A two-way analytical investigation of ancient gold coins: Elemental and colorimetric description of precious materials.

The investigation of ancient artifacts is often constrained by their scarce availability and high protection and custody protocols. Among these, coinage represents an especially valuable kind-of-samples given their uniqueness and the subjacent information that is hidden behind their composition. Their analysis are often carried out using non-destructive techniques in order to avoid any alteration of the samples. In the field of Cultural Heritage analysis, smartphone-based methodologies have experienced a significant increase during the last few years, given their wide availability and ability to yield fast results. However, their analytical application demands a thorough and careful tuning during the methodology optimization. In this work, 21 historical gold and golden coins spanning a historical period of more than 2000 years have been analytically investigated. To that end, a two-fold approach has been implemented: first, the elemental composition has been analysed using portable X-ray fluorescence; and second, an innovative smartphone-based imaging method has been applied to measure their colour. Results allowed to describe the coins from their elemental profile, identifying some potentially debased ones, as well as some others not containing any gold. When possible, the results have been compared to previously reported cases, but our samples include some previously unreported cases representing new insights. All in all, this article provides new analytical data on unanalysed unique historical samples, in terms of their elemental profile and colorimetric properties, making use of an innovative, non-invasive nor destructive, fast and affordable colorimetric smartphone-based method to characterise historical coins.

A smartphone image-based method for the colorimetric characterization of historical pigments in mural paintings.

In this article, the detailed description of a smartphone-based analytical method to turn a smartphone into a colorimeter is described and applied to mural painting replicas. The method consists of a camera characterization process, to estimate CIELAB values from RGB camera responses, correcting for potential experimental interferences, like the effect of the lighting/capture geometry or software for color modification and enhancement. Next, the estimated CIELAB descriptors were used to build a chemometric Support Vector Classifier to objectively distinguish among the colors of the different pigments. The method was validated in terms of color reproduction and classification performance.•A smartphone-based method is described to capture mural painting color.•A color gamut-specific camera characterization procedure is developed and the performance of the smartphone-based colorimeter is compared with a spectrophotometer.•A classification method based on the estimated CIELAB descriptors is validated in terms of classification performance.

3D-printed portable device for illicit drug identification based on smartphone-imaging and artificial neural networks.

In this manuscript, a 3D-printed analytical device has been successfully developed to classify illicit drugs using smartphone-based colorimetry. Representative compounds of different families, including cocaine, 3,4-methylenedioxy-methamphetamine (MDMA), amphetamine and cathinone derivatives, pyrrolidine cathinones, and 3,4-methylenedioxy cathinones, have been analyzed and classified after appropriate reaction with Marquis, gallic acid, sulfuric acid, Simon and Scott reagents. A picture of the colored products was acquired using a smartphone, and the corrected RGB values were used as input data in the chemometric treatment. ANN using two active layers of nodes (6 nodes in layer 1 and 2 nodes in layer 2) with a sigmoidal transfer function and a minimum strict threshold of 0.50 identified illicit drug samples with a sensitivity higher than 83.4 % and a specificity of 100 % with limits of detection in the microgram range. The 3D printed device can operate connected to a rechargeable lithium-ion cell portable battery, is inexpensive, and requires minimal training. The analytical device has been able to discriminate the analyzed psychoactive substances from cutting and mixing agents, being a useful tool for law enforcement agents to use as a screening method.

Automated H2O2 monitoring during photo-Fenton processes using an Arduino self-assembled automatic system.

A cheap and easy to use Arduino self-assembled automatic system was employed to continuously monitor the hydrogen peroxide consumption during the photo-Fenton degradation of caffeine, selected as model target compound. The automatic system made it possible to measure the H2O2 concentration in the reaction cell via a colorimetric reaction and to take samples for HPLC analysis minimising the operator manual intervention and exposure to UV radiation. The obtained results were compared in terms of LOD and LOQ with H2O2 measurements manually performed using UV-Vis spectrophotometry, evidencing better analytical performance when using the automatic system; LOD and LOQ were respectively 0.032 mM and 0.106 mM for the automatic system against 0.064 mM and 0.213 mM for UV-Vis spectrophotometry. Furthermore, the photo-Fenton treatment was optimised by means of a Design of Experiments (DoE) investigating the effect of added H2O2 concentration, iron concentration and caffeine initial concentration on system performances. The use of the automatic device for such monitoring provided several advantages: automation (with consequent reduction of the workload), measurement increased precision, reduced reagents consumption and waste production in agreement with the principles of Green Analytical Chemistry.

Unveiling origins, composition, and appearance of ancient Islamic gold coins through elemental and smartphone-based colorimetric studies.

In this article, the Islamic gold coins collections of the University of Valencia is studied for the first time for its elemental composition and colorimetric properties. To that end, non-destructive elemental analysis using energy-dispersive X-ray fluorescence is applied to obtain the coins' elemental profile. Additionally, the colour of the coins is assessed using smartphone-based colorimetry as an innovative non-invasive method. Results indicate that the Islamic coins could be attributed to Almoravids, and the gold origin could be the famous Sudanese gold, an ore which was valued all over the world. Also, the text found in the coins was translated and allowed to objectively identify the mint and year. Based on these results, it can be seen that the earliest coins struck in the Iberian Peninsula are characterised by slightly lower gold concentrations than the ones struck in the northern part of Africa, pointing towards a potential recycling of coins which already circulated in the area. In conclusion, this work provides new analytical insights into a peculiar and unique type of samples, allowing to draw some conclusions in terms of their origins and materials, and for the first time allows to characterise the chromatic coordinates of this type of samples.

Resistance to apoptosis in complicated Crohn's disease: Relevance in ileal fibrosis.

BACKGROUND AND AIMS: The stiffening of the extracellular matrix, and changes in its cellular and molecular composition, have been reported in the pathogenesis of fibrosis. We analyze the mechanisms that perpetuate ileal fibrosis in surgical resections of complicated Crohn's disease patients. METHODS: Ileal resections were obtained from affected and non-affected tissue of stenotic or penetrating Crohn's disease behavior. Ilea from non-IBD patients were used as control tissue. All samples underwent RNA sequencing. Human small intestinal fibroblasts were treated for 48 h with IL-1ß, TFGß1, PDGFB or TNF-α. Resistance to apoptosis was analysed by RT-PCR, western blot and immunohistochemistry in ileal tissue and by RT-PCR and FACS in cultured cells. RESULTS: Growth factor-driven signaling pathways and increased RAS GTPase activity were up-regulated in affected ilea in which we found expression of both the antiapoptotic molecule MCL1 and the transcription factor ETS1 in submucosal fibroblasts, and a senescence-associated secretory phenotype. In cultured intestinal fibroblasts, PDGFB induced an ETS1-mediated resistance to apoptosis that was associated with the induction of both of TGFB1 and IL1B, a cytokine that replicated the expression of SASP detected in ileal tissue. ETS1 drove fibroblast polarization between inflammatory and fibrogenic phenotypes in IL1ß-treated cells. CONCLUSIONS: Our data show resistance to apoptosis in complicated ileal CD, and demonstrate that PDGFB induce an ETS1-mediated resistance to apoptosis associated with an inflammatory and fibrogenic pattern of expression in intestinal fibroblasts. Results point to PDGFRB, IL1R1 or MCL1 as potential targets against ileal fibrosis.

Smartphone-based procedure to determine content of single synthetic dyes in food using the Arata-Possetto extraction method.

The use of additives, including dyes, is common in the preparation of food products. The analytical control of artificial food dye content is relevant since some, such as azo dyes, may produce cancer and attention deficit disorders and hyperactivity in children. Consequently, the maximum permitted concentration of azo dyes in food is regulated by current legislation. Therefore, it is of interest to find simple and fast procedures for the control of these compounds. The aim of this study is to determine the concentration of azo dyes in food samples by the Arata-Possetto method - based on the extraction of azo dyes employing natural wool -, followed by the analysis of an image captured by a smartphone camera. After experimentally determining the optimal extraction conditions, the calibration curves for standard solutions of different food dyes and the color of the dyed wool were obtained. Results from dyed wool image processing were compared with the absorbance spectra of the solutions before extraction as measured by a diode array spectrophotometer. The spectrophotometric and the image processing procedures were employed to obtain the calibration curves for different food dyes, which were subsequently employed to analyze food samples. Statistical treatment shows that the results of both methods are comparable.

The casts of Pompeii: Post-depositional methodological insights.

The casts of Pompeii bear witness to the people who died during the Vesuvius 79 AD eruption. However, studies on the cause of death of these victims have not been conclusive. A previous important step is the understanding of the post-depositional processes and the impact of the plaster in bones, two issues that have not been previously evaluated. Here we report on the anthropological and the first chemical data obtained from the study of six casts from Porta Nola area and one from Terme Suburbane. A non-invasive chemical analysis by portable X-ray fluorescence was employed for the first time on these casts of Pompeii to determine the elemental composition of the bones and the plaster. Elemental profiles were determined providing important data that cross-referenced with anthropological and stratigraphic results, are clearly helpful in the reconstruction of the perimortem and post-mortem events concerning the history of these individuals. The comparative analyses carried out on the bone casts and other collections from burned bones of the necropolis of Porta Nola in Pompeii and Rome Sepolcreto Ostiense, and buried bones from Valencia (Spain), reveal the extent of high temperature alteration and post-depositional plaster contamination. These factors make bioarchaeological analyses difficult but still allow us to support asphyxia as the likely cause of death.

Quality indicators in the rational management of severe asthma: A Spanish multidisciplinary consensus.

AIM: Severe asthma is a complex, heterogeneous condition that can be difficult to control despite currently available treatments. Multidisciplinary severe asthma units (SAU) improve control in these patients and are cost-effective in our setting; however, their implementation and development can represent an organizational challenge. The aim of this study was to validate a set of quality care indicators in severe asthma for SAU in Spain. METHODS: The Carabela initiative, sponsored by SEPAR, SEAIC, SECA and SEDISA and implemented by leading specialists, analyzed the care processes followed in 6 pilot centers in Spain to describe the ideal care pathway for severe asthma. This analysis, together with clinical guidelines and SEPAR and SEAIC accreditation criteria for asthma units, were used to draw up a set of 11 quality of care indicators, which were validated by a panel of 60 experts (pulmonologists, allergologists, and health-policy decision-makers) using a modified Delphi method. RESULTS: All 11 indicators achieved a high level of consensus after just one Delphi round. CONCLUSIONS: Experts in severe asthma agree on a series of minimum requirements for the future optimization, standardization, and excellence of current SAUs in Spain. This proposal is well grounded on evidence and professional experience, but the validity of these consensus indicators must be evaluated in clinical practice.

Development of an automated colorimeter controlled by Raspberry Pi4.

A low-cost new instrument to carry out automated colorimetric analysis has been developed. The device consists of a carousel sampler, built by a 3D-printer, and a Raspberry Pi4-controlled signal measurement module based on the RGBC (red, green, blue and clear) responses of a TCS34725 color light-to-digital converter with IR filter. The device has been tested with calibration standards of different food dyes (Tartrazine, Red Allure AC and Brilliant Blue FCF) and three food samples containing one of each food dye. The new device provides R2 > 0.995 and a LOD of 1.1, 1.4 and 0.1 µmol L-1 for each food dye, respectively. The results are statistically comparable to those obtained with a conventional benchtop spectrophotometer. The proposed device achieves a reduction in sample and waste volume and in analysis time, minimizes the use of energy, and allows in situ measurements, being an automated method it is safer for operators in comparison to the reference method, yielding similar analytical results and following the principles of green analytical chemistry.

Smartphone-based colorimetric study of adulterated tuna samples.

In this work, a colorimetric analysis of adulterated tuna samples is carried out using both a spectroradiometer and a smartphone as capture devices. Yellowfin tuna (Thunnus albacares) slices were treated with nitrate and nitrite salts, as well as with two different vegetable extracts (beetroot and radish), and the resulting NO2- and NO3- concentration was analysed using HPLC-DAD. The results indicate that both nitrite and beetroot treatments work properly as colouring agents in tuna, being nitrate also effective. When assessing the effect of radish, the final flesh had a more whitish colour. Overall, this approach allows to obtain colorimetric data which can distinguish among the different adulterating agents.

Aplicación del Sistema de Clasificación Biofarmacéutica al Cuadro Básico de Medicamentos de Cuba: ¿bioequivalencia in vivo o disolución in vitro? / Application of the Biopharmaceutical Classification System to the Basic Table of Medicines of Cuba: bioequivalence in vivo or dissolution in vitro?

El siguiente trabajo tiene como objetivos clasificar los ingredientes farmacéuticos activos (IFAs) de los sólidos orales de liberación inmediata del Cuadro Básico de Medicamentos de Cuba (CBM) que son producidos nacionalmente, según el Sistema de Clasificación Biofarmacéutica (SCB), y proponer aquellos que podrían demostrar su intercambiabilidad terapéutica a través de ensayos de disolución in vitro. Para ello se utilizó el listado de medicamentos del CBM de Cuba del 2019 y se realiza una clasificación biofarmacéutica provisional consenso, a partir de diferentes clasificaciones biofarmacéuticas publicadas y de una extensiva revisión de la literatura. Se identificó que aproximadamente el 48% de los IFAs del CBM presentan polimorfismo y que el 12,3% de las formas sólidas orales del CBM de Cuba tienen un estrecho margen terapéutico, por lo que no pueden ser bioexonerados mediante estudios de bioequivalencia in vitro basados en el SCB. Se constató que un 50,8% de los IFAs de formas sólidas orales de liberación inmediata del CBM de Cuba han sido clasificados según el SCB por la OMS. La aplicación conjunta de diversas metodologías de clasificación biofarmacéutica permitió clasificar provisionalmente todos los IFAs de las formas sólidas orales del CBM, demostrando que el 66,1% pertenece a las clases I, III y I/III del SCB, por lo que podrían ser bioexonerados de ensayos de bioequivalencia in vivo en humanos

The goals of the present work are to classify the active pharmaceutical ingredients (APIs) of the oral solids of immediate release of the Essential List of Medicines of Cuba (CBM) that are produced nationally, according to the Biopharmaceutical Classification System (BCS), and to propose those that could demonstrate their therapeutic interchangeability through in vitro dissolution tests. For this was used the Cuban CBM drug list of 2019, and a provisional consensus biopharmaceutical classification is proposed, based on different published biopharmaceutical classifications and an extensive review of the literature. It was identified that approximately 48% of the CBM IFAs present polymorphism and that 12.3% of the oral solid forms of CBM in Cuba have a narrow therapeutic margin, for which reason they cannot be bioexonerated through in vitro bioequivalence studies based on BCS. It was found that 50.8% of the oral solid forms of CBM in Cuba have been classified according to SCB by WHO. The joint application of diverse methodologies of biopharmaceutical classification allowed to provisionally classify all the IFAs of the oral solid forms of CBM, demonstrating that 66.1% belongs to classes I, III and I/III of the SCB, reason why they could be biowaivered from in vivo bioequivalence assays in humans

Partial least squares modelization of energy dispersive X-ray fluorescence.

As a proof of concept, a green methodology has been developed for the energy dispersive X-ray fluorescence (ED-XRF) determination of calcium, potassium, iron, magnesium, aluminum, chromium, strontium, phosphorus and nickel in the peel of untreated kaki fruit (Diospyros kaki. L) samples. ED-XRF spectra of fifty-six kakis purchased in the local area of LLombay (Valencia) were obtained directly from samples without any previous treatment and without sample damage just after cleaning the fruit with distilled water. Inductively Couple Plasma Optical Emission Spectrometry (ICP-OES) was used as a reference method to determine the mineral elements after microwave assisted acid digestion. XRF spectra and concentration values obtained by ICP-OES were processed using partial least squares (PLS) data treatment to build the corresponding chemometric models for prediction of mineral profile of samples. PLS-ED-XRF permits a direct and accurate determination of Ca and K in kaki peel. For Al, Fe, Mg, Ni and Sr screening semiquantitative results were obtained. Concentrations obtained directly by the internal calibration of instrument, using GeoChem Trace model, were also compared with data predicted by chemometric models being found that PLS models must replace the calibration of the instrument for thus kind of analysis.

Direct determination by portable ED-XRF of mineral profile in cocoa powder samples.

The present study has exploited the rapidity of the analysis and the multi-elemental capability of the energy dispersive X- ray fluorescence (ED-XRF) technique for the mineral profile determination in cocoa powder. A fast, cheap and environmental sustainable method without reagent consumption or toxic waste generation has been proposed. The samples can be prepared in the form of pellets of 13 mm in diameter and 2-3 mm thickness. The different internal calibrations used by ED-XRF equipment did not provide accurate results when comparing the mineral profile with the concentration obtained by Inductively Couple Plasma Optical Emission Spectroscopy (ICP-OES) after microwave assisted digestion of samples. For direct ED-XRF analysis of the cocoa samples, an external calibration using as standards the cocoa samples diluted with sugar was prepared. The analytical parameters of Relative Standard Deviation and Limit of Detection for the determined elements are adequate to the concentration levels found in the samples.

miR-1226 detection in GCF as potential biomarker of chronic periodontitis: A pilot study.

BACKGROUND: The study and identification of new biomarkers for periodontal disease, such as microRNAs (miRNAs), may give us more information about the location and severity of the disease and will serve as a basis for treatment planning and disease-monitoring. miRNAs are a group of small RNAs which are involved in gene regulation by binding to their messenger RNA target (mRNA). In this pilot study, the procedure for purifying miRNAs from gingival crevicular fluid (GCF) was, for the first time, described. In addition, the concentration of miRNAs in GCF was analyzed and compared between patients with moderate or severe chronic periodontitis (CP) and healthy controls. MATERIAL AND METHODS: GCF samples were collected from single-rooted teeth of patients with moderate or severe CP (n=9) and of healthy individuals (n=9). miRNAs were isolated from GCF using miRNeasy Serum/Plasma kit (Qiagen, CA. USA). Reverse transcription polymerase chain reaction (qRT-PCR) was used to determine the expression of a series of miRNAs candidates that are related to bone metabolism. The significance of differences in miRNA levels between both groups was determined using Mann-Whitney U test. RESULTS: The results from this pilot study indicate that miRNAs can be isolated from GCF. Six different miRNAs were analyzed (miR-671, miR-122, miR-1306, miR-27a, miR-223, miR-1226), but only miR-1226 showed statically significant differences between the CP group and healthy controls (p<0.05). This miRNA was downregulated in patients with CP. CONCLUSIONS: Within the limitations of the present study, it may be concluded that miR-1226 can be a promising biomarker for periodontal disease, adding relevant information to common clinical parameters used for diagnosis and prognosis of periodontitis.

hTERT mRNA expression in urine as a useful diagnostic tool in bladder cancer. Comparison with cytology and NMP22 BladderCheck Test®. / Expresión de ARNm de hTERT en orina como herramienta diagnóstica útil en cáncer de vejiga. Comparación con citología y NMP22 BladderCheck Test®.

INTRODUCTION: To study the relationship between quantitative mRNA determination (hTERT) in patients with bladder tumor, history of bladder tumor, and in subjects without a history of this neoplasia. MATERIAL AND METHODS: A prospective randomized controlled study with 91 subjects included. The value of mRNA-hTERTN was determined in 63 patients with a history or suspicion of bladder tumor and in 28 controls. Urine samples were sent for evaluation of the mRNA level (hTERT), the cytological study and the NMP22 result. RESULTS: Differences were observed in mean hTERTN levels in each of the groups: tumor presence 21.33+/- 40.66, tumor history 2.16+/- 2.67, controls 0.9+/- 1, 75 (p<0.001). In patients with tumor, there was no difference in mean hTERTN levels between the different grades and stages, although there was a tendency: low grade tumor 9.04+/- 16.95, high grade 28.95+/- 48.36 (p=.069), stage Ta 10.33+/- 19.39, T1 17.88+/- 27.14, T2 54.8+/- 74.05 (p=.056). In addition, the sensitivity of hTERTN was superior to that of other test (76%), although specificity and positive and negative predictive values were better for cytology (94%, 88.4% and 72.3% respectively) and NMP22 (88%, 80.6% and 73.3% respectively). CONCLUSIONS: hTERTN mRNA levels in urine were higher in patients with bladder tumors compared to patients with a history of bladder tumor and with negative cystoscopy, as well as in the control group. This determination showed a higher diagnostic yield compared with the detection of NMP22 and urinary cytology.

Inter-genotypic differences in drought tolerance of maritime pine are modified by elevated [CO2].

Background and Aims: Despite the importance of growth [CO 2 ] and water availability for tree growth and survival, little information is available on how the interplay of these two factors can shape intraspecific patterns of functional variation in tree species, particularly for conifers. The main objective of the study was to test whether the range of realized drought tolerance within the species can be affected by elevated [CO 2 ]. Methods: Intraspecific variability in leaf gas exchange, growth rate and other leaf functional traits were studied in clones of maritime pine. A factorial experiment including water availability, growth [CO 2 ] and four different genotypes was conducted in growth rooms. A 'water deficit' treatment was imposed by applying a cycle of progressive soil water depletion and recovery at two levels of growth [CO 2 ]: 'ambient [CO 2 ]' (aCO 2 400 µmol mol -1 ) and 'elevated [CO 2 ]' (eCO 2 800 µmol mol -1 ). Key Results: eCO2 had a neutral effect on the impact of drought on growth and leaf gas exchange of the most drought-sensitive genotypes while it aggravated the impact of drought on the most drought-tolerant genotypes at aCO2. Thus, eCO2 attenuated genotypic differences in drought tolerance as compared with those observed at aCO2. Genotypic variation at both levels of growth [CO2] was found in specific leaf area and leaf nitrogen content but not in other physiological leaf traits such as intrinsic water use efficiency and leaf osmotic potential. eCO2 increased Δ 13 C but had no significant effect on δ 18 O. This effect did not interact with the impact of drought, which increased δ 18 O and decreased Δ 13 C. Nevertheless, correlations between Δ 13 C and δ 18 O indicated the non-stomatal component of water use efficiency in this species can be particularly sensitive to drought. Conclusions: Evidence from this study suggests elevated [CO 2 ] can modify current ranges of drought tolerance within tree species.