Synthesis based on cyclohexadienes .23. Total synthesis of 5-epi-pupukean-2-one

A new strategy for the construction of the isotwistane skeleton is reported from easily available cyclohexadienes which involves stereoselective alkylation of a bicyclooctenone derivative and a decarboxylative 5-exo-trig radical cyclisation as the key steps in the total synthesis of 5-epi-pupukean-2-one.

Conformational Diversity in Contryphans from Conus Venom: cis-trans Isomerisation and Aromatic/Proline Interactions in the 23-Membered Ring of a 7-Residue Peptide Disulfide Loop

Conformational diversity or shapeshifting in cyclic peptide natural products can, in principle, confer a single molecular entity with the property of binding to multiple receptors. Conformational equilibria have been probed in the contryphans, which are peptides derived from Conus venom possessing a 23-membered cyclic disulfide moiety. The natural sequences derived from Conus inscriptus, GCV(D)LYPWC* (In936) and Conus loroisii, GCP(D)WDPWC* (Lo959) differ in the number of proline residues within the macrocyclic ring. Structural characterisation of distinct conformational states arising from cis-trans equilibria about Xxx-Pro bonds is reported. Isomerisation about the C2-P3 bond is observed in the case of Lo959 and about the Y5-P6 bond in In936. Evidence is presented for as many as four distinct species in the case of the synthetic analogue V3P In936. The Tyr-Pro-Trp segment in In936 is characterised by distinct sidechain orientations as a consequence of aromatic/proline interactions as evidenced by specific sidechain-sidechain nuclear Overhauser effects and ring current shifted proton chemical shifts. Molecular dynamics simulations suggest that Tyr5 and Trp7 sidechain conformations are correlated and depend on the geometry of the Xxx-Pro bond. Thermodynamic parameters are derived for the cis trans equilibrium for In936. Studies on synthetic analogues provide insights into the role of sequence effects in modulating isomerisation about Xxx-Pro bonds.

Prudentia Iuris, 1990, n° 23 (número completo)

Contenido: Doctor Santiago de Estrada / Alfredo Di Pietro – Jornadas sobre “La reforma del Estado”: Las alternativas de financiamiento del mercado de capitales / Joaquín R. Ledesma – Una reflexión sobre la ley de reforma del Estado / Carlos Raúl Sanz – Las privatizaciones / Juan Carlos Cassagne – La concesión de obra pública / Rodolfo Barra – Constitucionalidad de las privatizaciones / Néstor Pedro Sagüés – Aspectos laborales de la ley 23.696 / Hugo R. Carcavallo – Estado nacional y bien común / José Giménez Rébora – Atribuciones, conducta y control de los funcionarios públicos en la época hispánica / Julio R. Lascano – Notas acerca de las relaciones Iglesia-Estado / Néstor Daniel Villa – Interdictos y acciones populares en Roma/ Fernando M. Zamora – Ciencias políticas: Ortega y la “sociedad de naciones” / Enrique Aguilar -- Documentos

Letras, 1990-1991, nº 23-24 (número completo)

Contenido: Un pequeño gran gigante. Más notas acerca de la hipérbole de lo corporal en la obra de Rabelais / Susana G. Artal – Una lectura de los cuatro cuartetos de T. S. Eliot (segunda parte) / Inés de Cassagne – Los estudios lingüísticos con base computacional / María Amalia García Jurado – Bucolismo en una carta de Sidonio Apolinar / Raúl Lavalle – La seducción estética de la barbarie como poesía de lo original originario / María Rosa Lojo – La elegía a María Blanchard / Lía Noemí Uriarte Rebaudi – Nota – Reseñas bibliográficas

南海北部湾23/25太阳区块海底工程地质调查与评价

<正> 本项成果,是承包美国太阳东方勘探公司任务而完成的。在系统分析总结了南海西部石油公司“南海—503工程地质取芯船”在南海北部湾23/25太阳区块所进行的测深、侧扫声纳、地震声学剖面测量,及4口孔深40米的工程地质浅钻土柱等材料的基础上,详细阐述了

[Discurso do Deputado Antunes de Oliveira : Sessão Conjunta do Congresso Nacional de 23 de novembro de 1978]

Afirma ser favorável à Proposta de Emenda Constitucional n. 14/78 do Senador Cattete Pinheiro, que estabelece representação política para o Distrito Federal. Compara a situação de Brasília com a de Washington, capital dos Estados Unidos.

Edital nº 23, de 28 de outubro de 1992 : concurso público para Agente de Segurança Legislativa

Em conformidade com o Edital nº 1/1992, torna público o resultado da prova de Conhecimentos Específicos do concurso público para o cargo de Agente de Segurança Legislativa.

Edital nº 14, de 23 de setembro de 1992 : concurso público para Operador de Audiovisual

Em conformidade com os Editais nº 1/1992 e nº 10/1992, comunica aos candidatos a data de realização da Prova Prática para a categoria funcional de Operador de Audiovisual.

Edital nº 68, de 23 de agosto de 1995 : concurso público para Analista Legislativo : Fisioterapeuta

Em conformidade com o Edital nº 7/1994, torna público o resultado final do concurso público para Analista Legislativo – Fisioterapeuta.

Edital nº 27, de 23 de dezembro de 1992 : concurso público para Assistente Administrativo

Em conformidade com o Edital nº1/1992, torna público o resultado da prova de Datilografia do concurso público para o cargo de Assistente Administrativo.

Presidentes da Câmara dos Deputados : 23º - Bilac Pinto

Resumo da vida pública de Bilac Pinto. Inclui bibliografia, discursos, pareceres.

Flood of September 20-23, 1969 in the Gadsden County area, Florida

The center of low pressure of a tropical disturbance which moved northward in the Gulf of Mexico, reached land between Panama City and Port St. Joe, Florida, on September 20, 1969. This system was nearly stationary for 48 hours producing heavy rainfall in the Quincy-Havana area, 70-80 miles northeast of the center. Rainfall associated with the tropical disturbance exceeded 20 inches over a part of Gadsden County, Florida, during September 20 through 23, 1969, and the maximum rainfall of record occurred at Quincy with 10.87 inches during a 6-hour period on September 21. The 48-hour maximum of 17.71 inches exceeded the 1 in 100-year probability of 16 inches for a 7-day period. The previous maximum rainfall of record at Quincy (more than 12 inches) was on September 14-15, 1924. The characteristics of this historical storm were similar in path and effect to the September 1969 tropical disturbance. Peak runoff from a 1.4-square mile area near Midway, Florida, was 1,540 cfs (cubic feet per second) per square mile. A peak discharge of 45,600 cfs on September 22 at the gaging station on the Little River near Quincy exceeded the previous peak of 25,400 cfs which occurred on December 4, 1964. The peak discharge of 89,400 cfs at Ochlockonee River near Bloxham exceeded the April 1948 peak of 50,200 cfs, which was the previous maximum of record, by 1.8 times. Many flood-measurement sites had peak discharges in excess of that of a 50-year flood. Nearly $200,000 was spent on emergency repairs to roads. An additional $520,000 in contractual work was required to replace four bridges that were destroyed. Agricultural losses were estimated at $1,000,000. (44 page document)

Constituição dos Estados Unidos do Brazil de 1890 : publicada com o Decreto n. 914 A de 23 de outubro de 1890

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