Aurophilic interactions in polynuclear Au(I) complexes with phosphine ligands containing imidazole rings

Aurophilic interactions in polynuclear Au(I) complexes with phosphine ligands containing imidazole rings Fiorella Bachechiaa*, Alfredo Burinib, Rossana Galassib aIstituto di Strutturistica Chimica, C.N.R., Area della Ricerca di Roma, C.P. 10, 00016 Monterotondo St. (Roma), Italy., bDipartimento di Scienze Chimiche, Università di Camerino, 62032 Camerino, Italy. E-mail: [email protected] Keywords: gold complexes, aurophilicity, crystal structures The tertiary phosphines of the type (Bzim)3-nPhnP, where Bzim is 1-benzyl-2-imidazolylphosphine and n varies from 0 to 2, were synthesised as part of a program aimed to the study of the coordination chemistry of phosphines containing imidazole rings. The softer character of imidazole, with respect to other heterocycles, turned out to be useful in the stabilization of complexes with soft metals as those of Group 11 in low oxidation states. These ligands can behave as monodentate or as P, N bidentate forming dinuclear cationic complexes. With Au(I) they were found to be able to favour the formation of intraand intermolecular aurophilic interactions. TheAu(I) complexes assume considerable interest when aurophilic bonds occur between gold atoms, since their chemical and physical properties change to particular characteristics with potential applications in electronic, optical or sensor devices. In particular short Au•••Au interactions are considered related to optoelectronic properties as observed in a number of polynuclear gold compounds. Here the structures of two Au(I) complexes are reported. The binuclear complex [μ-(Bzim)Ph2PAu2(C6F5)2] adopts a folded conformation with parallel, eclipsed C6F5 rings and a corresponding short AucccAu contact of 3.033(2)Å. The tetranuclear cluster complex {[μ-N,N’-(Bzim)3PAuCl]2 Au2}2+c AuCl2 - c AuCl4 - consists in a 12-membered macrocycle with two gold atoms coordinated to two (Bzim)3P molecules, in bridging mode, through the nitrogen atoms of the imidazole rings and two gold atoms coordinated to the phosphorus atoms of the (Bzim)3P ligands. Two chloride atoms complete the Au bicoordination. Three strong aurophilic interactions, Au(1)cccAu(4) [2.989(2)Å], Au(2)cccAu(3) [3.014(2)Å] andAu(1)cccAu(2) [3.257(3)Å], occur.Aweak gold-gold contact, Au(3)cccAu(4) [3.766(2)Å], is also present. Understanding molecular interactions 23r

Coinage metals trinuclear metallocycles: old and new aspects of this class of compounds

Coinage metals trinuclear metallocycles: old and new aspects of this class of compounds Galassi R. a, Oumarou C. S. a, Omary A. M. b, Nesterov V. b, Burini A.a aSchool of Science and Technology, Chemistry Division, University of Camerino, Via S. Agostino 1, 62032 Camerino; e-mail: [email protected] b Department of Chemistry, University of North Texas, Denton, 1155 Union Circle, TX 76203, USA; e-mail: [email protected] Azoles such as imidazoles and pyrazoles are optimal bridging ligands to obtain C,N or N,N trinuclear coinage metals metallocycles. Since past decade till now, few worldwide research groups including us have focused their attention to their synthesis and characterization.[1] Moreover, the photophysical properties[2] the extended network of metallophilic bondings in the supramolecular structure and the pi-acid/pi-base chemistry[3] of these compounds directed the research to theoretical studies bringing to a better interpretation of the experimental behaviors.[4] Here we report the synthesis of new coinage metals metallocycles and their spectroscopic characterizations highlighting points of continuity with the previous analogs and new features for new perspective research lines. As in example, the 1-vinylimidazole resembles the acid-base chemistry of the 1-benzylimidazole gold(I) metallocycle, while substitution in position 4,5 of 1-benzylimidazole with electron-withdrawing group, do not allow the formation of metallocycles with the same synthethic route and mononuclear gold(I) derivatives have been obtained. The nature of the heterocycle and of the substituents, in addition to their position in the azolate ligand defines and tunes the properties of the final products. References: 1) Galassi, R.; Burini, A.; Omary-Rawanashed, M., Omary, M. A., Comm. Inorg. Chem. 2014, in submission. 2) Rawashdeh-Omary, M. A.; Omary, M. A.; Fackler Jr, J. P, Galassi R., Pietroni, B. R.; Burini, A. J. Am. Chem. Soc 2001, 123; 9689-9691. 3) Burini, A.;. Fackler Jr, J. P; Galassi R., Grant, T. A.. Omary, M. A; Rawashdeh-Omary, M. A.; Pietroni, B. R.; Staples R. J. J. Am. Chem. Soc., 2000; 11264-11265. 4) Galassi, R.; Ricci, S.; Burini, A.; Macchioni, A; Marmottini, F.; Tekarli, S. M.; Nesterov, N.V.; Omary, M. A. Inorg. Chem. 2013, 52, 14124-14137

Sudden unexpected death in epilepsy and ictal asystole in patients with autoimmune encephalitis: a systematic review

Objective: As autoimmune encephalitis (AE) often involves the mesial temporal structures which are known to be involved in both sudden unexpected death in epilepsy (SUDEP) and ictal asystole (IA), it may represent a good model to study the physiopathology of these phenomena. Herein, we systematically reviewed the occurrence of SUDEP and IA in AE. Methods: We searched 4 databases (MEDLINE, Scopus, Embase, and Web of Science) for studies published between database inception and December 20, 2022, according to the PRISMA guidelines. We selected articles reporting cases of definite/probable/possible/near-SUDEP or IA in patients with possible/definite AE, or with histopathological signs of AE. Results: Of 230 records assessed, we included 11 cases: 7 SUDEP/near-SUDEP and 4 IA. All patients with IA were female. The median age at AE onset was 30 years (range: 15–65), and the median delay between AE onset and SUDEP was 11 months; 0.9 months for IA. All the patients presented new-onset seizures, and 10/11 also manifested psychiatric, cognitive, or amnesic disorders. In patients with SUDEP, 2/7 were antibody-positive (1 anti-LGI1, 1 anti-GABABR); all IA cases were antibody-positive (3 anti-NMDAR, 1 anti-GAD65). Six patients received steroid bolus, 3 intravenous immunoglobulin, and 3 plasmapheresis. A pacemaker was implanted in 3 patients with IA. The 6 survivors improved after treatment. Discussion: SUDEP and IA can be linked to AE, suggesting a role of the limbic system in their pathogenesis. IA tends to manifest in female patients with temporal lobe seizures early in AE, highlighting the importance of early diagnosis and treatment

Supramolecular Chemistry and photophysical Properties of a New Gold (I) Cyclic Trinuclear Complex, [Au(µ-C2,N3-1-vinylimidazole)]3

Supramolecular Chemistry and photophysical Properties of a New Gold (I) Cyclic Trinuclear Complex, [Au(µ-C2,N3-1-vinylimidazole)]3 R. Galassia, A. Burinia, C. S. Oumaroua, V. N. Nesterov b, M. A. Omary b. a Dipartimento di Scienze Chimica, Università di Camerino, Via Sant Agostino, 1, 62032 Camerino, Italia b Department of Chemistry, University of North Texas, Denton, TX 76203, USA email: [email protected] In the past years several cyclic trinuclear complexes (CTC’s) have been synthetized and characterized on the basis of the capacity of d10 transition metal ions to give bicoordinated linear compounds. This intriguing class of compounds display pi-acid/ pi-base properties that can be finely tuned by: the nature of the metal, the substituents on the ligand or the ligand itself. [1] These complexes are attractive building blocks to obtain supramolecular compounds showing interesting photopysical properties [2] or heterobimetallic cyclic trinuclear complexes with potential use in mixed-metal catalysis [3]. Here we report the synthesis of a novel gold (I) CTC, [Au(µ-C2,N3-1-vinylimidazole)]3, and the study of some photophysical properties of its supramolecular derivatives obtained by the intercalation of metal ions in between the metallocycles. [1] S.M. Terkali, T.R. Cundari, M.A. Omary, J. Am. Chem. Soc. 2008, 130, 1669 [2] a) A. Burini, R. Bravi, J. P. Fackler Jr, Galassi R., T. A. Grant, M. A. Omary, B. R. Pietroni, R. J. Staples . Inorg. Chem. 2000, 39; 3158.b) Burini A, Fackler J. P, JR, Galassi R., Grant T. A, Omary M. A, Rawashdeh-Omary M. A, Pietroni B. R, Staples R.J. J. Am. Chem. Soc. 2000, 122; 11264. [3] A. Mohamed, R. Galassi, F. Papa, A. Burini, J.P. Fackler , Jr. Inorg. Chem. 2006, 45, 7770-7776 [5] R. Galassi, S. Ricci, A. Burini, A. Macchioni, L. Rocchiagiani, F. Marmottini, S.M. Terkali, V.N. Nesterov, M.A. Omary, Inorg. Chem. 2013, 52, 14124-1413

Estudo antropométrico e dietético de nadadores competitivos de áreas metropolitanas da região sudeste do Brasil

The daily food intake and alimentary frequency of competitive swimmers of two clubs representative of the two largest cities in Brazil (S.Paulo and Rio de Janeiro) were studied. The 30 males and 37 females studied belonged to the swimming categories "junior" (15-17 yrs old) and "senior" (18-25 yrs old). Food intake obtained from self-register and 24 hour-recall showed similar results and therefore the 24 hour-recall was used for comparisons with the literature. Ages within both sexes were anthropometrically similar. The most frequently eaten foodstaffs were similar to those quoted by the metropolitan population of the respective areas. Moroever, the athletes from both cities reported similar food-supplements. The energy intake was found to average almost double the estimated value for the respective metropolitan populations, but were similar to results obtained for swimmers all over the world. Snacks between meals supplied 25-28% of the overall energy intake. The main caloric source were cereals. However, despite their contribution of almost 50% of the total energy intake, carbohydrates attained a level of only 55-60% of that recommended for competitive athletes. On the other hand, the protein intake found (2.5-3.0 g/kg/day) exceeded the recommended values by 100%. The fat intake particularly of satured fat, was also considered high. The swimmers' intake of micronutrients was well abone that quoted by the regular population of these metropolitan areas, when related to the caloric intake, but the values of Mg, Fe and vitamins A and D were somecohot lower than those recommended. This is due to the higers energy intake of the swimmers. From these overall results it may be concluded that the alimentary pattern of the swimmers studied does not differ greatly from that of the local population, being distinguished by its higher and more frequent intake of caloric foods rather than by its qualitative aspects.Com o objetivo de caracterizar os ábitos alimentares de nadadores competitivos de dois clubes das cidades do Rio de Janeiro e de São Paulo, foram estudados atletas, 30 homens e 37 mulheres pertencentes às equipes juvenil (15-17 anos) e "seniors" (18-25 anos). Concomitantemente à avaliação antropométrica, foi feito o inquérito alimentar mediante os métodos de registro alimentar, recordatório de 24 horas e freqüência de consumo alimentar. Os resultados mostraram semelhança antropométrica entre as duas faixas etárias para cada um dos sexos, semelhança dos alimentos prevalentemente ingeridos com aqueles referidos pela população da área metropolitana das duas cidades e semelhança entre os suplementos alimentares ingeridos pelos atletas dos dois clubes. A ingestão calórica observada foi quase o dobro da referida para a população daquelas localidades, mas equivalente à descrita para nadadores de outros países. Os lanches, entre refeições, contribuíram com 25-28% da ingestão calórica global e a maior contribuição energética alimentar foi dada pelo grupo de cereais. Apesar de contribuir com quase 50% do aporte calórico diário, a ingestão glicídica foi menor que a recomendada para atletas competitivos (55-60%). A ingestão protéica de 2,5-3,0 g/kg/dia superou em 100% o valor recomendado para atletas e ultrapassou os 15% na participação calórica diária. A ingestão lipídica foi considerada elevada, particularmente a de gordura saturada. O aporte de micronutrientes foi acima do referido para as populações locais em função da ingestão calórica elevada, mas mostrou-se relativamente inadequado em magnésio, ferro e vitaminas A e D. Conclui-se que o padrão alimentar dos nadadores estudados não difere, muito, do da população local, distinguindo-se pelo elevado e freqüente consumo de alimentos energéticos, maior no sexo masculino que no feminino

A qualitative study exploring experiences of racial minority stress in pharmacy education and practice

\ua9 2024 The AuthorsBackground: Despite 49.1% of registered pharmacists in the UK being from a Black, Asian and Minority Ethnic (BAME) background, senior management roles within pharmacy are dominated by white males. People from BAME communities may experience minority stress which contributes to a professional attainment gap compared with non-BAME colleagues. Minority stress describes additional stressors, such as unconscious bias, micro-aggression and racial minority stress, experienced by minoritized people to adhere to the social norms of the majority. There is little evidence describing experiences of minority stress in pharmacy practice and education. The aim was to explore experiences of racial minority stress in pharmacy education and practice. Methods: A convenience sample of pharmacy students and pharmacists were recruited via email and social media posts to volunteer to take part in interviews and focus groups. A topic guide was used to explore experiences of unconscious bias, microaggressions and racial minority stress in education and practice. Interviews and focus groups were transcribed verbatim and inductively analysed using thematic analysis underpinned by a phenomenological approach. Ethical approval was granted from Newcastle University (5340/2020, 2430/2593). Results: Forty-five participants were recruited. Six focus groups and sixteen one-to-one semi-structured interviews were conducted. The sample was varied, with 56% (n = 25) students and 33% (n = 15) registered pharmacists from community, hospital, primary care, academia and an additional 11% (n = 5) still in foundation training in these sectors. The sample include diversity of racial identities, including 40% (n = 18) South Asian, 27% (n = 12) White, 15% (n = 7) Black, 7% (n = 3) Chinese and Arab mixed, 2% (n = 1) and 2% (n = 1) Not disclosed. Three themes were identified – Theme 1) Experiences of racial minority stress, Theme 2) Making sense of racial minority stress, and Theme 3) Responding to racial minority stress. Participants characteristics (for example skin colour, dialect, religious dress) made them feel susceptible to judgement, racist comments and microaggressions in education and practice. Participants required time to interpret, understand and make sense of incidents of racial minority stress. Responses to stressors included ‘ignoring ignorance’ and using a ‘professional identity’ to mask feelings. However, malicious comments and actions from other pharmacy staff were responded to differently to experiences from patients. Participants reported poor self-confidence to challenge racist behaviours in the workplace. Conclusions: The aim of this study was to explore experiences of racial minority stress in pharmacy education and practice. This study shows dealing with microaggression, racial minority stress and judgement in pharmacy education and practice is a burden experienced by people from BAME backgrounds. These experiences could contribute to the professional attainment gap in pharmacy, as making sense of these experiences is an additional burden pharmacists and trainees must bear in comparison to people from non-BAME backgrounds. Further work is needed to explore interventions to reduce minority stress in pharmacy practice and education to reduce the attainment gap across the sector

Change detection of isolated housing using a new hybrid approach based on object classification with optical and TerraSAR-X data

Optical and microwave high spatial resolution images are now available for a wide range of applications. In this work, they have been applied for the semi-automatic change detection of isolated housing in agricultural areas. This article presents a new hybrid methodology based on segmentation of high-resolution images and image differencing. This new approach mixes the main techniques used in change detection methods and it also adds a final segmentation process in order to classify the change detection product. First, isolated building classification is carried out using only optical data. Then, synthetic aperture radar (SAR) information is added to the classification process, obtaining excellent results with lower complexity cost. Since the first classification step is improved, the total change detection scheme is also enhanced when the radar data are used for classification. Finally, a comparison between the different methods is presented and some conclusions are extracted from the study. © 2011 Taylor & Francis.Vidal Pantaleoni, A.; Moreno Cambroreno, MDR. (2011). Change detection of isolated housing using a new hybrid approach based on object classification with optical and TerraSAR-X data. International Journal of Remote Sensing. 32(24):9621-9635. doi:10.1080/01431161.2011.571297S962196353224BLAES, X., VANHALLE, L., & DEFOURNY, P. (2005). Efficiency of crop identification based on optical and SAR image time series. Remote Sensing of Environment, 96(3-4), 352-365. doi:10.1016/j.rse.2005.03.010Chen, Y., Shi, P., Fung, T., Wang, J., & Li, X. (2007). Object‐oriented classification for urban land cover mapping with ASTER imagery. International Journal of Remote Sensing, 28(20), 4645-4651. doi:10.1080/01431160500444731Dalla Mura, M., Benediktsson, J. A., Bovolo, F., & Bruzzone, L. (2008). An Unsupervised Technique Based on Morphological Filters for Change Detection in Very High Resolution Images. IEEE Geoscience and Remote Sensing Letters, 5(3), 433-437. doi:10.1109/lgrs.2008.917726Dell’Acqua, F., & Gamba, P. (2006). Discriminating urban environments using multiscale texture and multiple SAR images. International Journal of Remote Sensing, 27(18), 3797-3812. doi:10.1080/01431160600557572Haralick, R. M., Shanmugam, K., & Dinstein, I. (1973). Textural Features for Image Classification. IEEE Transactions on Systems, Man, and Cybernetics, SMC-3(6), 610-621. doi:10.1109/tsmc.1973.4309314Im, J., Jensen, J. R., & Tullis, J. A. (2008). Object‐based change detection using correlation image analysis and image segmentation. International Journal of Remote Sensing, 29(2), 399-423. doi:10.1080/01431160601075582Lhomme, S., He, D., Weber, C., & Morin, D. (2009). A new approach to building identification from very‐high‐spatial‐resolution images. International Journal of Remote Sensing, 30(5), 1341-1354. doi:10.1080/01431160802509017LOBO, A., CHIC, O., & CASTERAD, A. (1996). Classification of Mediterranean crops with multisensor data: per-pixel versus per-object statistics and image segmentation. International Journal of Remote Sensing, 17(12), 2385-2400. doi:10.1080/01431169608948779Lu, D., Mausel, P., Brondízio, E., & Moran, E. (2004). Change detection techniques. International Journal of Remote Sensing, 25(12), 2365-2401. doi:10.1080/0143116031000139863Shimabukuro, Y. E., Almeida‐Filho, R., Kuplich, T. M., & de Freitas, R. M. (2007). Quantifying optical and SAR image relationships for tropical landscape features in the Amazônia. International Journal of Remote Sensing, 28(17), 3831-3840. doi:10.1080/01431160701236829Stramondo, S., Bignami, C., Chini, M., Pierdicca, N., & Tertulliani, A. (2006). Satellite radar and optical remote sensing for earthquake damage detection: results from different case studies. International Journal of Remote Sensing, 27(20), 4433-4447. doi:10.1080/01431160600675895Yuan, D., & Elvidge, C. D. (1996). Comparison of relative radiometric normalization techniques. ISPRS Journal of Photogrammetry and Remote Sensing, 51(3), 117-126. doi:10.1016/0924-2716(96)00018-

Avaliação do estado nutricional de cadelas com câncer de mama

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Cupriphication of gold to sensitize d10–d10 metal–metal bonds and near-unity phosphorescence quantum yields

Outer-shell s0/p0 orbital mixing with d10 orbitals and symmetry reductionuponcupriphicationofcyclic trinucleartrigonal-planargold(I) complexes are found to sensitize ground-state Cu(I)–Au(I) covalent bonds and near-unity phosphorescence quantum yields. Heterobimetallic Au4Cu2 {[Au4(μ-C2,N3-EtIm)4Cu2(μ-3,5-(CF3)2Pz)2], (4a)}, Au2Cu {[Au2(μ-C2,N3-BzIm)2Cu(μ-3,5-(CF3)2Pz)], (1) and [Au2(μ-C2, N3-MeIm)2Cu(μ-3,5-(CF3)2Pz)], (3a)}, AuCu2 {[Au(μ-C2,N3-MeIm)Cu2(μ3,5-(CF3)2Pz)2], (3b) and [Au(μ-C2,N3-EtIm)Cu2(μ-3,5-(CF3)2Pz)2], (4b)} and stacked Au3/Cu3 {[Au(μ-C2,N3-BzIm)]3[Cu(μ-3,5-(CF3)2Pz)]3, (2)} formuponreactingAu3 {[Au(μ-C2,N3-(N-R)Im)]3 ((N-R)Im = imidazolate; R =benzyl/methyl/ethyl =BzIm/MeIm/EtIm)} with Cu3 {[Cu(μ-3,5(CF3)2Pz)]3 (3,5-(CF3)2Pz = 3,5-bis(trifluoromethyl)pyrazolate)}. The crystal structures of 1 and 3a reveal stair-step infinite chains whereby adjacent dimer-of-trimer units are noncovalently packed via twoAu(I)⋯Cu(I)metallophilicinteractions,whereas 4a exhibitsa hexanuclear cluster structure wherein two monomer-of-trimer units are linked by a genuine d10–d10 polar-covalent bond with ligandunassisted Cu(I)–Au(I) distances of 2.8750(8) Å each—the shortest such an intermolecular distance ever reported between any two d10 centers so as to deem it a “metal–metal bond” vis-à-vis “metallophilic interaction.” Density-functional calculations estimate 35– 43kcal/molbindingenergy,akintotypicalM–Msingle-bondenergies. Congruently, FTIR spectra of4a showmultiple far-IR bands within 65– 200 cm−1, assignable to vCu-Au as validated by both the Harvey–Gray method of crystallographic-distance-to-force-constant correlation and dispersive density functional theory computations. Notably, the heterobimetallic complexes herein exhibit photophysical properties that are favorable to those for their homometallic congeners, due to threefold-to-twofold symmetry reduction, resulting in cuprophilicsensitizationinextinctioncoefficientandsolid-state photoluminescence quantum yields approaching unity (ΦPL = 0.90–0.97 vs. 0–0.83 for Au3 and Cu3 precursors), which bodes well for potential future utilization in inorganic and/or organic LED applications