Supramolecular assembly of an amphiphilic Gd(III) chelate: tuning the reorientational correlation time and the water exchange rate.

We report the synthesis and characterization of the novel ligand H(5)EPTPA-C(16) ((hydroxymethylhexadecanoyl ester)ethylenepropylenetriaminepentaacetic acid). This ligand was designed to chelate the Gd(III) ion in a kinetically and thermodynamically stable way while ensuring an increased water exchange rate (kappa(ex)) on the Gd(III) complex owing to steric compression around the water-binding site. The attachment of a palmitic ester unit to the pendant hydroxymethyl group on the ethylenediamine bridge yields an amphiphilic conjugate that forms micelles with a long tumbling time (tau(R)) in aqueous solution.

Duplication of the hypophysis associated with precocious puberty: presentation of two cases and review of pituitary embryogenesis.

Pituitary duplication is a rare malformation commonly associated with other major neural/craniofacial anomalies, easily shown by magnetic resonance imaging. The authors describe two girls with duplication of the pituitary gland and thickening of the hypothalamus, facial dysmorphism and precocious pubertal development. The pathogenesis of pituitary duplication and its relationship with precocious pubertal development are discussed.

Multivariate analysis of nystatin and metronidazole in a semi-solid matrix by means of diffuse reflectance NIR spectroscopy and PLS regression.

A multivariate method of analysis of nystatin and metronidazole in a semi-solid matrix, based on diffuse reflectance NIR measurements and partial least squares regression, is reported. The product, a vaginal cream used in the antifungal and antibacterial treatment, is usually, quantitatively analyzed through microbiological tests (nystatin) and HPLC technique (metronidazole), according to pharmacopeial procedures. However, near infrared spectroscopy has demonstrated to be a valuable tool for content determination, given the rapidity and scope of the method.

Analysis of the genetic polymorphism of Paracoccidioides brasiliensis and Paracoccidioides cerebriformis "Moore" by random amplified polymorphic DNA (RAPD) and 28S ribosomal DNA sequencing--Paracoccidioides cerebriformis revisited.

Our purpose was to compare the genetic polymorphism of six samples of P. brasiliensis (113, 339, BAT, T1F1, T3B6, T5LN1), with four samples of P. cerebriformis (735, 741, 750, 361) from the Mycological Laboratory of the Instituto de Medicina Tropical de São Paulo, using Random Amplified Polymorphic DNA Analysis (RAPD).

Food poisoning by clenbuterol in Portugal.

This paper describes the occurrence of four cases of acute food poisoning, involving a total of 50 people, due to the ingestion of lamb and bovine meat containing residues of clenbuterol. Symptoms shown by the intoxicated people may be generally described as gross tremors of the extremities, tachycardia, nausea, headaches and dizziness. Analytical methodology developed for the determination of clenbuterol in meat, liver and blood samples is described.

Atypical serological response marked by a lack of detectable anti-gp43 antibodies in a patient with disseminated paracoccidioidomycosis.

Serological tests are frequently used to diagnosis paracoccidioidomycosis. A glycoprotein of 43 kDa is considered to be the main diagnostic antigen, being recognized by virtually all patients' sera. A case of atypical serological response, consisting of a lack of detectable anti-gp43 antibodies, in a patient with disseminated paracoccidioidomycosis is presented.

Prediction of drug dissolution profiles from tablets using NIR diffuse reflectance spectroscopy: a rapid and nondestructive method.

A comparison between dissolution profiles obtained by using a dissolution apparatus (conventional method) and the NIR diffuse reflectance spectra of a series of clonazepam-containing batches is reported. Ten different formulations with fixed amount of clonazepam and varying proportions of excipients were analyzed at seven dissolution times and three different media. The percentages of dissolution of each sample were correlated with the NIR spectra of three tablets of each batch, through a multivariate analysis using the PLS regression algorithm.

Polystyrene-supported organotin dichloride as a recyclable catalyst in lactone ring-opening polymerization: assessment and catalysis monitoring by high-resolution magic-angle-spinning NMR spectroscopy.

Dialkyltin dichloride grafted to a cross-linked polystyrene, with the formula [P-H]((1-t))[P-(CH2)nSnBuCl2]t (P=[CH2CH(pC6H4)], t=the degree of functionalization, and n=6 or 11), is investigated as a recyclable catalyst in the ring-opening polymerization (ROP) of epsilon-caprolactone (CL). It is demonstrated that high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy is an invaluable tool to characterize completely the supported catalyst. The 2D 1H-13C HSQC HR-MAS spectrum, in particular, allowed extensive assignment of the 1H and 13C resonances, as well as accurate measurement of the (n)J((1)H-(117/119)Sn) and (n)J((13)C-(117/119)Sn) coupling constants.

[Esophageal pH monitoring study of eight hours in pediatric patients with suspected gastroesophageal reflux].

Purpose: To study the pH monitoring over eight hours, analyzing variables such symptomatology and esophagogastroduodenoscopy, as well as the following pH monitoring parameters: number of reflux episodes, number of episodes longer than five minutes, length of reflux time during the eight hours, and the episode of longest duration, for the diagnosis of gastroesophageal reflux.

Methods: A prospective study. Continuous measurement of esophageal pH was performed over eight hours on 35 patients whose ages ranged from four months to 11 years.

Cholesterol-lowering effects of dietary blue lupin (Lupinus angustifolius L.) in intact and ileorectal anastomosed pigs.

The present study was undertaken to investigate the effect of cholesterol-enriched casein (CAS) and blue lupin seed (BL) diets on the cholesterol metabolism of intact (INT) and ileorectal anastomosed (IRA) pigs. For 3 weeks, four groups of six pigs were allocated to the treatments (CAS-INT, CAS-IRA, BL-INT, and BL-IRA). Diet-induced hypercholesterolemia was inhibited by the BL through a substantial decrease in plasma LDL-cholesterol.

Unusual case of epigastric heteropagus twinning.

Asymmetrical conjoined twins or heteropagus twins are extremely rare. They are characterized by an incomplete component (parasite) that is normally smaller and dependent on the host (autosite). In cases of an epigastric heteropagus twin, the insertion occurs in the epigastrium.

In situ evaluation of interfacial affinity in CeO2 based hybrid nanoparticles by pulsed field gradient NMR.

Complexation affinity of laurate ligands (C(12)H(23)O(2)) grafted onto the surface of cerium(IV) oxide nanoparticles can be probed and quantified in situ, by pulsed field gradient (1)H NMR through the dependence of the diffusion coefficient on the size of a species.

Dietary raw peas (Pisum sativum L.) reduce plasma total and LDL cholesterol and hepatic esterified cholesterol in intact and ileorectal anastomosed pigs fed cholesterol-rich diets.

Previous studies demonstrated the cholesterol-lowering effect of dietary legumes (mainly soybeans) in animals and humans, but the mechanisms by which they exert this effect are not completely understood. The contribution of the hindgut to this hypocholesterolemic effect is also not well documented. The present work was undertaken to investigate the effect of cholesterol-enriched (2.

Sacral ratio and fecal continence in children with anorectal malformations.

Objective: To evaluate the sacral ratio (SR) in patients with an anorectal malformation (ARM) and verify whether it has predictive value for fecal continence.

Patient And Methods: From January 1990 to April 2002, 42 patients (aged 3-14 years) with an ARM and having already been operated on were reassessed and enrolled in the study. Patients with solid or paste-like stools but no soiling were deemed continent, those with similar stool and episodes of soiling partially continent, and those with no sphincter control, incontinent.

Lanthanide(III) complexes of DOTA-glycoconjugates: a potential new class of lectin-mediated medical imaging agents.

The synthesis and characterization of a new class of DOTA (1,4,7,10-tetrakis(carboxymethyl)-1,4,7,10-tetraazacyclododecane) monoamide-linked glycoconjugates (glucose, lactose and galactose) of different valencies (mono, di and tetra) and their Sm(III), Eu(III) and Gd(III) complexes are reported. The 1H NMR spectrum of Eu(III)-DOTALac2 shows the predominance of a single structural isomer of square antiprismatic geometry of the DOTA chelating moiety and fast rotation about the amide bond connected to the targeting glycodendrimer. The in vitro relaxivity of the Gd(III)-glycoconjugates was studied by 1H nuclear magnetic relaxation dispersion (NMRD), yielding parameters close to those reported for other DOTA monoamides.

Assessing weak intramolecular donor-acceptor interactions using 1H-117Sn J-HMQC spectroscopy.

It is demonstrated that long-range nJ(1H,117Sn) coupling constants down to 0.3 Hz, can be accurately quantified from non-linear fitting of the sine modulation of the associated 1H-117Sn correlation cross-peak intensities sampled as a function of the heteronuclear antiphase coherence preparation time in the 1H-117Sn J-HMQC pulse sequence. The contribution of additional, undesired modulations is illustrated and assessed using the product operator formalism, and is traced back to contributions that arise from miss-setting of the wandering 180 degrees pulse angle in the constant time period.

Aortico-left ventricular tunnel: 35-year experience.

Objectives: The purpose of this study was to review our 35 years of experience with aortico-left ventricular tunnel (ALVT), with emphasis on diagnosis, surgical details, and follow-up.

Background: Aortico-left ventricular tunnel is a rare congenital anomaly. Neonatal surgery has been advocated in all due to long-term concern of valvar aortic regurgitation (AR).

The structure of a triple mutant of pI258 arsenate reductase from Staphylococcus aureus and its 5-thio-2-nitrobenzoic acid adduct.

Structural insights into formation of the complex between the ubiquitous thiol-disulfide oxidoreductase thioredoxin and its oxidized substrate are under-documented owing to its entropical instability. In vitro, it is possible via a reaction with 5,5'-dithiobis-(2-nitrobenzoic acid) to make a stable mixed-disulfide complex between thioredoxin from Staphylococcus aureus and one of its substrates, oxidized pI258 arsenate reductase (ArsC) from S. aureus.

How thioredoxin can reduce a buried disulphide bond.

We present a study of the interaction between thioredoxin and the model enzyme pI258 arsenate reductase (ArsC) from Staphylococcus aureus. ArsC catalyses the reduction of arsenate to arsenite. Three redox active cysteine residues (Cys10, Cys82 and Cys89) are involved.

Effects of ileo-rectal anastomosis on cholesterol metabolism in pigs fed either casein or extruded soya beans.

The importance of legume proteins in cholesterol metabolism has been recognised, but the hindgut contribution is still unclear. The present work was undertaken to address the role of the caecum-colon in cholesterol metabolism in intact (I) and ileo-rectal anastomosed (IRA) pigs fed with casein or extruded soyabean (ES) diets. Four groups of six growing pigs were assigned to the treatments (casein-I, casein-IRA, ES-I, ES-IRA) for 3 weeks.

Solution structures of the C-terminal headpiece subdomains of human villin and advillin, evaluation of headpiece F-actin-binding requirements.

Headpiece (HP) is a 76-residue F-actin-binding module at the C terminus of many cytoskeletal proteins. Its 35-residue C-terminal subdomain is one of the smallest known motifs capable of autonomously adopting a stable, folded structure in the absence of any disulfide bridges, metal ligands, or unnatural amino acids. We report the three-dimensional solution structures of the C-terminal headpiece subdomains of human villin (HVcHP) and human advillin (HAcHP), determined by two-dimensional 1H-NMR.

Probing ionic association on metal oxide clusters by pulsed field gradient NMR spectroscopy: the example of Sn12-oxo clusters.

Pulsed field gradient (1)H NMR spectroscopy has been applied to investigate the association behavior of the Sn(12)-oxo cluster macrocation [(BuSn)(12)O(14)(OH)(6)](2+) with two different and smaller anions, p-toluenesulfonate (PTS(-)) and diphenylphosphinate (Ph(2)PO(2) (-)). By monitoring the translational diffusion coefficients of the various species involved, it is shown that the association depends on the anion involved and on the solvent used. Moreover, the possibility to individually monitor the diffusion characteristics of multiple anionic and cationic species in mixtures, by virtue of resolved (1)H resonances available from each species, allows us to evidence the occurrence of ion exchange in such systems.

Measurement of the effect of Amazon smoke on inhibition of cloud formation.

Urban air pollution and smoke from fires have been modeled to reduce cloud formation by absorbing sunlight, thereby cooling the surface and heating the atmosphere. Satellite data over the Amazon region during the biomass burning season showed that scattered cumulus cloud cover was reduced from 38%in clean conditions to 0%for heavy smoke (optical depth of 1.3).

Dermatophyte agents in the city of São Paulo, from 1992 to 2002.

Dermatophytosis are superficial mycoses caused by fungi that can invade stratum corneum and keratinized tissues. In order to study the frequency of dermatophytes species and the clinical manifestations caused by these fungi, in São Paulo, SP, Brazil, the authors analyzed cultures isolated at the Mycology Laboratory from a selected population (15,300 out-patients of the Hospital das Clínicas, Department of Dermatology, Faculty of Medicine of University of São Paulo) from January 1992 to June 2002. The most prevalent dermatophyte was Trichophyton rubrum (48.