Methyl- and phenylmercury(II) derivatives of 2-mercaptobenzothiazole. Crystal structure of (2-mercaptobenzothiazolato)methylmercury(II)

The complexes MeHgL and PhHgL (HL = 2-mercaptobenzothiazole) have been obtained from the reaction of the ligand with methylmercury hydroxide and phenylmercury acetate, respectively, in methanol. MeHgL, which has been characterized by single-crystal X-ray diffraction analysis (crystal data: triclinic, space group P1, with a = 8.009 (4) Å, b = 10.042 (4) Å, c = 13.074 (3) Å, α = 101.25 (2)°, β = 102.61(3)°, γ = 101.42 (3)°, R = 0.067), crystallizes with two independent molecules, I and I′, contained in each asymmetric unit with a coordination geometry based on the almost linear C-Hg-S group (Hg-S = 2.369 (6) Å, Hg-C = 2.06 (2) Å, and C-Hg-S = 177.7 (7)° for I; Hg-S = 2.375 (6) Å, Hg-C = 2.10 (3) Å, and C-Hg-S = 178.8 (6)° for I′). A secondary intramolecular interaction between the mercury atom and the C=N group of the ring and some weak intermolecular interactions between the metal and sulfur atoms were also found. The vibrational spectra of this compound and the phenylmercury(II) compound are discussed in light of the crystal structure. Diagnostic criteria of the bonding modes for the ligand are assessed. © 1985 American Chemical Society.

Mercury(II) and thallium(III) organometallic derivatives of 2-Mercaptobenzoxazole

Some derivatives of 2-mercaptobenzoxazole (HL) of the type MRnL [M = Hg or Tl, R = Me or Ph and n = 1 (Hg) or 2 (Tl)] have been prepared. The structure of HgMeL has been determined by an X-ray diffraction study; in the crystal there are two independent planar molecules in each asymmetric unit, with the ligand in its thiolic form and an almost linear CHgS linkage. Weak intramolecular and intermolecular secondary interactions complement the mercurysulphur bond. The spectroscopic (IR, Raman, mass, 13C-NMR), conductimetric, and dipolar properties of this and the other compounds are discussed. © 1991.

2-Mercaptobenzothiazole clay as matrix for sorption and preconcentration of some heavy metals from aqueous solution

2-Mercaptobenzothiazole loaded on previously polystyrene treated clay was prepared, characterized and used for sorption and preconcentration of Hg(II) Pb(II), Zn(II) and Cd(II) from an aqueous solution. The support used was a natural clay previously treated with sulphuric acid solution. Adsorptiou isotherms of metal ions from aqueous solutions as function of pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The chemically treated clay was very selective to Hg(II) in solution in which Zn(II), Cd(II), Pb(II) and some transition metal ions were also present.

Sorption and preconcentration of some heavy metals by 2-mercaptobenzothiazole-clay

2-Mercaptobenzothiazole loaded on previously treated clay was prepared, characterized and used for sorption and preconcentration of Hg(II), Pb(II), Zn(II), Cd(II), Cu(II) and Mn(II) from an aqueous solution. The support used was a natural clay previously treated with sulphuric acid solution. Adsorption isotherms of metal ions from aqueous solutions as function of pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The chemically treated clay was very selective to Hg(II) in solution in which Zn(II), Cd(II), Pb(II), Cu(II) and Mn(II) were also present. © 1995.

Preconcentration and determination of mercury(II) at a chemically modified electrode containing 3-(2-thioimidazolyl)propyl silica gel

A mercury-sensitive chemically modified graphite paste electrode was constructed by incorporating modified silica gel into a conventional graphite paste electrode. The functional group attached to the (3-chloropropyl) silica gel surface was 2-mercaptoimidazole, giving a new product denoted by 3-(2-thioimidazolyl)propyl silica gel, which is able to complex mercury ions. Mercury was chemically adsorbed on the modified graphite paste electrode containing 3-(2-thioimidazolyl)propyl silica (TIPSG GPE) by immersion in a Hg(II) solution, and the resultant surface was characterized by cyclic and differential pulse anodic stripping voltammetry. One cathodic peak at 0.1 V and other anodic peak at 0.34 V were observed on scanning the potential from -0.1 to 0.8 V (0.01 M KNO3; ν = 2.0 mV s-1 νs. Ag/AgCl). The anodic peak at 0.34 V show an excellent sensitivity for Hg(II) ions in the presence of several foreign ions. A calibration graph covering the concentration range from 0.02 to 2 mg L-1 was obtained. The detection limit was estimated to be 5 μg L-1. The precision for six determinations of 0.05 and 0.26 mg L-1 Hg(II) was 3.0 and 2.5% (relative standard deviation), respectively. The method can be used to determine the concentration of mercury(II) in natural waters contaminated by this metal. 2005 © The Japan Society for Analytical Chemistry.

The influence of seasonalness on the structural characteristics of aquatic humic substances extracted from Negro River (Amazon state) waters: Interactions with Hg(II)

In this work, humic substances were extracted from water samples collected monthly from the Negro River basin in the Amazon state (Brazil) to study their properties in the Amazonian environment and interactions with the mercury ion considering the influence of seasonalness in this formation. The C/H, C/N and C/O atomic ratio parameters, functional groups, concentration of semiquinone-type free radicals, pH, pluviometric and fluviometric indices, and mercury concentrations were interpreted using hierarchical cluster analysis (HCA) and principal component analysis (PCA). The statistical analyses showed that when the pluviometric index was greater and the fluviometric index was smaller, the degree of humification of aquatic substances was greater. The following decreasing order of the degree of humification of the AHS collected monthly was established: Nov/02 to Feb/03 > Mar/02 to May/02 > Jun/02 to Oct/02. The greatest concentrations of mercury were detected in more humidified samples. These results suggest that due to inter and/or intra-molecular rearrangements, the degree of humification of aquatic humic substances is related to its affinity for Hg(II) ions. ©2007 Sociedade Brasileira de Química.

Continuous measurement of cerebral oxygen saturation (rSO 2) for assessment of cardiovascular status during hemorrhagic shock in a swine model

Background: Early trauma care is dependent on subjective assessments and sporadic vital sign assessments. We hypothesized that near-infrared spectroscopy-measured cerebral oxygenation (regional oxygen saturation [rSO 2]) would provide a tool to detect cardiovascular compromise during active hemorrhage. We compared rSO 2 with invasively measured mixed venous oxygen saturation (SvO2), mean arterial pressure (MAP), cardiac output, heart rate, and calculated pulse pressure. Methods: Six propofol-anesthetized instrumented swine were subjected to a fixed-rate hemorrhage until cardiovascular collapse. rSO 2 was monitored with noninvasively measured cerebral oximetry; SvO2 was measured with a fiber optic pulmonary arterial catheter. As an assessment of the time responsiveness of each variable, we recorded minutes from start of the hemorrhage for each variable achieving a 5%, 10%, 15%, and 20% change compared with baseline. Results: Mean time to cardiovascular collapse was 35 minutes ± 11 minutes (54 ± 17% total blood volume). Cerebral rSO 2 began a steady decline at an average MAP of 78 mm Hg ± 17 mm Hg, well above the expected autoregulatory threshold of cerebral blood flow. The 5%, 10%, and 15% decreases in rSO 2 during hemorrhage occurred at a similar times to SvO2, but rSO 2 lagged 6 minutes behind the equivalent percentage decreases in MAP. There was a higher correlation between rSO 2 versus MAP (R =0.72) than SvO2 versus MAP (R =0.55). Conclusions: Near-infrared spectroscopy- measured rSO 2 provided reproducible decreases during hemorrhage that were similar in time course to invasively measured cardiac output and SvO2 but delayed 5 to 9 minutes compared with MAP and pulse pressure. rSO 2 may provide an earlier warning of worsening hemorrhagic shock for prompt interventions in patients with trauma when continuous arterial BP measurements are unavailable. © 2012 Lippincott Williams & Wilkins.

Avaliação da contaminação mercurial mediante análise do teor de Hg total em amostras de cabelo em comunidades ribeirinhas do Tapajós, Pará, Brasil

Este estudo avalia a contaminação mercurial em comunidades de pescadores em quatro localidades nas margens do rio Tapajós: Rainha, Barreiras, São Luís do Tapajós e Paraná-Mirim. Análises toxocológicas das amostras de cabelo foram realizadas por espectofotometria de absorção atômica. Os níveis de mercúrio total em amostras de cabelo variaram entre 2,9µg/g e 71,5µg/g. Os valores mais baixos foram encontrados na comunidade de Paraná-Mirim. Os mais elevados, em São Luís do Tapajós e Barreiras, cerca de seis a sete vezes superiores ao valor estabelecido. As diferenças entre as concentrações médias de mercúrio total nas amostras, coletadas em populações ribeirinhas, a montante e a jusante do rio Tapajós em Itaituba, não apresentaram significância estatística (p > 0,05). Conclui-se que a exposição humana ao mercúrio por ingestão de peixes contaminados constitui risco potencial para o aparecimento de sintomas e sinais da doença de Minamata, o que recomenda a manutenção de um programa de vigilância epidemiológica.

Investigação espectroscópica dos carbonilos heterobimetálicos cis-[Fe(CO)4(HgX)2], X = Cl, Br, I

ABSTRACT: Spectroscopic studies of heterobimetallic carbonyls cis-[Fe(CO)₄(Hgx)₂], X=Cl, Br, I.The series of compounds cis-[Fe(CO)₄(HgX)₂], X=Cl,Br, I shows an octahedral geometry around the iron atom with the two HgX groups cis to each other. In this paper the assignment for the carbonyl stretching modes and the calculation of their force constants were performed on the basis of the Cotton-Krainhanzel model. Taking into account all the data from the IR, ¹⁹⁹Hg NMR and UV-vis spectra it is possible to verify the influence of X on the electronic densities at the metallic centers.

Sintese e aplicação de filmes biocomponentes nanoestruturados de 'TI'/'TI''O IND.2'/'W''O IND.3' por template e 'SI'/'TI''O IND.2'/'PT' por heterojunção em conversão de energia solar e remediação ambiental

Pós-graduação em Química - IQ

Intraocular pressure, specular microscopy, and prostaglandin E-2 concentration in dogs with mature and hypermature cataract

This study aimed to evaluate and correlate intraocular pressure (IOP), endothelial cell density (CD), and hexagonality (HEX), and the aqueous humor prostaglandin E-2 (PGE(2)) concentration in dogs with mature (MG, n = 8) and hypermature (HG, n = 8) cataracts. Eight laboratory beagles with no ocular abnormalities were included as a control group (CG). The IOP was measured using a digital applanation tonometer. Noncontact specular microscopy was used to evaluate CD and HEX. Samples of aqueous humor were used to determine prostaglandin E-2 concentration using enzyme-linked immunoassay. Data were compared by ANOVA and Bonferroni's multiple comparison test, and possible correlations among the PGE(2) aqueous concentration and corneal endothelium cell parameters were assessed by Person's test (P < 0.05). Average values of IOP (P = 0.45) and CD (P = 0.39) were not significantly different between MG, HM, and CG. Average values of HEX were lower, and PGE(2) concentration was increased in the MG and HG in comparison with CG (P < 0.05); however, such parameters did not change significantly between MG and HG (P > 0.05). PGE(2) values did not correlate with IOP, CD, and HEX in any group (P > 0.05). Although there were a small number of dogs studied, our results demonstrated that cataract progression from mature to hypermature did not have a significant change in PGE(2) aqueous concentration, IOP, corneal endothelial cell count, or morphology. In addition, PGE(2) concentration was not correlated with parameters of the corneal endothelium or IOP in dogs with mature or hypermature cataracts.

Thermal study of the solid-state reactions on Pt-15%Rh/Hg system

Thermogravimetry (TG), energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), mapping surface and X-ray diffraction (XRD) were used for the study of solid-state reaction on Pt-15%Rh with electrodeposited mercury. The results suggest when heated the mercury film react with the Pt-15%Rh alloy to form intermetallics having different thermal stabilities indicated by three mass loss steps. The first mass loss step occurs between room temperature and 184 degrees C only the bulk Hg is removed and PtHg4, PtHg2 and RhHg2 were characterized by XRD. The second step, between 184 and 271 degrees C, was attributed to PtHg4 decomposition with formation of PtHg2 stabilized by RhHg2. The third step, between 271 and 340 degrees C, was attributed to decomposition of a solid-solution of PtHg2/RhHg2. The fourth step, between 340 and 600 degrees C, was ascribed to: (1) a thermal decomposition of PtHg2, formed by a PtHg eutectoid reaction (similar to 340 degrees C) on the surface and (2) Hg removal from a solid solution of Pt-15%Rh(Hg). (C) 2013 Elsevier B.V. All rights reserved.

Laser locking to the Hg-199 S-1(0)-P-3(0) clock transition with 5.4x10(-15)/root tau fractional frequency instability

With Hg-199 atoms confined in an optical lattice trap in the Lamb-Dicke regime, we obtain a spectral line at 265.6 nm for which the FWHM is similar to 15 Hz. Here we lock an ultrastable laser to this ultranarrow S-1(0) - P-3(0) clock transition and achieve a fractional frequency instability of 5.4 x 10(-15) / root tau for tau <= 400 s. The highly stable laser light used for the atom probing is derived from a 1062.6 nm fiber laser locked to an ultrastable optical cavity that exhibits a mean drift rate of -6.0 x 10(-17) s-(1) (-16.9 mHzs(-1) at 282 THz) over a six month period. A comparison between two such lasers locked to independent optical cavities shows a flicker noise limited fractional frequency instability of 4 x 10(-16) per cavity. (c) 2012 Optical Society of America

Use of Hg-Electroplated-Pt Ultramicroelectrode for Determining Elemental Sulphur in Naphtha Samples

This paper describes the applicability of a Hg-electroplated-Pt ultramicroelectrode in the quantification of elemental sulphur in naphtha samples by square-wave voltammetry. A reproducible deposition methodology was studied and is reported in this paper. This methodology is innovative and relies on the quality of the mercury stock solution to obtain reproducible surfaces required for the analytical methodology. All analyses were performed using a Hg-electroplated-Pt ultramicroelectrode (Hg-Pt UME) due to the low sensibility of such devices to ohmic drops in resistive solutions. The responses of the peak areas in voltammetric experiments were linear in all of the range studied. The method developed here is accurate and reproducible, with a detection limit of 0.010 mg L-1 and a good recovery range for both standard solutions of elemental sulphur (85 to 99%) and real naphtha sample (79%). These results attest to the potential for the application of this electroanalytical methodology in determining elemental sulphur in naphtha samples containing mercaptans and disulphides.

Atorvastatin Prevents the Downregulation of Aquaporin-2 Receptor After Bilateral Ureteral Obstruction and Protects Renal Function in a Rat Model

OBJECTIVE To assess the effects of atorvastatin (ATORV) on renal function after bilateral ureteral obstruction (BUO), measuring inulin clearance and its effect on renal hemodynamic, filtration, and inflammatory response, as well as the expression of Aquaporin-2 (AQP2) in response to BUO and after the release of BUO. METHODS Adult Munich-Wistar male rats were subjected to BUO for 24 hours and monitored during the following 48 hours. Rats were divided into 5 groups: sham operated (n = 6); sham + ATORV (n = 6); BUO (n = 6); BUO + ATORV (10 mg/kg in drinking water started 2 days before BUO [n = 5]; and BUO + ATORV (10 mg/kg in drinking water started on the day of the release of BUO [n = 5]). We measured blood pressure (BP, mm Hg); inulin clearance (glomerular filtration rate [GFR]; mL/min/100 g); and renal blood flow (RBF, mL/min, by transient-time flowmeter). Inflammatory response was evaluated by histologic analysis of the interstitial area. AQP2 expression was evaluated by electrophoresis and immunoblotting. RESULTS Renal function was preserved by ATORV treatment, even if initiated on the day of obstruction release, as expressed by GFR, measured by inulin clearance. Relative interstitial area was decreased in both BUO + ATORV groups. Urine osmolality was improved in the ATORV-treated groups. AQP2 protein expression decreased in BUO animals and was reverted by ATORV treatment. CONCLUSION ATORV administration significantly prevented and restored impairment in GFR and renal vascular resistance. Furthermore, ATORV also improved urinary concentration by reversing the BUO-induced downregulation of AQP2. These findings have significant clinical implication in treating obstructive nephropathy. UROLOGY 80: 485.e15-485.e20, 2012. (c) 2012 Elsevier Inc.