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Photoresponsive polyvinylidene fluoride (PVDF) fibers doped with naphthopyran-functionalized silica nanoparticles (SiO2@NPT) were successfully prepared by dry–jet wet spinning. The incorporated photochromic nanomaterials, SiO2@S1 and SiO2@S2, were previously prepared by covalent post-grafting of the silylated NPTs – 2H-naphtho[1,2-b]pyran derivatives, S1 and S2 – onto nano-sized SiO2 (15 ± 3 nm). The morphological and chemical characterization of the resulting doped fibers PVDF@SiO2@S1 and PVDF@SiO2@S2 was evaluated by scanning electron microscopy with energy dispersive spectroscopy and Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR). Both PVDF@SiO2@S1 and PVDF@SiO2@S2 fibers presented average diameters of 133 ± 8 μm and 98 ± 7 μm, respectively, and a porous outer surface. The presence of the SiO2@NPT within the fibers was confirmed through the observation of dense clusters embedded within the polymeric matrix. Furthermore, the FTIR-ATR spectra of the fibers revealed that the PVDF matrix was composed of α and β crystalline and amorphous phases. The PVDF@SiO2@S1 and PVDF@SiO2@S2 fibers showed photoresponsive properties under UV and sunlight irradiation, exhibiting fast coloration kinetics and good optical contrast (ΔE*ab = 7.2 and 15.1, respectively), and changing from a pale orange and an off-white color to a more intense yellow-orange and purple coloration, respectively, in less than 1 min. Moreover, they showed an initial fast bleaching, losing half of their color in less than 30 min (t1/2 = 28 and 20 min for PVDF@SiO2@S1 and PVDF@SiO2@S2 fibers, respectively), but displaying a residual coloration that took 1 and 2 h to return to the initial uncolored state (t3/4 = 95 and 49 min, respectively). The PVDF@SiO2@S2 fibers presented the best photochromic performance.

The conversion of nitroarenes to aminoarenes is of great industrial interest since they are prevalent pollutants in water and aminoarenes are important intermediates in the synthesis of pharmaceuticals, natural products and in bulk chemical production. In this work, two new catalysts for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) were prepared by immobilization of gold nanoparticles onto the surface of K10 montmorillonite clay (K10) functionalized with two new l -serine derivative organosilanes. Transmission electron microscopy showed the presence of 4–5 nm gold nanoparticles after catalysis. The reduction reaction of 4-NP to 4-AP at 25 °C, using NaBH4 as reducing agent, led to nearly 100% conversion in only 1 minute, presenting pseudo-first-order rate constants normalized for Au loading of K = 630 and 430 mmol−1 s−1. The catalysts showed high stability, leading to substrate conversions of 95–100% after 10 consecutive cycles, with negligible Au leaching.

Military orders have historically played a key role in defining borders, both in a mental sense, by favouring an awareness of alterity in the most peripheral territories (Christians against Muslims and Christians against Pagans), and also in more direct ways, as owners of land in these territories. This article1 discusses both the influence, in the broadest sense, of territory and periphery upon the medieval military orders, and the relationship between the crown and the military orders. It will be done through a comparative historical analysis of two cases: Portugal and Denmark in the 12th–16th centuries. Both countries were placed at the periphery of the Western world in the Middle Ages, and they were both active agents in the Crusading movement.

Microdeletions in AZFa, AZFb and AZFc regions lead to different patterns of male infertility, from severe oligozoospermia to non-obstructive azoospermia. Intrachromosomal homologous recombination mechanisms were already identified in patients with simultaneous microdeletions in the AZFb and AZFc regions. Ten patients with atypical AZFb and AZFc deletion patterns were studied. The definition of those microdeletions and the fine characterization of the respective breakpoints were performed using sequence tagged sites/single nucleotide variants-PCR and DNA sequencing. Y-chromosome haplogroups were determined to establish a putative association with the patterns obtained. Seven deletion patterns were identified, P5/terminal (30%; 3/10), P5/P1 distal (20%; 2/10), IR4/distal-P2, IR2/proximal-P1, IR4/distal-P1, P4/terminal and complete AZFb/c deletion (10%; 1/10). Breakpoint sequence analysis suggests that only in one patient the P5/P1 distal deletion pattern was due to a homologous recombination mechanism. Sequence alignment of the other deletion patterns suggest that they have resulted from non-homologous recombination mechanisms.

The DAZ gene, a contributing factor in infertility, lies on the human Y chromosome's AZFc region, whose deletion is a common cause of spermatogenic failure. Y chromosome binary polymorphisms on the non-recombining Y (NRY) region, believed to be a single occurrence on an evolutionary scale, were typed in a sample of fertile and infertile men with known DAZ backgrounds. The Y single-nucleotide polymorphisms (Y-SNPs) with low mutation rates are currently well characterized and permit the construction of a unique phylogeny of haplogroups. DAZ haplotypes were defined using single-nucleotide variant (SNV)/sequence tagged-site (STS) markers to distinguish between the four copies of the gene. The variation of 10 Y chromosome short tandem repeat (STRs) was used to determine the coalescence age of DAZ haplotypes in a comparable time frame similar to that of SNP haplogroups. An association between DAZ haplotypes and Y chromosome haplogroups was found, and our data show that the DAZ gene is not under selective constraints and its evolution depends only on the mutation rate. The same variants were common to fertile and infertile men, although partial DAZ deletions occurred only in infertile men, suggesting that those should only be used as a tool for infertility diagnosis when analysed in combination with haplogroup determinations.