to TGF-beta1 expressed a myofibroblast phenotype associated with overexpression of PAR-2, while PAR-1 expression was unaffected. Intracellular Ca(2+) mobilization by PAR-2 agonists in myofibroblasts was increased as compared to fibroblasts, whereas the effect of PAR-1 agonists was unchanged. Our in vivo study indicates that PAR-1 and PAR-2 are expressed in cells involved in physiological and pathological scar formation and suggests that in vitro overexpression and exaggerated functional response of PAR-2 may play a role in the function of myofibroblasts in scar evolution from a physiological repair process to a pathological tissue response.

Phthalate esters immunolocalized in the gastrointestinal tract of shi drum Umbrina cirrosa (L.) and rainbow trout, Oncorhynchus mykiss (W.).

The occurrence of phthalate esters in freshwater and marine aquacultural species like rainbow trout Oncorhynchus mykiss and shi drum Umbrina cirrosa, respectively, were determined by immunohistochemical approach. The results showed a similar distribution in the gastrointestinal tract of both species. In particular, intense immunoreactivity was found at gastric gland level. In the intestinal tract, goblet cells failed to stain, whereas enterocytes showed the highest binding of phthalates restricted to the apical cytoplasm. This distribution of phthalate esters at gastric gland and enterocyte level may have implications for the physiology of the digestive process and intestinal biotransformation. Phthalates are confirmed to be widely diffused contaminants, absorbed via the alimentary canal; thus a multidisciplinary approach could be useful to examine sea and freshwater environments.

Cattle breeding: A fast screening procedure to control the bovine fodder contamination.

The European Commission has adopted a large number of emergency measures to prevent the spread of the Bovine spongiform encephalopathy (BSE) in the Member States, and among them, a European Regulation prohibits the feeding to ruminants of animal protein and animal feed containing such protein. Aim of this work has been to propose the thermal analysis as a new rapid and sensitive screening tool for a preliminary determination of possible contamination in products destined to bovine growth, since the possibility to screen the samples by a rapid and sensitive tool could reduce the time of analysis required by the actual methodology and could allow the systematic surveillance of bovine feeding, with the official EU methods applied only to positive samples.

Applications of evolved gas analysis Part 1: EGA by infrared spectroscopy.

The analytical applications of the evolved gas analysis (EGA) performed by infrared spectroscopy, for the period extending from 2001 to 2004, are collected in this review. By this technique, the nature of volatile products released by a substance subjected to a controlled temperature program are on-line determined, with the possibility to prove a supposed reaction, either under isothermal or under heating conditions.

Applications of evolved gas analysis Part 2: EGA by mass spectrometry.

The analytical applications of the evolved gas analysis (EGA) performed by mass spectrometry, for the period extending from 2001 to 2004, are collected in this review. By this technique, the nature of volatile products released by a substance subjected to a controlled temperature program is on-line determined, with the possibility to prove a supposed reaction, either under isothermal or under heating conditions.

In situ visualization of o-phthalate esters in gastrointestinal tract of the frog Rana esculenta.

The regional distribution and relative occurrence of phthalates were studied immunohistochemically by confocal laser scanning microscopy in the alimentary tract of the green frog, Rana esculenta, using an antibody against o-phthalate esters. Many positive sites indicating the basal presence of phthalate esters were identified. The immunoreactive cells were located in the gastric glands of the stomach and in the intestinal epithelium regions with variable frequencies. The regional distribution of phathalate-accumulating cells resembled that of fish and demonstrated that these endocrine disruptors not only enter via the alimentary canal, but also bioaccumulate inside cells specialized in secretion as well as absorption functions.

Effects of phthalate esters on actin cytoskeleton of Py1a rat osteoblasts.

We evaluated, by confocal laser scanning microscopy, the actin cytoskeleton of immortalized rat Py1a osteoblasts treated with phthalate esters (butyl benzyl phthalate, BBP and dibutyl phthalate, DBP), endocrine disruptors with estrogenic activity. We observed some peculiar modifications of actin cytoskeleton and cells changing from a spindle shape to a rounded form. In particular, F-actin formed thick bundles around the cell membrane but only a weak labeling was observed in rounded cells. Also influence on apoptosis and short-term effects on FGF-2 were studied. It was found that BBP and DBP exert their action in a similar way, act in a transient manner and do not induce apoptosis.

Phthalate esters influence FGF-2 translocation in Py1a rat osteoblasts.

Exposure of the Py1a rat osteoblastic cells to butyl benzyl phthalate (BBP) and dibutyl phthalate (DBP) showed that these endocrine disrupting chemicals (EDC) strongly and reversibly affect the cytoplasmic fibroblast growth factor-2 (FGF-2) translocation into the nucleus in a dose-dependent and time-related manner. Stimulation of cells with high concentrations of BBP or DBP for short timing gave results comparable to those of cells treated with low concentrations for long timing. By confocal laser scanning microscope (CLSM) analysis it was found that the first relevant effect resulted in an accumulation of FGF-2 near the nuclear envelope, sometimes in the shape of clusters; the growth factor was then translocated into the nucleus and, finally, after long periods of exposure, the basal nuclear and cytoplasmic binding, typical of unstimulated cells, was re-established. In addition it was found that phthalate esters did not affect the FGF receptor 2 (FGFR-2) but decreased Con A binding indicating a possible inhibition of collagen fiber assembly. The different concentrations and timing of exposure of BBP and DBP affected the FGF-2 modulation in a similar way. Noticeable cumulative effects of BBP and DBP were not observed.

Solubility and thermal stability of some amino-mellitate compounds.

By reaction between the anion of mellitic acid (benzenehexacarboxylic acid) and some protonated linear polyamines (diethylenetriamine, triethylenetetramine, tetraethylene-pentamine, pentaethylenehexamine, spermidine, and spermine), fairly insoluble complexes have been obtained, with the general formula (amine)(x)(mellitate)H(6) (diethylenetriamine and spermidine, x=1; triethylenetetramine and spermine, x=0.75; tetraethylenepentamine, x=0.6 and 0.8; pentaethylenehexamine, x=0.5). K(s0) values for these complexes have been determined at I=0 mol dm(-3) and T=25 degrees C (logK(s0) ranges between -48.2 and -56.6). The solubility has been studied as a function of pH and of ionic strength. The thermal analysis, performed using air or argon flow, showed that all the solids behave in a similar way. In the range 20-120 degrees C the loss of hydration water occurs, and in the range 150-350 degrees C the first step of non oxidative decomposition takes place, with complete decomposition at 650 degrees C in air flow, whilst in argon flow the decomposition is still incomplete at 900 degrees C. Preliminary results of a parallel diffractometric study are also reported.

Short-term effects of secretagogues on the mouse parotid and sublingual gland tissular water.

The effects of isoproterenol and pilocarpine on the tissular water of mouse parotid and sublingual glands were studied by thermogravimetry (TG) coupled with Fourier transform infrared spectroscopy (FTIR). Results demonstrated that the short-term effects partly resemble the long-term action of these substances on the above-mentioned organs. Due to the different stages examined, it is difficult to speculate on the comparison between previous and the present findings. The original data resulting from the present research corresponded to the dimorphism expressed in the thermoanalytical profile of the parotid glands treated with secretagogues.

Quantitative and qualitative fluctuation of water in the mouse submandibular gland under secretagogue effect.

The short-term effects of two different secretagogues on the water contained in the mouse submandibular gland were studied using the thermal analysis as investigation method. Isoproterenol induced a retention while pilocarpine promoted a release of weakly and strongly bound water. In addition, submandibular glands of subjects administered with isoproterenol were characterized by a thermal behaviour different in males and females above all as concerns the time of reaction to the secretagogue; the reaction delay observed in females was correlated with the effects of this pharmacological substance on the convoluted granular tubules that are responsible for the sexual dimorphism in mice.

Thermal behaviour of the rabbit sublingual gland.

The purpose of this study was to show how some aspects of the biological matrix water can be investigated by thermoanalytical methods when using thermogravimetry and differential scanning calorimetry. Such methods allow to investigate the water in the rabbit sublingual gland and to quantitate it. The results supported the view that the water contained in this secretory organ show a large number of energetic interactions established on the basis of differential steps of water release by thermal disruption.