José Carlos Campos Torres

Synthesis of 1-ferrocenyl-2-aryl(heteroaryl)acetylenes and 2-ferrocenylindole derivatives via the Sonogashira–Heck–Cassar reaction

Abstract The Sonogashira–Heck–Cassar reaction of ferrocenylacetylene with aryl- and heteroaryl halides was shown to be a facile and convenient route for the synthesis of 1-ferrocenyl-2-aryl- and 1-ferrocenyl-2-heteroarylacetylenes in high yields. Additionally, annulation reactions of some of the 1-ferrocenylacetylene compounds gave 2-ferrocenyl-2-benzo[ b ]furan and 2-ferrocenylindoles in good yields.

Risk-of-Malignancy Index in preoperative evaluation of clinically restricted ovarian cancer

CONTEXTnThere is no adequate preoperative method for differentiating between benign and malignant pelvic masses. Evaluations of CA 125 serum levels, ultrasonography findings and menstrual state have been tested in isolation as diagnostic methods. The evaluation of these three methods in association with each other could improve diagnostic performance.nnnOBJECTIVEnTo evaluate the risk-of-malignancy index by combining serum CA 125 levels, ultrasound score and menopausal status in preoperative diagnoses for women with pelvic masses clinically restricted to the ovaries and without clear evidence of malignancy.nnnDESIGNnCross-sectional study.nnnSETTINGnCentro de Atenção Integral à Saúde da Mulher, Universidade Estadual de Campinas, Campinas, São Paulo, Brazil.nnnPARTICIPANTSn158 women admitted between January 1996 and March 1998 for surgical exploration of pelvic masses.nnnPROCEDURESnThe risk-of-malignancy index was calculated as US x M x CA 125, performed preoperatively. Ultrasound findings were classified according to the shape, size, multiplicity, presence of wall expansion involvement or ascites, using a score system (US). Menopausal status was considered as 1 for premenopausal and 3 for postmenopausal (M), and CA 125 serum levels were considered in absolute values.nnnSTATISTICAL ANALYSISnMost relevant variables were included in a logistic multiple regression model, fitted using the ultrasound score, the serum CA 125 level and the menopausal status. The model was used for evaluating the performance of each individual predictor in determining the malignancy of these tumors and identifying the risk-of-malignancy index.nnnRESULTSnThe best individual performance was found in CA 125 levels (sensitivity of 78%, specificity of 75%), followed by ultrasound score (sensitivity of 75%, specificity of 73%) and menopausal status (sensitivity of 73%, specificity of 69%). The performance obtained for the risk-of-malignancy index at the cut-off point of 150 was a sensitivity and specificity of 79%. The area under the ROC curve for the risk-of-malignancy index was 0.90, which was greater than the area for CA 125 levels (0.83) or ultrasound score (0.79).nnnCONCLUSIONnThe risk-of-malignancy index using ultrasound morphological score, serum CA 125 levels and menopausal status might be of value in the preoperative assessment of ovarian carcinomas.

Synthesis of novel naphthoquinone-spermidine conjugates and their effects on DNA-topoisomerases I and II-alpha

Novos derivados do lapachol 2, nor-lapachol 3 e da lausona 4 foram sintetizados atraves do deslocamento nucleofilico das metoxinaftoquinonas 2a, 3a e 4a pela poliamina (PA) N1-Boc-N5-Bn-espermidina 1a. Os produtos, 2b, 3b e 4b, respectivamente, foram obtidos em bons rendimentos e caracterizados por metodos espectroscopicos e analiticos. Os ensaios preliminares de inibicao das enzimas topoisomerases (topo) I e II-a mostraram-se promissores: todos os compostos (1a 2b, 3b e 4b) inibiram a atividade catalitica da enzima topo II-a na dose de 2 µM. Considerando que somente a PA 1a nao inibiu a atividade da enzima na dose de 0,2 µM, as naftoquinonas apresentam-se como fragmentos em potencial para melhorar a atividade de PAs. Nenhum dos compostos inibiu a topo I na dose de 200 µM.

Electronic interactions in [Ru3(mu3-R² CCC6H4-4-R¹)(mu -dppm)(mu-CO) (CO)7] (R¹ = NO2 and R² = Fc; R¹ = NO2, CN and R² = Ph)

The co-ordination of FcCCC6H4-4-NO2 (1) to a ruthenium carbonyl cluster to yield [Ru3(m 3-FcCCC6H4-4-NO2) (m-dppm)( m-CO)(CO)7] (2) is reported. The cyclic voltammograms of these compounds and of the analogous clusters [Ru3(m3 -h2-C6 H5CCC6H4-4-R)(m -dppm)(m -CO)(CO)7] (R= H, 3; CN, 4; NO2, 5) allowed an evaluation of the electronic communications between the different redox sites (ferrocenyl and -NO2 groups, and Ru3 moiety) and an analysis of the relative electron donor-acceptor capabilities of each of the three redox centres that compose 2. Furthermore, the inertness of 2, compared with clusters 3-5 which loose CO readily was attributed to the interaction between the ferrocenyl group and the metallic frame.

Relação entre tumores ovarianos epiteliais borderline e francamente invasores: epidemiologia, histologia e prognóstico

Purpose: to determine some epidemiological, diagnostic and prognostic aspects in women with borderline and invasive epithelial ovarian tumors. Methods: the charts of 198 women treated at CAISM/UNICAMP from 1986 to 1996 were revised. For statistical assessment, c2, Fishers exact and t Students tests were used when appropriate, followed by survival curves by the Kaplan-Meyer method, compared by the log-rank test. The mean follow-up was 50 months (11 to 168). Results: the overall rate of borderline tumors was 12% (24 cases), and for invasive carcinoma, 88% (174 cases). The mean age of the patients with borderline tumors was significantly lower than that of those with invasive carcinoma (43 ± 14.8 years vs. 52 ± 12.6 years, p<0.002). The most frequent histologic types were the serous (81 cases: 41%) and the mucinous (46 cases: 23%) tumor. The women with borderline tumors had their diseases diagnosed in earlier stages when compared with the invasive carcinoma patients (p<0.0001). The frozen biopsy, performed on 77 patients, showed a high agreement with the paraffin fixed tissue in the invasive carcinoma cases. However, in borderline tumors, the rate of failure was higher (13%) and the major rate of failure was in mucinous tumors. Regarding prognosis, the survival rate was significantly higher in borderline tumors (p<0.001). Conclusions: women with epithelial ovarian tumors were younger, presented the disease at earlier stages, and had a better prognosis when compared with those with invasive carcinoma.

Invasão linfática clinicamente não detectável do câncer vulvar

OBJECTIVE: To assess the neoplastic invasion of superficial and deep inguinal lymph nodes of women with invasive vulvar squamous carcinoma smaller than 5 centimeters with a clinically normal inguinal region. METHODS: the medical records of 59 women cared at the State University of Campinas with invasive vulvar squamous carcinoma T1 and T2 and who presented clinically normal inguinal regions (N0) were reviewed. Clinical characteristics of both tumor and patients were evaluated as well as the follow-up data. Odds ratios and Fishers Exact Test were used to assess the correlations between the invasion of inguinal lymph nodes and tumor size, grade, relapses and clinical complications. Confidence limits of 95% were used. RESULTS: Age of the patients ranged from 34 to 91 years (mean 67 years), and follow-up time ranged from 3 days (peri-operatory death) to 252 months (mean 27 months). Clinically, 22 (37%) women had lesions T1 lesions and 37 (63%) T2. Histological analysis showed unilateral lymphatic invasion in six (10%) women and bilateral in three (5%). There was no significant association between tumor size and lymph node invasion. Also, pathologic tumor size and grade were not associated with lymph node neoplastic involvement. Relapses and late complications were not correlated with lymph node neoplastic invasion. CONCLUSIONS: Superficial and deep inguinal dissection disclosed clinically undetectable lymph node neoplastic invasion, although tumor size and histological grade, relapses and late complications were not associated with node involvement.