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Structure, Chemical And Photochemical Reactivity And Biological Activity Of Some Ruthenium Amine Nitrosyl Complexes
No full textThrough spectroscopic (X-ray, Infrared, 1H-NMR, EPR, UV-vis) and electrochemical (cyclic voltammetry, differential pulse polarography) data and quantum mechanical calculations, the formulation [Ru(II)NO+] was attributed to a series of new ruthenium(II) amine compounds. A remarkable stability of the Ru(II) relative to Ru(III) was observed upon coordination to NO. The presence of nitrosyl in the coordination sphere results in dramatic implications in the lability, acidity and redox properties of the ligand trans to NO. These effects are higher than expected just on the basis of one unity increment in the metal center charge. Based on molecular orbital (MO) analysis and on reduction product analysis, the site of the reduction [Ru(NO)]3+ +e- → [Ru(NO)]2+ was assigned to the NO ligand. The dissociation of the coordinated NO0 is dependent on the trans effect and trans influence of the trans ligand L. Irradiation of the nitrosyl complexes with 300-350 nm light results in NO aquation and formation of the corresponding aquaruthenium(III) complex, i.e. S0010854502001777 Irradiation in the visible region (400-500 nm) did not result in any observable reaction in solution; however, at low temperature and in the solid state, evidence in favor of the formation of linkage isomers has been obtained. The hypotensive properties of trans[Ru(NO)(NH3)4(P(OC2 H5)3)](PF6)3 and trans -[Ru(NO)Cl(cyclam)](ClO4)2 have been demonstrated in mice and rats. © 2002 Elsevier Science B.V. All rights reserved.23601/02/155769Richter-Addo, G.B., Legzdins, P., (1992) Metal Nytrosyls, , (and references therein), Oxford University Press, New YorkBottomley, F., (1989) Reactions of Coordinated Ligands, 2. , P.S. Braterman (Ed.), (references therein), Plenum Press, New YorkEnemark, J.H., Feltham, R.D., (1974) Chem. 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Evaluation Of Brazilian Woods As An Alternative To Oak For Cachaças Aging
No full textCachaça was aged for 6 months in small casks of oak and eight different Brazilian woods (amarelo, amendoim, balsamo, jatoba, louro, pau d'arco, pau d'oleo, and pereiro) in order to determine total phenols, UV-visible spectra differences, and sensorial acceptance. Also used were 200-l casks of oak and pereiro for aging cachaça for 4 years to characterize sensorial descriptors and acceptance. The results suggest that amendoim and pereiro followed by jatobá are good candidates to replace oak in the construction of cachaça aging casks. It was also observed that when using oak casks as a standard the major changes in the sensory properties occurred in the first 21 months of aging. The principal components analysis of UV-visible absorption spectra of the same beverage stored in casks made of different woods allowed identification of the wood in which the beverage had been aged. © Springer-Verlag 2003.21818387(2001) Cachaça: The Authentic Brazilian Drink, , ABRABE, São PauloNascimento, R.F., Cardoso, D., Lima-Neto, B.S., Franco, D.W., (1998) Chromatography, 48, pp. 758-762Boscolo, M., Lima-Neto, B.S., Franco, D.W., (1995) Engarrafador Mod, 41, pp. 30-33Lima-Neto, B.S., Bezerra, C.W.B., Polastro, L.R., Campos, P., Nascimento, R.F., Furuya, S.M.B., Franco, D.W., (1994) Quím Nova, 17, pp. 220-224Nascimento, R.F., Marques, J.C., Lima-Neto, B.S., Franco, D.W., (1997) J Chromatography, 782, pp. 13-16Bettin, S.M., Isique, D.I., Franco, D.W., Andersen, M.L., Knudsen, S., Skibsted, L.H., (2002) Eur Food Res Technol, 215, pp. 169-175Cardello, H.M.A.B., Faria, J.B., (1997) Bol CEPPA, 15, pp. 87-100Cardello, H.M.A.B., Faria, J.B., (1998) Ciênc Tecnol Aliment, 18, pp. 169-175Faria, J.B., Deliza, R., Rossi, E.A., (1998) Ciênc Tecnol Aliment, 13, pp. 90-93Nishimura, K., Matsuyama, R., Maturation and maturation chemistry (1989) The Science and Technology of Whiskies, pp. 235-263. , Piggott JR, Sharp R, Duncan REB (eds). Longman, Essex, EnglandReazin, G.H., (1981) Am J Enol Vit, 32, pp. 283-289Kloster, M.B., (1974) J Am Water Works Assoc, 66, pp. 44-46Stone, H., Sidel, J., (1993) Sensory Evaluation Practices, 2nd Edn., , Academic, New YorkMeilgaard, M., Civille, G.V., Carr, B.T., (1987) Sensory Evaluation Techniques, 3rd Edn., , CRC, Florida(1983) SAS User's Guide, , SAS Inst, Cary, USACadet, F., Offman, B., (1997) J Agric Food Chem, 15, pp. 1166-1171Massart, D.L., Vandeginste, B.G.M., Deming, S.N., Michote, Y., Kaufman, L., (1988) Chemometrics: A Textbook, , Elsevier, New YorkBoscolo, M., Andrade-Sobrinho, L.G., Lima-Neto, B.S., Franco, D.W., (2002) J Assoc off Anal Chem Int, 85, pp. 1-7Dias, S., Maia, A., Nelson, D., (1998) Ciênc Tecnol Aliment, 18, pp. 331-33
Nitric Oxide As An Activation Agent For Nucleophilic Attack In Trans-[ru(no)(nh3)4{p(oet)3}](pf 6)3
No full textThe complex trans-[Ru(NO)(NH3)4{P(OEt) 3}](PF6)3 undergoes nucleophilic attack on the phosphorus ester ligand in the solid state yielding trans-[Ru(NO)(NH 3)4{P(OH)(OEt)2}](PF6)3. The reaction was monitored and the products analyzed using nuclear magnetic resonance spectroscopy (31P{1H} CP-MAS NMR and 31P{1H} NMR), infrared spectroscopy (FTIR), electron paramagnetic resonance spectroscopy (EPR), cyclic voltammetry (CV), electronic spectroscopy (UV-Vis) and elemental analysis. According to experimental data and quantum mechanical calculations (DFT), the reaction proceeds in the solid state by the nucleophilic attack on the phosphorus ligand, promoted by the strong polarization along the PIII-RuII-NO+ axis induced by the nitrosyl ligand, and takes place following the Michaelis-Arbusov type mechanism for phosphorus ester hydrolysis. 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Going Beyond Counting First Authors in Author Co-citation Analysis
Get PDFThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
Get PDF“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Get PDFWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
Spectroscopic And Electrochemical Study Of [ru(nh3)5oh2]3+, [ru(nh3)5cl]2+, And [os(nh3)5oh2]3+ Immobilized On Thin Film Of Ti(iv) Oxide Dispersed On The Silica Gel Surface
No full text[Ru(NH3)5H2O]3+, [Ru(NH3)5Cl]2+ and [Os(NH3)5H2O]3+ were supported on the hydrated titanium alkoxide grafted on silica gel surface. The mononuclear complexes on the matrix surface have been characterized by specific surface area, elemental analysis, UV-Vis spectroscopy and electrochemical techniques (cyclic voltammetry, differential pulse polarography). These supported species exhibit one defined band on the visible region of the electronic spectrum: band [Ru(NH3)5H2O]3+ (668 nm), [Ru(NH3)5 Cl]2+ (676 nm) and [Os(NH3)5H2O]3+ (825 nm), attributed to MIII → TiIV (M = Ru(III) and Os(III)) metal to metal charge transfer process. For the mononuclear anchored species [Ru(NH3)5H2O]3+, [Ru(NH3)5Cl]2+ and [Os(NH3)5H2O]3+, the (E1/2) for the M(III)/M(II) couple at 25°C are, respectively: -0.22, -0.28, and - 1.15 V versus SCE. A formation of an oxo bridge Ti-O-M(NH3)5 (M = Ru, Os) and chloro bridge Ti-Cl-Ru(NH3)5 was postulated for the grafted complexes on the SiO2/TiO2 surface. © 2000 Elsevier Science B.V.1922-2322772282Siperko, L.M., Kuwana, T., (1983) Electrochim. Acta, 130, p. 765Gushikem, Y., Peixoto, C.R.M., Rodrigues-Filho, U.P., Kubota, L.T., Stadler, E., (1996) J. Colloid Interface Sci., 184, p. 236Denofre, S., Gushikem, Y., Castro, S.C., Kawano, Y., (1993) J. Chem. Soc., Faraday Trans., 89, p. 1057Hoffmann, M.T., Neiva, S.M.C., Martins, M.R., Franco, D.W., (1992), p. 257. , H.A. Mottola, J.R. Steinmezt (Eds.), Chemically Modified Surfaces, Elsevier, New YorkNeiva, S.M.C., Santos, J.A.V., Moreira, J.C., Gushikem, Y., Vargas, H., Franco, D.W., (1995) Langmuir, 9, p. 239Lorencetti, L., Gushikem, Y., Kubota, L.T., Neto, G.O., Fernandes, J.R., (1995) Mikrochim. Acta, 117, p. 239Kubota, L.T., Gouvea, F., Andrade, A.N., Milagres, B.G., Neto, G.O., (1996) Electrochim. Acta, 41, p. 1465Rebenstorf, B., Andersson, S.L.T., (1990) J. Chem. Soc., Faraday Trans., 86, p. 2783Kubota, L.T., Milagres, B.G., Gouvea, F., Neto, G.O., (1996) Anal. Lett., 29, p. 893Walcarius, A., (1998) Electroanalysis, 10, p. 1217Kubota, L.T., Gushikem, Y., (1992) Electochim. Acta, 37, p. 2477Carmo, D.R., Gushikem, Y., Franco, D.W., (1999), p. 325. , J.P. Blitz, C.B. Little (Eds.), Fundamental and Applied Aspects of Chemically Modified Surfaces, The Royal Society of Chemistry, CambridgeFord, P.C., (1970) Coord. Chem. Rev., 5, p. 75Taube, H., (1979) Pure Appl. Chem., 51, p. 901Stritar, J.A., Taube, H., (1969) Inorg. Chem., 8, p. 2281Taube, H., (1981) Comm. Inorg. Chem., 1, p. 17Forlano, P., Baraldo, L.M., Olabe, J.A., Della Védora, C.O., (1994) Inorg. Chim. Acta, 223, p. 37Bezerra, C.W.B., Silva, S.C., Gambardella, M.T.P., Santos, R.H.A., Plicas, L.M.A., Tfouni, E., Franco, D.W., (1999) Inorg. Chem., 38, p. 5660Wilkins, R.G., (1991) Kinetics and Mechanism of reactions of Transition Metal Chemistry, second ed., p. 183. , Wenhein, New YorkEllis, I.D., Sykes, G., (1973) J. Chem. Soc., Dalton Trans., p. 573Kubota, L.T., (1993), Ph.D. Dissertation, Unicamp, BrazilShriver, D.F., (1969) Manipulation of Air Sensitive Compounds, , Mc-Graw-Hill, New YorkDixon, N.E., Lawrance, G.A., Lay, P.A., Sargeson, A.M., (1984) Inorg. Chem., 23, p. 2940Meyer, T., Taube, H., (1968) Inorg. Chem., 7, p. 2369Lay, P.A., Mangunson, R.H., Sen, J., Taube, H., (1982) J. Am. Chem. Soc., 104, p. 7658Kalcher, K., Kauffmann, J.M., Wang, J., Svancara, I., Vytras, K., Neuhold, Z., Zang, Z.C., (1995) Electroanalysis, 7, p. 5Kormann, C., Bahnemann, D.W., Hoffmann, M.R., (1991) Environ. Sci. Technol., 25, p. 494Kondo, M.M., (1996), Ph.D. Dissertation, Delaware University, USACheng, S.F., Tsai, S.-J., Lee, Y.F., (1995) Catal. Today, 26, p. 87Adegite, A., Iyun, J.F., Ojo, J.F., (1977) J. Chem. Soc., Dalton Trans., 2, p. 115Allen, A.D., Stevens, J.R., (1972) Can. J. Chem., 51, p. 92Krentizen, H., (1976), Ph.D. Dissertation, Stanford University, USABhur, J.D., (1978), Ph.D. Dissertation, Stanford University, USATaube, H., (1976) Surv. Prog. Chem., 6, p. 31Endicott, J.F., Taube, H., (1989) Inorg. Chem., 4, p. 437Endicott, J.F., Taube, H., (1962) J. Am Chem. Soc., 84, p. 4984Kubota, L.T., Gushikem, Y., Perez, J., Tanaka, A., (1995) Langmuir, 11, p. 1009Kubota, L.T., Gushikem, Y., (1993) J. Electroanal. Chem., 362, p. 219Lim, H.S., Baclay, D.J., Anson, F., (1972) Inorg. Chem., 11, p. 1460Coleman, G.M., Gesler, J.W., Shirley, F.A., Kuemptel, J.R., (1973) Inorg. Chem., 12, p. 1036Shi, C., Anson, F., (1997) Inorg. Chem., 36, p. 263
4,4′-dithiodipyridine As A Bridging Ligand In Osmium And Ruthenium Complexes: The Electron Conductor Ability Of The -s-s- Bridge
No full textThe compounds [Ru(NH 3) 5(dtdp)](TFMS) 3, [Os(NH 3) 5(dtdp)](TFMS) 3, [(NH 3) 5Os(dtdp)Os(NH 3) 5](TFMS) 6, [(NH 3) 5Os(dtdp)Ru(NH 3) 5](TFMS) 3(PF 6) 2, and [(NH 3) 5Os(dtdp)Fe(CN) 5] (dtdp = 4,4′-dithiodipyridine, TFMS = trifluoromethane-sulfonate) have been synthesized and characterized by elemental analysis, cyclic voltammetry, electronic, vibrational, EPR, and 1H NMR spectroscopies. Changes in the electronic and voltammetric spectra of the ion complex [Os(NH 3) 5(dtdp)] 3+ as a function of the solution pH enable us to calculate the pK a for the [Os(NH 3) 5(dtdpH)] 4+ and [Os(NH 3) 5(dtdpH)] 3+ acids as 3.5 and 5.5, respectively. The comparison of the above pK a data with that for the free ligand (pK 1 = 4.8) provides evidence for the -S-S- bridge efficiency as an electron conductor between the two pyridine rings. The symmetric complex, [(NH 3) 5Os(dtdp)Os(NH 3) 5] 6+, is found to exist in two geometric forms, and the most abundant form (most probably trans) has a strong conductivity through the -S-S- bridge, as is shown by EPR, which finds it to have an S = 1 spin state with a spin-spin interaction parameter of 150-200 G both in the solid sate and in frozen solution. Further the NMR of the same complex shows a large displacement of unpaired spin into the π orbitals of the dttp ligand relative to that found in [Os(NH 3) 5(dtdp)] 3+. The comproportionation constant, K c = 2.0 × 10 5, for the equilibrium equation [Os IIOs II] + [Os IIIOs III] ⇌ 2[Os IIOs III] and the near-infrared band energy for the mixed-valence species (MMCT), [(NH 3) 5Os(dtdp)Os(NH 3) 5] 5+ (λ MMCT = 1665 nm, ε = 3.5 × 10 3 M -1 cm -1, Δν̄ 1/2 = 3.7 × 10 3 cm -1, α = 0.13, and H AB = 7.8 × 10 2 cm -1), are quite indicative of strong electron delocalization between the two osmium centers. The electrochemical and spectroscopic data for the unsymmetrical binuclear complexes [(NH 3) 5Os III(dtdp)Ru II(NH 3) 5] 5+ (λ MMCT = 965 nm, ε = 2.2 × 10 2 M -1 cm -1, Δν̄ 1/2 = 3.0 × 10 3 cm -1, and H AB = 2.2 × 10 2 cm -1) and [(NH 3) 5Os III(dtdp)Fe II(CN) 5] (λ MMCT = 790 nm, ε = 7.5 × 10 M -1 cm -1, Δν̄ 1/2 = 5.4 × 10 3 cm -1, and H AB = 2.0 × 10 2 cm -1) also suggest a considerable electron delocalization through the S-S bridge. As indicated by a comparison of K c and energy of the MMCT process in the iron, ruthenium, and osmium complexes, the electron delocalization between the two metal centers increases in the following order: Fe < Ru < Os.422168986906Johnson, M.K., King, R.B., Kurtz D.M., Jr., Kutal, C., Norton, M.L., Scott, R.A., (1990) Electron Transfer in Biology in the Solid State Inorganic Compounds with Unusual Properties, , American Chemical Society, WashingtonZuckerman, J.J., (1986) Electron Transfer and Electrochemical ReactionsPhotochemical and Other Energized Reactions in Inorganic Reactions and Methods, Vol. 15, , VCH Publishers: Deerfield Beach, FLIsied, S.S., (1991) Metal Ions in Biological Systems, pp. 1-56. , Sigel H., Ed.Dekker: New YorkLewis, N.A., Obeng, S.Y., Taveras, D.V., Van Eldik, R.J., (1989) J. Am. Chem. Soc., 111, pp. 924-927Moreira, I.S., Franco, D.W., (1994) Inorg. Chem., 35, pp. 1607-1613Moreira, I.S., Franco, D.W., (1997) Adv. Chem. 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Chem., 27, pp. 3604-3608Perrin, D.D., Armarego, W.L.F., Perrin, D.R., (1980) Purification of Laboratory Chemicals, 2nd Ed., , Pergamon Press: New YorkLay, P.A., Magnuson, R.H., Sen, J., Taube, H., (1982) J. Am. Chem. Soc., 104, pp. 7658-7659Lay, P.A., Magnuson, R.H., Taube, H., (1986) Inorg. Synth., 24, pp. 271-273Kreuztian, H., (1976) Mixed Valence Ruthenium Ammine Dinitrile and Related Complexes, , Ph.D. Thesis, Stanford UniversityKuehn, C.G., Taube, H., (1976) J. Am. Chem. Soc., 98, pp. 689-702Brauer, G., (1965) Handbook of Preparative Inorganc Chemistry, , Academic Press: New YorkShriver, D.F., (1969) The Manipulation of Air-Sensitive Compounds, , McGraw-Hill Co. New YorkMeites, L., (1965) Polarographic Techniques, 2nd Ed., , Interscience: New York, Chapter 5(1997) Microcal Origin, Version 5.0, , Microcal Software: Northampton, MAMoreira, I.S., Parente, L.T.S., Franco, D.W., (1998) Quím. Nova., 21 (5), pp. 545-550Forchioni, A., Pappalardo, G., (1975) Spectrochim. 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Dispelling the Myths Behind First-author Citation Counts
Get PDFWe conducted a full-scale evaluative citation analysis study of scholars in the XML research field to explore just how different from each other author rankings resulting from different citation counting methods actually are, and to demonstrate the capability of emerging data and tools on the Web in supporting more realistic citation counting methods. Our results contest some common arguments for the continued
use of first-author citation counts in the evaluation of scholars, such as high correlations between author rankings by first-author citation counts and other citation
counting methods, and high costs of using more realistic citation counting methods that are not well-supported by the ISI databases. It is argued that increasingly available digital full text research papers make it possible for citation analysis studies to go beyond what the ISI databases have directly supported and to employ more
sophisticated methods
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