Small angle X-ray scattering and IR spectroscopy study of metal carbonyl complexes immobilized on a silica gel surface chemically modified with piperazine

The carbonyl complexes [WCl(CO)(3)(bipy) (HgCl)] (1), [Fe(CO)(4)(HgCl)(2)] (2) and W(CO)(6)] (3) were immobilized on a silica gel surface organofunctionalized with piperazine groups. The products obtained were studied by IR spectroscopy and small angle X-ray scattering (SAXS) techniques. The IR data show that the immobilization of heterobimetallic compounds 1 and 2, on the functionalized surface, occurred through the mercury atom, while for 3 the displacement of one CO group by the nitrogen of a piperazine molecule was observed. The data obtained from SAXS indicate that particles have a uniform size and reveal suitable modifications on the functionalized surface after immobilization of metal carbonyl complexes. The average intermolecular distance (l(ij)) for piperazine ligands on support is 8.7 Angstrom, for the metal carbonyl complex 1 it is 18.8 Angstrom, for complex 2 it is 16.2 Angstrom and for complex 3 it is 15.3 Angstrom. Copyright (C) 1996 Elsevier B.V. Ltd

Polymerization of ethylene by the tris(pyrazolyl)borate titanium(IV) compound immobilized on MAO-modified silicas

The immobilization of soluble catalyst {Tp(Ms)}TiCl3 (Tp(Ms*)HB(3-mesityl-pyrazolyl)(2)(5-mesityl-pyrazolyl)(-)) on silica and MAO-modified silicas containing 4.0, 8.0 and 23.0 wt.% Al/SiO2 yields active supported catalysts for ethylene polymerization. Among the supported catalysts studied by XRF spectroscopy, higher titanium content was obtained using MAO-modified silica containing 8.0 wt.% Al/SiO2 as support. For the ethylene polymerization reactions carried out in hexane at 60degreesC using a combination of triisobutylaluminum (TiBA) and methylaluminoxane (MAO) (1:1), the activities varied between 24.4 and 113.5 kg of PE/mol [Ti] h. The highest activity is reached using MAO-modified silica containing 4.0 wt.% Al/SiO2 as support. The viscosity-average molecular weights ((M) over bar (v)) of the PE's produced with the supported catalysts varying from 1.44 to 9.94 x 10(5) g/mol with melting temperatures in the range of 125-140degreesC. The use of other Lewis acid cocatalysts, including TiBA, diethylaluminium chloride (DEAC), and trimethylaluminum (TMA) resulted also in the formation of active catalysts for ethylene polymerization. However, the activities are lower than that one using a combination of TiBA and MAO. The viscosity-average molecular weights (R,) of PE's are influenced by varying the cocatalysts as well as the Al/Ti molar ratio. The supported catalyst generated in situ under ethylene atmosphere is roughly four times more active than supported one containing 4.0 wt.% Al/SiO2. (C) 2003 Elsevier B.V. All rights reserved.

Differential vascular adaptive response in spontaneously hypertensive and Wistar rats: Role of nitric oxide, and prehypertensive and hypertensive states

Stress-induced vascular adaptive response in SHR was investigated, focusing on the endothelium. Noradrenaline responses were studied in intact and denuded aortas from 6-week-old (prehypertensive) and 14-week-old (hypertensive) SHR and age-matched Wistar rats submitted or not to acute stress (20-min swimming and I-h immobilization 25 min apart), preceded or not by chronic stress (2 sessions 2 days apart of 1-h day immobilization for 5-consecutive days). Stress did not alter the reactivity of denuded aorta. Moreover, no alteration in the EC50 values was observed after stress exposure. In intact aortas, acute stress-induced hyporeactivity to noradrenaline similar between strains at both age. Chronic stress potentiated this adaptive response in 6- and 14-week-old Wistar but not in 6-week-old SHR, and did not alter the reactivity of 14-week-old SHR. Maximum response (g) in intact aortas [6-week-old: Wistar 3.25 +/- 0.12, Wistar/acute 1.95 +/- 0.12*, Wistar/chronic 1.36 +/- 0.21*(+), SHR 1.75 +/- 0.11, SHR/acute 0.88 +/- 0.08*, SHR/chronic 0.85 +/- 0.05*; 14-week-old: Wistar 3.83 +/- 0.13, Wistar/acute 2.72 +/- 0.13*, Wistar/chronic 1.91 +/- 0.19*', SHR 4.03 +/- 0.17, SHR/acute 2.26 +/- 0.12*, SHR/chronic 4.10 +/- 0.23; inside the same strain: *P < 0.05 relate to non-stressed rat, (+)P < 0.05 related to acute stressed rat; n = 6-18]. Independent of age and strain, L-NAME and endothelium removal abolished the stress-induced aorta hyporeactivity. Conclusion: the vascular adaptive response to stress is impaired in SHR, independently of the hypertensive state. Moreover, this vascular adaptive response is characterized by endothelial nitric oxide-system hyperactivity in both strains. (c) 2006 Elsevier B.V. All rights reserved.

Acid Black 48 dye biosorption using Saccharomyces cerevisiae immobilized with treated sugarcane bagasse

The textile industry consumes large quantities of water and chemicals, especially in dyeing and finishing processes. Textile dye adsorption can be accomplished with natural or synthetic compounds. Cell immobilization using biomaterials allows the reduction of toxicity and mechanical resistance and opens spaces within the matrix for cell growth. The use of natural materials, such as sugarcane bagasse, is promising due to the low costs involved. The aim of the present study was to evaluate the use of sugarcane bagasse treated with either polyethyleneimine (PEI), NaOH or distilled water in the cell immobilization of Saccharomyces cerevisiae for textile dye removal. Three different adsorption tests were conducted: treated sugarcane bagasse alone, free yeast cells and bagasse-immobilized yeast cells. Yeast immobilization was 31.34% with PEI-treated bagasse, 8.56% with distilled water and 22.54% with NaOH. PEI-treated bagasse exhibited the best removal rates of the dye at all pH values studied (2.50, 4.50 and 6.50). The best Acid Black 48 adsorption rates were obtained with use of free yeast cells. At pH 2.50, 1 mg of free yeast cells was able to remove 5488.49 g of the dye. The lowest adsorption capacity rates were obtained using treated bagasse alone. However, the use of bagasse-immobilized cells increased adsorption efficiency from 20 to 40%. The use of immobilized cells in textile dye removal is very attractive due to adsorbed dye precipitation, which eliminates the industrial need for centrifugation processes. Dye adsorption using only yeast cells or sugarcane bagasse requires separation methods.

Electrocatalytic study of an electrode modified with Reactive Blue 4 dye covalently immobilized on amine-functionalized silica

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Jacalin interaction with human immunoglobulin A1 and bovine immunoglobulin G1: Affinity constant determined by piezoelectric biosensoring

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

Magneto Immunoassays for Plasmodium falciparum Histidine-Rich Protein 2 Related to Malaria based on Magnetic Nanoparticles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Stimulation of polygalacturonase production in an immobilized system by Aspergillus sp.: effect of pectin and glucose

The synthesis of polygalacturonases (PG) is known to be influenced by Aspergillus growth conditions, namely, environmental factors and pectin content in the cultivation medium containing a mixed carbon source. Optimal conditions were attained at a temperature of 30 A degrees C and an initial pH of 4.5. PG activity (3.29 and 2.48 U/mL) was determined after a two-day culture of Aspergillus sp. HC1 and Aspergillus sp. CC1, respectively, in a basic medium containing 2% citrus pectin as the sole carbon source. The addition of glucose (2% w/v) to the basic medium led to a 2-fold increase in PG production. However, enzyme synthesis was repressed when a higher concentration of glucose was used in the medium containing the mixed carbon source. Spores from the two fungi were immobilized in a 3% Ca-alginate system and the mechanical strength of the gel beads allowed the use of this process system 6-fold longer (288 h) than the free culture. In the Aspergillus sp. CC1 immobilized system, PG production increased nearly 10-fold in the medium with 2% glucose added (5.95 U/mL) in comparison to the medium without sugar (0.55 U/mL). The results demonstrate that a different response in activity was produced by free and entrapped spore systems. PG production remained approximately constant throughout the six 48 h cycles in the medium containing citrus pectin (2% w/v) as the sole carbon source.

Cadmium and exposure to stress increase aggressive behavior

Environmental toxicants and stress influence the health and behavior of people from different parts of the world. In the present study, aggressive behavior was evaluated in rats exposed to cadmium (Cd) for four weeks and subjected to immobilization stress (IS) based on the resident/intruder paradigm. Latency to the first bite (LB), total number of attacks (NA), total duration of attack manifestations (DAM), and a composite aggression score (CAS) were used to assess aggressiveness. Cadmium concentrations in the blood and the brain were determined. We observed that the parameters of aggressiveness were not altered by either Cd or IS when administered separately. However, animals exposed to Cd + IS had increased NA, DAM, and CAS. Cadmium was detected in the blood and the brain after treatment and Cd + IS exposure modified Cd distribution in these tissues. These results suggest that exposure to low levels of Cd associated with stress may lead to increased aggressiveness in rats. (C) 2011 Elsevier B.V. All rights reserved.

New option for anterior traction of the face by using a cervical collar

This case required anteroposterior traction of the maxilla. Once none of the traditional methods could be used because of the lack of support in the chin and in the frontal region. Thus, we opted to use a cervical collar.

Oxalate determination in urine using an immobilized enzyme on Sorghum vulgare seeds in a flow injection conductimetric system

A flow-injection (FI) method was developed for the determination of oxalate in urine. It was based on the use of oxalate oxidase (E.C. 1.2.3.4) immobilized on ground seeds of the BR-303 Sorghum vulgare variety. A reactor was filled with this activated material, and the samples (200 μL) containing oxalate were passed through it, carried by a deionized water flow. The carbon dioxide produced by the enzyme reaction permeated through a microporous PTFE membrane, and was received in a water acceptor stream, promoting conductivity changes proportional to the oxalate concentration in the sample. The results obtained showed a useful linear range from 0.05 to 0.50 mmol dm-3. The proposed method, when compared with the Sigma enzymatic procedure, showed good correlation (Y = 0.006(±0.016) + 0.98(±0.019)X; r = 0.9995, Y = conductivity in μS, and X = concentration in mmol dm-3), selectivity, and sensitivity. The new immobilization approach promotes greater stability, allowing oxalate determination for 6 months. About 13 determinations can be performed per hour. The precision of the proposed method is about ± 3.2 % (r.s.d).

Relationship of venom ontogeny and diet in Bothrops

We studied ontogenetic changes in venom toxicity of the pitvipers Bothrops jararaca and B. alternatus in order to evaluate the relationship between venom action and diet. Toxicity tests (LD50) were performed for the venoms of adult and juvenile snakes on mice and bullfrog froglets, which represented endothermic and ectothermic prey respectively. The venom of juveniles of B. jararaca, but not of B. alternatus, had a higher toxicity on anurans than that of adults. This finding is consistent with the feeding habits of these two species, because juveniles of B. jararaca feed mainly on small anurans and lizards, shifting to endothermic prey at maturity, whereas B. alternatus preys mainly on endotherms throughout its life. Venom toxicity in endotherms was higher for adults of B. jararaca compared to juveniles, a feature not observed for B. alternatus. It is proposed that prey death/immobilization is the main function of the venom of juvenile snakes. As the snake grows, the digestive role of venom may become increasingly important, because adults prey upon large and bulky prey. The importance of adult venoms in prey digestion is reflected in their higher proteolytic activity.

The natural history of carpal tunnel syndrome: A study of 20 hands evaluated 4 to 9 years after initial diagnosis

Carpal tunnel syndrome (CTS) is the most frequent entrapment neuropathy. In the last decade several papers have been published on epidemiology, clinical aspects, diagnosis, and treatment, but little is known about its natural history. The objective of this work was to study the natural history of CTS syndrome. From 358 patients with clinical and conduction study diagnosis of CTS, 12 cases were identified that had refused surgical treatment, had not used anti-inflammatory medications, and had not undergone orthopaedic procedures, such as immobilization or anaesthetic infiltration. These 12 patients have 20 compromised hands which have been followed up for between 4 and 9 years. In all cases sensory and motor conduction studies were performed on the median nerve, at the beginning and end of follow-up period. Electrical improvement was marked in 5 hands and slight in 3; there was no significant change in 10, and deterioration in 2. As 8 hands (7 patients) showed improved clinical symptoms and conduction studies over several years, this brings the universally accepted procedure of surgical treatment into doubt.

Endocrine Disruptors and Hypothalamic Sexual Differentiation

The so-called endocrine disruptors have been described as compounds which interfere with the estrogen action in their receptors and may exert a crucial role in the development of the reproductive tract and in the brain sexual differentiation. Thus, conducts and/or exposure to these drugs in the perinatal period that apparently do not endanger the neonate may cause side effects. During embrionary development, the gonads, through discharge of a small quantity of reproductive hormones, will guarantee the phenotype of male or female at birth, as well as actuate in specific areas sexual differentiation of the central nervous system. Several experimental models have shown an interference of drugs acting as endocrine disruptors in hypothalamic sexual differentiation. Thus, reproductive function is impaired by exposure to estrogen in the perinatal life of rats and the mechanisms involved in this effect are distinct for males and females. Perinatal exposure to drugs which may be considered endocrine disrupters may induce an incomplete masculinization and defeminization of the central nervous system. Alterations in these processes, if present, generally are perceived only at puberty or adult reproductive life. These later alterations may include anomalies in the process of fertility or in sexual behavior.

Effects of tiletamine/zolazepam-romifidine-atropine in ocelots (Leopardus pardalis)

Objectives: To evaluate the effects of a combination of tiletamine-zolazepam-romifidine-atropine in ocelots. Design: Prospective experimental trial. Animals: Eight captive adult ocelots (three females and five males). Methods: Calculated doses of tiletamine-zolazepam (3.75 mg kg -1), romifidine (50 μg kg-1) and atropine (0.04 mg kg-1) were administered intramuscularly. After immobilization, animals were weighed and the real doses determined. Heart rate, respiratory frequency, noninvasive systolic, diastolic, and mean arterial pressure, arterial oxygen hemoglobin saturation, and rectal temperature were measured. Data were analyzed by means of ANOVA for repeated measures, followed by the Tukey test to compare values over time. Results: Doses administered were 3.4 ± 0.6 mg kg-1 of tiletamine-zolazepam, 0.04 ± 7.0 mg kg-1 of romifidine, and 0.03 ± 0.007 mg kg-1 of atropine. The mean time to recumbency and duration of immobilization were 7.0 ± 4.5 and 109.2 ± 27.9 minutes, respectively. The median times to standing and walking were 52.3 [0-90] and 2.3 [0-69.3] minutes, respectively. A decrease in heart rate was observed 45 minutes following drug administration. Arterial blood pressure was maintained during the study. Conclusions and clinical relevance: This protocol produced good immobilization in ocelots with minimal changes over time in cardiovascular parameters.