omega-Transaminases as efficient biocatalysts to obtain novel chiral selenium-amine ligands for Pd-catalysis

omega-Transaminases have been evaluated as biocatalysts in the reductive amination of organoselenium acetophenones to the corresponding amines, and in the kinetic resolution of racemic organoselenium amines. Kinetic resolution proved to be more efficient than the asymmetric reductive amination. By using these methodologies we were able to obtain both amine enantiomers in high enantiomeric excess (up to 99%). Derivatives of the obtained optically pure o-selenium 1-phenylethyl amine were evaluated as ligands in the palladium-catalyzed asymmetric alkylation, giving the alkylated product in up to 99% ee.

Chemoenzymatic synthesis: a strategy to obtain xylitol monoesters

BACKGROUND: Fatty acid sugar esters are used as non-ionic surfactants in cosmetics, foodstuffs and pharmaceuticals. In particular, monoesters of xylitol have attracted industrial interest due to their outstanding biological activities. In this work, xylitol monoesters were obtained by chemoenzymatic synthesis, in which, first, xylitol was made soluble in organic solvent by chemo-protecting reaction, followed by enzymatic esterification reaction using different acyl donors. A commercial immobilized Candida antartica lipase was used as catalyst, and reactions with pure xylitol were carried out to generate data for comparison. RESULTS: t-BuOH was found to be the most suitable solvent to carry out esterification reactions with both pure and protected xylitol. The highest yields were obtained for reactions carried out with pure xylitol, but in this case by-products, such as di- and tri-esters isomers were formed, which required a multi-step purification process. For the systems with protected xylitol, conversions of 86%, 58% and 24% were achieved using oleic, lauric and butyric acids, respectively. The structures of the monoesters were confirmed by (13)C- and (1)H-NMR and microanalysis. CONCLUSION: The chemoenzymatic synthesis of xylitol monoesters avoided laborious downstream processing when compared with reactions performed with pure xylitol. Monoesters production from protected xylitol was shown to be a practical, economical, and clean route for this process, allowing a simple separation, because there are no other products formed besides xylitol monoesters and residual xylitol. (C) 2009 Society of Chemical Industry

Osteopontin expression according to molecular profile of invasive breast cancer: a clinicopathological and immunohistochemical study

Osteopontin (OPN) is a secreted, calcium-binding phosphorylated glycoprotein involved in several physiological and pathological events such as angiogenesis, apoptosis, inflammation, wound healing, vascular remodeling, calcification of mineralized tissues, and induction of cell proteases. There is growing interest in the role of OPN in breast cancer. In an attempt to obtain new insight into the pathogenesis of OPN-associated breast carcinomas, an immunohistochemical panel with 17 primary antibodies including cytokeratins and key regulators of the cell cycle was performed in 100 formalin-fixed paraffin-embedded samples of invasive breast carcinomas. OPN was expressed in 65% of tumors and was negatively correlated with estrogen (p=0.0350) and progesterone (p=0.0069) receptors, but not with the other markers and clinicopathological features evaluated including age, menstrual status, pathological grading, tumor size, and metastasis. There was no correlation between OPN expression and carcinomas of the basal-like phenotype (p=0.1615); however, OPN correlated positively with c-erbB-2 status (p=0.0286) and negatively with carcinomas of the luminal subtype (p=0.0353). It is well known that carcinomas overexpressing c-erbB-2 protein have a worse prognosis than luminal tumors. Here, we hypothesize that the differential expression of OPN in the first subtype of carcinomas may contribute to their more aggressive behavior. (Int J Biol Markers 2008; 23: 154-60)

A NEW METHOD TO OBTAIN GOOD ANATOMICAL SLIDES OF HETEROGENEOUS PLANT PARTS

A new method is presented to prepare anatomical slides of plant materials including a combination of soft and hard tissues, such as stems with cambial variants, arboreal monocotyledons, and tree bark The method integrates previous techniques aimed at softening the samples and making them thereby more homogeneous, with the use of anti-tearing polystyrene foam solution In addition, we suggest two other alternatives to protect the sections from tearing adhesive tape and/or Mayer`s albumin adhesive, both combined with the polystyrene foam solution This solution is cheap and easy to make by dissolving any packaging polystyrene m butyl acetate It is applied before each section is cut on a sliding microtome and ensures that all the tissues in the section will hold together This novel microtechnical procedure will facilitate the study of heterogeneous plant portions, as shown in some illustrated examples

Mixing alternating copolymers containing fluorenyl groups with phospholipids to obtain Langmuir and Langmuir-Blodgett films

The control of molecular architectures may be essential to optimize materials properties for producing luminescent devices from polymers, especially in the blue region of the spectrum. In this Article, we report on the fabrication of Langmuir-Blodgett (LB) films of polyfluorene copolymers mixed with the phospholipid dimyristoyl phosphatidic acid (DMPA). The copolymers poly(9.9-dioetylfluorene)-co-phenylene (copolymer I) and poly(9,9-dioctylfluorene)-co-quaterphenylene) (copolymer 2) were synthesized via Suzuki reaction. Copolymer I could not form a monolayer on its own, but it yielded stable films when mixed with DMPA. In contrast, Langmuir monolayers could be formed from either the neat copolymer 2 or when mixed with DMPA. The surface pressure and surface potential measurements, in addition to Brewster angle microscopy, indicated that DMPA provided a suitable matrix for copolymer I to form a stable Langmuir film, amenable to transfer as LB films, while enhancing the ability of copolymer 2 to form LB films with enhanced emission, as indicated by fluorescence spectroscopy. Because a high emission was obtained with the mixed LB films and since the molecular-level interactions between the film components can be tuned by changing the experimental conditions to allow For further optimization, one may envisage applications of these films in optical devices such as organic light-emitting diodes (OLEDs).

Rhinometric evaluation of nasal cavity geometry and its relation to the upper arch transverse distance

The objective of this study was to evaluate children's respiratory patterns in the mixed dentition, by means of acoustic rhinometry, and its relation to the upper arch width development. Fifty patients were examined, 25 females and 25 males with mean age of eight years and seven months. All of them were submitted to acoustic rhinometry and upper and lower arch impressions to obtain plaster models. The upper arch analysis was accomplished by measuring the interdental transverse distance of the upper teeth, deciduous canines (measurement 1), deciduous first molars (measurement 2), deciduous second molars (measurement 3) and the first molars (measurement 4). The results showed that an increased left nasal cavity area in females means an increased interdental distance of the deciduous first molars and deciduous second molars and an increased interdental distance of the deciduous canines, deciduous first and second molars in males. It was concluded that there is a correlation between the nasal cavity area and the upper arch transverse distance in the anterior and mid maxillary regions for both genders.

Forced convection to laminar flow of liquid egg yolk in circular and annular ducts

The steady-state heat transfer in laminar flow of liquid egg yolk - an important pseudoplastic fluid food - in circular and concentric annular ducts was experimentally investigated. The average convection heat transfer coefficients, determined by measuring temperatures before and after heating sections with constant temperatures at the tube wall, were used to obtain simple new empirical expressions to estimate the Nusselt numbers for fully established flows at the thermal entrance of the considered geometries. The comparisons with existing correlations for Newtonian and non-Newtonian fluids resulted in excellent agreement. The main contribution of this work is to supply practical and easily applicable correlations, which are, especially for the case of annulus, rather scarce and extensively required in the design of heat transfer operations dealing with similar shear-thinning products. In addition, the experimental results may support existing theoretical analyses.

Within- and between-person variations as determinant factors to calculate the number of observations to estimate usual dietary intake of adolescents

This cross-sectional study describes the variation in the dietary intake of energy and macronutrients based on estimated coefficients of within- and between-person variation and intends to calculate the number of days required to evaluate the dietary intake of adolescents in Piracicaba, Brazil. The sample was made up by ninety-two adolescents aged between eleven and sixteen years. Interviews were performed to assess demographic, anthropometric and dietary variables, which were evaluated by the answers obtained through two 24-hour recalls. Descriptive analyses were performed and variances and Coefficients of variation within- and between-person were obtained by results of one-way ANOVA. The mean energy intake observed was 2,326.2 kilocalories; mean macronutrient intake came to 89.0 grams of fatty acids, 305.3 grams of carbohydrates and 82.2 grams of proteins. Coefficients of within-person variation ranged from 36% to 45%, while between-person coefficients varied from 26% to 31%. Variance ratios ranged from 1.35 (carbohydrate) to 2.62 (protein). The lowest number of observations required to correctly evaluate the usual diet calculated (r = 0.90) was six days, for carbohydrates while the highest was eleven, for proteins. Coefficients of variation were similar to those observed in international studies. We conclude that, in this study, two observations were sufficient to obtain reasonable correlations. However, six evaluations are necessary for these adolescents in order to obtain excellent correlations.

Monitoring Millennium Development Goals in Brazilian municipalities: challenges to be met in facing up to iniquities

The Healthy Cities and Agenda 21 programs improve living and health conditions and affect social and economic determinants of health. The Millennium Development Goals (MDG) indicators can be used to assess the impact of social agendas. A data search was carried out for the period 1997 to 2006 to obtain 48 indicators proposed by the United Nations and a further 74 proposed by the technical group for the MDGin Brazil. There is a scarcity of studies concerned with assessing the MDG at the municipal level. Data from Brazilian health information systems are not always consistent or accurate for municipalities. The lack of availability and reliable data led to the substitution of some indicators. The information systems did not always provide annual data; national household surveys could not be disaggregated at the municipal level and there were also modifications on conceptual definitions over time. As a result, the project created an alternative list with 29 indicators. MDG monitoring at the local community can be important to measure the performance of actions toward improvements in quality of life and social iniquities.

Relationships of blood lead to calcium, iron, and vitamin C intakes in Brazilian pregnant women

Background & aims. This study aimed to determine the relationship between blood lead concentrations and calcium, iron and vitamin C dietary intakes of pregnant women. Methods. Included in the study were 55 women admitted to a hospital, for delivery, from June to August 2002. A food frequency questionnaire was applied to determine calcium, iron and vitamin C intakes, and a general questionnaire to obtain data on demographic-socioeconomic condition, obstetric history, smoking habit, and alcohol intake. Blood lead and haemoglobin were determined, respectively, by atomic absorption spectrometry and by the haemoglobinometer HemoCue®. Multiple linear regression models were used to determine the relationship between blood lead and calcium, iron and vitamin C intakes, and haemoglobin levels, controlling for confounders. Results. The final model of the regression analysis detected an inverse relationship between blood lead and age of the women (p=0.011), haemoglobin (p=0.001), vitamin C (p=0.012), and calcium intake (p<0.001) (R2=0.952). One hundred percent, 98.2% and 43.6% of the women were below the adequate intake (AI) for calcium, and below the recommended dietary allowances (RDA) for iron, and vitamin C, respectively. Conclusion. Despite the small sample size, the results of this study suggest that maternal age, haemoglobin, vitamin C intake, and calcium intake may interfere with blood concentrations of lead

Transcriptional profiling reveals the expression of novel genes in response to various stimuli in the human dermatophyte Trichophyton rubrum

Background: Cutaneous mycoses are common human infections among healthy and immunocompromised hosts, and the anthropophilic fungus Trichophyton rubrum is the most prevalent microorganism isolated from such clinical cases worldwide. The aim of this study was to determine the transcriptional profile of T. rubrum exposed to various stimuli in order to obtain insights into the responses of this pathogen to different environmental challenges. Therefore, we generated an expressed sequence tag (EST) collection by constructing one cDNA library and nine suppression subtractive hybridization libraries. Results: The 1388 unigenes identified in this study were functionally classified based on the Munich Information Center for Protein Sequences (MIPS) categories. The identified proteins were involved in transcriptional regulation, cellular defense and stress, protein degradation, signaling, transport, and secretion, among other functions. Analysis of these unigenes revealed 575 T. rubrum sequences that had not been previously deposited in public databases. Conclusion: In this study, we identified novel T. rubrum genes that will be useful for ORF prediction in genome sequencing and facilitating functional genome analysis. Annotation of these expressed genes revealed metabolic adaptations of T. rubrum to carbon sources, ambient pH shifts, and various antifungal drugs used in medical practice. Furthermore, challenging T. rubrum with cytotoxic drugs and ambient pH shifts extended our understanding of the molecular events possibly involved in the infectious process and resistance to antifungal drugs.

Low-Level Laser Therapy on the Viability of Skin Flap in Rats Subjected to Deleterious Effect of Nicotine

Objective: The purpose of this study was to evaluate the effect of 830-nm laser in blocking the action of nicotine on the viability of skin flap. Background data: The authors have analyzed the deleterious effect of cigarette smoke or nicotine on the skin flap alone with evidence of increased skin necrosis in the flap. Materials and methods: Twenty-four Wistar-albino rats were divided into three groups of eight animals each: Group 1 (control), subjected to a surgical technique to obtain a flap for cranial base, laser irradiation simulation, and a subcutaneous injection of saline; Group 2, similar to Group 1, with subcutaneous injection of nicotine (2mg/kg/day) for a period of 1 week before and 1 week after surgery; and Group 3, similar to Group 2, with skin flaps subjected to a lambda 830-nm laser irradiation. The laser parameters used were: power 30 mW, beam area 0.07cm(2), irradiance 429 mW/cm(2), irradiation time 84 sec, total energy 2.52J, and energy density 36J/cm(2). The laser was used immediately after surgery and for 4 consecutive days, in one point at 2.5 cm of the flap cranial base. The areas of necrosis were examined by two macroscopic analyses: paper template and Mini-Mop (R). The pervious blood vessels were also counted. Results: The results were statistically analyzed by ANOVA and post-test contrast orthogonal method (multiple comparisons), showing that the laser decreased the area of necrosis in flaps subjected to nicotine, and consequently, increased the number of blood vessels (p < 0.05). Conclusions: The laser proved to be an effective way to decrease the area of necrosis in rats subjected to nicotine, making them similar to the control group.

Bose-Einstein condensation in antiferromagnets close to the saturation field

At zero temperature and strong applied magnetic fields the ground state of an anisotropic antiferromagnet is a saturated paramagnet with fully aligned spins. We study the quantum phase transition as the field is reduced below an upper critical H(c2) and the system enters a XY-antiferromagnetic phase. Using a bond operator representation we consider a model spin-1 Heisenberg antiferromagnetic with single-ion anisotropy in hypercubic lattices under strong magnetic fields. We show that the transition at H(c2) can be interpreted as a Bose-Einstein condensation (BEC) of magnons. The theoretical results are used to analyze our magnetization versus field data in the organic compound NiCl(2)-4SC(NH(2))(2) (DTN) at very low temperatures. This is the ideal BEC system to study this transition since H(c2) is sufficiently low to be reached with static magnetic fields (as opposed to pulsed fields). The scaling of the magnetization as a function of field and temperature close to H(c2) shows excellent agreement with the theoretical predictions. It allows us to obtain the quantum critical exponents and confirm the BEC nature of the transition at H(c2).

A sampling device to quantify offspring release of sessile marine invertebrates

Quantifying the rate of propagule release is of most importance to estimate reproductive output of natural populations, but simple methods to obtain such data are seldom reported. We designed and tested an inexpensive apparatus capable of reliably measure the release of gametes, eggs or larvae of sessile marine invertebrates in vertical walls. A population of the acom barnacle Chthamalus bisinuatus was sampled with this trap over 68d to obtain a time series of naupliar release. An apparent semilunar trend is shown, indicating the effectiveness of this sampling method.

Optimization of Heat Treatment Profiles Applied to Nanometric-Scale Nb(3)Sn Wires With Cu-Sn Artificial Pinning Centers

Nb(3)Sn is one of the most used superconducting materials for applications in high magnetic fields. The improvement of the critical current densities (J(c)) is important, and must be analyzed together with the optimization of the flux pinning acting in the material. For Nb(3)Sn, it is known that the grain boundaries are the most effective pinning centers. However, the introduction of artificial pinning centers (APCs) with different superconducting properties has been proved to be beneficial for J(c). As these APCs are normally in the nanometric-scale, the conventional heat treatment profiles used for Nb(3)Sn wires cannot be directly applied, leading to excessive grain growth and/or increase of the APCs cross sections. In this work, the heat treatment profiles for Nb(3)Sn superconductor wires with Cu(Sn) artificial pinning centers in nanometric-scale were analyzed in an attempt to improve J(c) . It is described a methodology to optimize the heat treatment profiles in respect to diffusion, reaction and formation of the superconducting phases. Microstructural, transport and magnetic characterization were performed in an attempt to find the pinning mechanisms acting in the samples. It was concluded that the maximum current densities were found when normal phases (due to the introduction of the APCs) are acting as main pinning centers in the global behavior of the Nb(3)Sn superconducting wire.