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1.
BMC Nutr ; 9(1): 79, 2023 Jun 29.
Article in English | MEDLINE | ID: mdl-37386602

ABSTRACT

BACKGROUND: Since bottle feeding has an impact on the effectiveness of breastfeeding and appropriate supplemental feeding, the World health organization recommends being avoided for infant and early child feeding. Thus, this study aimed to assess the level of the bottle-feeding practice and its associated factors among mothers of 0-24 month's children in Asella town, Oromia region, Ethiopia. METHODS: Community-based cross-sectional study design was conducted from March 8-April 8, 2022, among a sample of 692 mothers of children aged 0-24 months. A multi-stage sampling technique was used to select the study subjects. Data were collected using a pretested and structured questionnaire by face-to-face interview technique questionnaire. The outcome variable bottle-feeding practice (BFP) was assessed using WHO and UNICEF UK healthy baby initiative BF assessment tools. Binary logistic regression analysis was used to identify the association between explanatory and outcome variables. Adjusted Odds ratio (AOR) with a 95% confidence interval was used to measure the strength of the association and a p-value < 0.05 was used to declare statistical significance. RESULTS: A total of 692 mothers with mean age and standard deviation (SD) of 31.86 (± 4.87) participated in the study. The prevalence of bottle-feeding practice was 246(35.5% with 95% CI: (31.8, 39.5). Mothers who were government-employed (AOR: 1.64, 95% CI: 1.02, 2.64), mothers who delivered at home (AOR: 3.74, 95% CI: 2.58-5.42), mothers who did not attend postnatal care (AOR: 3.76, 95% CI: 2.60,5.44) and mother who had negative attitude (AOR: 1.94, 95%CI: 1.34,2.8) were significantly associated with bottle feeding practices. CONCLUSION: The BFP were higher in the study area when compared with national reports of practices. The occupational status of the mothers, place of delivery, attending postnatal care, and attitude of the mothers were factors that increased bottle-feeding practice in the study area. Strengthening dietary behavioral modification for mothers who have children 0-24 months of the child to practice appropriate feeding is recommended.

2.
Heliyon ; 8(12): e12324, 2022 Dec.
Article in English | MEDLINE | ID: mdl-36582681

ABSTRACT

Cooking consumes a tremendous amount of energy on a regular basis. Solar energy is a very versatile and free energy source that could be used for different applications, including solar cooking. The aim this study is intended to experimentally investigate the effect of different reflectors on the performance of solar box cookers. Box-type solar cooker has been produced and tested with no reflector, aluminum foil reflectors, and mirror glass reflectors cases. Load and no-load tests have been conducted for all three reflector cases and the performances of cookers for each cases reflector have been determined. Several cooking tests was conducted in the outdoors, to investigate the thermal performance of the cooker using water as the absorbing medium. The results of the experimental demonstrate that, the cooker with three side mirror glass reflectors could reach a reasonably high temperature with better efficiency. 1.5 kg of water boiled in 51 min and its second figure of merit was found as 0.533 using mirror glass reflectors. The mirror glass reflector increases the efficiency of the experimental box-type solar cooker by 134% as compared with the cooker having no reflector. The experimental cooker with no reflector did not boil water during the testing period, so it is not recommended for cooking applications; whereas the cooker with the mirror glass reflector has been confirmed to cook most Ethiopian dishes with reasonable performance.

3.
Redox Biol ; 5: 66-70, 2015 Aug.
Article in English | MEDLINE | ID: mdl-25838067

ABSTRACT

Lyme borreliosis is transmitted through the bite of a tick that is infected by the bacterial spirochete Borrelia burgdorferi. Clinical manifestation of the disease can lead to heart conditions, neurological disorders, and inflammatory disorders. Oxidative stress has been implicated in the pathogenesis of many human diseases. The aim of this study was to investigate the mechanisms of oxidative stress and intracellular communication in Lyme borreliosis patients. Mitochondrial superoxide and cytosolic ionized calcium was measured in peripheral blood mononuclear cells (PBMCs) of Lyme borreliosis patients and healthy controls. Mitochondrial superoxide levels were significantly higher (p<0.0001) in Lyme borreliosis patients (n=32) as compared to healthy controls (n=30). Significantly low (p<0.0001) levels of cytosolic ionized calcium were also observed in Lyme borreliosis patients (n=11) when compared to healthy controls (n=11). These results indicate that there is an imbalance of reactive oxygen species and cytosolic calcium in Lyme borreliosis patients. The results further suggest that oxidative stress and interrupted intracellular communication may ultimately contribute to a condition of mitochondrial dysfunction in the immune cells of Lyme borreliosis patients.


Subject(s)
Lyme Disease/pathology , Adolescent , Adult , Aged , Borrelia burgdorferi/physiology , Calcium/metabolism , Child , Cytosol/metabolism , Female , Humans , Leukocytes, Mononuclear/cytology , Leukocytes, Mononuclear/metabolism , Lyme Disease/immunology , Lyme Disease/metabolism , Male , Middle Aged , Mitochondria/metabolism , Oxidative Stress , Reactive Oxygen Species/metabolism , Superoxides/metabolism , Young Adult
4.
Biochemistry ; 52(18): 3171-81, 2013 May 07.
Article in English | MEDLINE | ID: mdl-23566219

ABSTRACT

Although cytotoxic alkylating agents possessing two electrophilic reactive groups are thought to act by cross-linking cellular biomolecules, their exact mechanisms of action have not been established. In cells, these compounds form a mixture of DNA lesions, including nucleobase monoadducts, interstrand and intrastrand cross-links, and DNA-protein cross-links (DPCs). Interstrand DNA-DNA cross-links block replication and transcription by preventing DNA strand separation, contributing to toxicity and mutagenesis. In contrast, potential contributions of drug-induced DPCs are poorly understood. To gain insight into the biological consequences of DPC formation, we generated DNA-reactive protein reagents and examined their toxicity and mutagenesis in mammalian cells. Recombinant human O(6)-alkylguanine DNA alkyltransferase (AGT) protein or its variants (C145A and K125L) were treated with 1,2,3,4-diepoxybutane to yield proteins containing 2-hydroxy-3,4-epoxybutyl groups on cysteine residues. Gel shift and mass spectrometry experiments confirmed that epoxide-functionalized AGT proteins formed covalent DPC but no other types of nucleobase damage when incubated with duplex DNA. Introduction of purified AGT monoepoxides into mammalian cells via electroporation generated AGT-DNA cross-links and induced cell death and mutations at the hypoxanthine-guanine phosphoribosyltransferase gene. Smaller numbers of DPC lesions and reduced levels of cell death were observed when using protein monoepoxides generated from an AGT variant that fails to accumulate in the cell nucleus (K125L), suggesting that nuclear DNA damage is required for toxicity. Taken together, these results indicate that AGT protein monoepoxides produce cytotoxic and mutagenic DPC lesions within chromosomal DNA. More generally, these data suggest that covalent DPC lesions contribute to the cytotoxic and mutagenic effects of bis-electrophiles.


Subject(s)
Cell Death , DNA-Binding Proteins/metabolism , DNA/metabolism , Epoxy Compounds/pharmacology , Mutagenesis , Alkylation , Amino Acid Sequence , Cell Line, Tumor , Chromatography, High Pressure Liquid , Electrophoresis, Polyacrylamide Gel , Humans , Molecular Sequence Data , Recombinant Proteins/metabolism , Spectrometry, Mass, Electrospray Ionization
5.
J Proteome Res ; 12(5): 2151-64, 2013 May 03.
Article in English | MEDLINE | ID: mdl-23506368

ABSTRACT

1,2,3,4-Diepoxybutane (DEB) is the key carcinogenic metabolite of 1,3-butadiene (BD), an important industrial and environmental chemical present in urban air and in cigarette smoke. DEB is a genotoxic bis-electrophile capable of cross-linking cellular biomolecules to form DNA-DNA and DNA-protein cross-links (DPCs). In the present work, mass spectrometry-based proteomics was employed to characterize DEB-mediated DNA-protein cross-linking in human fibrosarcoma (HT1080) cells. Over 150 proteins including histones, high mobility group proteins, transcription factors, splicing factors, and tubulins were found among those covalently cross-linked to chromosomal DNA in the presence of DEB. A large portion of the cross-linked proteins are known factors involved in DNA binding, transcriptional regulation, cell signaling, DNA repair, and DNA damage response. HPLC-ESI(+)-MS/MS analysis of total proteolytic digests revealed the presence of 1-(S-cysteinyl)-4-(guan-7-yl)-2,3-butanediol conjugates, confirming that DEB forms DPCs between cysteine thiols within proteins and the N-7 guanine positions within DNA. However, relatively high concentrations of DEB were required to achieve significant DPC formation, indicating that it is a poor cross-linking agent as compared to antitumor nitrogen mustards and platinum compounds.


Subject(s)
Cross-Linking Reagents/chemistry , DNA-Binding Proteins/chemistry , Epoxy Compounds/chemistry , Proteome/chemistry , Amino Acid Sequence , Cell Line, Tumor , Cell Survival/drug effects , Cross-Linking Reagents/pharmacology , DNA/chemistry , DNA/metabolism , DNA-Binding Proteins/metabolism , Epoxy Compounds/pharmacology , Fibrosarcoma , Genome, Human , Humans , Molecular Sequence Annotation , Protein Binding , Proteome/metabolism , Proteomics , Spectrometry, Mass, Electrospray Ionization , Tandem Mass Spectrometry
6.
Chem Res Toxicol ; 25(7): 1472-83, 2012 Jul 16.
Article in English | MEDLINE | ID: mdl-22642258

ABSTRACT

The bioactivation of both endogenous and equine estrogens to electrophilic quinoid metabolites has been postulated as a contributing factor in carcinogenic initiation and/or promotion in hormone sensitive tissues. Bearing structural resemblance to estrogens, extensive studies have shown that many selective estrogen receptor modulators (SERMs) are subject to similar bioactivation pathways. Lasofoxifene (LAS), a third generation SERM which has completed phase III clinical trials for the prevention and treatment of osteoporosis, is currently approved in the European Union for this indication. Previously, Prakash et al. (Drug Metab. Dispos. (2008) 36, 1218-1226) reported that similar to estradiol, two catechol regioisomers of LAS are formed as primary oxidative metabolites, accounting for roughly half of the total LAS metabolism. However, the potential for further oxidation of these catechols to electrophilic o-quinones has not been reported. In the present study, LAS was synthesized and its oxidative metabolism investigated in vitro under various conditions. Incubation of LAS with tyrosinase, human liver microsomes, or rat liver microsomes in the presence of GSH as a trapping reagent resulted in the formation of two mono-GSH and two di-GSH catechol conjugates which were characterized by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Similar conjugates were also detected in incubations with P450 3A4, P450 2D6, and P450 1B1 supersomes. Interestingly, these conjugates were also detected as major metabolites when compared to competing detoxification pathways such as glucuronidation and methylation. The 7-hydroxylasofoxifene (7-OHLAS) catechol regioisomer was also synthesized and oxidized either chemically or enzymatically to an o-quinone that was shown to form depurinating adducts with DNA. Collectively, these data show that analogous to estrogens, LAS is oxidized to catechols and o-quinones which could potentially contribute to in vivo toxicity for this SERM.


Subject(s)
Estradiol/metabolism , Pyrrolidines/metabolism , Quinones/metabolism , Selective Estrogen Receptor Modulators/metabolism , Tetrahydronaphthalenes/metabolism , Animals , Catechols/chemistry , Catechols/metabolism , Cattle , Chromatography, High Pressure Liquid , Cytochrome P-450 Enzyme System/metabolism , DNA/chemistry , Estradiol/chemistry , Glutathione/metabolism , Humans , Microsomes, Liver/metabolism , Monophenol Monooxygenase/metabolism , Oxidation-Reduction , Pyrrolidines/chemistry , Quinones/chemistry , Rats , Selective Estrogen Receptor Modulators/chemistry , Stereoisomerism , Tandem Mass Spectrometry , Tetrahydronaphthalenes/chemistry
7.
Chem Biol Interact ; 196(1-2): 1-10, 2012 Mar 05.
Article in English | MEDLINE | ID: mdl-22290292

ABSTRACT

o-Quinone forming estrogens and selective estrogen receptor modulators (SERMs) have been associated with carcinogenesis. LY2066948, a novel SERM in development by Eli Lilly for the treatment of uterine fibroids and myomas, has structural similarity to the equine estrogen equilenin present in hormone replacement formulations; both contain a naphthol group susceptible to oxidative metabolism to o-quinones. LY2066948 was synthesized and assayed for antiestrogenic activity, and in cell culture was confirmed to be a more potent antiestrogen than the prototypical SERM, 4-hydroxytamoxifen. Oxidation of LY2066948 with 2-iodoxybenzoic acid gave an o-quinone (t(1/2)=3.9 ± 0.1h) which like 4-hydroxyequilenin-o-quinone (t(1/2)=2.5 ± 0.2 h) was observed to be exceptionally long-lived with the potential to cause cytotoxicity and/or genotoxicity. In model reactions with tyrosinase, the catechol metabolites of LY2066948 and equilenin were products; interestingly, in the presence of ascorbate to inhibit autoxidation, these catechols were formed quantitatively. Tyrosinase incubations in the presence of GSH gave the expected GSH conjugates resulting from trapping of the o-quinones, which were characterized by LC-MS/MS. Incubations of LY2066948 or equilenin with rat liver microsomes also gave detectable o-quinone trapped GSH conjugates; however, as observed with other SERMs, oxidative metabolism of LY2066948 mainly occurred on the amino side chain to yield the N-dealkylated metabolite. CYP1B1 is believed to be responsible for extra-hepatic generation of genotoxic estrogen quinones and o-quinone GSH conjugates were detected in equilenin incubations. However, in corresponding incubations with CYP1B1 supersomes, no o-quinone GSH conjugates of LY2066948 were detected. These studies suggest that although the naphthol group is susceptible to oxidative metabolism to long-lived o-quinones, the formation of these quinones by cytochrome P450 can be attenuated by the chemistry of the remainder of the molecule as in the case of LY2066948.


Subject(s)
Equilenin/analogs & derivatives , Naphthalenes/chemistry , Piperidines/chemistry , Quinones/chemistry , Selective Estrogen Receptor Modulators/chemistry , Animals , Aryl Hydrocarbon Hydroxylases/metabolism , Cell Line, Tumor , Cell Survival/drug effects , Cytochrome P-450 CYP1B1 , Cytochrome P-450 CYP3A/metabolism , Dose-Response Relationship, Drug , Equilenin/chemistry , Equilenin/metabolism , Female , Half-Life , Inhibitory Concentration 50 , Kinetics , Magnetic Resonance Spectroscopy , Microsomes, Liver , Naphthalenes/metabolism , Naphthalenes/pharmacology , Oxidation-Reduction , Piperidines/metabolism , Piperidines/pharmacology , Quinones/metabolism , Quinones/pharmacology , Rats , Rats, Sprague-Dawley , Selective Estrogen Receptor Modulators/metabolism , Selective Estrogen Receptor Modulators/pharmacology , Tandem Mass Spectrometry
8.
Acta Crystallogr C ; 66(Pt 1): m1-3, 2010 Jan.
Article in English | MEDLINE | ID: mdl-20048411

ABSTRACT

The asymmetric unit of the title salt, 2NH(4)(+).B(10)H(10)(2-).1.5H(2)O or (NH(4))(2)B(10)H(10).1.5H(2)O, (I), contains two B(10)H(10)(2-) anions, four NH(4)(+) cations and three water molecules. (I) was converted to the anhydrous compound (NH(4))(2)B(10)H(10), (II), by heating to 343 K and its X-ray powder pattern was obtained. The extended structure of (I) shows two types of hydrogen-bonding interactions (N-H...O and O-H...O) and two types of dihydrogen-bonding interactions (N-H...H-B and O-H...H-B). The N-H...H-B dihydrogen bonding forms a two-dimensional sheet structure, and hydrogen bonding (N-H...O and O-H...O) and O-H...H-B dihydrogen bonding link the respective sheets to form a three-dimensional polymeric network structure. Compound (II) has been shown to form a polymer with the accompanying loss of H(2) at a faster rate than (NH(4))(2)B(12)H(12) and we believe that this is due to the stronger dihydrogen-bonding interactions shown in the hydrate (I).

9.
Facts Views Vis Obgyn ; 2(2): 119-24, 2010.
Article in English | MEDLINE | ID: mdl-25302106

ABSTRACT

AIM: Criteria for future accreditation of breast cancer centres in Belgium will be mainly based on the case load per surgeon or per centre. We would like to argue that the prospective collection of relevant data and the analysis of treatment related outcome derived from these data is feasible and should be the ultimate criterion for quality assessment and thus for accreditation since outcome is a more direct measurement of quality. METHODS: Data were prospectively collected on 715 invasive non metastatic breast cancers between 2002 and 2007 treated according to standard, best-evidence protocols in the setting of a large district hospital. Univariate and multivariate survival analysis were performed and compared to national and international databases. RESULTS: 5 year disease-free survival (DFS) and overall survival (OS) in our series were respectively 77 and 84%. In the multivariate analysis of DFS, only her-2-neu status (her-2-neu positivity being associated with a poor prognosis) and age (older age being a worse prognostic factor) were statistically significant prognostic factors. For OS, her-2-neu, age, and positive nodes were statistically significant prognostic factors. The outcome is comparable to other data sets. CONCLUSION: Centres dedicated to the care of women with breast cancer have the moral duty to produce outcome based results of their treatment. This report shows that such a collection of data is feasible and can be imposed as a prerequisite for accreditation. We also argue that outcome based data of treatment are a more solid base for quality assurance than case load.

10.
Chemistry ; 15(9): 2190-9, 2009.
Article in English | MEDLINE | ID: mdl-19145600

ABSTRACT

Chains of cages: Neutral/ionic [B(12)H(12)](2-) boron-cage-functionalized methacrylate and styrene homopolymers or copolymers (see picture) are non-crystalline solids, T(g) increases as the number of B(12) cages in the chain of polystyrene increases, and homopolymers retain more weight than the copolymers when heated to 400 degrees C.New [B(12)H(12)](2-) boron cage functionalized neutral and ionic methacrylate and styrene monomers (1, 2, 3) were synthesized and these monomers were used to prepare homopolymers (4, 5, 6) and copolymers with methylmethacrylate (MMA) (7, 8), 2-hydroxyethylmethacrylate (HEMA) (11, 12, 13, 17), 2-hydroxyethylacrylate (HEA) (14, 15, 18), acrylamide (AA) (16), and styrene (9, 10, 19) with different monomer ratios. Free-radical initiated bulk and solution polymerization methods were used to synthesize these polymers and they were characterized by (1)H NMR, (11)B NMR, and IR spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and gel permeation chromatography (GPC). Generally, the polymers show broad (1)H NMR and (11)B NMR peaks compared to their respective monomers. The copolymers have high molecular weights with higher [B(12)H(12)](2-) boron cage mole ratios. All the polymers on which DSC experiments were conducted (4 b, 5 b, 6 b, 7, 8, 9, 10, 17, 18, and 19) are non-glassy amorphous solids, except styrene copolymers (9, 19) and homopolymer (6 b) which show T(g) values of 100, 117, and 162 degrees C, respectively. Copolymers 9 and 10 have higher thermal stability (320 degrees C) than polymers 5 b, 4 b, and 8, which are stable up to 244, 250, and 260 degrees C, respectively. The homopolymers retained more weight than the copolymers when they were heated to 400 degrees C.


Subject(s)
Boron Compounds/chemistry , Boron Compounds/chemical synthesis , Polymers/chemistry , Polymers/chemical synthesis , Hot Temperature , Magnetic Resonance Spectroscopy , Methacrylates/chemical synthesis , Methacrylates/chemistry , Molecular Structure , Polystyrenes/chemical synthesis , Polystyrenes/chemistry , Spectrophotometry, Infrared
11.
Acta Crystallogr Sect E Struct Rep Online ; 65(Pt 9): o2175, 2009 Aug 19.
Article in English | MEDLINE | ID: mdl-21577581

ABSTRACT

In the title salt, C(15)H(17)N(2) (+)·ClO(4) (-), the isoindoline N atom is protonated and an intra-molecular N-H⋯N hydrogen bond occurs. In the crystal, N-H⋯O and numerous weak C-H⋯O inter-actions occur between the cation and anion. The O atoms of the perchlorate anion are disordered over four sets of sites with occupancies of 0.438 (4), 0.270 (9), 0.155 (8) and 0.138 (5).

12.
Ethiop. j. health dev. (Online) ; 23(2): 98-106, 2009.
Article in English | AIM (Africa) | ID: biblio-1261725

ABSTRACT

Background: Child malnutrition is a major public health problem in Ethiopia. Surprisingly; the highest level of stunting is found in food surplus areas of the country. Objective: To identify the determinants of stunting in food surplus areas of West Gojam Zone. Method: A community based cross-sectional survey was conducted on 622 mother-child pairs of 0-59 month old children in Mecha and Wenberma Woredas of West Gojam Zone; Northern Ethiopia between May and June 2006. The study investigated the differential impact of demographic and socio-economic factors; health related factors and dietary factors on stunting among under-five children. Both bivariate analysis and multivariate analysis (logistic regression model) were used to identify the determinants of under-five stunting. Results: The analyses revealed that 43.2 (12.0-17.6) 95CI percent of the children under age five were suffering from chronic malnutrition; 14.8 (39.3-47.1) 95CI percent were acutely malnourished and 49.2 (45.3-53.1) 95CI percent were found to be under-weight. The main contributing factors for under-five stunting were found to be sex of the child; child's age; diarrhea episode; deprivation of colostrum; duration of breastfeeding; pre-lacteal feeds; type of food; age of introduction of complementary feeding and method of feeding. Conclusion: The findings of this study led to the realization that inappropriate feeding practice is the principal risk factor which brought about nutritional deprivation among under-five children in food surplus areas of Ethiopia. Thus; the importance of appropriate feeding during infancy and childhood cannot be overstated even in food surplus areas. The high prevalence of malnutrition in the study area points out the need to revisit the impression held by many people that malnutrition is not a problem in food surplus areas. Development and implementation of preventive policies aimed at addressing child malnutrition should also consider food surplus areas of the country


Subject(s)
Epidemiologic Factors , Malnutrition
13.
Acta Crystallogr Sect E Struct Rep Online ; 64(Pt 2): m323, 2008 Jan 09.
Article in English | MEDLINE | ID: mdl-21201292

ABSTRACT

Each Cu atom in the dinuclear centrosymmetric title complex, [Cu(2)Br(2)(C(14)H(17)N(3))(2)](ClO(4))(2), is ligated in a distorted square-pyramidal geometry (τ = 0.31) by a tridentate bis-[2-(2-pyrid-yl)eth-yl]amine ligand, and by two bridging Br atoms. In addition, the dinuclear species is stabilized by two hydrogen-bonded perchlorate anions.

14.
Acta Crystallogr Sect E Struct Rep Online ; 64(Pt 2): o377-8, 2008 Jan 04.
Article in English | MEDLINE | ID: mdl-21201408

ABSTRACT

The title compound, C(8)H(14)N(2) (2+)·C(12)H(8)N(2)O(8)P(-)·ClO(4) (-), was formed by the reaction of α,α-bis-m-xylenediamine and sodium bis-p-nitro-phenyl-phosphate in the presence of Zn(ClO(4))·6H(2)O in methanol solution. The two amine groups of the m-xylenediammonium ion are each protonated and each hydrogen-bonded to two O atoms of the phosphate anion, which acts as a 1,3-bridge. The ammonium groups are arranged matched face to face and each pair is doubly bridged by two perchlorate ions through hydrogen bonding. In addition, there are also weak C-H⋯O inter-actions. Both the N-H⋯O and C-H⋯O inter-actions are contained in a channel down the a axis. The perchlorate oxygen atoms are disordered over two positions with site occupancy factors of ca 0.7 and 0.3.

15.
Acta Crystallogr Sect E Struct Rep Online ; 64(Pt 1): m233-4, 2007 Dec 21.
Article in English | MEDLINE | ID: mdl-21200577

ABSTRACT

In the title compound, [Cu(ClO(4))(2)(C(12)H(13)N(3))(C(2)H(3)N)], the Cu(II) atom is six-coordinate in a Jahn-Teller distorted octahedral geometry, with coordination by the tridentate chelating ligand, an acetonitrile mol-ecule, and two axial perchlorate anions. The tridentate ligand bis-(2-pyridylmeth-yl)amine chelates meridionally and equatorially while an acetonitrile mol-ecule is coordinated at the fourth equatorial site. The two perchlorate anions are disordered with site occupancy factors of 0.72/0.28. The amine H is involved in intra-molecular hydrogen bonding to the perchlorate O atoms and there are extensive but weak inter-molecular C-H⋯O inter-actions.

16.
Acta Crystallogr Sect E Struct Rep Online ; 64(Pt 1): m74-5, 2007 Dec 06.
Article in English | MEDLINE | ID: mdl-21200643

ABSTRACT

The title compound, [Cu(C(6)H(8)N(2))(C(13)H(15)N(3))](ClO(4))(2), is a mixed ligand complex with the Cu(II) atom coordinated by (6-methyl-2-pyridylmeth-yl)(2-pyridylmeth-yl)amine, acting as a tridentate ligand, and 2-(2-amino-meth-yl)pyridine, as a bidentate ligand, leading to an N(5) square-pyramidal geometry. The amine H atoms are involved in hydrogen bonding to the perchlorate O atoms and there are extensive but weak inter-molecular C-H⋯O inter-actions in the crystal structure. The perchlorate ions are each disordered over two positions, with site occupancies of 0.601 (8):0.399 (8) and 0.659 (11):0.341 (11).

17.
Inorg Chem ; 45(7): 3023-33, 2006 Apr 03.
Article in English | MEDLINE | ID: mdl-16562958

ABSTRACT

The dinucleating ligand, 2,6-bis{[(2-(2-pyridyl)ethyl)(2-pyridylmethyl)-amino]-methyl}-4-methylphenol) (L1OH) reacts with Mn(ClO4)2.6H2O to form the dinuclear complex [Mn2(II,II)(L1O)(mu-OOCCH3)2]ClO4 (1). The electrolytic oxidation of 1 at 0.7 V (vs Ag/AgCl) produces the mixed valent complex [Mn2(II,III)(L1O)(mu-OOCCH3)2](ClO4)2 (1ox) quantitatively, while electrolysis at 0.20 V converts 1ox back to 1. X-ray crystallographic structures show that both 1 and 1ox are dinuclear complexes in which the two manganese ions are each in distorted octahedral coordination environments bridged by the phenoxo oxygen and two acetate ions. The structural changes that occur upon the oxidation 1 to 1ox suggest an extended pi-bonding system involving the phenoxo ring C-O(phenoxo)-Mn(II)-N(pyridyl) chain. In addition, as 1 is oxidized to 1ox, the rearrangements in the coordination sphere resulting from the oxidation of one Mn(II) ion to Mn(III) are transmitted via the bridging Mn-O(phenoxo) bonds and cause structural changes that render the site of the second manganese ion unfit for the +3 state and hence unstable to reduction. Thus the electrolytic oxidation of 1ox in acetonitrile at 1.20 V takes up slightly greater than 1 F of charge/mol of 1ox, but the starting complex, 1ox, is recovered, showing the instability of the Mn2(III,III) state that is formed with respect to reduction to 1ox. Variable-temperature magnetic susceptibility measurements of 1 and 1ox over the temperature range from 1.8 to 300 K can be modeled with magnetic coupling constants J = -4.3 and -4.1 cm(-1), respectively showing the weak antiferromagnetic coupling between the two manganese ions in each dinuclear complex, which is commonly observed among similar phenoxo- and bis-1,3-carboxylato-bridged dinuclear Mn2(II,II) and Mn2(II,III) complexes.


Subject(s)
Manganese/chemistry , Organometallic Compounds/chemistry , Crystallography, X-Ray , Electrochemistry , Ligands , Magnetics , Models, Molecular , Molecular Structure , Organometallic Compounds/chemical synthesis , Oxidation-Reduction , Temperature
18.
Inorg Chem ; 42(6): 1857-67, 2003 Mar 24.
Article in English | MEDLINE | ID: mdl-12639118

ABSTRACT

The syntheses and structural, spectral, and electrochemical characterization of the dioxo-bridged dinuclear Mn(III) complexes [LMn(mo-O)(2)MnL](ClO(4))(2), of the tripodal ligands tris(6-methyl-2-pyridylmethyl)amine (L(1)) and bis(6-methyl-2-pyridylmethyl)(2-(2-pyridyl)ethyl)amine (L(2)), and the Mn(II) complex of bis(2-(2-pyridyl)ethyl)(6-methyl-2-pyridylmethyl)amine (L(3)) are described. Addition of aqueous H(2)O(2) to methanol solutions of the Mn(II) complexes of L(1) and L(2) produced green solutions in a fast reaction from which subsequently precipitated brown solids of the dioxo-bridged dinuclear complexes 1 and 2, respectively, which have the general formula [LMn(III)(mu-O)(2)Mn(III)L](ClO(4))(2). Addition of 30% aqueous H(2)O(2) to the methanol solution of the Mn(II) complex of L(3) ([Mn(II)L(3)(CH(3)CN)(H(2)O)](ClO(4))(2) (3)) showed a very sluggish change gradually precipitating an insoluble black gummy solid, but no dioxo-bridged manganese complex is produced. By contrast, the Mn(II) complex of the ligand bis(2-(2-pyridyl)ethyl)(2-pyridylmethyl)amine (L(3a)) has been reported to react with aqueous H(2)O(2) to form the dioxo-bridged Mn(III)Mn(IV) complex. In cyclic voltammetric experiments in acetonitrile solution, complex 1 shows two reversible peaks at E(1/2) = 0.87 and 1.70 V (vs Ag/AgCl) assigned to the Mn(III)(2) <--> Mn(III)Mn(IV) and the Mn(III)Mn(IV) <--> Mn(IV)(2) processes, respectively. Complex 2 also shows two reversible peaks, one at E(1/2) = 0.78 V and a second peak at E(1/2) = 1.58 V (vs Ag/AgCl) assigned to the Mn(III)(2) <--> Mn(III)Mn(IV) and Mn(III)Mn(IV) <--> Mn(IV)(2) redox processes, respectively. These potentials are the highest so far observed for the dioxo-bridged dinuclear manganese complexes of the type of tripodal ligands used here. The bulk electrolytic oxidation of complexes 1 and 2, at a controlled anodic potential of 1.98 V (vs Ag/AgCl), produced the green Mn(IV)(2) complexes that have been spectrally characterized. The Mn(II) complex of L(3) shows a quasi reversible peak at an anodic potential of E(p,a) of 1.96 V (vs Ag/AgCl) assigned to the oxidation Mn(II) to Mn(III) complex. It is about 0.17 V higher than the E(p,a) of the Mn(II) complex of L(3a). The higher oxidation potential is attributable to the steric effect of the methyl substituent at the 6-position of the pyridyl donor of L(3).

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