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This pioneering work studied the medieval color palette of four manuscripts produced in the scriptorium of Alfonso X, king of the Crown of Castile (r. 1252-84), including the Songs of Holy Mary (Cantigas de Santa Maria, in Rich Codex and Musicians’ Codex), Lapidary (Lapidario), and Book of Games (Libro de los juegos). Scientific analysis based on fiber-optics reflectance spectroscopy in the visible and Raman spectroscopy showed a color palette based on lapis lazuli, indigo, azurite, vermilion, red lead, orpiment, yellow ochre, two different greens (bottle green and vergaut), lead white, carbon-based black, and most importantly, brazilwood pinks, reds, and purples. So, it is now the first reported use of this lake pigment in European medieval manuscript illumination. The painting technique is also discussed. The diversity of colors and techniques, with the presence of lapis lazuli, brazilwood lake pigments, purple, and gold, demonstrates Alfonso X’s desire to produce sumptuous manuscripts.

Soil properties influence greatly the status of vine plants which consequently influences the quality of wine. Therefore, in the context of viticulture management, it is extremely important to assess the physical and chemical parameters of vineyards soils. In this study, the soils of two vineyards were analysed by near-infrared (NIR) spectroscopy and established analytical reference procedures. The main objective of this study was to verify if NIR spectroscopy is a potential tool to discriminate the soils of both vineyards as well as to quantify differences of soil's parameters. For that, a total of eight sampling spots were selected at each vineyard taking into consideration the soil type and sampled at different depths. The data analysis was performed using analysis of variance (ANOVA), principal component analysis (PCA) and partial least squares discriminant analysis (PLS-DA) and partial least squares (PLS) regression. The ANOVA results revealed that 12 out of the 18 parameters analysed through the reference procedures can be considered statistically different (p

Melanins play a fundamental role in the biology and ecology of several fungal species. Unfortunately, this group of amorphous macromolecules also severely (and most times irreversibly) stains cultural heritage objects. Despite efforts made throughout the years, knowledge of the chemical composition and structure of melanins is still insufficient, which hampers the task of safely cleaning these colourants from cultural heritage materials in a targeted way without causing further deterioration. This work aimed therefore to contribute towards enlightening the characteristics of fungal melanins from three fungi that are common paper colonizers: Aspergillus niger, Chaetomium globosum and Cladosporium cladosporioides. The extracted melanins were characterized by FTIR, Raman, UV-vis, Solid-State NMR and MALDI-TOF MS spectroscopies and the effect of inhibitors of DHN-melanin and DOPA-melanin pathways on colony pigmentation and growth was evaluated. Although all the extracted colourants show a predominantly aromatic structure with carbonyl and phenolic groups, some differences between the melanins can be highlighted. Melanins obtained from Ch. globosum and Cl. cladosporioides exhibited similar structures and composition and both presented DHN-melanin characteristics, while A. niger’s melanins revealed a more complex and ordered structure, with a higher prevalence of highly conjugated carbonyls than the others, besides the additional presence of a yellow/green component. These conclusions cannot be overlooked while selecting targeted cleaning methodologies for melanin stains on cultural heritage materials.

Abstract Iron-gall ink is one of the most important inks in the history of western civilization. The deep black colour results from Fe3+ complexes with phenolic compounds available in gall extracts. Unfortunately, it induces the degradation of both ink and support over time. Furthermore, our knowledge of these complex molecular structures is limited. This work aims to overcome this gap, revealing essential information about the complex structures of these pigments and dyes that will create a breakthrough in the next generation of conservation treatments. It presents the first in-depth phenolic identification and quantification of extracts and inks, prepared with and without gum arabic (an essential additive in medieval recipes). Five representative Iberian recipes were selected and prepared. Their phenolic profile was analysed by HPLC–DAD and HPLC–ESI–MS, which revealed that the phenolic compounds present in higher concentration, in the gall extracts, are pentagalloylglucose and hexagalloylglucose (0.15 ± 0.01–32 ± 3 mg/mL), except for one recipe, in which gallic acid is the main phenolic. The influence of the ingredients is also discussed by deconstructing the recipes: extracts of additives as pomegranate peel and solvents used in the extraction of the galls (vinegar and white wine) were characterized.

Abstract This work presents the first proof of concept for the use of molecular fluorescence signatures in medieval colours based on lac dye and brazilwood lake pigments. These two important medieval dyes were tested as markers using their UV–Visible emission and excitation spectra. These medieval paints had been previously fully characterized through a multi-analytical approach. In this work, molecular fluorescence spectra were acquired in manuscripts dating from 12th to 15th c., which were produced in monastic scriptoria or workshops. First, the spectral distribution and relative intensity of the emission and excitation spectra were discussed in detail by comparison with reference compounds, including reproductions of paints based on medieval technical texts. It was possible to group the spectra according to recipe specificities. Then, statistical methods (principal component analysis and hierarchical cluster analysis) were applied to the same fluorescence spectra and the generated clusters were compared with the previous ones. Principal component analysis was initially employed to eliminate redundancy in fluorescence data, so minimizing bias on the hierarchical cluster analysis results. Except for some misplaced spectra, the placement of samples per group was confirmed. The outliers resulted from either a poor signal to noise ratio or occurred because certain paints were unique, such as the colour produced by mixing lac dye and brazilwood, which was found in manuscripts from the Alcobaça monastic scriptorium. Previously, by using infrared or Raman spectroscopies, only lac dye could be detected. Notably, these paints compare well with a recipe that was reproduced from the text by Jean Le Begue, in which both dyes were required.

In situ amorphization is a promising approach, considered in the present work, to enhance the solubility and dissolution rate of olanzapine, while minimizing the exposure of the amorphous material to the stress conditions applied during conventional processing. The production of pellets by extrusion/spheronization and the coating of inert beads were investigated as novel methods to promote the co-amorphization of olanzapine, a poorly water-soluble drug, and saccharin. Samples were characterized using differential scanning calorimetry, X-ray powder diffraction, Fourier-transform infrared spectroscopy and scanning electron microscopy, and dissolution and stability testing. The co-amorphous produced were compared with crystalline olanzapine, or physical mixture of olanzapine and saccharin. Results suggested that the addition of water to mixtures containing olanzapine and saccharin during the production of pellets, and the coating of inert beads, induced the in situ co-amorphization of these substances. The coating of inert beads enhanced the solubility and dissolution rate of olanzapine, especially when compared to pellets coated with the crystalline drug, but also with pellets containing the co-amorphous entity in the matrix of beads. Nine months stability tests (23 °C/60% RH) confirmed the preservation of the solid-state properties of the co-amorphous form on/in pellets. Overall, results highlighted the feasibility and benefits of in situ co-amorphization, either when the drug was entrapped in the pellets matrix, or preferentially applied directly on the surface of pellets.

Anthocyanins are among the best-known phenolic compounds and possess remarkable biological activities, including antioxidant, anti-inflammatory, anticancer, and antidiabetic effects. Despite their therapeutic benefits, they are not widely used as health-promoting agents due to their instability, low absorption, and, thus, low bioavailability and rapid metabolism in the human body. Recent research suggests that the application of nanotechnology could increase their solubility and/or bioavailability, and thus their biological potential. Therefore, in this review, we have provided, for the first time, a comprehensive overview of in vitro and in vivo studies on nanocarriers used as delivery systems of anthocyanins, and their aglycones, i.e., anthocyanidins alone or combined with conventional drugs in the treatment or management of chronic diseases.

ABSTRACT Genomics-based population analysis of multidrug-resistant (MDR) Klebsiella pneumoniae motivated a renewed interest on the capsule as an evolutionary and virulence marker of clinically relevant strains. Whole-genome sequencing (WGS)-based approaches have provided great insights into the genetic variability of the capsular locus, but genotypic-biochemical capsular (K)-type correlations are lacking, hindering the establishment of a reliable framework for K-type characterization and typing. To fill this gap, we combined molecular, comparative genomics, and multivariate data analysis tools with biochemical data on the capsular locus to support the usefulness of Fourier transform infrared (FT-IR) spectroscopy as a reliable K typing tool. To validate our approach, we used a representative collection of well-defined MDR K. pneumoniae lineages involved in local or nationwide epidemics in multiple countries. With this, we demonstrate a high accuracy and resolution of our FT-IR-based spectroscopy approach for K-type discrimination that is even higher than that provided by WGS. Moreover, the specific associations established between certain K types and specific K. pneumoniae lineages with high clinical relevance, together with the accuracy, simplicity, short time to result, and inexpensive features of the method, support the value of the developed FT-IR-based approach for an easy, fast, and cost-effective strain typing. This fulfills a still unmet need for tools to support real-time monitoring and control of K. pneumoniae infections. In addition, the genotypic-biochemical correlations established provide insights on sugar composition/structure of newly defined K. pneumoniae capsular types. IMPORTANCE Klebsiella pneumoniae is nowadays recognized as one of the most defiant human pathogens, whose infections are increasingly more challenging to treat and control. Whole-genome sequencing (WGS) has been key for clarifying the population structure of K. pneumoniae, and it is still instrumental to provide insights into potential pathogenicity and evolutionary markers, such as the capsular locus. However, this information and WGS are still far from being accessible and translated into routine clinical microbiology laboratories as quick and cost-efficient strain diagnostic tools. Here, we propose a biochemical fingerprinting approach based on Fourier transform infrared spectroscopy (FT-IR) and multivariate data analysis tools for K. pneumoniae capsular typing that, because of its high resolution, speed, and low cost, can be an asset to provide enough information to support real-time epidemiology and infection control decisions. Besides, it provides a simple framework for phenotypic/biochemical validation of K. pneumoniae capsular diversity.

Abstract Microspectrofluorimetry offers high sensitivity, selectivity, fast data acquisition, good spatial resolution (down to 2 μm), and the possibility of in-depth profiling. It has proved to be a powerful analytical tool in identifying dyes and lake pigments in works of art. To maximize the extraction of the information present in fluorescence emission and excitation spectra, we propose a chemometric approach to discriminate dark reds to pink colours based on brazilwood, cochineal, kermes and lac dye. These range of hues was obtained using a diverse range of medieval recipes for brazilwood, kermes and lac colourants and Winsor and Newton archive for cochineal lake pigments; the lake pigments were analyzed as colour paints (arabic-gum and glair were the medieval binders selected). Unsupervised (HCA & PCA) and supervised (SIMCA) modelling were tested, allowing to explore similarities between colourants and classify the spectral data into the different lake pigments classes. It was possible to separate the four different chromophores based on their excitation spectra or bringing together the emission and excitation spectra. The first method could also differentiate between the cochineal lake pigments, in particular between crimson lakes with different aluminates and an extender (gypsum) and between carmines with different complexing ions (aluminum and calcium).

Angola is one of the countries at the bottom of the ranking in achieving the Sustainable Development Goals (SDGs). Creating sustainable businesses can accelerate the achievement of the SDGs. The present study analyses the antecedents of sustainability-oriented entrepreneurial intention (SOEI) among Angolan higher education students. It starts from the relationships established by the Theory of Planned Behavior (TPB) that were adapted to the sustainable strand. New possible behavioural antecedents of SOEI were added. The Partial Least Square method was applied to a sample of 308 Angolan higher education students. The results show that the TPB dimensions can be adapted and used as antecedents of SOEI and that the TPB can be extended, comprising new antecedents of SOEI also related to individuals' behaviours such as risk-taking propensity, internal locus of control, creativity and proactivity. These unknown antecedents can be taught, learned and stimulated, with universities, policymakers and organisations playing a pivotal role.

Recién nacido a término, de sexo femenino, con displasia tanatofírica tipo II, acondroplasia, hipertelorismo, implantación baja de la oreja, múltiples malformaciones osteoarticulares, macrocefalia, craneoestenosis y otras anomalías. Tras la evaluación por el equipo de neurocirugía, se constató el rostro sindrómico y signos de hipertensión intracraneal, debida a hidrocefalia, asociada a disyunción bilateral de la sutura temporal y craneoestenosis de la sutura sagital. Se realizó cirugía de compensación de la HIC a los 10 días del nacimiento. La paciente evolucionó con fontanela anterior normotensa y mejoría de la disyunción de la sutura. A los 45 días de la primera cirugía, la paciente volvió a presentar signos progresivos de HIC. Anticipando cirugía para corrección de la craneoestenosis sagital. Realizada con ayuda de neuroendoscopia para resección ósea de la sutura fusionada. La craniostenosis es una enfermedad rara caracterizada por la fusión prematura de las suturas craneales. Su resultado son anomalías del desarrollo cerebral, HIC y disminución de la función cognitiva. Se han identificado patrones de herencia genética y mutaciones como causantes de esta patología. El primer y más común signo de craneoestenosis es la forma anormal del cráneo. La tomografía computarizada 3D del cráneo es el método estándar para el diagnóstico. La cirugía abierta es la más común en la craneoestenosis sindrómica. Sin embargo, deben considerarse enfoques más conservadores en espera de la cirugía. La intervención quirúrgica endoscópica es la más adecuada hasta los 6 meses de edad. El paciente del caso descrito tiene una craneostenosis sindrómica, y el tratamiento endoscópico no es frecuente. En los casos quirúrgicos en los que la enfermedad se identificó precozmente, el pronóstico tiende a ser positivo. Palabras clave: Sutura craneal, craniostenosis sindrómica, craneostenosis sagital, tratamiento endoscópico, neurocirugía, técnicas. Full-term newborn, female, with tanatophyric dysplasia type II, achondroplasia, hypertelorism, low ear implantation, multiple osteoarticular malformations, macrocephaly, craniostenosis and other anomalies. Upon evaluation by the neurosurgery team, the syndromic face and signs of Intracranial Hypertension were found, due to hydrocephalus, associated with bilateral temporal suture disjunction and craniostenosis of the sagittal suture. Surgery was performed for ICH compensation 10 days after birth. The patient evolved with normotensive anterior fontanel and improvement of the suture dysjunction. On the 45th day after the first surgery, the patient again presented progressive ICH signs. Anticipating surgery for correction of the sagittal craniostenosis. Performed with the aid of neuroendoscopy for bone resection of the fused suture. Craniostenosis is a rare condition characterized by premature fusion of cranial sutures. Its result is abnormalities of brain development, ICH, and decreased cognitive function. Patterns of genetic inheritance and mutations are identified as causing this pathology. The first and most common sign of craniostenosis is the abnormal shape of the skull. 3D Computed Tomography of the skull is the standard method for diagnosis. Open surgery is most common in syndromic craniostenosis. However, more conservative approaches should be considered pending surgery. Endoscopic surgical intervention is most appropriate until 6 months of age. The patient in the reported case has syndromic craniostenosis, and endoscopic treatment is not common. In surgical cases in which the disease was identified early, the prognosis tends to be positive. Key words: Cranial suture, syndromic craniostenosis, sagittal craniostenosis, endoscopic management., Introduction Craniostenosis or craniosynostosis is a rare medical condition featured by the premature fusion of one or more cranial sutures, its incindence is 1 in 2,000-2,500 live births per year, [...]

As environmental concerns continue to arise, companies are increasingly turning to green marketing strategies and promoting green purchasing decisions to meet consumer demand for sustainable products and services. Peripheral regions, often overlooked in discussions about sustainability, have a unique opportunity to position themselves as leaders in environmentally responsible practices through green marketing strategies. This can represent an opportunity to boost economic growth while protecting the environment for future generations. This paper studies the influencers of consumer purchasing decisions in a country located in the periphery of Europe. One thousand two hundred fifty-five responses were collected. A multiple linear regression analysis was conducted. It was found that the decision to purchase green products seems to be influenced by factors such as environmental awareness, the perceived quality of green products, the desire to purchase them, and the prospect of a greener future. This study’s key findings indicate that price awareness acts as a mediator, amplifying the influence of environmental concerns, perceived quality, willingness to purchase, future estimations, and perceived benefits on consumers’ green purchasing decisions. This underscores the importance of consumers’ awareness of the pricing for green products. Understanding the factors influencing green purchasing behavior in peripheral regions of Europe is crucial for businesses and policymakers seeking to promote sustainable consumption practices. The current study offers insights for promoting more sustainable consumption practices in these regions.