Stereochemistry of 2'-5' linked nucleic acids: crystal and molecular structure of ammonium adenylyl-2',5'-adenosine tetrahydrate: a core fragment of 2'-5' oligo A's produced by interferon induced adenylate synthetase

The preponderance of 3'-5' phosphodiester links in nucleic acids is well known. Albeit less prevalent, the 2'-5' links are specifically utilised in the formation of 'lariat' in group II introns and in the msDNA-RNA junction in myxobacterium. As a sequel to our earlier study on cytidylyl-2',5'-adenosine we have now obtained the crystal structure of adenylyl-2',5'-adenosine (A2'p5'A) at atomic resolution. This dinucleoside monophosphate crystallizes in the orthorhombic space group P2(1)2(1)2(1) with a = 7.956(3) A, b = 12.212(3) A and c = 36.654(3) A. CuK alpha intensity data were collected on a diffractometer. The structure was sloved by direct methods and refined by full matrix least squares methods to R = 10.8%. The 2' terminal adenine is in the commonly observed anti (chi 2 = 161 degrees) conformation and the 5' terminal base has a syn (chi 1 = 55 degrees) conformation more often seen in purine nucleotides. A noteworthy feature of A2'p5'A is the intranucleotide hydrogen bond between N3 and O5' atoms of the 5' adenine base. The two furanose rings in A2'p5'A show different conformations - C2' endo, C3' endo puckering for the 5' and 2' ends respectively. In this structure too there is a stacking of the purine base on the ribose O4' just as in other 2'-5' dinucleoside structures, a feature characteristically seen in the left handed Z DNA. In having syn, anti conformation about the glycosyl bonds, C2' endo, C3' endo mixed sugar puckering and N3-O5' intramolecular hydrogen bond A2'p5'A resembles its 3'-5' analogue and several other 2'-5' dinucleoside monophosphate structures solved so far. Striking similarities between the 2'-5' dinucleoside monophosphate structures suggest that the conformation of the 5'-end nucleoside dictates the conformation of the 2' end nucleoside. Also, the 2'-5' dimers do not favour formation of miniature classical double helical structures like the 3'-5' dimers. It is conceivable, 2-5(A) could be using the stereochemical features of A2'p5'A which accounts for its higher activity.

Syntheses, spectroscopy, structures, and conformations of .lambda.3-cyclotriphosphazanes: role of negative hyperconjugation

The reactions of As-chlorocyclotriphosphazane [EtNPCl], with phenols or trifluoroethanol yield the respective aryloxy- or trifluoroethoxy-containingX 3-cyclotriphosphazanes [EtNP(OR)]3 (R = C6H4Br-4 (2),C 6H5 (3C,6 H3-Mez-3,5 (4), C6H3Mez-2,6 (5), CH2CF3 (6)) as their cis-transisomericmixtures. The products have beencharacterized by IRand NMRspectroscopy. Thecrystalstructuresofboth thecis (2a) and trans(2b) isomer_softhep-bromophenoxy derivative have been determined by X-ray diffraction. Crystal data for 2a: triclinic, P1, a = 9.872(4) A, b = 13.438(6) A, c = 13.548(8) A, CY = 117.02(5)', 0 = 96.00(6)', y = 105.38(4)O, Z = 2, final R = 0.080. Crystal data for 2b: monoclinic, P21/n, a = 12.721(6) A, b = 13.468(7) A, c = 17.882(5) A, /3 = 101.62(3)O, Z = 4, final R = 0.066. The cis isomer exhibits a chair-triaxial conformation and the trans isomer a boat-triaxial conformation. Conformational preferences of X3-cyclotriphosphazanes have been probed by both MNDO and ab initio calculations on model systems [HNPXIp (X = H, F). In addition to vicinal lone pair repulsions, negative hyperconjugative interactions involving the nitrogen lone pairs and adjacent P-X Q* orbitals are found to be important (especially when X is an electronegative substituent) in determining the conformational preferences of X3-cyclotriphosphazanes. The calculations also show that the axial - equatorial conversion at phosphorus has a large activation barrier in these systems

Synthesis Based on Cyclohexadienes. 5. A New Approach to the Synthesis of a-Ring Aromatic Steroids - a Formal Total Synthesis of (+/-)-Estrone

A new strategy for the construction of A-ring aromatic steroids which resulted in the formal total synthesis of estrone is described. Thus reaction of the adduct (9), obtained from 1-methoxy-4-methylcyclohexa-1,4-diene and acrolein, with 3-(m-methoxyphenyl)propylmagnesium bromide followed by oxidation afforded the bicyclo[2.2.2]octene derivative (14). Acid-catalysed rearrangement of (14) followed by an intramolecular Michael addition resulted in the cis tetraenone (18) which was dehydrogenated with palladium chloride to the pentaenone (22). Li/NH3 reduction of (22) gave 3-methoxy-D-homoestra-1,3,5(10)-trien-16-one (31) which has been converted into the methyl ether (37) of marrianolic acid, and its methyl ester (38).

Microwave ECR Plasma Assisted MOCVD of Y(2)O(3) Thin Films Using Y(tod)(3) Precursor and Their Characterization

Yttrium oxide (Y(2)O(3)) thin films were deposited by microwave electron cyclotron resonance (ECR) plasma assisted metal organic chemical vapour deposition (MOCVD) process using indigenously developed metal organic precursors Yttrium 2,7,7-trimethyl-3,5-octanedionates, commonly known as Y(tod)(3) which were synthesized by an ultrasound method. A series of thin films were deposited by varying the oxygen flow rate from 1-9 sccm, keeping all other parameters constant. The deposited coatings were characterized by X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and infrared spectroscopy. Thickness and roughness for the films were measured by stylus profilometry. Optical properties of the coatings were studied by the spectroscopic ellipsometry. Hardness and elastic modulus of the films were measured by nanoindentation technique. Being that microwave ECR CVD process is operating-pressure-sensitive, optimum oxygen activity is very essential for a fixed flow rate of precursor, in order to get a single phase cubic yttrium oxide in the films. To the best of our knowledge, this is the first effort that describes the use of Y(tod)(3) precursor for deposition of Y(2)O(3) films using plasma assisted CVD process.

Synthesis, characterization and pharmacological study of 4,5-dihydropyrazolines carrying pyrimidine moiety

A series of 5-bromo-2-(3,5-diaryl-4,5-dihydro-1H-Pyrazol-1-yl)pyrimidine were prepared under conventional heating as well as microwave reaction condition. The newly synthesized compounds were characterized on the basis of elemental, spectral and single crystal X-ray studies. These new compounds were screened for their antioxidant, anti-inflammatory and analgesic activities. Some of these compounds exhibited potent biological activities compared to the standard drug. (C) 2012 Elsevier Masson SAS. All rights reserved.

Electron rich supramolecular polymers as fluorescent sensors for nitroaromatics

Three pi-electron rich fluorescent supramolecular polymers (1-3) have been synthesized incorporating 2-methyl-3-butyn-2-ol groups in reasonable yield by employing Sonagashira coupling. They were characterized by multinuclear NMR (H-1, C-13), ESI-MS and single crystal X-ray diffraction analyses 1 = 1( 2-methyl-3-butyn-2-ol) pyrene; 2 = 9,10-bis(2-methyl-3-butyn-2-ol) anthracene; 3 = 1,3,6,8-tetrakis(2methyl- 3-butyn-2-ol) pyrene]. Single crystal structures of 1-3 indicated that the incorporation of hydroxy (-OH) groups on the peripheral of the fluorophores helps them to self-associate into an infinite supramolecular polymeric network via intermolecular hydrogen bonding interactions between the adjacent discrete fluorophore units. All these compounds showed fluorescence characteristics in chloroform solution due to the extended pi-conjugation and were used as selective fluorescent sensors for the detection of electron deficient nitroaromatics. The changes in photophysical properties of fluorophores (1-3) upon complex formation with electron deficient nitroaromatic explosives were studied in chloroform solution by using fluorescence spectroscopy. All these fluorophores showed the largest quenching response with moderate selectivity for nitroaromatics over various other electron deficient/ rich aromatic compounds tested (Chart 1). Analysis of the fluorescence titration profile of 9,10-bis(2-methyl-3butyn- 2-ol) anthracene fluorophore (2) with 1,3,5-trinitrotoluene/ 2,4-dinitrotoluene provided evidence that this particular fluorophore detects nitroaromatics in the nanomolar range 2.0 ppb for TNT, 13.7 ppb for DNT]. Moreover, sharp visual color change was observed upon mixing nitroaromatic (DNT) with fluorophores (1-3) both in solution as well as in solid phase. Furthermore, the vapor-phase sensing study of thin film of fluorophores (1-3) showed efficient quenching responses for DNT and this sensing process is reproducible. Selective fluorescence quenching response including a sharp visual color change for nitroaromatics make these tested fluorophores (1-3) as potential sensors for nitroaromatic compounds with a detection limit of ppb level.

Phase transformation, improved ferroelectric and magnetic properties of (1-x) BiFeO3-xPb(Zr0.52Ti0.48)O-3 solid solutions

The authors prepared (1 - x) BiFeO3 - (x)Pb(Zr0.52Ti0.48)O-3 for x <= 0.30 by sol-gel method and investigated the material's structures, magnetic and electrical properties. Detailed Rietveld analysis of X-ray diffraction data revealed that the system retains distorted rhombohedral R3c structure for x <= 0.10 but transforms to monoclinic (Cc) structure for x > 0.10. Disappearance of some Raman modes corresponding to A1 modes and the decrease in the intensities of the remaining A1 modes with increasing x in the Raman spectra, which is a clear indication of structural modification and symmetry changes brought about by PZT doping. Enhanced magnetization with PZT doping content may be attributed to the gradual change and destruction in the spin cycloid structure of BiFeO3. The leakage current density at 3.5 kV/cm was reduced by approximately three orders of magnitude by doping PZT (x = 0.30), compared with BFO ceramics. (C) 2014 AIP Publishing LLC.

大庆RP-3航空煤油热物性分析

针对广泛应用于超燃冲压发动机的吸热碳氢燃料,简要介绍了用于模拟燃料热物理特性的替代燃料方法和广义对应状态法则.以大庆RP-3航空煤油为例,选择了一个由49%（摩尔比）正十烷,44%1,3,5-三甲基环己烷以及7%正丙基苯组成的替代煤油用来模拟RP-3航空煤油进行热物理特性研究,并采用广义对应状态法则对替代煤油热力学和输运特性进行了数值研究.在此基础上,提出了预测超临界态流体通过音速喷管流量的新方法并得到了实验验证.

Analysis of Thermophysical Properties of Daqing RP-3 Aviation Kerosene

针对广泛应用于超燃冲压发动机的吸热碳氢燃料,简要介绍了用于模拟燃料热物理特性的替代燃料方法和广义对应状态法则.以大庆RP-3航空煤油为例,选择了一个由49%（摩尔比）正十烷,44%1,3,5-三甲基环己烷以及7%正丙基苯组成的替代煤油用来模拟RP-3航空煤油进行热物理特性研究,并采用广义对应状态法则对替代煤油热力学和输运特性进行了数值研究.在此基础上,提出了预测超临界态流体通过音速喷管流量的新方法并得到了实验验证.

La formación permanente de los sacerdotes

Sumario: 1. Concepto. 2. Importancia. 3. Areas. 3.1. Area Teológica. 3.2. Area Espiritual. 3.3. Area Humana. 3.4. Area Pastoral. 3.5. Jurídico-canónica. 3.6. El área de las ciencias auxiliares de la pastoral. 4. Los responsables de la formación permanente. 4.1. Los sacerdotes. 4.2. El Obispo (o el Superior). 4.3. Maestros idóneos. 4.4. El pueblo de Dios. 5. Etapas. 6. Medios para realizarla. 7. Conclusión

Chemical recycling of municipal packaging waste by pyrolysis

[EN]The present doctoral thesis centers on studying pyrolysis as a chemical recycling technique for rejected packaging waste fractions coming from separation and sorting plants. The pyrolysis experiments have been carried out in a lab-scale installation equipped with a 3.5 L semi-batch reactor and a condensation and collection system for the liquids and gases generated. In the present thesis, an experimental study on the conventional pyrolysis process applied to the aforementioned waste fractions has been conducted, as well as the study of non-conventional or advanced pyrolysis processes such as catalytic and stepwise pyrolysis. The study of the operating parameters has been carried out using a mixed plastics simulated sample, the composition of which is similar to that found in real fractions, and subsequently the optimized process has been applied to real packaging waste. An exhaustive characterization of the solids, liquids and gases obtained in the process has been made after each experiment and their potential uses have been established. Finally, an empirical model that will predict the pyrolysis yields (% organic liquid, % aqueous liquid, % gases, % char, % inorganic solid) as a function of the composition of the initial sample has been developed. As a result of the experimental work done, the requirements have been established for an industrial packaging waste pyrolysis plant that aims to be sufficiently versatile as to generate useful products regardless of the nature of the raw material.

Diário da Constituinte [gravação de vídeo] : [programa n. 703]

Poder Legislativo recupera prerrogativas. Constituinte garante direitos dos servidores públicos e acaba com os marajás. A Constituinte acelera as votações, garantindo a aprovação de vários dispositivos, entre os quais a limitação dos salários no serviço público. Nos municípios o teto passa a ser o salário dos prefeitos e as câmaras municipais terão salários fixados por lei. Será assegurada a igualdade de vencimentos para servidores da administração direta, foi retirada do texto a isonomia para autarquias e fundações públicas. Foi rejeitada emenda que suprimia do texto a expressão servidor público militar, sendo mantida a equiparação salarial o entre servidores públicos civis e militares. Fica garantida aos servidores a aposentadoria proporcional, a revisão dos proventos e pensão integral. O legislativo recupera as prerrogativas da Constituição de 1946, como decidir sobre matéria financeira e arrecadação de tributos, modificar o efetivo das forças armadas, definir orçamento e aprovação concessão de canais de televisão, os decretos-leis não serão mais editados. Foi mantido o sistema presidencialista e foi retirada a moção de censura. Emendas à constituição serão votadas em dois turnos com a presença de 3/5 de cada Casa.

Diário da Constituinte [gravação de vídeo] : [programa n. 474]

A Constituinte começou a votar hoje o Título 4 da futura Carta, que trata da Organização dos Poderes e do Sistema de Governo. Está dividido em 5 capítulos: 1. Poder Legislativo, 2.Presidência da República,3. Governo, 4.Poder Judiciário e 5.Administração da Justiça. São ao todo 103 artigos, divididos em várias sessões, estabelecendo as tarefas de cada Poder da Nação. Os Líderes de todos os partidos começam a discutir os destaques para o primeiro capítulo, que trata do Poder Legislativo. No começo da Sessão foi aprovado todo o capítulo do Poder Legislativo, ressalvados os destaques. O primeiro destaque a ser votado foi que estabelecia o voto distrital misto. A emenda foi rejeitada. Enquanto isso o relator Bernardo Cabral se reunia com os relatores adjuntos para discutir o impasse da questão da greve dos servidores públicos. Já um texto básico, baseado no tratamento dado em outras constituições do hemisfério norte. Este texto assegura o direito de greve com restrições. Parlamentarista e presidencialistas fazem as contas a espera da votação do Sistema do Governo. Hélio Jaguaribe faz palestra em defesa do parlamentarismo. Os parlamentaristas já decidiram que não faram vinculação do Sistema de Governo com o mandato do Presidente Sarney. Segundo eles, o mandato é transitório enquanto o Sistema de Governo é permanente.Os presidencialistas convictos reagem e afirmam a vitória do presidencialismo. O presidente da Constituinte apela para que os constituintes estejam presentes no Plenário.

Construcción 3. Construcción industrializada

Nivel educativo: Grado. Duración (en horas): Más de 50 horas