Judicial Independence and Party Politics in the Kelsenian Constitutional Courts: The Case of Portugal

In this paper we test to what extent the Kelsenian-type of constitutional judges are independent from political parties by studying of the Portuguese Constitutional Court. The results yield three main conclusions. First, constitutional judges in Portugal are quite sensitive to their political affiliations and their political party\u27s presence in government when voting. Second, peer pressure is very relevant. Third, the 1997 reform that was enacted to increase judicial independence has had no robust statistically significant effect

Effect of wood aging on wine mineral composition and 87Sr/86Sr isotopic ratio

The evolution of mineral composition and wine strontium isotopic ratio 87Sr/86Sr (Sr IR) during wood aging were investigated. A red wine was aged in stainless steel tanks with French oak staves (Quercus sessiliflora Salisb.), with three industrial scale replicates. Sampling was carried out after 30, 60, and 90 days of aging, and the wines were evaluated in terms of general analysis, phenolic composition, total polysaccharides, multielement composition, and Sr IR. Li, Be, Mg, Al, Sc, Ti, V, Mn, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Mo, Sb, Cs, Ba, Pr, Nd, Sm, Eu, Dy, Ho, Er, Yb, Lu, Tl, and Pb elements and 87Sr/86Sr were determined by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS) and Na, K, Ca, and Fe by flame atomic absorption spectrometry (FAAS). Two-way ANOVA was applied to assess wood aging and time effect on Sr IR and mineral composition. Wood aging resulted in significantly higher concentrations of Mg, V, Co, Ni, and Sr. At the end of the aging period, wine exhibited statistically identical Sr IR compared to control. Study suggests that wood aging does not affect 87Sr/86Sr, not precluding the use of this parameter for wine traceability purposesinfo:eu-repo/semantics/publishedVersio

application in C-H activation catalysis

This work was supported by the Spanish Government, the Spanish National Research Council (CSIC). We also thank Dr Martinez from Novozymes. Publisher Copyright: © 2023 RSC.The effect of the temperature in the synthesis of Pd nanoparticles in the metal-enzyme biohybrids is evaluated. The effect on the formation, size, and morphology of nanoparticles was evaluated using C. antarctica B lipase as the protein scaffold. XRD analyses confirmed the formation of crystalline Pd(0) as the metal species in all cases. TEM analyses revealed spherical crystalline nanoparticles with average diameter size from 2 nm at 4 °C synthesis to 10 nm obtained at 50 °C synthesis. The thermal phenomenon was also critical in the final hybrid formation using more complex enzymes, where the relation of the protein structure and temperature and the influence of the latter has been demonstrated to be critical in the reducing efficiency of the enzyme in the final Pd nanoparticle formation, in the metal species, or even in the final size of the nanoparticles. Different Pd biohybrids were evaluated as catalysts in the C-H activation of protected l-tryptophan under mild conditions. Pd@CALB4 showed the best results, with >99% conversion for C-2 arylation in methanol at room temperature with a TOF value of 64 min−1, being 2 or 4 times higher than that of the other synthesized hybrids. This catalyst showed a very high stability and recyclability, maintaining >95% activity after three cycles of use.publishersversionpublishe

Exploring Thermomyces lanuginosus Lipase (TLL)-PdNPs Nanohybrid as Suitable Catalyst for One-pot Synthesis of Bis(3-indolyl)phenylmethane

This work was supported by the Spanish Government, the Spanish National Research Council (CSIC). project PTDC/QUI‐QOR/0712/2020. We also thank Dr. Martinez from Novozymes. We acknowledge support of the publication fee by the CSIC Open Access Publication Support Initiative through its Unit of Information Resources for Research (URICI) Publisher Copyright: © 2023 The Authors. ChemCatChem published by Wiley-VCH GmbH.Palladium nanohybrids were synthesized and applied to the one-pot synthesis of bis(3-indolyl)methanes by selective C−C bond reaction from benzyl alcohol and indole. A T. lanuginosus lipase-palladium nanoparticles hybrid (Pd@TLL) was synthesized, yielding PdNPs with an average diameter size of 5 nm. This heterogeneous catalyst was first tested in the selective oxidation of benzyl alcohol to benzaldehyde in different solvents. Then, the direct formation of bis(3-indolyl)methane, by in situ oxidation and C−C coupling, was successfully evaluated under different conditions, obtaining >99 % conversion at 80 °C in toluene, with a TOF value of 9 min−1 and 89 % in pure water, demonstrating the versatility of these biohybrids.publishersversionpublishe

Barriers to Accessing Eye Health Services in Suburban Communities in Nampula, Mozambique

Globally, an estimated 2.2 billion people are visually impaired (VI) or blind, and a large proportion (90%) of those affected live in low- and middle-income countries (LMICs), where access to eye health services is limited. This study aimed to identify barriers to accessing eye health services and associated factors in suburban communities of Nampula. A cross-sectional community-based study was carried out on adults ≥18 years old. A total of 338 adults were randomly selected from three communities (Muthita, Piloto, and Nthotta). Individual interviews were carried out and socio-demographic data, eye symptoms, date of last eye examination, and barriers to access to eye health services were extracted. Among participants, 49.4% had eye symptoms and 41.7% did not have their eye examinations up to date. The most cited barriers were crowding in hospitals (40.7%), financial difficulties (30.0%), self-medication (20.5%), traditional treatment (17.8%), and buying eyeglasses on the street (11.6%). Barriers limited the service target to 33%. Lower levels of schooling and monthly family income and farmer occupation were statistically associated with the most barriers as risk factors. The use of eye health services was lower due to barriers to accessing eye services. More specific intervention plans and greater cooperation between sectors are needed to improve these indicators

Immune-Related Transcriptional Responses to Parasitic Infection in a Naturally Inbred Fish: Roles of Genotype and Individual Variation

Parasites are strong drivers of evolutionary change and the genetic variation of both host and parasite populations can co-evolve as a function of parasite virulence and host resistance. The role of transcriptome variation in specific interactions between host and parasite genotypes has been less studied and can be confounded by differences in genetic variation. We employed two naturally inbred lines of a self-fertilizing fish to estimate the role of host genotype in the transcriptome response to parasite infection using RNA-seq. In addition, we targeted several differentially expressed immune-related genes to further investigate the relative role of individual variation in the immune response using RT-qPCR, taking advantage of the genomic uniformity of the self-fertilizing lines. We found significant differences in gene expression between lines in response to infection both in the transcriptome and in individual gene RT-qPCR analyses. Individual RT-qPCR analyses of gene expression identified significant variance differences between lines for six genes but only for three genes between infected and control fish. Our results indicate that although the genetic background plays an important role in the transcriptome response to parasites, it cannot fully explain individual differences within genetically homogeneous lines, which can be important for determining the response to parasites

'Syncing' Up with the Quinn-Rand-Strogatz Constant: Hurwitz-ZetaFunctions in Non-Linear physics

This work extends the analytical and computationalinvestigation of the Quinn-Rand-Strogatz (QRS) constants from non-linearphysics. The QRS constants (c1, c2, ..., cN) are found in a Winfreeoscillator mean-field system used to examine the transition of coupledoscillators as they lose synchronization. The constants are part of anasymptotic expansion of a function related to the oscillatorsynchronization. Previous work used high-precision software packages toevaluate c1 to 42 decimal-digits, which made it possible to recognize andprove that c1 was the root of a certain Hurwitz-zeta function. Thisallowed a value of c2 to beconjectured in terms of c1. Therefore thereis interest in determining the exact values of these constants to highprecision in the hope that general relationships can be establishedbetween the constants and the zeta functions. Here, we compute the valuesof the higher order constants (c3, c4) to more than 42-digit precision byextending an algorithm developed by D.H. Bailey, J.M. Borwein and R.E.Crandall. Several methods for speeding up the computation are exploredand an alternate proof that c1 is the root of a Hurwitz-zeta function isattempted

Tuning the Diradical Character of Indolocarbazoles: Impact of Structural Isomerism and Substitution Position

In this study, a set of 10 positional indolocarbazole (ICz) isomers substituted with dicyanomethylene groups connected via para or meta positions are computationally investigated with the aim of exploring the efficiency of structural isomerism and substitution position in controlling their optical and electronic properties. Unrestricted density functional theory (DFT), a spin-flip time-dependent DFT approach, and the multireference CASSCF/NEVPT2 method have been applied to correlate the diradical character with the energetic trends (i.e., singlet–triplet energy gaps). In addition, the nucleus-independent chemical shift together with ACID plots and Raman intensity calculations were used to strengthen the relationship between the diradical character and (anti)aromaticity. Our study reveals that the substitution pattern and structural isomerism represent a very effective way to tune the diradical properties in ICz-based systems with meta-substituted systems with a V-shaped structure displaying the largest diradical character. Thus, this work contributes to the elucidation of the challenging chemical reactivity and physical properties of diradicaloid systems, guiding experimental chemists to produce new molecules with desirable properties.Funding for open access charge: Univesidad de Málaga/CBUA. The work at the University of Málaga was funded by the MICINN (PID2019-110305GB-I00) and Junta de Andalucía (UMA18-FEDERJA-080, P09FQM-4708, and P18-FR-4559) projects. The authors thankfully acknowledge the computer resources, technical expertise, and assistance provided by the SCBI (Supercomputing and Bioinformatics) centre of the University of Málaga. The work at the University of Alicante was supported by the MICINN (PID2019-106114GB-I00). The work at the University of Bologna was supported by University of Bologna (RFO) funds

Smell of Infection:a novel, non-invasive method for detection of fish excretory- secretory proteins

Chemical signals are produced by aquatic organisms following predatory attacks or perturbations such as parasitic infection. Ectoparasites feeding on fish hosts are likely to cause release of similar alarm cues into the environment due to the stress, wounding, and immune response stimulated upon infection. Alarm cues are often released in the form of proteins, antimicrobial peptides, and immunoglobulins that provide important insights into bodily function and infection status. Here we outline a noninvasive method to identify potential chemical cues associated with infection in fish by extracting, purifying, and characterizing proteins from water samples from cultured fish. Gel free proteomic methods were deemed the most suitable for protein detection in saline water samples. It was confirmed that teleost proteins can be characterized from water and that variation in protein profiles could be detected between infected and uninfected individuals and fish and parasite only water samples. Our novel assay provides a noninvasive method for assessing the health condition of both wild and farmed aquatic organisms. Similar to environmental DNA monitoring methods, these proteomic techniques could provide an important tool in applied ecology and aquatic biology

A Novel Role For Nanog As An Early Cancer Risk Marker In Patients With Laryngeal Precancerous Lesions

NANOG is a master regulator of embryonic stem cell pluripotency, found to be frequently aberrantly expressed in a variety of cancers, including laryngeal carcinomas. This study investigates for the first time the role of NANOG expression in early stages of laryngeal tumourigenesis and its potential utility as cancer risk marker. NANOG protein expression was evaluated by immunohistochemistry using two large independent cohorts of patients with laryngeal precancerous lesions, and correlated with clinicopathological parameters and laryngeal cancer risk. NANOG expression was detected by immunohistochemistry in 49 (60%) of 82 laryngeal dysplasias, whereas expression was negligible in patient-matched normal epithelia. Strong NANOG expression was found in 22 (27%) lesions and was established as cut-off point, showing the most robust association with laryngeal cancer risk (P = 0.003) superior to the histological classification (P = 0.320) the current gold standard in the clinical practice. Similar trends were obtained using a multicenter validation cohort of 86 patients with laryngeal dysplasia. Our findings uncover a novel role for NANOG expression in laryngeal tumourigenesis, and its unprecedented application as biomarker for cancer risk assessment