Modeling Lanthanide Complexes: Towards the Theoretical Design of Light Conversion Molecular Devices

Theoretical techniques have been developed and/or improved to predict the molecular structure of lanthanide complexes which were used to calculate their electronic properties, in particular, their electronic spectra and energy levels necessary to calculate the rates of energy transfer from the ligands to the metal ion. The molecular structure has been obtained by the SMLC/AM1 (Sparkle Model for the Calculation of Lanthanide Complexes – Austin Model 1) model where the lanthanide ion is simulated by a sparkle implemented into the AM1 Hamiltonian used to perform a HF-SCF (Hartree-Fock Self-Consistent Field) calculation. The previous implementation of the SMLC/AM1 model (sparkle/1) involving only two parameters has been generalized to be consistent with the AM1 Hamiltonian and the new model (sparkle/2) significantly improved the prediction of molecular structures of Eu(III) complexes. For the electronic spectra and energy level calculations of the lanthanide complexes the model replaces the metal ion by a point charge with the ligands held in their positions as determined by the SMLC/AM1 model, and uses a INDO/S-CI (intermediate neglect of differential overlap/spectroscopic-configuration interaction) model. A preliminary study of the solvent effects on the absorption spectra of the free ligand is also presented. For the ligand-lanthanide ion energy transfer Fermi's golden rule is used with the multipolar and exchange mechanisms being implemented and tested for several complexes. These theoretical techniques have been applied to several complexes yielding very good results when compared to experimental data as well as predictions for the molecular and electronic structures and the relative contributions of the mechanisms for the energy transfer rates. This revised version was published online in June 2006 with corrections to the Cover Date.     

Identification of Ser-Pro and Thr-Pro Phosphorylation Sites in Chicken Neurofilament-M Tail Domain

Abstract: The tail domain of the midsize chicken neurofilament polypeptide (NF-M) contains several different types of Ser-Pro and Thr-Pro putative phosphorylation sites. We determined which of these sites are actually phosphorylated in vivo. Chick sensory neuron cultures were incubated in [³²P]phosphate, and the cytoskeletal fraction was mixed with a neurofilament fraction prepared from adult chicken brain. NF-M was purified by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and digested with chymotrypsin, and two large fragments were isolated. These were individually cleaved with trypsin, endoprotease Lys-C, or endoprotease Glu-C, and peptides separated by two-dimensional high-voltage electrophoresis and thin-layer chromatography. ³²P-labeled phosphopeptides were eluted from the cellulose plates and subjected to microsequencing and mass spectometry. We found that of 21 potential Ser-Pro and Thr-Pro phosphoacceptor sites, at least 20 are phosphorylated in vivo: all four Lys-Ser-Pro sites and at least 16 of the 17 Lys-Xaa-Xaa-Ser/Thr-Pro repeats. In addition, a novel Ser-Pro site in the extreme carboxy terminus is phosphorylated. This site, which has no proximal Lys residue, is also found in mammalian NF-M, but has not been reported to be phosphorylated. Together with three casein kinase I sites we have found recently in the acidic amino-terminal segment of the tail, a total of 24 or 25 Ser and Thr phosphoacceptor sites have now been located in the chicken NF-M tail.     

Cutaneous zygomycosis caused byAbsidia corymbifera in a leukemic patient

A case of cutaneous zygomycosis caused byAbsidia coryabifera in a leukemic patient submitted to chemotherapy is reported. The lesion was located on the little finger of the right hand and probably resulted from a latent osteomyelitis. It progressed to form extensive necrotic area. No systemic infection was detected and the lesion did not appear to be associated with any trauma.     

Neurochemical effects ofl-pyroglutamic acid

The effect ofl-pyroglutamic acid, a metabolite that accumulates in pyroglutamic aciduria, on different neurochemical parameters was investigated in adult male Wistar rats. Glutamate binding, adenylate cyclase activity and G protein coupling to adenylate cyclase were assayed in the presence of the acid.l-pyroglutamic acid decreased Na⁺-dependent and Na⁺-independent glutamate binding Basal and GMP-PNP stimulated adenylate cyclase activity were not affected by the acid. Furthermore, rats received unilateral intrastriatal injections of 10–300 nmol of bufferedl-pyroglutamic acid. Vehicle (0.25 M Tris-Cl, pH 7.35–7.4) was injected into the contralateral striatum. Neurotoxic damage was assessed seven days after the injection by histological examination and by weighing both cerebral hemispheres. No difference in histology or weight could be identified between hemispheres. These results suggest that, although capable of interfering with glutamate binding, pyroglutamate did not cause a major lesion in the present model of neurotoxicity.     

Partial characterization of the cohemolytic factor produced by Streptococcus uberis and comparison with the CAMP-factor

Abstract Exosubstances (cohemolysins) produced by Streptococcus agalactiae (CAMP-factor) and Streptococcus uberis (Uberis-factor) showing hemolytic synergism with β-lysin produced by Staphylococcus aureus were compared. Cohemolytic activity was evaluated in the supernatants of bacterial cultures, before and after ammonium sulfate precipitation. Sheep erythrocytes sensitized with β-lysin were used as substrate. The assays were performed in microtiter plates and results were expressed as cohemolytic units/ml. Maximum cohemolytic activity was detected, respectively, after 8 h and 14 h of growth in Columbia broth in S. uberis and S. agalactiae cultures. Cohemolytic activities of both microorganisms showed similarities when submitted to various physical and chemical treatments. They were significantly decreased by heating at 60°C and 100°C, or in presence of trypsin, and were abolished in the presence of Tween 20. Activities were found to be stable in crude supernatants and concentrated preparations maintained at −20°C for 3 months. Differences were related to levels of activity and kinetics of detection during the growth cycle. The results indicate the proteic nature, at least in part, of the Uberis factor. Analysis by PAGE in the presence or absence of SDS allowed us to correlate Uberis activity with a protein band with apparent molecular mass of 42 kDa, while CAMP activity was associated with a protein band of 27 kDa.     

Parental care in the rocky intertidal: a case study of adaptation and exaptation in Mediterranean and Atlantic blennies

Summary The main features of the behavioural ecology of rocky intertidal species are compared both within families — though concentrated on blennies — and between habitats. It is suggested that, at the behavioural level, the reduction of vertical and swimming elements in the male sexual and agonistic displays of Blennioidei may constitute an adaptation to typical intertidal conditions, especially in those species that inhabit areas exposed to strong wave action. The other aspect which is discussed is the prevalence of parental care in rocky intertidal fishes. In these fishes parental care is much more frequent than for marine fishes as a whole. Taken alone, this could also suggest that guarding evolved as an adaptation during the process of colonization of these habitats. The hypothesis proposed in this paper is that guarding was already present in the ancestors of the resident species, at least in the majority of cases. Many differences in interhabitat studies may express the action of the environment, not as an agent of natural selection, but as a filter, which prevented some groups from invading a given habitat and, at the same time, made colonization easier for other groups. When a number of taxa that colonized a given habitat display clear similarities in their behaviour and their biology, adaptation is not necessarily demonstrated. There is evidence in the literature to support the hypothesis that those traits were already present in the ancestors of the rocky intertidal resident fishes, thus being best viewed as exaptations.     

Coprecipitating IgG asymmetric antibodies: A possible role for Fab glycosylation,and speculations on their formation and functions in disease

IgG asymmetric antibodies are synthesized by the same cellular clones as the symmetric ones but appear in the immune response in different proportions. The evidence suggests that they are caused by asymmetric glycosylation on some IgG molecules in the Fab region. The cause of this is unknown but it could be speculated that there are cellular factors that induce glycosyl transferases or cause the molecule to be more accessible to glycosylation. The production of asymmetric antibodies can be modified by the physical status (soluble or particulate) of the antigen used as immunogen by the number and frequency of stimulation, and by physiological factors such as the ones secreted by the placenta and by lymphocytes that express progesterone receptors in response to hormone. An increase of these antibodies can be beneficial or harmful to the host, depending on the situation in which they act and the character of self or non-self of the antigens recognized. Editors note—Many of the ideas proposed in this article are very speculative, but it was thought appropriate to publish it in order to stimulate further discussion of the subject. It is an interesting role for Fab glycosylation that is proposed by Professor Margni. The ideas discussed are not necessarily those held by the Editorial Board or the reviewers, who felt that the evidence for many of the deductions made was very limited. It was also emphasized by the reviewers that the author's case would be substantially improved if more corroborative evidence was available from other groups. The Editors would welcome any comments on the subject for publication in future issues of the journal.     

Ecological degradation and agricultural intensification in the Andean highlands

Andean cultural ecologists have made two claims in recent years: ecological decomposition is absent due to effective indigenous management of communal resources, and agricultural intensification is inversely related to altitude. Drawing on material from the Jukumani Indians of Northern Potosi, Bolivia, these assertions are challenged. First, there is little evidence to prove or disprove ecological degradation. Second, the location of agricultural intensification, as the Jukumani data suggests, is influenced by altitude as well as by the presence of market.Fieldwork in Bolivia was carried out between January 1979 and May 1981. This essay was originally presented at a conference entitled, How Communities Resolve Common Property Problems, sponsored by the Harvard Institute for International Development and the Center for Population Studies of Harvard University in the spring semester of 1983.     

A model of the spatial-temporal characteristics of the alpha rhythm

A linear spatially distributed model of a chain of neurons and interneurons was investigated in relation to the generation of propagated alpha rhythmic activity. It was assumed that the elements of the chain were interconnected by means of recurrent collaterals and inhibitory fibres in such a way that the connectivity functions were assumed to be homogeneous and their strength was an exponentially decreasing function of distance. It was found that such a neuronal chain shows propagation properties for frequencies in the alpha band. The results obtained with the model are in agreement with the phase velocities encountered experimentally. In this way, it was possible to estimate the length of the neural fibres responsible for the phenomenon of propagated activity. The estimates obtained are in good agreement with recent quantitative neuroanatomical data on the circuitry of the neocortex.