Combined Crystallographic and Solution Molecular Dynamics Study of Allosteric Effects in Ester and Ketone p-tert-Butylcalix[4]arene Derivatives and Their Complexes with Acetonitrile, Cd(II), and Pb(II)

We describe here a procedure to bridge the gap in the field of calixarene physicochemistry between solid-state atomic-resolution structural information and the liquid-state low-resolution thermodynamics and spectroscopic data. We use MD simulations to study the kinetics and energetics involved in the complexation of lower rim calix[4]arene derivatives (L), containing bidentate ester (1) and ketone (2) pendant groups, with acetonitrile molecule (MeCN) and Cd2+ and Pb2+ ions (M2+) in acetonitrile solution. On one hand, we found that the prior inclusion of MeCN into the calix to form a L(MeCN) adduct has only a weak effect in preorganizing the hydrophilic cavity toward metal ion binding. On the other hand, the strong ion-hydrophilic cavity interaction produces a wide open calix which enhances the binding of one MeCN molecule (allosteric effect) to stabilize the whole (M2+)1(MeCN) bifunctional complex. We reach two major conclusions: (i) the MD results for the (M2+)1(MeCN) binding are in close agreement with the ""endo"", fully encapsulated, metal complex found by X-ray diffraction and in vacuo MD calculations, and (ii) the MD structure for the more flexible 2 ligand, however, differs from the also endo solid-state molecule. In fact, it shows strong solvation effects at the calixarene lower bore by competing MeCN molecules that share the metal coordination sphere with the four C=O oxygens of an ""exo"" (M2+)2(MeCN) complex.

INSECT CHYMOTRYPSINS: CHLOROMETHYL KETONE INACTIVATION AND SUBSTRATE SPECIFICITY RELATIVE TO POSSIBLE COEVOLUTIONAL ADAPTATION OF INSECTS AND PLANTS

Insect digestive chymotrypsins are present in a large variety of insect orders but their substrate specificity still remains unclear. Ewer insect chymotrypsins from 3 different insect orders (Dictyoptera, Coleoptera and two Lepidoptera) were isolated using affinity chromatography. Enzymes presented molecular masses in the range of 20 to 31 kDa and pH optima in the range of 7.5 to 10.0. Kinetic characterization. using different, colorimetric and fluorescent substrates indicated that insect chymotrypsins differ from, bovine chymotrypsin in their primary specificity toward small substrates (like N-benzoyl-L-Tyr p-nitroanilide) rather than on their preference for large substrates (exemplified by Succynil-Ala-Ala-Pro-Phe P-nitroanilide). Chloromethyl ketones (TPCK, N-alpha-tosyl-L-Phe chloromethyl ketone and Z-GGF-CK, N-carbobenzoxy-Gly-Gly-phe-CK) inactivated all chymotrypsins legated. Inactivation rates follow apparent first-order kinetics with variable second order rates (TPCK, 42 to 130 M(-1)s(-1); Z-GGF-CK, 150 to 450 M(-1)s(-1) that may be remarkably low for S. frugiperda chymotrypsin (TPCK, 6 M(-1)s(-1); Z-GGF-CK, 6.1 M(-1) s(-1)). Homology modelling and sequence alignment showed that. in lepidopteran chymotrypsins, differences in the amino acid residues in the neighborhood of the catalytic His 57 may affect its pKa, value. This is Proposed as the cause of the decrease in His 57 reactivity toward chloromethyl ketones. Such amino acid replacement in the active site is proposed. to be an adaptation to the presence of dietary ketones. (C) 2009 Wiley Periodicals, Inc.

Adsorption of di-2-pyridyl ketone salicyloylhydrazone on Amberlite XAD-2 and XAD-7 resins: Characteristics and isotherms

The adsorption of DPKSH onto Amberlite XAD-2 (styrene resin) and XAD-7 (acrylic ester resin) has been investigated, at (25 +/- 1)degrees C and pH 4.7. The experimental equilibrium data were fitted to the Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) models. These three models provide a very good fit for both resins and the respective constants K(L), K(F), and K(DR) were calculated. For the same DPKSH concentration interval, the minimum time of contact for adsorption maximum at XAD-7 was smaller than at XAD-2 and the maximum amount of DPKSH adsorbed per gram of XAD-2 is smaller than at XAD-7. The investigation indicates that the mean sorption energy (E) characterizes a physical adsorption and the surfaces of both resins are energetically heterogeneous. The constants obtained in these studied systems were correlated and compared with those obtained for the silica gel/DPKSH system. (C) 2008 Published by Elsevier Inc.

Spectrophotometric determination of zinc in pharmaceutical and biological samples with di-2-pyridyl ketone benzoylhydrazone: A simple, fast, accurate and sensitive method

A simple, fast, accurate, and sensitive spectrophotometric method was developed to determine zinc(II). This method is based on the reaction of Zn(II) with di-2-pyridyl ketone benzoylhydrazone (DPKBH), at pH=5.5 and 50% (v/v) ethanol. Beers law was obeyed in the range 0.020-1.82 mu g mL(-1) with a molar apsorptivity of 3.64 x 10(4) L mol(-1) cm(-1), and a detection limit (3) of 2.29 mu g L-1. The action of some interfering ions was verified and the developed method applied to pharmaceutical and biological samples. The results were then compared with those obtained by using a flame atomic absorption technique.

Identification of non-zein proteins in BR473 maize protein bodies by LC-nanoESI-MS/MS

The nutritional value of maize seed is limited due to its high content of storage proteins (zeins), which are deficient in essential amino acids such as lysine and tryptophan. In a previous paper, we showed that protein bodies obtained from BR473 maize variety, developed by Embrapa (Brazilian Agricultural Research Corporation), were mainly constituted by Z27 and a smaller quantity of Z50 gamma-zeins. Besides zein proteins, other not identified protein band in the SDS/PAGE was also observed, which could indicate the presence of non-zein proteins additionally to gamma-zeins. In the present paper, we have demonstrated the presence of non-zein proteins in BR473 maize protein bodies by LC-nanoESI-MS/MS and database searching. This fact could be related to the excellent energetic value and higher protein quality of BR473 maize grains, since high lysine concentration in some maize varieties has been related to the presence of cytoskeleton proteins that are non-zeins. We have identified the following proteins: Brittle-1 protein (chloroplast precursor), Legumin-1, glyceroldehyde-3-phosphate dehydrogenase, and elongation factor 1-alpha.

Materialising bodies : there is nothing more material than a socially constructed body.

Over the last one of two decades, researchers within the physical education (PE) and sport pedagogy research frequently use the concept ‘the material body’. An initial purpose of this article is to explore what a concept of a ‘material body’ might mean. What other bodies are there? Who would dispute the materiality of bodies? I suggest that the use of a concept as ‘the material body’ suggests a hesitation before the radicalism of the linguistic turn in the sense that the concept ‘discourse’ does not include a material dimension. In this way ‘the material body’ relates to an interpretation of ‘the socially (or discursively) constructed body’ as void of matter. A further purpose with the article is to re-inscribe matter in the concept of ‘discourse’. This is done by way of discussing what theorists like Michel Foucault and, in particular, Judith Butler, has to say about the materiality of the body. In their writings, discourse should not be limited to spoken and/or written language. Rather, discourse is understood in terms of actions and events that create meanings—that matters. One conclusion of the article is that it is important to problematise the mundane view of discourse as ‘verbal interchange’ because it reinforces the promise of an objective knowledge that will eventually shed light on the ‘real’ body and the mysteries of sexual difference, what its origins are, what causes it. Another conclusion is that the PE and sport pedagogy research should pay less attention to the body as an object (what it ‘is’), and pay more attention to how the body matters, and e.g. how movements make bodies matter.

Fire Incidences, Water Bodies, and Population in Maine

http://digitalcommons.colby.edu/atlasofmaine2009/1021/thumbnail.jpg

Lipid and energy contents in the bodies of queens of Atta sexdens rubropilosa Forel (Hymenoptera, Formicidae): pre-and post-nuptial flight

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

New morphological data on fat bodies of semi-engorged females of Amblyomma cajennense (Acari : Ixodidae)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Temporal and morphological differences in post-embryonic differentiation of the mushroom bodies in the brain of workers, queens, and drones of Apis mellifera (Hymenoptera, Apidae)

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

The dynamics of RNA participation in the vitellogenesis of Rhipicephalus sanguineus ticks Latreille 1806 (Acari:Ixodidae). I. Nucleoli or Cajal bodies?

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The dynamics of RNA participation in the vitellogenesis of Rhipicephalus sanguineus ticks Latreille 1806 (Acari: Ixodidae). I. Nucleoli or Cajal bodies?

To understand the morphological and histological aspects of internal systems of ticks has become important matter since these arthropods have an impact in the areas of the economy and public health. In this context, this study has provided morphological data on female germinative cells of Rhipicephalus sanguineus ticks, ectoparasites of dogs that maintain a close relationship with human on a daily basis. Oocytes of engorged females were analyzed, through the PAS reaction (detection of polysaccharides) counterstained by methyl green (detection of RNA) revealing information that allowed to infer for the first time the presence of Cajal bodies, in the germinal vesicles (nuclei) of developing oocytes, as well as showing how the RNA and the polysaccharides are involved in the dynamics of the vitellogenesis in this species. [copyright] 2010 Elsevier Ltd. All rights reserved.

Differences in mushroom bodies morphogenesis in workers, queens and drones of Apis mellifera: Neuroblasts proliferation and death

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