A Family of Hexacopper Phenylsilsesquioxane/Acetate Complexes: Synthesis, Solvent-Controlled Cage Structures, and Catalytic Activity.

Convenient self-assembly synthesis of copper(II) complexes via double (phenylsilsesquioxane and acetate) ligation allows to isolate a family of impressive sandwich-like cage compounds. An intriguing feature of these complexes is the difference in the structure of a pair of silsesquioxane ligands despite identical (Cu6) nuclearity and number (four) of acetate fragments. Formation of particular combination of silsesquioxane ligands (cyclic/cyclic vs condensed/condensed vs cyclic/condensed) was found to be dependent on the synthesis/crystallization media. A combination of Si4-cyclic and Si6-condensed silsesquioxane ligands is a brand new feature of cage metallasilsesquioxanes. A representative Cu6-complex (4) (with cyclic silsesquioxanes) exhibited high catalytic activity in the oxidation of alkanes and alcohols with peroxides. Maximum yield of the products of cyclohexane oxidation attained 30 %. The compound 4 was also tested as catalyst in the Baeyer-Villiger oxidation of cyclohexanone by m-chloroperoxybenzoic acid: maximum yields of 88 % and 100 % of ϵ-caprolactone were achieved upon conventional heating at 50 °C for 4 h and MW irradiation at 70 or 80 °C during 30 min, respectively. It was also possible to obtain the lactone (up to 16 % yield) directly from the cyclohexane via a tandem oxidation/Baeyer-Villiger oxidation reaction using the same oxidant.

Cage-like Cu5Cs4-Phenylsilsesquioxanes: Synthesis, Supramolecular Structures, and Catalytic Activity.

A small family of nonanuclear Cu5Cs4-based phenylsilsesquioxanes 1-2 were prepared by a convenient self-assembly approach and characterized by X-ray diffraction studies. The compounds 1 and 2 show some unprecedented structural features such as the presence of a [Ph14Si14O28]14- silsesquioxane ligand and a CuII5CsI4 nuclearity in which the metal cations occupy unusual positions within the cluster. Copper ions are "wrapped" into a silsesquioxane matrix, while cesium ions are located in external positions. This resulted in cesium-involved aggregation of coordination polymer structures. Both compounds 1 and 2 realize specific metallocene (cesium-phenyl) linkage between neighboring cages. Compound 2 is evaluated as a catalyst in the Baeyer-Villiger (B-V) oxidation of cyclohexanone and tandem cyclohexane oxidation/B-V oxidation of cyclohexanone with m-chloroperoxybenzoic acid (mCPBA) as an oxidant, in an aqueous acetonitrile medium, and HNO3 as the promoter. A quantitative yield of ε-caprolactone was achieved under conventional heating at 50 °C for 4 h or MW irradiation for 30 min (for cyclohexanone as substrate); 17 and 19% yields of lactone upon MW irradiation at 80 °C for 30 min and heating at 50 °C for 4 h, respectively (for cyclohexane as a substrate), were achieved. Complex 2 was evaluated as a catalyst for the oxidation of alkanes to alkyl hydroperoxides and alcohols to ketones with peroxides at 60 °C in acetonitrile. The maximum yield of cyclohexane oxidation products was 30%. Complex 2 exhibits high activity in the oxidation of alcohols.

Peripheral blood stem cells collection by apheresis in very low-weight children with malignant diseases-A single center experience.

BACKGROUND: Hematopoietic stem cell transplantation is used in the treatment of children with malignant and non-malignant diseases. However, apheresis of peripheral blood stem cells (PBSC) represents a challenge in children below 10 kg. METHODS: A retrospective trial was conducted in the Cellular Therapy Department of Portuguese Oncology Institute of Porto. INCLUSION CRITERIA: children with body weight inferior to 10 kg who underwent autologous PBSC apheresis until 2021. Demographic and clinical data were collected and our institutional protocol was described. COBE Spectra apheresis system (TerumoBCT, Lakewood, Colorado) until 2012 and then Spectra Optia (TerumoBCT) were used. RESULTS: Sixteen leukocytaphereses were performed in 13 patients-nine females (69%). Mean age and weight were 13.31 months (±5.26) and 8.31 kg (±1.17), respectively. The initial CD34+ cells/µL in peripheral blood was 70.8 (±61.9). A central venous catheter (CVC) was exclusively used in all but one patient, in whom a peripheral vein was also required. In 10 procedures, both heparin and anticoagulant citrate dextrose solution-formula A (ACD-A) were used; in the remaining ones, only ACD-A was employed. The median duration of each procedure was 168 minutes (±45) and 2.96 blood volumes (±0.31) were processed. Median CD34+ cells yield per leukocytapheresis was 6.52 × 106 /kg (±9.87 × 106 ). CD34+ cell extraction rates were not significantly different between the two apheresis systems. Platelet and magnesium levels were significantly lower after collection (P < .001 and P = .009, respectively). CONCLUSIONS: Although recommendations are lacking, we have successfully and safely performed leukocytaphereses in children with body weight below 10 kg. The authors believe that a permanent and dynamic comprehensive evaluation of each child is paramount for attaining good results.

New members of the polynuclear manganese family: MnMn single-molecule magnets and MnMn antiferromagnetic complexes. Synthesis and magnetostructural correlations.

The synthesis, crystal structures and magnetic properties are reported for three novel mixed-valence tetranuclear [MnII2MnIII2(HBuDea)2(BuDea)2(EBA)4] (1), [MnII2MnIII2(HBuDea)2(BuDea)2(DMBA)4] (2) and undecanuclear [MnII3MnIII8O4(OH)2(BuDea)6(DMBA)8] (3) clusters, where H2BuDea is N-butyldiethanolamine, HEBA is 2-ethylbutyric acid and HDMBA is 2,2-dimethylbutyric acid. The compounds have been prepared through self-assembly reactions of manganese(ii) chloride with H2BuDea and respective carboxylic acid in methanol solution in air, affording 1 with HEBA, and 2 or 3 with HDMBA, depending on the experimental conditions. The single crystal X-ray analysis reveals that 1 and 2 have similar centrosymmetric structures based on the {M4(µ3-O)2(µ-O)4} core, while 3 discloses the unprecedented {M11(µ-O)4(µ3-O)12} one. The Mn4 complexes display single-molecule magnet (SMM) behavior with a S = 9 spin ground state and a high energy barrier Ueff/kB of up to 51 K. The magnetic properties of 2 are successfully modeled with JMnIII-MnIII/hc = 25.7 cm-1 and two JMnIII-MnII/hc constants of 3.1 and -0.93 cm-1 (data correspond to the H = -Js1·s2 formalism). The Mn11 cluster exhibits a paramagnetic behavior with dominant antiferromagnetic coupling. A possible influence of intermolecular effects and of different peripheries of the magnetic cores designed by using 2-ethylbutyrate (in 1) or 2,2-dimethylbutyrate (in 2) on the magnetic properties of 1 and 2 is discussed. The experimental magnetostructural correlations for the {MnII2MnIII2(µ3-O)2(µ-O)4} cores, supported by broken symmetry DFT calculations, disclose the X-MnIIIMnIII angle and MnIII-O distance (where MnIII-X and MnIII-O are axial Jahn-Teller bonds) as the structural factors having the strongest influence on JMnIII-MnIII exchange coupling. It is shown that two JMnIII-MnII constants are necessary for the correct description of magnetic exchange couplings in the {MnII2MnIII2(µ3-O)2(µ-O)4} tetranuclear unit.

Synthesis, Characterization and Biological Activity of Novel Cu(II) Complexes of 6-Methyl-2-Oxo-1,2-Dihydroquinoline-3-Carbaldehyde-4n-Substituted Thiosemicarbazones.

Three new 6-methyl-2-oxo-1,2-dihydroquinoline-3-carbaldehyde-thiosemicarbazones-N-4-substituted pro-ligands and their Cu(II) complexes (1, -NH2; 2, -NHMe; 3, -NHEt) have been prepared and characterized. In both the X-ray structures of 1 and 3, two crystallographically independent complex molecules were found that differ either in the nature of weakly metal-binding species (water in 1a and nitrate in 1b) or in the co-ligand (water in 3a and methanol in 3b). Electron Paramagnetic Resonance (EPR) measurements carried out on complexes 1 and 3 confirmed the presence of such different species in the solution. The electrochemical behavior of the pro-ligands and of the complexes was investigated, as well as their biological activity. Complexes 2 and 3 exhibited a high cytotoxicity against human tumor cells and 3D spheroids derived from solid tumors, related to the high cellular uptake. Complexes 2 and 3 also showed a high selectivity towards cancerous cell lines with respect to non-cancerous cell lines and were able to circumvent cisplatin resistance. Via the Transmission Electron Microscopy (TEM) imaging technique, preliminary insights into the biological activity of copper complexes were obtained.

The effectiveness of connective tissue massage in the treatment of primary dysmenorrhea among young women / Efetividade da massagem do tecido conjuntivo no tratamento da dismenorréia primária em mulheres jovens

OBJECTIVE: to evaluate the possible effectiveness of connective tissue massage for the non-medical treatment of primary dysmenorrhea. METHODS: this was a pilot observational cohort study. SETTING: University clinics. PARTICIPANTS: Seventy two young women presenting primary dysmenorrhea. INTERVENTION: Physiotherapy students in their last year at university and physiotherapists were trained for 20 hours to apply the massage. All volunteers were submitted to lumbar connective tissue massage twice weekly, while they were not menstruating, during the three menstrual cycles that followed admission. The following regions were manipulated: sacral, lumbar, last thoracic vertebrae and subcostal. INDICATORS: Pain score, use of pain medication and other menstrual systemic symptoms over time (before treatment, after each of the three menstrual periods during treatment, and in the second and in the third month following treatment). RESULTS: after the first treatment month, the pain score decreased significantly (p<0.001). The percentage of women requiring pain medication and reporting systemic symptoms decreased over time, although there was no correlation between the number of massages and the pain score in the multiple regression analysis. CONCLUSIONS: connective tissue massage may cause a reduction in menstrual pain but the study design does leaves open the possibility of a placebo effect. The results justify performing a randomized clinical trial to confirm whether such an effect exists or not.

OBJETIVO: avaliar a possível efetividade da massagem do tecido conjuntivo para o tratamento não medicamentoso da dismenorréia primária. MÉTODOS: estudo piloto, do tipo observacional de coorte com setenta e duas mulheres jovens com dismenorréia primária em Clínica Universitária. Estudantes de fisioterapia e fisioterapeutas receberam treinamento de 20 horas para aplicar a massagem. Todas as voluntárias receberam massagem do tecido conjuntivo lombar duas vezes por semana, no período intermenstrual durante os três ciclos menstruais após a admissão. As regiões manipuladas foram: sacral, lombar, última vértebra torácica e sub-costal. Desfechos avaliados: Escore de dor, uso de medicamentos e ocorrência de outros sintomas sistêmicos ao longo do tempo (antes do tratamento, após cada ciclo menstrual durante o tratamento e nos dois meses após o tratamento). RESULTADOS: o escore de dor diminuiu significativamente após o primeiro mês de tratamento (p<0,001). A porcentagem de voluntárias que precisou de medicamentos para dor e que relatou sintomas sistêmicos diminuiu com o tempo de tratamento, mas não houve correlação entre o número de massagens e o escore de dor na análise multivariada. CONCLUSÃO: a massagem do tecido conjuntivo pode causar uma redução da dor menstrual, mas o tipo de estudo não permite excluir um efeito placebo. Os resultados justificam a realização de estudo clínico randomizado para confirmar ou não esse efeito.

O trabalho com famílias de pacientes atendidos na unidade psiquiátrica do Hospital Säo Paulo da Escola Paulista de Medicina

Os autores propöem relatar a experiência grupas de atendimento a familiares durante o tratamento de pacientes em situaçöes de "crise" em uma unidade psiquiátrica inserida num Hospital General. Considera-se que a crise é também do grupo familiar, e que este deve ser vinculado ao atendimento oferecido, para ter condiçöes de se reorganizar e conseguir reabsorver esse membro do grupo täo logo o período de tensäo tenha sido atenuado. Oferecem-se entäo aos familiares espaços onde possam expressar e tentar elaborar os conflitos que surgem em decorrência da situaçäo de internaçäo, permitindo assim maior aderência ao tratamento, bem como a busca de um rearranjo familiar que tente evitar novosepisódios como esse. Podem-se evidenciar nessa experiência três momentos: período de internaçäo, licença e/ou alta hospitlar e reintegraçäo ao meio social. Tenciona-se comentar as particularidades do atendimento integrado de pacientes e familiares