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1.
Sci Rep ; 14(1): 12254, 2024 05 28.
Article in English | MEDLINE | ID: mdl-38806593

ABSTRACT

Migration of nib Cd to the testa during fermentation can be achieved with high temperatures (> 45 °C) and low nib pH values (< 5.0) using spontaneous fermentation. However, this low pH can lead to low flavor quality. This study used three controlled temperature fermentation treatments on three cacao genotypes (CCN 51, ICS 95, and TCS 01) to test its effects on the nib pH, the migration of nib Cd to the testa, and the liquor flavor quality. All treatments were effective in reducing the total nib Cd concentration. Nevertheless, the treatment with the higher mean temperature (44.25 °C) and acidification (pH 4.66) reached the highest mean nib Cd reductions throughout fermentation, a 1.37 factor in TCS 01, promoting the development of fine-flavor cocoa sensorial notes. In unfermented beans, the Cd concentration of nibs was higher than that of the testa, and the Cd migration proceeded down the total concentration gradient. However, Cd migration was observed against the concentration gradient (testa Cd > nib Cd) from the fourth day. Cd migration could increase by extensive fermentation until the sixth day in high temperatures and probably by the adsorbent capacity of the testa. Genotype-by-treatment interactions were present for the nib Cd reduction, and a universal percentage of decrease of Cd for each genotype with fermentation cannot be expected. Selecting genotypes with highly adsorbent testa combined with controlled temperatures would help reduce the Cd concentration in the cacao raw material, improving its safety and quality.


Subject(s)
Cacao , Cadmium , Fermentation , Cacao/metabolism , Hydrogen-Ion Concentration , Cadmium/metabolism , Taste , Hot Temperature , Flavoring Agents/metabolism , Temperature
2.
Food Addit Contam Part B Surveill ; 16(3): 234-243, 2023 Sep.
Article in English | MEDLINE | ID: mdl-37331975

ABSTRACT

Lettuce is Colombia's most widely cultivated leafy vegetable, but in the absence of good agricultural practices, there is the risk of some pesticide residues that affect its safety and quality. This work aimed to identify the pesticides used by farmers for the lettuce crop, the iceberg variety (Lactuca sativa var. capitata), in some municipalities of Cundinamarca (Colombia) and to investigate their residues by sampling and analysis. The farmers reported in the survey 44 active ingredients, most fungicides (54%), while the laboratory analysis showed 23 chemical compounds (52% insecticides, 39% fungicides and 9% herbicides). In addition, dithiocarbamates, procymidone and some organophosphates were among the active ingredients that exceeded the maximum residue limits (MRLs). About 80% of the identified pesticides were not registered with the regulatory entity Instituto Colombiano Agropecuario (ICA) for their use in lettuce, but some were in commercial products legally registered in Latin American and Caribbean countries.


Subject(s)
Fungicides, Industrial , Pesticide Residues , Pesticides , Pesticide Residues/analysis , Lactuca/chemistry , Fungicides, Industrial/analysis , Colombia , Food Contamination/analysis , Pesticides/analysis , Vegetables/chemistry
3.
Asian Pac J Cancer Prev ; 23(10): 3237-3245, 2022 Oct 01.
Article in English | MEDLINE | ID: mdl-36308344

ABSTRACT

OBJECTIVE: Handgrip strength (HGS) is an indicator of general muscular strength and in cancer patients acts as a relevant marker associated with mortality and health. This study aimed to evaluate the association between peripheral muscle function and health-related quality of life (HRQoL) in breast cancer (BC) survivors. METHODS: Systematic review registered on PROSPERO under number: CRD 42021225206. The searches were carried out on MEDLINE via Pubmed, PEDro, Cochrane Library, Embase, CINAHL via EBSCO and Science Direct databases. Observational studies evaluating the association between handgrip strength (HGS) and HRQoL in adult female BC survivors were included. No linguistic or time restrictions were applied. Two reviewers reviewed full texts for inclusion and performed data extraction and risk of bias using the Newcastle and Ottawa scale (NOS). RESULTS: Five articles were included and involved 587 patients, mean age of 47 to 59 years. The percentage of decreased HGS ranged from 38.3% to 60.3%. HGS was associated with different quality of life measures. From meta-analysis including 220 patients, the correlation coefficient between HGS and HRQoL was 0.26 (95% CI: 0.07-0.35). CONCLUSIONS: Breast cancer survivors face decline of HGS. In this population HGS was correlated with HRQoL. However, more evidence are necessary.


Subject(s)
Breast Neoplasms , Cancer Survivors , Adult , Humans , Female , Middle Aged , Quality of Life , Hand Strength/physiology , Breast Neoplasms/epidemiology , Survivors
4.
Gastroenterol. hepatol. (Ed. impr.) ; 45(2): 91-98, Feb. 2022. tab, graf
Article in English | IBECS | ID: ibc-204136

ABSTRACT

Introduction: Endoscopic ultrasound (EUS) is a more sensitive technique than transabdominal ultrasound for the diagnosis of gallstones. This greater sensitivity, especially in the diagnosis of microlithiasis/biliary sludge, facilitates the indication of cholecystectomy in patients with symptoms of probable biliary origin but may result in over-indication of this surgery.Objectives: Evaluate the role of EUS in the diagnosis of minilithiasis/biliary sludge in patients with digestive symptoms of probable biliary origin by resolving the symptoms after cholecystectomy. Analyse factors related to the remission of symptoms following cholecystectomy.Patients and methods: Retrospective, longitudinal, single-centre study based on a prospective database of 1.121 patients undergoing EUS. Seventy-four patients were identified as meeting inclusion-exclusion criteria (diagnosed with minilithiasis/sludge by EUS after presenting digestive symptoms of probable biliary origin without a history of complicated cholelithiasis). A telephone questionnaire for symptoms was conducted with cholecystectomized patients. Factors related to a good response were analysed with logistic regression analysis.Results: Of the 74 patients, 50 were cholecystectomized (67.5%), mean age 49 years (SEM 2.26) (41 women). Seventy percent of patients (35/50) presented remission of symptoms with median follow-up 353.5 days (95% CI, 270–632.2). The only variable associated with remission of symptoms was the presence of typical biliary colic with an OR of 7.8 (95% CI, 1.8–34; p=0.006). No complications associated with EUS were recorded. One patient (2%) suffered haemoperitoneum and 18% (9/50) suffered diarrhoea following cholecystectomy.Conclusions: EUS is a very useful technique for the indication of cholecystectomy in patients with minilithiasis/sludge and typical symptoms of biliary colic.


Introducción: La ecoendoscopia (USE) presenta mayor sensibilidad que la ecografía abdominal para el diagnóstico de litiasis biliar. Esta mayor sensibilidad, sobre todo en diagnóstico de microlitiasis/barro biliar, facilitaría una colecistectomía en pacientes con clínica digestiva de probable origen biliar, aunque podría inducir su sobre indicación.ObjetivosEvaluar el papel de la USE en el diagnóstico de minilitiasis-barro biliar en pacientes con clínica digestiva de probable origen biliar y ecografía normal mediante la resolución de los síntomas después de colecistectomía. Analizar los factores relacionados con la remisión de la sintomatología tras colecistectomía.Pacientes y método: Estudio retrospectivo, longitudinal, en un centro, sobre base de datos prospectiva de 1.121 pacientes sometidos a USE. Setenta y cuatro pacientes cumplían criterios inclusión-exclusión (realización USE para estudio de minilitiasis/barro por síntomas digestivos de probable origen biliar, sin historia de colelitiasis complicada). Se realizó cuestionario telefónico de síntomas a los pacientes colecistectomizados. Los factores relacionados con buena evolución se analizaron con análisis de regresión logística.Resultados: De los 74 pacientes, 50 fueron colecistectomizados (67,5%), edad media 49 años (ESM 2,26) (41 mujeres). El 70% de pacientes (35/50) presentó remisión de la sintomatología (mediana de seguimiento 353,5 días) (IC 95%, 270-632,2). La única variable asociada con una remisión de la sintomatología fue la presencia de cólico biliar típico con una OR de 7,8 (IC 95%, 1,8-34; p=0,006). No se registró ninguna complicación asociada a la USE. Un paciente (2%) sufrió hemoperitoneo y un 18% (9/50) presentaron diarrea post-colecistectomía.Conclusiones: La USE es de gran utilidad para la indicación de colecistectomía en los pacientes con minilitiasis-barro biliar y clínica típica de cólico biliar.


Subject(s)
Humans , Adult , Endosonography , Cholecystectomy , Cholelithiasis , Bile/diagnostic imaging , Cholecystectomy/adverse effects , Cholecystectomy/statistics & numerical data , Diarrhea , Postoperative Complications , Retrospective Studies , Gastroenterology , Longitudinal Studies , Surveys and Questionnaires
5.
Gastroenterol Hepatol ; 45(2): 91-98, 2022 Feb.
Article in English, Spanish | MEDLINE | ID: mdl-34023476

ABSTRACT

INTRODUCTION: Endoscopic ultrasound (EUS) is a more sensitive technique than transabdominal ultrasound for the diagnosis of gallstones. This greater sensitivity, especially in the diagnosis of microlithiasis/biliary sludge, facilitates the indication of cholecystectomy in patients with symptoms of probable biliary origin but may result in over-indication of this surgery. OBJECTIVES: Evaluate the role of EUS in the diagnosis of minilithiasis/biliary sludge in patients with digestive symptoms of probable biliary origin by resolving the symptoms after cholecystectomy. Analyse factors related to the remission of symptoms following cholecystectomy. PATIENTS AND METHODS: Retrospective, longitudinal, single-centre study based on a prospective database of 1.121 patients undergoing EUS. Seventy-four patients were identified as meeting inclusion-exclusion criteria (diagnosed with minilithiasis/sludge by EUS after presenting digestive symptoms of probable biliary origin without a history of complicated cholelithiasis). A telephone questionnaire for symptoms was conducted with cholecystectomized patients. Factors related to a good response were analysed with logistic regression analysis. RESULTS: Of the 74 patients, 50 were cholecystectomized (67.5%), mean age 49 years (SEM 2.26) (41 women). Seventy percent of patients (35/50) presented remission of symptoms with median follow-up 353.5 days (95% CI, 270-632.2). The only variable associated with remission of symptoms was the presence of typical biliary colic with an OR of 7.8 (95% CI, 1.8-34; p=0.006). No complications associated with EUS were recorded. One patient (2%) suffered haemoperitoneum and 18% (9/50) suffered diarrhoea following cholecystectomy. CONCLUSIONS: EUS is a very useful technique for the indication of cholecystectomy in patients with minilithiasis/sludge and typical symptoms of biliary colic.


Subject(s)
Bile/diagnostic imaging , Cholecystectomy/statistics & numerical data , Endosonography , Gallstones/diagnostic imaging , Cholecystectomy/adverse effects , Colic/epidemiology , Diarrhea/epidemiology , Female , Gallstones/surgery , Humans , Male , Middle Aged , Postoperative Complications/epidemiology , Remission Induction , Retrospective Studies , Symptom Assessment
6.
Sci Rep ; 11(1): 16746, 2021 08 18.
Article in English | MEDLINE | ID: mdl-34408194

ABSTRACT

Several research efforts on cocoa have been focused on parameters for controlling the transformation process to guarantee homogeneity and quality of cocoa beans, the main raw material in the chocolate industry. The main changes that determine the final quality of cocoa-and also the product's homogeneity-occur during fermentation, given the great number of factors that affect the process. This research seeks to identify the most relevant factors affecting quality in order to offer higher-quality and more homogeneous cocoa for the chocolate industry. The dynamics of the fermentation process were observed in three contrasting locations, monitoring different variables and evaluating the final quality of the cocoa. Results show that temperature and pH profile are the key factors to be monitored and controlled in order to achieve high-quality cocoa beans.

7.
Rev Bras Parasitol Vet ; 30(3): e002521, 2021.
Article in English | MEDLINE | ID: mdl-34406211

ABSTRACT

To investigate the in vitro anthelmintic efficacy of dividivi (Caesalpinia coriaria), a traditional medicinal plant used in Central America and the northern part of South America, extracts from the foliage of this plant were subjected to the egg hatching test (EHT) and larval exsheathment inhibition test (LEIT), against Haemonchus contortus. Four different extracts were evaluated: acetone-water (AW), methanol-water (MW), acetone-water-dichloromethane (AWD) and methanol-water-dichloromethane (MWD). The concentrations used for the EHT and LEIT tests ranged from 500 to 4000 µg mL-1 and six repetitions per concentration. The effective concentrations (EC50) were calculated using Probit analysis. The EC50 for EHT were 2947.0, 3347.0, 3959.6 and 4538.7 µg mL-1 for MWD, MW, AW and AWD, respectively. The EC50 for LEIT were 2883.4, 5927.4, 9876.3 and 9955.4 µg mL-1 for AWD, AW, MWD and MW, respectively. The methanol extracts were the most effective in inhibiting the hatching of eggs, while the acetone extracts showed efficacy in inhibiting larval exsheathment. This study explains the importance that C. coriaria has as a medicinal plant in Central and South American countries.


Subject(s)
Anthelmintics , Caesalpinia , Haemonchus , Animals , Anthelmintics/pharmacology , Larva , Plant Extracts/pharmacology
8.
Endosc Int Open ; 9(8): E1269-E1275, 2021 Aug.
Article in English | MEDLINE | ID: mdl-34447875

ABSTRACT

Background and study aims The poor flexibility of large-bore EUS needles often leads to technical failure when sampling from the duodenum. The aim of this study was to evaluate the technical and diagnostic performances of a new Menghini tip 19G nitinol EUS needle for sampling pancreatic solid lesions in the head and uncinate process. Patients and methods This was a European prospective multicenter single-arm study. A maximum of four passes were allowed. In case of failure, different needles were permitted. Results We included 75 patients (51 % males) with lesions in the head (n = 68; 91 %) and uncinate process (n = 7; 9 %) (mean size: 33 ±â€Š12 mm; number of passes: 1.8 ±â€Š0.9). Technical success was seen in 71 of 75 (94.7 %). Diagnostic rates were 89.3 % (67/75) and 94.4 % (67/71) in the intention-to-treat (ITT) and per-protocol (PP) analysis, respectively. In the eight cases with failure, diagnosis was obtained with another needle (n = 4), from another lesion (n = 3) or with follow-up (n = 1). A histological sample was obtained in 64 patients (ITT 85.3 % and PP 90 %) and immunohistochemistry was successfully performed in 13 of 15 lesions in which it was required. No differences between rapid on-site evaluation (ROSE) and non-ROSE groups were observed regarding diagnostic success (87.5 % vs 91 %, P  = 0.582) and diagnosis at the first pass (70 % vs 81 %, P  = 0.289). Number of passes was lower in the ROSE group (1.4 + 0.9 vs 2.2 + 0.7, P  < 0.001). One adverse event was recorded (1.3 %) consisting in a duodenal perforation after a single session EUS-ERCP. Conclusions The new nitinol Menghini tip 19G EUS needle showed high technical diagnostic success in safely sampling solid lesions in the head and uncinate process of the pancreas.

9.
Chemosphere ; 266: 129202, 2021 Mar.
Article in English | MEDLINE | ID: mdl-33310517

ABSTRACT

Sandy soils in Florida are vulnerable to toxic metal pollution, and it is necessary to identify desirable amendments for the remediation of metal contaminated soils. Sorption and incubation experiments were conducted to compare the effectiveness of dolomite phosphate rock (DPR), humic acid activated dolomite phosphate rock (ADPR) and biochar (BC) in immobilizing Cd2+ and Pb2+ in two representative agricultural soils in south Florida (Alfisol-Riviera and Spodosol -Ankona series). The results showed that the soils had a low sorption capacity for metals with maximum sorption of 0.767-3.30 mg/g. Application of amendments increased the maximum sorption by 4.2-4.8 times for Pb2+ and 1.5-2.2 times for Cd2+ in Alfisol soil, and 7.1-7.9 times for Pb2+ and 1.7-3.1 times for Cd2+ in Spodosol soil. ADPR was the most effective amendment for increasing the soil's sorption capacity for Cd2+ and Pb2+. 0.01 M CaCl2 extractable metals in the contaminated soils were significantly decreased by all the amendments, especially ADPR, which reduced extractable Cd2+ and Pb2+by 87.2 and 76.0% in Alfisol and 91.3 and 76.3% in Spodosol soil as compared to control. The amounts of extractable Cd2+ and Pb2+ were negatively correlated with soil pH and available P, indicating that the change of soil characteristics by amendments was the dominant mechanism for enhanced immobilization of metals in the contaminated soils. These results indicate that ADPR has great potential for remediating toxic levels of Cd2+ and Pb2+ in contaminated soils.


Subject(s)
Metals, Heavy , Soil Pollutants , Cadmium/analysis , Calcium Carbonate , Charcoal , Florida , Lead , Magnesium , Metals, Heavy/analysis , Phosphates , Soil , Soil Pollutants/analysis
10.
Rev. bras. parasitol. vet ; 30(3): e002521, 2021. tab, graf
Article in English | LILACS, VETINDEX | ID: biblio-1288711

ABSTRACT

Abstract To investigate the in vitro anthelmintic efficacy of dividivi (Caesalpinia coriaria), a traditional medicinal plant used in Central America and the northern part of South America, extracts from the foliage of this plant were subjected to the egg hatching test (EHT) and larval exsheathment inhibition test (LEIT), against Haemonchus contortus. Four different extracts were evaluated: acetone-water (AW), methanol-water (MW), acetone-water-dichloromethane (AWD) and methanol-water-dichloromethane (MWD). The concentrations used for the EHT and LEIT tests ranged from 500 to 4000 µg mL-1 and six repetitions per concentration. The effective concentrations (EC50) were calculated using Probit analysis. The EC50 for EHT were 2947.0, 3347.0, 3959.6 and 4538.7 µg mL-1 for MWD, MW, AW and AWD, respectively. The EC50 for LEIT were 2883.4, 5927.4, 9876.3 and 9955.4 µg mL-1 for AWD, AW, MWD and MW, respectively. The methanol extracts were the most effective in inhibiting the hatching of eggs, while the acetone extracts showed efficacy in inhibiting larval exsheathment. This study explains the importance that C. coriaria has as a medicinal plant in Central and South American countries.


Resumo Para investigar a eficácia anti-helmíntica de Divi-divi (Caesalpinia coriaria), uma planta medicinal tradicional usada na América Central e no norte da América do Sul. Extratos das folhas dessa planta foram utilizados em testes in vitro de inibição da eclosão de ovos (EHT) e desembainhamento larvar (LEIT) de Haemonchus contortus. Quatro diferentes extratos foram avaliados: acetona-água (AW), metanol-água (MW), acetona-água-diclorometano (AWD) e metanol-água-diclorometano (MWD). Para os testes EHT e LEIT, as concentrações utilizadas variaram de 500 a 4000 µg mL-1, em seis repetições por concentração. As concentrações efetivas (EC50) foram calculadas, usando-se a análise Probit. A EC50 para EHT foram 2947,0; 3347,0; 3959,6 e 4538,7 µg mL-1 para MWD, MW, AW e AWD, respectivamente. As EC50 para LEIT foram 2883,4; 5927,4; 9876,3 e 9955,4 µg mL-1 para AWD, AW, MWD e MW, respectivamente. Os extratos de metanol foram os mais eficazes em inibir a eclosão de ovos, enquanto os extratos de acetona mostraram-se eficazes em inibir a desembainhamento larvar. Este estudo ajuda a explicar a importância da C. coriaria como planta medicinal nos países da América Central e América do Sul.


Subject(s)
Animals , Caesalpinia , Haemonchus , Anthelmintics/pharmacology , Plant Extracts/pharmacology , Larva
11.
Endosc Int Open ; 8(3): E266-E273, 2020 Mar.
Article in English | MEDLINE | ID: mdl-32118100

ABSTRACT

Background and study aims EUS-FNA has suboptimal accuracy in diagnosing gastrointestinal subepithelial tumors (SETs). EUS-guided 22-gauge fine needle biopsy (EUS-FNB) and single-incision with needle knife (SINK) were proposed to increase accuracy of diagnosis. This study aimed to prospectively compare the diagnostic accuracy and safety of EUS-FNB with SINK in patients with upper gastrointestinal SETs. Patients and methods All adult patients referred for EUS evaluation of upper gastrointestinal SETs ≥ 15 mm in size were eligible for inclusion. Patients were randomized to undergo EUS-FNB or SINK. Lesions were sampled with a 22-gauge reverse beveled core needle in the EUS-FNB group and by a conventional needle-knife sphincterotome and biopsy forceps in the SINK group. Patients were blinded to the technique used. The primary outcome was diagnostic accuracy. Secondary outcomes included adverse events, histological yield and procedure duration. Study enrollment was terminated early due to poor recruitment. Results A total of 56 patients (31 male (55.37 %); mean age, 67.41 ±â€Š12.70 years) were randomized to either EUS-FNB (n = 26) or SINK (n = 30). Technical success was 96.15 % and 96.66 %, respectively. The majority of lesions were gastrointestinal stromal tumors (51.78 %). No significant difference was found between EUS-FNB and SINK in terms of diagnostic accuracy for a malignant or benign disease (76 % vs. 89.28 %, respectively; P  = 0.278). The rate of adverse events (none severe) was also comparable (7.69 % vs. 10 %, respectively; P =  1.0) including two abdominal pain episodes in the EUS-FNB group compared to two delayed bleeding (one requiring hospitalization and radiologic embolization) and 1 abdominal pain in the SINK group. Conclusion EUS-FNB and SINK are equally effective techniques for upper gastrointestinal SETs sampling. SINK can be associated with mild to moderate delayed bleeding.

13.
Endosc Int Open ; 7(4): E576-E582, 2019 Apr.
Article in English | MEDLINE | ID: mdl-30994113

ABSTRACT

Background and study aims Endoscopic resection requires use of submucosal injection. This study was conducted to assess efficacy and impact on early healing of hyaluronic acid combined with chondroitin sulfate and poloxamer 407 (Ziverel) when used as a solution for submucosal injection. Materials and methods Prospective and comparative study of gastric endoscopic mucosal resection (EMR) with three groups of two Yorkshire pigs. Six submucosal cushions were created in each animal by injecting 2 mL of Ziverel (Group 1) or succinylated gelatin (SG) (Group 2), enabling 12 EMR in each group. Submucosal cushions were created with Ziverel in Group 3, without resection. Electrosurgery unit settings were the same in all cases. EMR defects and injection sites were marked with clips. The animals were sacrificed 7 days later. EMR specimen size and duration of procedure were recorded. EMR specimens and EMR scars and injection sites were evaluated by a blinded pathologist. Results We successfully performed 24 EMR (15 en-bloc and 9 piecemeal, without differences between groups 1 and 2). Mean EMR specimen dimensions were significantly larger in Group 1 (median 19 mm, range 6 - 40 vs 16.6 mm, range 5­25; P  = 0.019), without changing the electrocautery unit settings. Blinded histopathologist assessment of EMR specimens showed less fibrosis in the submucosa and a trend to fewer cautery artifacts with Ziverel and did not identify any significant differences in early healing of resection sites. Conclusion The combination of Ziverel enables EMR and does not negatively affect early healing.

15.
Ann Intensive Care ; 8(1): 1, 2018 Jan 09.
Article in English | MEDLINE | ID: mdl-29330618

ABSTRACT

BACKGROUND: The early prediction of the severity of acute pancreatitis still represents a challenge for clinicians. Experimental studies have revealed the generation of specific halogenated lipids, in particular oleic acid chlorohydrin, in the early stages of acute pancreatitis. We hypothesized that the levels of circulating oleic acid chlorohydrin might be a useful early prognostic biomarker in acute pancreatitis in humans. METHODS: In a prospective, multicenter cohort study, plasma samples collected within 24 h after presentation in the emergency room from 59 patients with acute pancreatitis and from 9 healthy subjects were assessed for oleic acid chlorohydrin levels. RESULTS: Pancreatitis was mild in 30 patients, moderately severe in 16 and severe in 13. Oleic acid chlorohydrin levels within 24 h after presentation were significantly higher in patients that later progressed to moderate and severe acute pancreatitis. Using 7.49 nM as the cutoff point, oleic acid chlorohydrin distinguished mild from moderately severe-to-severe pancreatitis with high sensitivity/specificity (96.6/90.0%) and positive/negative predictive values (90.3/96.4%). Using 32.40 nM as the cutoff value sensitivity, specificity, positive and negative predictive values were all 100% for severe acute pancreatitis. It was found to be a better prognostic marker than BISAP score, hematocrit at 48 h, SIRS at admission, persistent SIRS or C-reactive protein at 48 h. CONCLUSIONS: Oleic acid chlorohydrin concentration in plasma is elevated in patients with acute pancreatitis on admission and correlates with a high degree with the final severity of the disease, indicating that it has potential to serve as an early prognostic marker for acute pancreatitis severity.

16.
J Inorg Biochem ; 118: 108-14, 2013 Jan.
Article in English | MEDLINE | ID: mdl-23153690

ABSTRACT

The reactivity of coordinated nitroxyl (HNO) has been explored with the [Fe(II)(CN)(5)HNO](3-) complex in aqueous medium, pH 6. We discuss essential biorelevant issues as the thermal and photochemical decompositions, the reactivity toward HNO dissociation, the electrochemical behavior, and the reactions with oxidizing and reducing agents. The spontaneous decomposition in the absence of light yielded a two-electron oxidized species, the nitroprusside anion, [Fe(II)(CN)(5)NO](2-), and a negligible quantity of N(2)O, with k(obs)≈5×10(-7)s(-1), at 25.0°C. The value of k(obs) represents an upper limit for HNO release, comparable to values reported for other structurally related L ligands in the [Fe(II)(CN)(5)L](n-) series. These results reveal that the FeN bond is strong, suggesting a significant σ-π interaction, as already postulated for other HNO-complexes. The [Fe(II)(CN)(5)HNO](3-) ion showed a quasi-reversible oxidation wave at 0.32 V (vs normal hydrogen electrode), corresponding to the [Fe(II)(CN)(5)HNO](3-)/[Fe(II)(CN)(5)NO](3-),H(+) redox couple. Hexacyanoferrate(III), methylviologen and the nitroprusside ion have been selected as potential oxidants. Only the first reactant achieved a complete oxidation process, initiated by a proton-coupled electron transfer reaction at the HNO ligand, with nitroprusside as a final oxidation product. Dithionite acted as a reductant of [Fe(II)(CN)(5)HNO](3-), in a 4-electron process, giving NH(3). The high stability of bound HNO may resemble the properties in related Fe(II) centers of redox active enzymes. The very minor release of N(2)O shows that the redox conversions may evolve without disruption of the FeN bonds, under competitive conditions with the dissociation of HNO.


Subject(s)
Coordination Complexes/chemistry , Ferrous Compounds/chemistry , Nitrogen Oxides/chemistry , Coordination Complexes/chemical synthesis , Dithionite/chemistry , Electrochemistry , Ferricyanides/chemistry , Ferrous Compounds/chemical synthesis , Kinetics , Nitroprusside/chemistry , Oxidants/chemistry , Oxidation-Reduction , Paraquat/chemistry , Photochemical Processes , Reducing Agents/chemistry , Solutions , Spectrophotometry, Ultraviolet
17.
Angew Chem Int Ed Engl ; 48(23): 4213-6, 2009.
Article in English | MEDLINE | ID: mdl-19425036

ABSTRACT

Not so elusive: [Fe(II)(CN)(5)(HNO)](3-) has been characterized spectroscopically after the two-electron reduction of nitroprusside (see scheme). The complex is stable at pH 6, slowly decomposing to [Fe(CN)(6)](4-) and N(2)O. It is deprotonated at increasing pH value with oxidation of bound NO(-) to [Fe(II)(CN)(5)(NO)](3-). [Fe(II)(CN)(5)(HNO)](3-) is the first non-heme iron-nitroxyl complex prepared in aqueous solution that is reversibly redox-active under biologically relevant conditions.


Subject(s)
Ferrous Compounds/chemistry , Nitric Oxide/chemistry , Nitroprusside/chemistry , Magnetic Resonance Spectroscopy , Oxidation-Reduction , Spectroscopy, Fourier Transform Infrared
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