The anions [(ZrOH(CO3)3)2]6− and [(ZrOH(C2O4)3)2]6−: single crystal X-ray diffraction studies of the complexes guanidinium zirconium carbonate [(C(NH2)3)3ZrOH(CO3)3·H2O]2 and sodium zirconium oxalate Na6(ZrOH(C2O4)3)2·7H2O

The complex [(C(NH2)3)3ZrOH(CO3)3·H2O]2 (A) has been shown by means of a single crystal X-ray diffraction study to contain [C(NH2)3]+ cations and dimeric anions of formulation [(ZrOH(CO3)3)2]6−. The anion is centrosymmetric with each metal being bonded to two bridging OH groups and three chelating CO2−3 ions. The Zr atoms are thus eight coordinate with a dodecahedral environments. The ZrO distances formed by the bridgng OH groups are shorter than those formed through zirconiu carbonate interactions. The non-bonded Zr…Zr distance is 3.47(2) Å. An infrared spectroscopic investigation of A provides data which support the findings of the crystallographic study. Likewise the complex Na6(ZrOH(CO2O4)3)2·7H2O (B) contains the anion [(ZrOH(C2O4)3)2]6−. This anion is structurally related to the anion in A as each Zr atom has an eight-coordinate dodecahedral environment being bonded to two bridging OH groups and three chelating oxalate ligands, but has no imposed crysallographic symmetry. The Zr…Zr non-bonded distance is 3.50(1) Å. The OZrO bridge angles are 69.7(4)° and A and 67.4(3)° in B.

Mesomorphic behaviour in copoly(ester-imide)s of poly(butylene-2,6-naphthalate) (PBN)

Copolycondensation of N,N’-bis(4-hydroxybutyl)-biphenyl-3,4,3',4'-tetracarboxylic diimide at 20 and 25 mol% with bis(4-hydroxybutyl)-2,6-naphthalate produces PBN-based copoly(ester-imide)s that not only crystallise but also form a (smectic) mesophase upon cooling from the melt. Incorporation of 25 mol% imide in PBN causes the glass transition temperature (measured by DSC) to rise from 51 to 74 °C, a significant increase relative to PBN. Furthermore, increased storage- (G'), loss- (G'') and elastic (E) moduli are observed for both copoly(ester-imide)s when compared to PBN itself. Structural analysis of the 20 mol% copolymer by X-ray powder and fibre diffraction, interfaced to computational modelling, suggests a crystal structure related to that of α-PBN, in space group P-1, with cell dimensions a = 4.74, b = 6.38, c = 14.45 Å, α = 106.1, β = 122.1, γ = 97.3°, ρ = 1.37 g cm-3.

2,6-Di-hidroxiacetofenona e tipo de corte basal no enraizamento de estacas semi-lenhosas de pessegueiro Okinawa

A propagação do pessegueiro (Prunus persica) no Brasil é baseada na enxertia sobre porta-enxertos oriundos de sementes. Outros métodos de propagação de frutíferas poderiam ser utilizados para o pessegueiro visando obtenção de materiais de melhor qualidade. Neste trabalho objetivou-se avaliar o efeito do 2,6-di-hidroxiacetofenona aplicado previamente ao ácido indol-butírico em estacas semi-lenhosas de pessegueiro da cultivar Okinawa preparadas com diferentes tipos de corte basal. Foram coletados ramos do porta-enxerto Okinawa em dezembro de 2001 para o preparo das estacas sem folhas, com 12cm de comprimento, 7mm de diâmetro, quatro gemas e diferentes tipos de cortes basais (corte longitudinal, corte lateral e corte da casca) tratado-as na base com 0 e 300mg L-1 de 2,6-di-hidroxiacetofenona por 4h em aeração (oxigenação) e depois com 2500mg L-1 ácido indol-butírico por 5s. As estacas foram plantadas em bandejas de poliestireno expandido (72 células) com vermiculita fina e colocadas em casa de nebulização por 45 dias. A aplicação de 300mg L-1 de 2,6-DHAP e a realização de lesões nas bases das estacas foram eficientes para aumentar o enraizamento das estacas semi-lenhosas do pessegueiro Okinawa , demonstrando que estas técnicas podem ser utilizadas para a propagação de pessegueiro por estaquia.

Characterization and catalytic activity of 2,6-dichlorophenyl substituted iron(III) porphyrin supported on silica gel and imidazole propyl gel

In this work we have made use of the study of the interaction between Fe(TDCPP)(+) and the axial ligands OH- and imidazole in order to help characterize the heterogenized catalysts Fe(TDCPP)SG and Fe(TDCPP)IPG through UV-VIS and EPR spectroscopies and thus, better understand their different catalytic activity in the oxidation of cyclohexane by PhIO. We have found out that in Fe(TDCPP)SG (containing 1.2 X 10(-6) mol Fe(TDCPP)(+)/g of support), the FeP bis-coordinates to silica gel through Fe-O coordination and it is high-spin (FeP)-P-III species. In Fe(TDCPP)IPG 1 (containing 1.1 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-4) mol imidazole/g of support), the FeP is bis-ligated to imidazole propyl gel through Fe-imidazole coordination and using NO as a paramagnetic probe, we present evidence that Fe(TDCPP)(+) is present as a mixture of low-spin (FeP)-P-III and (FeP)-P-II species. This catalyst led to a relative low yield of cyclohexanol (25%) because the bis-coordination of the (FeP)-P-III to the support partially blocks the reaction between Fe(TDCPP)(+) and PhIO, thus leading to the formation of only a small amount of the active species Fe-IV(OP+, while the (FeP)-P-II species do not react with the oxygen donor. Increasing the amount of Fe(TDCPP)(+) and decreasing the amount of imidazole in the support led to the obtention of high-spin (FeP)-P-III EPR signals in the spectra of Fe(TDCPP)IPG 5 (containing 4.4 X 10(-6) mol Fe(TDCPP)(+) and 2.2 X 10(-5) mol imidazole/g of IPG), together with low-spin (FeP)-P-III species. This latter catalyst led to better cyclohexanol yields (67%) than Fe(TDCPP)IPG 1. Fe(TDCPP)IPG 5 was further used in a study of the optimization of its catalytic activity and in recycling experiments in the optimized conditions. Recycling oxidation reactions of Fe(TDCPP)IPG 5 led to a total turnover number of 201 and total cyclohexanol yield of 201%, which could not be attained with Fe(TDCPP)Cl in homogeneous solution (turnover = 96) due to the difficulty in recovering and reusing it.

Farmacocinética pré-clínica do composto 1-(2,6-diclorofenil)indolin-2-ona (DICCIC), pró-fármaco de diclofenaco

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Desgaste e rugosidade superficial de um cimento de ionômero de vidro nanoparticulado

To compare the abrasion wear resistance and superficial roughness of different glass ionomer cements used as restorative materials, focusing on a new nanoparticulate material. Material and Method: Three glass ionomer cements were evaluated: Ketac Molar, Ketac N100 and Vitremer (3M ESPE, St. Paul, MN, USA), as well as the Filtek Z350 (3M ESPE, St. Paul, MN, USA). For each material were fabricated circular specimens (n=12), respecting the handling mode specified by the manufacturer, which were polished with sandpaper disks of decreasing grit. The wear was determined by the amount of mass (M) lost after brushing (10,000 cycles) and the roughness (Ra) using a surface roughness tester. The difference between the Minitial and Mfinal (ΔM) as well as beroughness of aesthetic restorative materials: an in vitro comparison. SADJ. 2001; 56(7): 316-20. 11. Yip HK, Peng D, Smales RJ. Effects of APF gel on the physical structure of compomers and glass ionomer cements. Oper. Dent. 2001; 26(3): 231-8. 12. Ma T, Johnson GH, Gordon GE. Effects of chemical disinfectants on the surface characteristics and color of denture resins. J Prosthet Dent 1997; 77(2): 197-204. 13. International organization for standardization. Technical specification 14569-1. Dental Materials – guidance on testing of wear resistance – PART I: wear by tooth brushing. Switzerland: ISO; 1999. 14. Bollen CML, Lambrechts P, Quirynen M. Comparison of surface roughness of oral hard materials to the threshold surface roughness for bacterial plaque retention: a review of the literature. Dent Mater.1997; 13(4): 258-9. 15. Kielbassa AM, Gillmann C, Zantner H, Meyer-Lueckel H, Hellwig E, Schulte-Mönting J. Profilometric and microradiographic studies on the effects of toothpaste and acidic gel abrasivity on sound and demineralized bovine dental enamel. Caries Res. 2005; 39(5): 380-6. 16. Tanoue N, Matsumara H, Atsuta M. Wear and surface roughness of current prosthetic composites after toothbrush/dentifrice abrasion. J Prosthet Dent. 2000; 84(1): 93-7. 17. Heath JR, Wilson HJ. Abrasion of restorative materials by toothpaste. J Oral Rehabil. 1976; 3(2): 121-38. 18. Frazier KB, Rueggeberg FA, Mettenburg DJ. Comparasion of wearresistance of class V restorative materials. J Esthet Dent. 1998; 10(6): 309-14. 19. Momoi Y, Hirosakil K, Kohmol A, McCabe JF. In vitro toothebrushdentifrrice abrasion of resin-modified glass ionomers. Dent Mater. 1997; 13(2): 82-8. 20. Turssi CP, Magalhães CS, Serra MC, Rodrigues Jr.AL. Surface roughness assessment of resin-based materials during brushing preceded by pHcycling simulations. Oper Dent. 2001; 26(6): 576-84. 21. Wang L, Cefaly DF, Dos Santos JL, Dos Santos JR, Lauris JR, Mondelli RF, et al. In vitro interactions between lactic acid solution and art glassionomer cements. J Appl Oral Sci. 2009; 17(4): 274-9. 22. Carvalho FG, Fucio SB, Paula AB, Correr GM, Sinhoreti MA, PuppinRontani RM. Child toothbrush abrasion effect on ionomeric materials. J Dent Child (Chic). 2008; 75(2): 112-6. 23. Coutinho E, Cardoso MV, De Munck J, Neves AA, Van Landuyt KL, Poitevin A, et al. Bonding effectiveness and interfacial characterization of a nano-filled resin-modified glass-ionomer. Dent Mater. 2009; 25(11): 1347-57. tween Rainitial and Rafinal (ΔRa) were also used for statistical analysis (α=0.05). Results: Except for the composite, significant loss of mass was observed for all glass ionomer cements and the ΔM was comparable for all of them. Significant increase in roughness was observed only for Vitremer and Ketac N100. At the end of the brushing cycle, just Vitremer presented surface roughness greater than the composite resin. Conclusion: All glass ionomer cements showed significant weight loss after 10,000 cycles of brushing. However, only Vitremer showed an increase of roughness greater than the Z350 resin, while the nanoparticulate cement Ketac N100 showed a smooth surface comparable to the composite.

Warum Pentose- und nicht Hexose-Nucleinsäuren??. Teil V. (Purin-Purin)-Basenpaarung in der homo-DNS-Reihe: Guanin, Isoguanin, 2,6-Diaminopurin und Xanthin

Why Pentose- and Not Hexose-Nucleic Acids? Purine-Purine Pairing in homo-DNA: Guanine,Isoguanine, 2,6-Diaminopurine, and Xanthine This paper concludes the series of reports in this journal [1–4] on the chemistry of homo-DNA, the constitutionally simplifie dmodel system of hexopyranosyl-(6′ → 4′)-oligonucleotide systems stidued in our laboratory as potentially natural-nucleic-acid alternatives in the context of a chemical aetiology of nucleic-acid structure. The report describes the synthesis and pairing properties of homo-DNA oligonucleotides which contain as nucleobases exclusively purines, and gives, together with part III of the series [3], a survey of what we know today about purine-purine pairingin homo-DNA. In addition, the paper discusses those aspects of the chemistry of homo-DNA which, we think, influence the way how some of the structural features of DNA (and RNA) are to be interpreted on a qualitative level. Purine-purine pairing occurs in the homo-DNA domain in great variety. Most prominent is a novel tridentate Watson-Crick pair between guanine and isoguanine, as well as one between 2,6-diaminopurine and xanthinone, both giving rise to very stable duplexes containing the all-purine strands in antiparallel orientation. For the guanine-isoguanine pair, constitutional assignment is based on temperature-dependent UV and CD spectroscopy of various guanine- and isoguanine-containg duplexes in comparison with duplexes known to be paired in the reverse guanine is replaced by 7-carbauguanine. Isoguanine and 2,6-diaminopurine also have the capability of self-pariring in the reverse-Hoogsteen mode, as previously observed for adenine and guanine [3]. In this type of pairing, the interchangeably. Fig. 36 provides an overall survey of the relative strength of pairing in all possible purine-purine combinations. Watson-Crick pairing of isoguanine with guanine demands the former to participate in its 3H-tautomeric form; hitherto this specific tautomer had not been considered in the pairing chemistry of isoguanine. Whereas (cumulative) purine-purine pairing in DNA (reverse-Hoogsten or Hoogsteen) seems to occur in triplexes and tetrapalexes only, its occurrence in duplexes in a characteristic feature of homo-DNA chemistry. The occurrence of purine-purine Watson-Crick base pairs is probably a consequence of homo-DNA's quasi-linear ladder structure [1][4]. In a double helix, the distance between the two sugar C-atoms, on which a base pair is anchored, is expected to be constrained by the dimensions of the helix; in a linear duplex, however, there would be no restrictions with regard to base-pair length. Homo-DNA's ladder-like model also allows one to recognize one of the reasons why nucleic-acid duplexes prefer to pair in antiparallel, rather than parallel strand orientation: in homo-DNA duplexes, (averaged) backbone and base pair axes are strongly inclined toward one another [4]; the stronger this inclination, the higher the preference for antiparallel strand orientation is expected to be (Fig. 16). In retrospect, homo-DNA turns out to be one of the first artificial oligonucleotide systems (cf. Footnote 65) to demonstrate in a comprehensive way that informational base pairing involving purines and pyrimidines is not a capability unique to ribofuranosyl systems. Stability and helical shape of pairing complexes are not necessary conditions of one another; it is the potential for extensive conformational cooperativity of hte backbone structure with respect to the constellational demands of base pairing and base stacking that determines whether or nor a given type of base-carrying backbone structure is an informational pairing system. From the viewpoint of the chemical aetiology of nucleic-acid structure, which inspired our investigations on hexopyranosyl-(6′ → 4′)-oligonucleotide systems in the first place, the work on homo-DNA is only an extensive model study, because homo-DNA is not to be considered a potential natural-nucleic-acid altenratie. In retrospect, it seems fortunate that the model study was carried out, because without it we could hardly have comprehended the pairing behavior of the proper nucleic-acid alternatives which we have studied later and which will be discussed in Part VI of this series. The English footnotes to Fig. 1–49 provide an extension of this summary.

Mus Hs 759 - Andante für Flauto 1mo et 2do, Br[uder]: Herbolt, Oechs, Clarinetto in A, Lause, Corno in E, Oestreich, Corno Pasetto in E, Bretschneider : No 17 ; dieses Andante haben wir in der [das Logensymbol eines Steines] Socrates beÿ der Aufnahme in 2|t|e Gr:. aufgeführt ; d 27|t|e August 5830

[Carl Oestreich]