The easy synthesis of the anionic palladium catalyst containing saccharinate as only ligand Na2[Pd(saccharinate)4] (I), starting from either Na2[PdCl4] or Pd(AcO)2, is reported here, together with its complete characterization. It includes high resolution powder X-ray diffraction pattern obtained on a synchrotron source, subsequent elucidation of the crystal structure, and structural refinement using the Rietveld method. The structure consists of linear chains that are linked by non-covalent interactions, and results in a porous structure with channels. This air and light water-soluble complex has shown an outstanding performance for room temperature Pd-catalyzed Suzuki functionalization of the purine base in unprotected nucleosides, improving the best results reported to date.

BACKGROUND:Squamous cell carcinoma of the head and neck (SCCHN) is an aggressive disease with poor prognosis. It is known that the activation of STAT3 signaling pathways promotes the development and progression of this neoplasia and it has been described the role of PTPRT as a negative regulator of STAT3. Then, we have evaluated the impact of them as biomarkers of outcome in a series of patients with recurrent and/or metastatic SCCHN treated with weekly paclitaxel-plus-cetuximab (ERBITAX) regimen. PATIENTS AND METHODS:Between 2008 and 2017, 52 patients with recurrent/metastatic SCCHN were treated with ERBITAX at our center, 34 of whom had available tumor samples. Phosphorylated STAT3 (pSTAT3) protein expression was analyzed by immunohistochemistry, STAT3 mRNA expression by qPCR, and PTPRT promoter methylation by methylation-specific PCR. Molecular results were correlated with response rate (RR), progression-free survival (PFS), and overall survival (OS). RESULTS:pSTAT3 overexpression was detected in 67% and PTPRT promoter hypermethylation in 41% of tumor samples. PTPRT promoter hypermethylation showed a trend towards an association with lower RR (21% vs. 60%; p = 0.06). A lower RR was also observed in patients with pSTAT3 overexpression (36% vs. 54%) and in those with high STAT3 mRNA levels (43% vs. 64%), but these differences did not reach statistical significance. PTPRT promoter hypermethylation correlated with pSTAT3 overexpression (p = 0.009) but not with STAT3 mRNA overexpression. OS and PFS was shorter in patients with activated STAT3, but the difference did not reach statistical significance. CONCLUSIONS:Although this was a relatively small retrospective study, it provides preliminary indications of the potential role of the STAT3 pathway on outcome in SCCHN and confirms that PTPRT acts as a negative regulator of STAT3. Our findings warrant investigation in a larger patient cohort to determine if inactivating this pathway through specific targeted treatments could improve outcomes in recurrent/metastatic SCCHN patients.

Infectious and parasitic agents (IPAs) and their associated diseases are major environmental stressors that jeopardize bee health, both alone and in interaction with other stressors. Their impact on pollinator communities can be assessed by studying multiple sentinel bee species. Here, we analysed the field exposure of three sentinel managed bee species (Apis mellifera, Bombus terrestris and Osmia bicornis) to 11 IPAs (six RNA viruses, two bacteria, three microsporidia). The sentinel bees were deployed at 128 sites in eight European countries adjacent to either oilseed rape fields or apple orchards during crop bloom. Adult bees of each species were sampled before their placement and after crop bloom. The IPAs were detected and quantified using a harmonised, high-throughput and semi-automatized qPCR workflow. We describe differences among bee species in IPA profiles (richness, diversity, detection frequencies, loads and their change upon field exposure, and exposure risk), with no clear patterns related to the country or focal crop. Our results suggest that the most frequent IPAs in adult bees are more appropriate for assessing the bees’ IPA exposure risk. We also report positive correlations of IPA loads supporting the potential IPA transmission among sentinels, suggesting careful consideration should be taken when introducing managed pollinators in ecologically sensitive environments.

An innovative synthetic route that involves the thermal treatment of selected Ru co−ordination complexes was used to prepare RuO2-based materials with catalytic activity for oxygen reduction (ORR) and oxygen evolution (OER) reactions. Extensive characterization confirmed the presence of Ru metal and RuP3O9 in the materials, with an improved electrocatalytic performance obtained from calcinated [(RuCl2(PPh3)3]. A mechanistic approach for the obtention of such singular blends and for the synergetic contribution of these three species to electrocatalysis is suggested. Catalysts added to carbon−based electrodes were also tested in all−solid and flooded alkaline Zn/air batteries. The former displayed a specific discharge capacity of 10.5 A h g−1 at 250 mA g−1 and a power density of 4.4 kW kg−1 cm−2. Besides, more than 800 discharge/charge cycles were reached in the flooded alkaline Zn/air battery

Designations of a number of type specimens of Dejean’s collection deposited in the Museum National d’Histoire Naturelle (MNHN) at Paris are given. Types correspond to species of carabid beetles belonging to the tribe Harpalini found in the West Palearctic except for Harpalus saxicola. The holotypes of the following species have been recognized: Anisodactylus intermedius Dejean, 1829, Ditomus cephalotes Dejean, 1826, Ditomus tomentosus Dejean, 1831, Ditomus cordatus Dejean, 1825, Acinopus giganteus Dejean, 1831, Harpalus lateralis Dejean, 1829, Harpalus oblitus Dejean, 1829, Harpalus pumilio Dejean, 1829, Harpalus saxicola Dejean, 1829, Harpalus siculus Dejean, 1829, Harpalus (Ophonus) quadricollis Dejean, 1831, Harpalus (Ophonus) chloroticus Dejean, 1829, Acupalpus lusitanicus Dejean, 1829 and Acupalpus suturalis Dejean, 1829. The lectotype of the following species was designated: Acupalpus mauritanicus Dejean, 1829, Acupalpus metallescens Dejean, 1829, Anisodactylus virens Dejean, 1829, Carterus interceptus Dejean, 1830, Harpalus cupreus Dejean, 1829, Harpalus dispar Dejean, 1829, Harpalus contemptus Dejean, 1829, Harpalus pumilus Dejean, 1829, Harpalus punctatostriatus Dejean, 1829, Harpalus pygmaeus Dejean, 1829, Harpalus sobrinus Dejean, 1829, Harpalus solitaris Dejean, 1829, Harpalus goudotii Dejean, 1829, Harpalus zabroides Dejean, 1829, Harpalus (Ophonus) cribricollis Dejean, 1829, Harpalus (Ophonus) meridionalis Dejean, 1829, Harpalus (Ophonus) pumilio Dejean, 1829, Harpalus (Ophonus) rotundatus Dejean, 1829, Harpalus (Ophonus) similis Dejean, 1829, Harpalus (Ophonus) subquadratus Dejean, 1829, Harpalus (Ophonus) incisus Dejean, 1829, Harpalus (Ophonus) diffinis Dejean, 1829, Harpalus (Ophonus) hirsutulus Dejean, 1829, Stenolophus elegans Dejean, 1829, Acupalpus exiguus Dejean, 1829, Acupalpus atratus Dejean, 1829, Acupalpus luridus Dejean, 1829, Acupalpus nigriceps Dejean, 1829, Acupalpus lusitanicus Dejean, 1829, Harpalus (Ophonus) obsoletus Dejean, 1829, Harpalus (Ophonus pallidus) Dejean, 1829, Stenolophus marginatus Dejean, 1829 and Stenolophus proximus Dejean, 1829. Notes are added about the types of Harpalus (Ophonus) opacus (Dejean, 1829), Harpalus fastiditus Dejean, 1829, Harpalus minutus Dejean, Harpalus (Ophonus) planicollis (Dejean, 1829) and Harpalus (Ophonus) hispanus (Rambur, 1838).

Commercially available Quadrol, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (THPEN), has been used for the first time as a N^N-donor neutral hydrophilic ligand in the synthesis and characterization of new water soluble palladium(II) complexes containing chloride, phthalimidate or saccharinate as co-ligands. [PdCl2(THPEN)] (1) [Pd(phthal)2(THPEN)] (2), [Pd(sacc)2(THPEN)] (3) and the analogous complex with the closely related N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediamine (THEEN) [Pd(sacc)2(THEEN)] (4) were efficiently prepared in a one-pot reaction from [PdCl2(CH3CN)2] or Pd(OAc)2. Structural characterization of 1 and 3 by single crystal X-ray diffraction produced the first structures reported to date of palladium complexes with Quadrol. The resultant palladium complexes are highly soluble in water and were found to be effective as phosphine-free catalysts for the synthesis of functionalized nucleoside analogues under room-temperature Suzuki-Miyaura cross-coupling conditions between 5-iodo-2'-deoxyuridine (& 5-iodo-2'-deoxycytidine) with different aryl boronic acids in neat water. This is the first report of the coupling process performed on nucleosides in water at room temperature.

Modification of nucleosides via cross‐coupling processes has been carried out extensively on unprotected halonucleosides to produce functionalized nucleosides that are often developed for incorporation into oligonucleotides or used as fluorescent probes. This approach requires protection of the 5′‐OH with the 4,4′‐dimethoxytrityl (DMTr) group, which is complicated and a common cause of reaction failure. Here we report a method for direct functionalization of 5′‐O‐DMTr‐5‐iodo‐2′‐deoxyuridine via Suzuki‐Miyaura cross‐coupling, Heck alkenylation, and carboamidation. This approach facilitates rapid synthesis of a variety of C5‐substituted 5′‐O‐DMTr‐2′‐deoxyuridine derivatives. © 2022 Wiley Periodicals LLC.

Se ha elaborado una versión nueva del Catálogo de los coleópteros caraboideos de la región de Murcia, gracias a miles de nuevas aportaciones sobre la distribución regional de estos insectos. Se conocen 372 especies, cifra que duplica la conocida del catálogo de 1987. En esta versión se incluye el mapa de citas de cada especie, la descripción de las comunidades que ocupan los biotopos más característicos de la Región y un análisis biogeográfico sobre la composición faunística y el origen histórico del poblamiento de Murcia por parte de estos coleópteros tan diversos. La obra proporciona además los datos fundamentales para estudios futuros sobre conservación de la biodiversidad y las respuestas de la fauna a un ambiente que está cambiando con gran celeridad.

The synthesis and characterization of new water-soluble dinuclear palladacycles of the general formula [{Pd(R-C<^>N-SO3Na)(mu-AcO)}(2)] (R = H (1), OMe (2), Cl (3)) incorporating an ortho-metalated sodium 4-(N-benzylideneamino)benzenesulfonate moiety is reported. These complexes have been revealed to be excellent phosphine-free catalysts for the synthesis of functionalized nucleoside analogues involving a low-temperature Suzuki-Miyaura coupling of 5-iodo-2'-deoxyuridine with different arylboronic acids in neat water. The potential of 1-3 as synthetic precursors was also tested, and bridging acetates were cleaved by reaction with neutral PPh3, yielding the corresponding mononuclear derivatives [Pd(R-C<^>N-SO3Na)(AcO)(PPh3)] (R = H (4), MeO (5), Cl (6)). Analytical and spectroscopic techniques confirmed the proposed formulas and reactivities reported for complexes 1-6. Structural characterization by X-ray diffraction of single crystals grown from samples of 4 and 6 produced the unexpected but valuable crystallization-mediated compounds 4cm and 6cm that also supported the results presented here.

Solid state transformations of PdCl2, [PdCl2(PPh3)(2)], [Pd(PPh3)(4)], RuCl3 center dot H2O, [RuCl2(p-cymene)](2) and [RuCl2(PPh3)(3)] in three different atmospheres (N-2, air and O-2) have been studied by heating to 1000 degrees C/1400 degrees C these palladium/ruthenium compounds. The products obtained this way have been characterized by X-ray diffraction and its specific formulation has shown a strong dependence on the precursor complex, the atmosphere used and the temperature. Thus it is possible to obtain different materials xPd(1-x)PdO and xRu(1-x)RuO2 with a variable x value ranging between 0 and 1 from complexes without PPh3 ligand. The decomposition pattern displayed by complexes containing PPh3 is clearly different, as metal phosphate is generated during the process.

In this chapter we discuss the contribution of palladacycles to the development of two specific cross-coupling reactions named after their discoverers: Negishi coupling and Buchwald-Hartwig amination. Since the main impact of palladacycles in Negishi coupling corresponds to the four generations (palladacycles G1–G4) developed by Buchwald and coworkers, we will first introduce these palladacycles in the frame of Buchwald-Hartwig amination. Thus the chapter starts by addressing this reaction, including an overview of its general features, such as the role of palladium source and the ancillary ligands. The subsequent discussion is organized in the following three groups of palladacycles: (i) Herrmann-Beller palladacycle and related that incorporate an ortho-metallated phosphine/P-donor atom, (ii) several CˆN Buchwald generations of catalysts and all those other incorporating a CˆN backbone, (iii) Nolan palladacycles and related that incorporate NHC ligands instead of phosphines. To end, we present the reports on palladacycles used as precatalysts in the Negishi coupling.

A molecular analysis of the genus Abax (Pterostichidae) has been carried out based on the sequencing of a mitochondrial cox gene fragment and the nuclear its-2 or 28S genes. The three subgenera which are included within Abax on morphological grounds, namely Abacopercus, Abax s. str. and Pterostichoabax were partially supported. Abacopercus is a monotypic subgenus including A. schueppeli and is sister to the other species of the genus. Pterostichoabax is sister to a clade made up by species of the ‘parallelus’ group (parallelus, carinatus, baenningeri, pilleri, oblongus, and continuus), which are currently members of the subgenus Abax. The other species of this subgenus (parallelepipedus, fiorii, ovalis and pyrenaeus) make up a separate clade, what renders the subgenus Abax as polyphyletic. The geographic framework of these results suggests that the ancestors of Abax appeared in the Carpathian area, where they gave rise to A. schueppeli. Successive cladogenetic events and expansion from the Carpathians to the Alps and the Pyrenees may have originated two main lineages, Abax sensu stricto and Pterostichoabax plus the ‘parallelus’ group. All these lineages have originated a number of species in temperate forests mostly concentrated in the southern axis of Eastern and Central Alps, but all the Pterostichoabax species and two taxa of the parallelus group shifted its habitat into the alpine grass mats above the treeline during one or more ice age times.

Ditomina is a subtribe of ground beetles included in the large tribe Harpalini, with most species restricted to the Mediterranean basin. To date, affinities within Harpalini have mainly been derived from morphological data, and the placement of several genera within Ditomina has been subject to discussion. In this study we provide a regional molecular phylogeny for Ditomina with representatives from seven of the eight known genera from the West Mediterranean region, the Australian Phorticosomus Schaum, 1862, and selected Harpalini outgroup taxa. DNA sequences from two different markers, the mitochondrial protein coding gene cox1 and the nuclear gene ITS2, were sequenced and analysed from 19 taxa. Molecular phylogenetic analyses consistently support (i) the sister relationship of genera Carterus Dejean, 1830 and Eocarterus Stichel, 1923; (ii) a close relationship among Ditomus Bonelli, 1810, Tschitscherinellus Csiki, 1906 and Odontocarus Solier, 1835, which form a lineage well separated from Dixus Billberg, 1820; and (iii) the exclusion of Graniger Motschulsky, 1864 and the Australian Phorticosomus from the subtribe Ditomina. In addition, phylogenetic trees indicate a vicariance event for the brachypterous genus Eocarterus on both sides of the Strait of Gibraltar, followed by further geographical differentiation in southern Iberia and northern Morocco. This pattern contrasts with the distribution of various fully winged species of ground beetles on both sides of the same barrier, suggesting the role of dispersal limitation in speciation. Finally, a new key to supraspecific taxa of the Ditomina of the West Mediterranean region is provided.

Schiff’s bases with specific π-electron system have been synthesized and used as additives in holographic polymer-dispersed liquid crystals. It was observed that these substances modify different parameters such as current intensity, voltage, and diffracted light intensity. In addition, the maximum diffraction efficiency obtained in the reconstruction of the holograms is related to the additive molecule. We propose a relationship between this behavior and the molecular structure of these substances.