Chemo- and regioselective reactions of 5-bromo enones/enaminones with pyrazoles.

Reaction of 5-bromo enones with pyrazoles provided a series of unexpected N,O-aminal derivatives, through a 1,4-conjugated addition at the ß-carbon of the 5-bromo enones instead of the expected nucleophilic substitution of the bromine. This reaction also furnished the 1,3-regioisomer of the pyrazole. A similar reaction of pyrazoles using 5-bromo enaminones furnished only N-alkylated pyrazoles-with high regioselectivity and at good yields-through nucleophilic substitution of the bromine.

Effect of slight structural changes on the gelation properties of N-phenylstearamide supramolecular gels.

Supramolecular gels present several applications in which the gelator properties are closely dependent on their structure and solvent. Despite this, there are few studies on the effect of the gelation ability of gelators with slight molecular changes. Therefore, N-arylestearamides (in which aryl = phenyl (1), 4-tolyl (2) and 4-acetylphenyl (3)) were evaluated in different solvents. The critical gelefication concentration (CGC) values indicated that the substituents can significantly affect the concentration at which the supramolecular gels are formed, mainly in non-aromatic solvents (e.g. cyclohexane, acetonitrile and DMSO). From UV-Vis and DSC data, we verified that the gel-sol and sol-gel transitions (Tgel-sol and Tsol-gel) increase in the order of 1 < 2 < 3. Organogel strength was evaluated for 1-3 as a function of concentration and solvent type using rheology data. Gel strength is concentration-dependent and a strength order was found in acetonitrile, cyclohexane and DMSO, in which: 1 ∼ 2 > 3. Dynamic viscoelastic measurements as a function of temperature sweeps indicate a predominantly enthalpic contribution to the elasticity of the organogels formed from 1-3. Temperature-dependent 1H NMR indicates that NHO interactions may be responsible for the molecular association of molecules into 1D fibers, while 3D fibers were formed from van der Waals interactions.

Endotracheal bioimpedance cardiography improves immediate postoperative outcome: a case-control study in off-pump coronary surgery.

The feasibility and clinical utility of the endotracheal cardiac output monitor (ECOM) to optimize intraoperative hemodynamics and improve short-term outcome in off-pump coronary artery bypass grafting (OPCAB) is unknown. We aimed to compare ECOM with a standard of care in that specific surgical setting. Twenty consecutive adult ECOM-monitored patients undergoing OPCAB were prospectively included (ECOM group) and retrospectively compared to 42 patients scheduled for similar surgery without ECOM monitoring (Control group). The primary endpoint was the global rate of postoperative admission to the intensive care unit (ICU). Secondary endpoints were the time to extubation, the length of stay in ICU and in hospital, the postoperative levels of lactate and troponin and the feasibility of ECOM. The rate of postoperative admission to the ICU was 38/42 (90%) in the Control group versus 11/20 (55%) in the ECOM group, P = 0.008. None unexpected admission for hemodynamic instability was observed in the ECOM group. The time to extubation, the length of stay in ICU, and both troponin level at admission and lactate level at H6 were all significantly decreased in the ECOM group. On a scale ranging from 0 to 5, convenience and satisfaction regarding ECOM were 4.30 ± 1.17 and 3.45 ± 0.68, respectively. The systematic use of ECOM is associated with a significant reduction in the rate of admission to the ICU and an improvement in immediate outcome in OPCAB.

Synthesis, Crystal Structure, and Supramolecular Understanding of 1,3,5-Tris(1-phenyl-1H-pyrazol-5-yl)benzenes.

Understanding the supramolecular environment of crystal structures is necessary to facilitate designing molecules with desirable properties. A series of 12 novel 1,3,5-tris(1-phenyl-1H-pyrazol-5-yl)benzenes was used to assess the existence of planar stacking columns in supramolecular structures of pyrazoles. This class of molecules with different substituents may assist in understanding how small structural changes affect the supramolecular environment. The obtained compounds did not present the formation of planar stacking interactions between benzenes in solid or liquid states. This supposition was indicated by single crystal diffraction, Density Functional Theory (DFT) and quantum theory of atoms in molecules (QTAIM) calculations, and concentration-dependent liquid-state ¹H nuclear magnetic resonance (NMR). NMR showed that chemical shifts of benzene and pyrazole hydrogens confirm that planar stacking interactions are not formed in solution. The crystalline structures presented different molecular conformations. The molecular structures of 5 and 9b are in a twisted conformation, while compound 7 showed a conformation analogous to a calyx form.

Synthesis, effect of substituents on the regiochemistry and equilibrium studies of tetrazolo[1,5-a]pyrimidine/2-azidopyrimidines.

An efficient synthesis methodology for a series of tetrazolo[1,5-a]pyrimidines substituted at the 5- and 7-positions from the cyclocondensation reaction [CCC + NCN] was developed. The NCN corresponds to 5-aminotetrazole and CCC to ß-enaminone. Two distinct products were observed in accordance with the ß-enaminone substituent. When observed in solution, the compounds can be divided into two groups: (a) precursor compounds with R = CF3 or CCl3, which leads to tetrazolo[1,5-a]pyrimidines in high regioselectivity with R at the 7-position of the heterocyclic ring; and (b) precursor compounds with R = aryl or methyl, which leads to a mixture of compounds, tetrazolo[1,5-a] pyrimidines (R in the 5-position of the ring) and 2-azidopyrimidines (R in the 4-position of the ring), which was attributed to an equilibrium of azide-tetrazole. In the solid state, all compounds were found as 2-azidopyrimidines. The regiochemistry of the reaction and the stability of the products are discussed on the basis of the data obtained by density functional theory (DFT) for energetic and molecular orbital (MO) calculations.

Avaliaçäo de crianças com suspeita de displasia congênita do quadril com idade entre zero e seis meses / Evaluation of 0 to 6 month children with suspect of congenital dysplasia of the hip

Para avaliar a importância dos diversos sinais clínicos, da ecografia e da readiografia, no diagnóstico e acompanhamento da displasia congênita do quadril (DCQ), foram revistas 686 crianças encaminhadas por pediatras por suspeita de DCQ. Destas, 314 crianças preencheram os critérios de inclusäo: idade máxima de seis meses na consulta inicial, submetidas a exame ecográfico e radiográfico e que tiveram seguimento por no mínimo até a idade de um ano. Ao final da avaliaçäo, 262 crianças (524 quadris) foram classificadas como normais e 52 crianças (78 quadris) apresentaram diagnóstico de displasia, subluxaçäo ou luxaçäo e necessitaram tratamento. A apresentaçäo pélvica e a história familiar de DCQ foram fatores associados à ocorrência de DCQ, principalmente em pacientes do sexo feminino. Os sinais de Barlow e Ortolani foram os mais freqüentemente encontrados nas crianças com quadris anormais (valor preditivo positivo acima de 87 por cento) "Clicks" ao exame do quadril, embora sejam causa freqüente de encaminhamenäao apresentaram nenhum sinal no exame clínico e dois, ecografia inicial normal, sendo que estes na evoluçäo apresentaram alteraçöes, sendo portanto classificadas como displasia do desenvolvimento. A ecografia apresentou alta sensibilidade e especificidade, mas permitiu poucos casos de falso-positivo (dez) e negativos (seis). Este trabalho reforça a importância dos fatores de risco, principalmente da apresentaçäo pélvica, associados a displasia do quadril e também confirma que o exame clínico é fundamental ao diagnóstico, sendo o exame ecográfico e, eventualmente radiográfico, úteis näo só ao diagnóstico como também no acompanhamento dos quadris suspeitos.

Autotransfusäo sanguinea em artroplastia total do quadril / Autologous blood transfusion in total hip arthroplasty

Foram feitas coletas de sangue no período pré-operatório em 91 pacientes submetidos a 107 artroplastias totais do quadril, com o objetivo de ser utilizado para autotransfusao. Foram coletadas 220 unidades de sangue e reinfundidas 197 (média de 2,05 e 1,84 unidades por operaçäo, respectivamente). Houve necessidade de complementaçäo com sangue homólogo em quatro ocasioes (3,62 por cento). Os critérios de indicaçäo de transfusäo foram baseados na evoluçäo clínica dos pacientes. Apenas o valor do volume globular baixo näo foi considerado como indicaçäo de transfusäo. Näo houve complicaçöes que pudessem ser atribuídas à coleta ou utilizaçäo do sangue autólogo. A evoluçäo clínica dos pacientes foi normal em todos os casos. Näo houve caso de infecçäo. Notou-se um esforço coletivo por parte de todos da equipe cirúrgica para reduçäo de transfusäo sanguínea. Isso resultou em menor utilizaçäo do estoque do banco de sangue e maior segurança para os pacientes, evitando-se os riscos da transfusäo de sangue homólogo.

Síndrome da criança espancada: aspectos legais e clínicos: relato de um caso / Battered child syndrome: legal and clinical aspects: report of a case

Os autores apresentam um caso de síndrome da criança espancada. Discutem a patologia com suas peculiaridades, dando enfoque aos aspectos jurídicos e à importância de seu diagnóstico com busca exaustiva, valorizando desta forma a relaçäo entre todas as partes envolvidas, o que pode culminar com o alívio de dor, a diminuiçäo de sofrimento e até mesmo o salvamento de uma vida.

Estudo comparativo entre duas técnicas de osteotomia no tratamento do hálux valgo: análise clínica e radiográfica / Comparative study between two techniques of osteotomy on the first metatarsal base for the treatment of hallux valgus

Neste estudo prospectivo foi avaliado o tratamento cirúrgico de 19 pacientes, 24 pés, portadores de hálux valgo com deformidade moderada ou grave. Todos os pacientes foram submetidos à reconstrução distal de partes moles pela mesma técnica cirúrgica, sendo empregados dois tipos distintos de osteotomia proximal, para correção do varismo do I metatarsal, efetuados em seqüência randomizada e intercalando-se as duas técnicas. Em 12 pés realizou-se a osteotomia tipo adição e nos outros 12 pés a osteotomia tipo "chevron". A avaliação foi clínica e radiográfica, concluindo-se que o índice de avaliação clínica e as medidas radiográficas, no período pós-operatório, melhoraram significantemente, à exceção da discrepância entre o I e II metatarsais, e que a comparação entre os parâmetros clínicos e radiográficos resultantes dos dois tipos de osteotomias foram equivalentes.