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81.
B. Eva Villaroya Luis A. Oro Fernando J. Lahoz Andrew J. Edwards Miguel A. Ciriano Pablo J. Alonso Antonio Tiripicchio Marisa Titipicchio Camellini 《Inorganica chimica acta》1996,250(1-2):241-264
The multiple coordination possibilities of 1,8-naphthyridine-2-one (HOnapy) and 5,7-dimethyl-1,8-napthyridine-2-one (HOMe2napy) ligands allow the synthesis of a variety of tri- di- and mononuclear complexes, showing fluxional behaviour and frequent exchange of the coordinated ML2 fragments. Thus, reactions of [M2(μ-OMe)2(cod)2] (cod = 1,5-cyclooctadiene) with HOnapy and HOMe2napy yield the compounds of the general formula [M(μ-OR2napy) (cod)]n (M = Ir, R = Me (1a, 1b, H (2); M = Rh, R = Me (3a, 3b). They crystallise as inconvertible yellow (a) and purple/orange (b) forms and also show a puzzling behaviour in solution. X-ray diffraction studies on both forms (3a, 3b) and spectroscopic data reveal that the yellow forms are mononuclear complexes whilst the dark-coloured crystals contain dinuclear complexes. In solution, the nuclearity of the complexes depends on the solvent. In addition both types of complexes are fluxional. The mixed-ligand complexes [M2(μ-OMe2napy)2(CO)2(cod)] M = Ir (5), Rh (6) have been isolated and characterised; they are found to be intermediates in the synthesis of the trinuclear complexes [M3(μ3-OMe2napy)2(CO)2(cod)2]+ M = Rh (8), Ir (9). Reactions of [IrCl(CO)2(NH2-p-tolyl] with the complexes [Rh(μ-OR2napy)(diolefin)]n followed by addition of a poor donor anion is a general one-pot synthesis for the hetertrinuclear complexes [Rh2Ir(μ3-OR2napy)2(CO)2(diolefin)2]+ (R=Me, DIOLEFIN = cod (10), tetrafluorobenzo-barrelene (tfbb) (11), 2,5-norbornadiene (nbd) (12); R=H, DIOLEFIN=cod (13)). This synthesis follows a stepwise mechanism from the mononuclear to the trinuclear complexes in which mixed-ligand heterodinuclear complexes are involved as intermediates of the type [(diolefin)Rh(μ-OMe2napy)2Ir(CO)2]. Heteronuclear complexes which possess the core [RhIr2]3+, such as [RhIr2(μ3-OR2napy)2(CO)2(cod)2]BF4 (R=Me (14), H (15)), result from the reaction of 1 or 2 with [Rh(CO)2Sx]+ (S = solvent). The trinuclear complexes undergo two chemically reversible one-electron oxidation processes. The chemical oxidation of 10, 14 and 9 with silver salts gives the mixed-valence trinuclear radicals [Rh2Ir(μ3-OMe2napy)2(CO)2(cod)2]2+ (16), [RhIr2(μ3-OMe2napy)2(CO)2(cod)2]2+ (17) and [Ir3(μ3-OMe2napy)2(CO)2(cod)2]2+ (18), which have been isolated as the perchlorate and tetrafluoroborate salts. The EPR spectrum of 16 indicates that the unpaired electron is essentially in an orbital delocalised on the metals. The molecular structures of the complexes 3a, 3b, 6, 10b and 16a are described. Crystals of 3a are triclinic, P-1, with a = 9.7393(2), b = 14.0148(4), c = 16.0607(4) Å, α = 88.122(3), β = 83.924(3), γ = 87.038(3)°, Z = 4; 3b crystallises in the Pna2i orthorhhombic space group, with a = 16.7541(3), B = 11.7500(8), c = 17.7508(7) Å, Z = 4; complex 6 is packed in the monoclinic space group P2i/c, a = 9.6371(1), b = 11.8054(4), c = 27.2010(9) Å, β = 90.556(4)°, Z = 4; crystals of 10b are monoclinic, P21/n, with a = 17.546(7), b = 13.232(6), c = 17.437(8) Å, β = 106.18(1)°, Z = 4; crystals of 16a are triclinic, P-1, with a = 10.318(4), b = 12.562(6), C = 19.308(8) Å, α = 92.12(8), β = 97.65(9), γ = 90.68(5)°, Z = 2. The five different structures show the coordination versatility of the OMe2napy molecule as ligand, which behaves as a N,N′-chelating (3a), bidentate N,O-donor (3b, 6), or as a tridentate N,N′,O-donor bridging ligand (10b, 16a). 相似文献
82.
Jose M. Sanchez-Ruiz 《European biophysics journal : EBJ》1996,24(4):261-274
Large increases in the strength of the hydrophobic effect and, consequently, in the estimates of the hydrophobic contribution to the thermodynamics of protein folding (and other biologically-relevant processes), have been recently advocated on the basis of the application, to model transfer thermodynamic data, of corrections for the solute/solvent size disparity. In this work we first examine the effect of molecular-size corrections on the values calculated from several types of model transfer data. For the transfer of a solute from an organic solvent to water, the above increase is exclusively associated with the application of a solute/water molecular-size correction. Secondly, we critically review and assess the several theoretical arguments that lead to these corrections. In particular, we show that, contrary to previous claims in the literature, the analysis of dissolution processes in terms of ideal-gas, intermediate states does not lead to the molecular-size correction term, but only to expressions equivalent (although not strictly identical) to those derived from the well-known Ben-Naim's statistical-mechanical approach. In general, the several analyses offered or discussed in this work disfavor the application of the solute/water molecular-size corrections. 相似文献
83.
Leonardo Legarreta Miguel A. Uliana 《Palaeogeography, Palaeoclimatology, Palaeoecology》1996,120(3-4):303-330
Jurassic rocks in west-central Argentina are predominantly marine and marginal-marine siliciclastics, associated with prominent but volumetrically subordinate carbonates and evaporites. Facies developments were ruled by paleogeographic persistence within the southern-infratropical latitude belt (within 40–50°S) and by siliciclastic derivation from the Patagonian hinterland to the southwest. Minor volcanic and volcaniclastic supply arrived from the west, out of a magmatic belt related to Circum-Pacific convergence. Timing of the main marine-flooding events and general correspondence with the high-rank stratal packaging recorded in western North America, suggest that global eustasy was also a factor in controlling the local stratigraphic record. Early Jurassic sedimentation occurred within a series of semi-isolated depocentres linked to fault-bounded Triassic troughs. The Sinemurian-Toarcian deposits record depocentre expansion and coalescence. These trends were coeval with progressively more widespread marine invasions from the northwest and west, leading to an elongate marine seaway which connected central Patagonia with the Pacific domain. During the Aalenian-Bajocian the region was subject to a more subdued tectonism and the foreland side of the basin became fringed by an extensive clastic embankment. Bathonian and Early Callovian were times when coarse clastics prograded into the basin, while the marine embayment shrank as a result of stepwise forced regressions. During Late Callovian to Oxfordian globally rising sea-level, the depocentre witnessed the appearance of cosmopolitan invertebrates and a stratal pattern of basin widening and depositional underbalance, that promoted cratonward onlap and inception of widespread carbonate deposition. Ooidal-coralline carbonate development was terminated after a relatively sudden (Messinian-style) event that desiccated a large tract of the Andean basin, and favored massive precipitation of anhydrite. In the course of the Kimmeridgian the evaporite basin was largely flooded by siliciclastics and turned into a broad and featureless mudflat-salina complex, linked to a widespread erg and to an ephemeral drainage system. By the Tithonian, at a period of peak oceanic stand, marine connection was reinstated and recorded as the most widespread Jurassic transgression across the Neuquén-Aconcagua embayment. Shelfal deposition consisted of molluscs and ooid-dominated carbonate terraces that grew in pulses tuned to eustatic fluctuations. Like in other prolific petroleum provinces around the world the Tithonian basinal strata involve widespread euxinic deposits featuring unusually high organic content. 相似文献
84.
Jose Pontón Fernando L. Hernando Maria Dolores Moragues Pedro L. Barea Mara Gerloni Stefania Conti Paola Fisicaro Cristina Cantelli Luciano Polonelli 《Mycopathologia》1996,133(2):89-94
The presence of heat shock mannoproteins (HSMPs) reactive with sIgA was demonstrated in several C. albicans strains. The subculture of the C. albicans isolated from mucosal surfaces on Sabouraud's dextrose agar at 25 °C switched off the HSMP expression. A re-expression of the HSMPs was obtained in the same medium by shifting the temperature of incubation to 37 °C. However, expression of HSMPs in two strains isolated from deep infections was maintained during several subcultures on Sabouraud's dextrose agar at 25 °C. A glycoprotein of 200 kDa seemed to be the main HSMP reacting with vaginal sIgA. The data presented in this study suggest that factors other than temperature can influence the expression of C. albicans HSMPs and therefore these antigens should be referred as stress mannoproteins.Abbreviations HSMPs
heat shock mannoproteins
- MAb
monoclonal antibody
- sIgA
secretory IgA 相似文献
85.
Incongruence between phylogenetic estimates based on nuclear and chloroplast DNA (cpDNA) markers was used to infer that there have been at least two instances of chloroplast transfer, presumably through wide hybridization, in subtribe Helianthinae. One instance involved Simsia dombeyana, which exhibited a cpDNA restriction site phenotype that was markedly divergent from all of the other species of the genus that were surveyed but that matched the restriction site pattern previously reported for South American species of Viguiera. In contrast, analysis of sequence data from the nuclear ribosomal DNA internal transcribed spacer (ITS) region showed Simsia to be entirely monophyletic and placed samples of S. dombeyana as the sister group to the relatively derived S. foetida, a result concordant with morphological information. A sample of a South American species of Viguiera was placed by ITS sequence data as the sister group to a member of V. subg. Amphilepis, which was consistent with cpDNA restriction site data. Samples of Tithonia formed a single monophyletic clade based on ITS sequence data, whereas they were split between two divergent clades based on cpDNA restriction site analysis. The results suggested that cpDNA transfer has occurred between taxa diverged to the level of morphologically distinct genera, and highlight the need for careful and complete assessment of molecular data as a source of phylogenetic information. 相似文献
86.
87.
88.
Antibodies directed against different visual pigment opsins, and an antibody raised against the C terminal of the -subunit of retinal G protein (transducin) labelled cerebrospinal fluid-contacting cells located within the hypothalamus (postoptic commissural nucleus and ventral hypothalamic nucleus) of ammocoete lampreys (Petromyzon marinus). These antibodies also labelled photoreceptor cells within the retina and the pineal and parapineal organs, but no other areas of the brain. Despite considerable behavioural and physiological evidence for the existence of deep brain photoreceptors, numerous studies have failed to identify photoreceptor proteins within the basal brain. The results presented in this paper support our recent results in the lizard Anolis carolinensis, suggesting that a group of cerebrospinal fluid-contacting neurons within the vertebrate brain have a photosensory capacity. We speculate that these cells mediate extraocular and extrapineal photoreception in nonmammalian vertebrates. 相似文献
89.
90.
Water potentials for developing cladodes and fruits of a succulent plant, including xylem-versus-phloem implications for water movement 总被引:4,自引:1,他引:3
Nobel Park S.; Andrade Jose Luis; Wang Ning; North Gretchen B. 《Journal of experimental botany》1994,45(12):1801-1807
Developing cladodes had lower water potentials and developingfruits had higher water potentials than the underlying cladodesof the widely cultivated prickly pear cactus, Opuntia ficus-indica.The 0.06 MPa lower value in 4-week-old daughter cladodes indicateda typical water potential gradient from the underlying clad-odealong the xylem of 0.2 MPa m1; the 0.17 MPa highervalue in 4-week-old fruits, which decreased to 0.07 MPa by 10weeks, implicated the phloem as their supplier of water. Thephloem sap of the underlying cladodes had an osmotic pressureof only 0.90 to 0.98 MPa, so the phloem could supply a relativelydilute solution to the photosynthetically dependent fruits (daughtercladodes of O. ficus-indica are photosynthetically independentat 4 weeks). Although the water potentials were similar foradjacent tissues, the osmotic pressures were lower for the water-storagecompared with the photosynthetic tissue; the osmotic pressureswere higher for xylem sap from fruits, for which xylary flowapparently occurred toward the underlying cladodes, than fordaughter cladodes. The relative capacitance (change in relativewater content divided by change in tissue water potential) wasapproximately 0.71 MPa1 for the water-storage tissueand the photosynthetic tissue of both daughter cladodes andfruits at 4 weeks of age. When these organs approached maturityat 10 weeks, the relative capacitance increased about 40% fortheir water-storage tissue, but decreased 30% for their photosynthetictissue. As the plant water content decreases during drought,about twice as much water will thus be lost per unit volumeof the water-storage tissue compared with the photosynthetictissue of maturing fruits and cladodes. Key words: Opuntia ficus-indica, phloem, relative water content, water capacitance, water potential 相似文献