Quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers have been synthesized as possible specific metal host systems. The synthesis and characterization of quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers have been described. The characterization of these host systems have been fully achieved in solution by using various techniques such as IR, 1H NMR, and 13C NMR spectroscopic methods, high-resolution mass spectrometry (HRMS), elemental microanalysis, and X-ray crystallographic analysis in case of one quinoxaline-functionalized, cage-annulated oxacrown ether compound. The synthesis of the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) is described. The substitution of the MeCN ligands in the activated cluster 1,2-Os3(CO)10(MeCN)2 by the diphosphine ligand bmi proceeds rapidly at room temperature to furnish a mixture of bridging and chelating Os3(CO)10(bmi) isomers and the ortho-metalated product HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)N(tolyl-p)C(O)]. Thermolysis of the bridging isomer 1,2-Os3(CO)10(bmi) under mild conditions gives the chelating isomer 1,1-Os3(CO)10(bmi), whose molecular structure has been determined by X-ray crystallography. The kinetics for the ligand isomerization have been investigated by UV-vis and 1H NMR spectroscopy in toluene solution over the temperature range of 318-348 K. On the basis of kinetic data conducted in the presence of added CO and the Eyring activation parameters, a non-dissociative phosphine migration across one of the Os-Os bonds is proposed. Orthometalation of one of the phenyl groups associated with the bmi ligand is triggered by near-UV photolysis of the chelating cluster 1,1- Os3(CO)10(bmi).

No description available.

The main goal of this study was to investigate space structure of pure pine stands, to assess optimal parameters of trees crown depending on stand age. The study was carried out in seven trials of 2 – 8 age classes pine stand. Trees crown horizontal projection area, the overlapping of crown, tree DBH, 5 years increment of diameter, tree developing class was measured of 200 trees in every trial. It was investigated that maximally possible crown projection area makes up from 12,0 thousand m2/ha to 6,5 thousand m2/ha while the age of stands changes from 2 to 8 age class. Depending upon the age of pine stand, maximally possible crown cover area makes up from 8,5 thousand m2/ha to 6,2 thousand m2/ha and decreases with increasing of stand age. The area of inevitable openings comprises 15-38 % of a forest area and increases with increasing of stand age. The overlapping comprises 43-6 % and decreases with increasing of stand age. The area of pine crown increases from 1,2 to 8,8 m2 while the age of stands changes from 2 to 8 age class. In the same age class the area of tree crown depends on tree developing class. The crown area of well-developed trees (class A) is 1.7-1.9 times bigger then crown area of poor-developed trees (class B) and 2.7-4.6 times bigger then crown area of trees being developed in a depressed state (class C). The crown area of vigorously-developed trees (class A’) is 1.8-3.5 times bigger than crown area of well-developed trees (class A). 1 m2 of the crown area... [to full text]

Crystal structures of anhydrous pinacol, the hexagonal pinacol, pinacol monohydrate, and pinacol hexahydrate were studied. In all the structures crystal packing is unusual and complicated. The origin of the complexity may be the difficulty in filling space densely and while also satisfying the H-bonding requirements when the molecule has few internal degrees of freedom. Five 15-crown-5 complexes of M(NO3)2 (M = Cu, Zn, Mg, Co, Mn) were synthesized and characterized using X-ray diffraction and differential scanning calorimetry. The system is rich in polymorphs. Nine definite solid-state phases were identified. More phases probably exist in the solid state at temperatures slightly above the room temperature. Most phase transformations in this system take place in single crystals without the loss of crystallinity. The nine phases crystallize in five crystal structures. The crown ether ligands have very similar conformation in all the structures. The asymmetric units in all the structures are complicated and pseudosymmetric, which is the consequence of the presence of the packing problem. The origin of the packing problem that leads to the complicated phase behavior is the odd number of -CH2-O-CH2- units in the crown ether ligand.

No description available.

Thirty-four cultivars of pea (Pisum sativum) were assayed for tumorigenesis after inoculation with Agrobacterium tumefaciens strain B6. The response of the 34 cultivars fell into 3 significantly different groups based on tumor weights: high, medium, and low susceptibility. The least susceptible cultivar, Sweet Snap, also formed the smallest tumors in comparison to 5 other cultivars when inoculated with 5 other strains of Agrobacterium. Preliminary experiments indicate that neither chemotaxis, binding, vir-gene induction, nor T-DNA expression are limiting factors in Sweet Snap's reduced susceptibility. In an inheritance study, the F1, F2, and F3 progeny from an initial cross between Sweet Snap and Wando (a more susceptible cultivar) formed tumors that were intermediate in weight between the two parents.

Para avaliar a confiabilidade à fadiga de coroas de dissilicato de lítio E.max CAD, com 1mm (monolítica) e 2mm de espessura, foi realizado um preparo para coroa total de um primeiro molar inferior com redução de 1 e 2mm. Réplicas em resina composta do preparo baseado em desenho auxiliado pelo computador (CAD) foram posicionadas em um articulador odontológico para fabricação dos corpos de prova. As coroas monolíticas de 1mm de dissilicato de lítio CAD/CAM (DLM) e coroas de 2.0mm, com 1,5mm de espessura vestibular de dissilicato de lítio CAD/CAM e recoberta com 0.5mm de porcelana (DLV), foram comparadas com coroas de zircônia (Y-TZP) e metalocerâmica (MC). As réplicas de resina composta foram envelhecidas em água por 30 dias e todas coroas cimentadas com cimento resinoso. Após cimentadas, todos os corpos de prova foram envelhecidos em água por 7 dias e testados com carga única ou com fadiga acelerada progressiva. As cargas foram posicionadas na cúspide mésiovestibular (n=21 para cada sistema cerâmico). A probabilidade Weibull e os gráficos de probabilidade (Alta Pro, Reliasoft) foram calculados (Best data fit QCP) e plotados. A evolução da trinca foi acompanhada e os espécimes analisados após o teste. A menor confiabilidade foi observada para o grupo Y-TZP e não houve diferença estatística entre o grupo MC, DLM e DLV. O grupo DLV demonstrou a maior resistência característica (Eta). O modo de fratura do grupo Y-TZP foi a fratura da porcelana de cobertura sem exposição da infraestrutura. O grupo MC apresentou fraturas da porcelana com exposição do metal. Enquanto os grupos DLM e DLV tiveram fraturas catastróficas. Os grupos DLM e DLV apresentaram uma resposta à fadiga semelhante à do grupo MC e melhor que o grupo Y-TZP. / To evaluate the fatigue reliability of monolithic 1mm and thinly veneered 2mm E.max CAD crowns. A preparation reduction of 1 and 2mm for a full crown was made on a first lower molar. The CAD-based preparation was replicated and positioned in a dental articulator for specimen fabrication. Monolithic 1mm lithium disilicate CAD/CAM crowns (DLM) and a 2mm lithium disilicate CAD/CAM with 1.5 mm thick at buccal aspect veneered with 0.5 mm thick of porcelain were compared to zirconia based (Y-TZP) and metaloceramic (MC) crowns. All composite dies were 30-day aged and all crowns were resin cemented to composite dies. After luting, all specimens were aged for 7 days in water and either single loaded to failure or step-stress fatigue tested. Loads were positioned on mesial-buccal cusp (n=21 for each ceramic system). Probability Weibull and Use level probability curves (Alta Pro, Reliasoft) were calculated (Best data fit QCP) and plotted. Crack evolution was followed and specimens were analyzed postmortem. Lower reliability was observed for Y-TZP group and no statistical difference was observed between MC and DLM e DLV groups. DLV group showed the highest characteristic strength (Eta). Fracture mode for Y-TZP group was veneer chipping without core exposition. MC fractures were mostly chipping with metal coping exposure. While the failure for DLM and DLV groups were bulk fracture. Groups DLM and DLV resulted in fatigue response of lithium disilicate comparable to MC and higher than Y-TZP.

As cerâmicas à base de dissilicato de lítio apresentam propriedades mecânicas, resistência química, biocompatibilidade, baixo índice de acúmulo de placa e resultados estéticos favoráveis. Entretanto, sua resistência à fadiga e probabilidade de sobrevida (confiabilidade) em sua forma estratificada e monolítica ainda é pouco conhecida. Este estudo tem como objetivo investigar a confiabilidade e o modo de falha das coroas estratificadas de dissilicato de lítio com e sem modificação do desenho da infraestrutura e de coroas monolíticas quando submetidas ao ensaio de fadiga por intermédio da ciclagem dinâmica em água. Trinta coroas foram divididas em 3 grupos: IEC (coroas estratificadas com infraestrutura convencional), IEM (coroas estratificadas com infraestrutura modificada) e MON (coroas monolíticas). Para os grupos IEC e IEM as infraestruturas apresentavam espessura de 0,8 mm. No entanto, no desenho modificado era adicionado uma cinta lingual de 2 mm de altura conectada a postes proximais de 3,5 mm de altura, ambos com 1,3 mm de espessura. As MON eram compostas inteiramente de dissilicato de lítio e apresentavam espessura oclusal de 1,5 mm. As coroas foram cimentadas em troqueis de resina composta e submetidas a ciclagem dinâmica em água (30-300 N). Um endentador monolítico de dissilicato de lítio aplicava carga axial sobre a crista marginal mesial até a fratura, e posteriormente na crista distal. Ao final, as coroas eram analisadas em estereomicroscópio e no microscópico eletrônica de varredura (MEV) para caracterização e classificação dos danos. As falhas encontradas nas coroas foram registradas a cada 125.000 ciclos. A distribuição Weibull a 2 parâmetros (Synthesis 9, Weibull ++; Reliasoft, Tucson, AZ, USA) foi utilizada para calculo da probabilidade de sobrevida em 1, 2 e 3 milhões de ciclos. Comparações entre os grupos também foram realizadas com o módulo de Weibull e a resistência característica (número de ciclos decorrido até a fratura). Tanto em 1 quanto em 2 milhões de ciclos, a probabilidade de sobrevida foi significativamente baixa para as IEM em relação as MON e as coroas IEC não apresentaram diferença entre as IEM e MON. Em 3 milhões, apenas as coroas monolíticas mantiveram a confiabilidade, considerandoque diminuiu significativamente para as estratificadas, independente da modificação da infraestrutura. Fraturas envolvendo os postes proximais e/ou a cinta lingual foram observadas para as IEM, enquanto as IEC o modo de falha predominante foi a fratura coesiva da porcelana de revestimento. As MON também apresentaram fraturas coesivas. As marcas fractográficas identificaram a superfície de contato com o endentador como origem das fraturas. Em conclusão, a alta confiabilidade foi observada para as coroas MON em 3 milhões. As coroas estratificadas não se beneficiaram da modificação das infraestrutura, pois não houve diferença na confiabilidade entre elas nos 3 tempos avaliados. Além disso, o modo de falha no grupo IEM não restringiu a fratura coesiva da porcelana, com presença de fraturas na infraestrutura. Falhas coesivas foram observadas apenas na porcelana de revestimento das IEC e na cerâmica no grupo MON. / Lithium disilicate glass-ceramic provides desirable mechanical properties, chemical resistance, biocompatibility, diminished plaque accumulation, esthetics, and favorable esthetic results. However, the fatigue life and probability of survival (reliability) of lithium disilicate in its monolithic or layered form is still poorly understood. This study aimed to investigate the reliability and failure modes of porcelain veneered lithium disilicate crowns with and without core design modification, and of monolithic crowns when subjected to cyclic fatigue in water. Thirty lithium disilicate molars crowns were made and divided into 3 groups: IEC (bilayer crown with even thickness coping, i.e. conventional core), IEM (bilayer crowns with modified core design) and MON (monolithic crowns). For groups IEC and IEM, copings presented an even thickness of 0.8 mm and the modified design consisted of 1.3 mm thickness with a lingual margin of 2.0mm height connected to full contour proximal struts of 3.5 mm height. Monolithic crowns had an occlusal thickness of 1.5 mm. Crows were luted on composite resin abutment replicas and subjected to cyclic fatigue in water (30-300 N). A monolithic indenter of lithium disilicate was used to deliver the load on the mesial marginal ridge until failure, then the same procedure was performed in the distal ridge. For failure characterization crowns were analyzed in stereomicroscope and scanning electron microscope (SEM). Failure inspection was performed every 125,000 cycles. The 2-parameter Weibull distribution (Synthesis 9, Weibull ++; Reliasoft, Tucson, AZ, USA) was used calculate the probability of survival at 1, 2, and 3 million cycles. Comparisons between groups were also made for Weibull modulus and characteristic strength (number of cycles elapsed until failure). At both 1 and 2 million cycles, reliability was significantly lower for IEM relative to MON and IEC showed no difference between the IEM and MON. At 3 million cycles, only monolithic crowns maintained the reliability, whereas it significantly decreased for porcelain veneered crowns, regardless of core design modification. Fractures involving the proximal struts and/or lingual collar were observed for IEM crowns, whereas IEC crowns chiefly presented porcelain cohesive failures. MON crowns fractured cohesively. All fractures started occlusaly, as depicted by telltale fratographic marks. In conclusion, the highest reliability was observed for MON crowns at 3 million cycles. Layered lithium disilicate crowns did not benefit from framework design modification, as there was no difference in reliability between them in 3 times evaluated. Also, failure modes differed between groups and IEM did not hinder porcelain cohesive failures, instead fractures involving the framework were observed. Cohesive failures were observed only for the porcelain veneer of IEC, and of the lithium dissilicate material in the MON group.

Neste trabalho foi realizada a síntese, purificação e caracterização de uma tetra crowned porfirina, a 5,10,15,20-tetraquis[2-(hexaoxacicloexadecano-3-amidafenil)]-porfirina, H2TCP, bem como a correspondente ferroporfirina, (FeTCP)Cl. Foi investigado a atividade catalítica desta ferroporfirina e da ferroporfirina mono-crowned substituída, (FeMCP)Cl, sintetizada anteriormente, na oxidação dos substratos (z)-ciclooocteno, estireno, cicloexano e do fármaco carbamazepina, por vários oxidantes: iodosilbenzeno, ácido meta-cloroperbenzóico e hipoclorito de sódio, em meio homogêneo (MeOH ou ACN) e bifásico (C2H4Cl2/H2O). Os resultados revelaram que estes sistemas metaloporfirinicos podem ser considerados bons modelos biomiméticos das enzimas citocromo P450, para oxidação dos substrados estudados, levando ao mesmo produto obtido in vivo na oxidação do fármaco carbamazepina, o cabamazepina-epóxido. Os rendimentos dos produtos de oxidação catalisada pelas ferro crowned porfirinas são, na maioria dos casos, mais expressivos do que aqueles observados com as metaloporfirinas amino-substituídas precursoras. Estes resultados indicam que o substituinte éter coroa confere maior estabilidade e reatividade ao catalisador, e leva à maior seletividade, resultado da interação do éter corôa com o substrato, direcionando-o para o sítio catalítico. Uma outra propriedade importante das crowned porfirinas estudadas é sua capacidade de atuar como agente transferidor de fases nas reações em meio bifásico, utilizando hipoclorito de sódio como oxidante. Os resultados catalíticos nestes sistemas mostraram que as unidades éter corôa foram capazes de carregar o oxidante do meio aquoso para o meio orgânico, onde se encontra o substrato. Foram avaliadas também as propriedades destas novas porfirinas e metaloporfirinas em extrair íons metálicos sódio e potássio do meio aquoso para o meio orgânico. As crowned porfirinas foram bastante eficientes na extração destes metais, principalmente utilizando a técnica de extração por fase única, levando a extrações superiores a 90 % do cátion potássio, e mostrando maior seletividade para este cátion, devido ao tamanho adequado da cavidade do éter corôa para ligar este íon. Foi realizada também a caracterização das porfirinas e ferroporfirinas crowned substituídas por voltametria cíclica, visando sua aplicação futura na análise eletroanalítica de íons potássio e/ou sódio. Observou-se que as porfirinas crowned substituídas sofrem reduções mais fáceis e oxidações mais difíceis quando comparadas com as porfirinas precursoras, mostrando o efeito sacador de elétrons dos substituintes éter corôa. Estes resultados ajudam a explicar os melhores resultados catalíticos obtidos com as ferro porfirinas crowned substituídas, mostrando o efeito do éter coroa em formar a metaloporfirina mais eletrofílica e aumentando a reatividade da espécie catalítica. / In this work we carried out the synthesis, purification and characterization of a tetra crowned porphyrin, 5,10,15,20-tetrakis[2- (hexaoxacyclohexanedecane-3-amidephenyl)]porphyrin, H2TCP, and its corresponding ironporphyrin, (FeTCP)Cl. We investigated the catalytic activity of both this ironporphyrin and the previously synthesized mono-crowned substituted (FeMCP)Cl in the oxidation of the substrates Z-cyclooctene, styrene, cyclohexane and the drug carbamazepine by oxidants like iodosylbenzene, metachloroperbenzoic acid and sodium hypochlorite, in homogeneous (methanol or acetonitrile) and biphasic (C2H2Cl2/H2O) media. Our results demonstrated that these metalloporphyrin systems can be considered good biomimetic models of the cytochrome P450 enzymes in the case of the substrates studied herein, since they led to the same product obtained in the in vivo oxidation of carbamazepine, the carbamazepine-epoxide. The product yields obtained in the oxidation reactions catalyzed by the crowned ironporphyrins were, in the majority of the cases, higher than those achieved with the precursor aminosubstituted metalloporphyrins. This indicates that the crown-ether substituent renders the catalyst more stable and reactive, thus leading to higher selectivity. This selectivity results from the interaction between the crown-ether and the substrate, which directs the latter toward the catalytic site. Another important feature of the studied crowned ironporphyrins is their ability to act as phase-transfer agent in the reactions carried out in biphasic medium, using sodium hypochlorite as oxidant. The catalytic results using such a system gave evidence that the crown ether entities were capable of carrying the oxidant from the aqueous to the organic medium, where the substrate was located. We also evaluated the ability of these novel porphyrins and ironporphyrins to extract sodium and potassium ions from aqueous solution to organic medium. The crowned porphyrins were efficient at extracting these metals, especially when the one-phase extraction technique was employed, leading to potassium ion extraction as high as 90 %. The complexes were more selective toward this latter ion due to the fact that the size of the crown ether cavity was more suitable for binding the larger K+. The crowned porphyrins and ironporphyrins were also characterized by cyclic voltammetry, aiming at their future application in the electroanalytical determination of sodium and potassium ions. When compared with the precursor aminosubstituted porphyrins, we observed that the crowned porphyrins undergo reduction more easily, but their oxidation is harder to achieve. This gives evidence of the electronwithdrawing effect of the crownether substituent. These results help explain the better catalytic results obtained with the crowned ironporphyrins, showing that the crown-ether entity must render the metalloporphyrin more electrophilic, thus increasing the reactivity of the active species.

Crown architecture affects tree growth through the control of leaf area and its display. Yet the linkages between crown structure, leaf traits, and productivity of elite selections of forest trees and responses to intensive silviculture are not fully understood. It was hypothesized that trees with crown and leaf traits governing efficient light capture and photosynthesis at the canopy scale would be the most productive. To this end, families of loblolly (Pinus taeda) and slash pine (Pinus elliottii) were grown at three experimental sites in the West Gulf Coastal Plain of Texas and Louisiana under two silvicultural treatments, including repeated fertilization with control of competing vegetation (HI), and a control (C) consisting of fertilization at planting. Families and species differed in crown traits and aboveground productivity, and genotype differences increased throughout the first 5 years of stand development. Crown shape was important for light interception and growth initially, but at the onset of canopy closure, crown size, stand leaf area and its distribution within crowns affected canopy light interception and tree growth. Among all families and treatments, aboveground biomass productivity was positively related to absorbed photosynthetically active radiation (APAR) and canopy photosynthesis. Light-use efficiency (ε) varied from 0.41 to 0.56 g MJ-1 among families and was lowest in slash pine. Variability in aboveground biomass growth was related more to stand leaf area and APAR than to differences in light-use efficiency in these young stands. Leaf physiological, chemical and morphological attributes changed within crowns in accordance with developing light availability gradients. Physiological attributes, such as net photosynthesis, were better predictors of family performance when integrated at the canopy level than leaf level in the examined pine species. Crown size, light absorption, and aboveground growth generally ranked higher in the HI treatment than in the control, although the effects of the intensive silvicultural treatments did not differ statistically. Family performance was independent of treatment. Crown and canopy attributes, such as high leaf area index and large crowns with low leaf area density per crown volume, may be useful in the selection of highly productive genotypes of loblolly and slash pine under intensive silviculture.