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The ferriannite KFe(3)(2+)(Al(0.26)Fe(0.76)(3+)Si(3))O(10)(OH)(2) at 100 and 270 K.

Unusually large and good-quality single crystals of the synthetic trioctahedral mica KFe(3)(2+)(Al(0.26)Fe(0.76)(3+)Si(3))O(10)(OH)(2) [potassium triiron(II) aluminasilaferrate(III) decaoxide dihydroxide] have been grown hydrothermally. X-ray diffraction data measured at 270 and 100 K have been used to refine the crystal structure, including the positions of the H atoms. This synthetic mica is similar to annite, KFe(3)AlSi(3)O(10)(OH)(2), and crystallizes with the same monoclinic C2/m symmetry. No phase transition has been observed down to 100 K. At low temperature, the ditrigonal distortion of the mica structure increases markedly, while the octahedral and tetrahedral bond lengths tend to decrease and increase, respectively. A detailed comparison of structural parameters in various Fe-rich micas is presented.

Journal Article↗

3D porous and 3D interpenetrating triple framework structures constructed by aurophilicity-coordination interplay in [Mn[Au(CN)2]2(H2O)2]n and [KFe[Au(CN)2]3]n.

Two cyano-bridged heterobimetallic coordination polymers [Mn[Au(CN)2]2(H2O)2]n (1) and [KFe[Au(CN)2]3]n (2), have been synthesized from [Au(CN)2]- building blocks and structurally characterized. In both complexes aurophilicity play an important role in determining the 3D open microporous framework and the interpenetrating triple framework for 1 and 2, respectively. Both aqueous solutions of 1 and 2 display interesting luminescent properties.

Journal Article↗

The effect of diet on tissue levels of kinin-forming enzyme in blood-free rat gastro-intestinal tract.

1. Kallikreins, kinin-forming enzymes, are present in the wall of the gastro-intestinal tract. The role of the kinin-forming system in the gut is unknown. In the present study, a modified bio-assay technique was used to detect the presence of tissue concentration gradients of kinin-forming enzyme (KFE) at different levels of the rat gastro-intestinal tract and the effect on them of diet.2. Segments of rat gut, perfused free of blood, were homogenized in 0.1 N-HCl and activated by autolytic processes. Total KFE content was then determined by incubation of extract with standard kinin-forming substrate, followed by bio-assay of the released kinin using superfused oestrous rat uterus. Acid extraction of the KFE gave a recovery of 127.4% when compared with simple water extraction.3. Tissue concentrations of KFE were determined in stomach, duodenum, jejunum, terminal ileum, caecum and proximal and distal colon. Concentrations were determined after (A) normal diet, (B) water ad libitum for 24 hr and (C) isotonic glucose ad libitum for 60 hr.4. All the gut tissues contained KFE. After diet A there was least (19.5 +/- 1.0 ng bradykinin equivalent formed per minute (KU) per gram wet weight) in the stomach and a single large peak (504 +/- 92 KU .g(-1) wet weight) in the caecum.5. The different dietary states produced changes only in the duodenum, the caecum and the distal colon. The duodenal level was raised when the organ was empty after diet B (140 +/- 29 KU .g(-1)) and fell when filled with solid or fluid after diets A (57 +/- 14 KU .g(-1)) and C (80 +/- 17 KU .g(-1)) respectively. The caecal KFE level, which was high when the lumen was full after diet A, fell progressively as it was increasingly emptied after diets B (213 +/- 41 KU .g(-1)) and C (105 +/- 42 KU .g(-1)) respectively. The KFE concentration in the distal colon was low when the lumen was full after diets A (58 +/- 10 KU .g(-1)) and B (66 +/- 17 KU .g(-1)) and rose when the lumen was nearly empty after diet C (118 +/- 17 KU .g(-1)).6. Kinin-forming activity in rat intestinal extracts had a pH optimum at pH 8.5 and formed a bradykinin-like spasmogen. The increased activity in the fasted rat duodenum was not significantly inhibited by soybean trypsin inhibitor (100 mug/ml.) while that in caeci from fed rats was inhibited by 17% (P < 0.05).7. These changes may indicate physiological involvement of the kallikrein-kinin system in these organs.

Animals↗

Property of kinin-forming enzyme in rat stomach.

The effects of inhibitors on the kinin-forming enzyme (KFE) activity in the rat stomach were investigated at pH 4.8. The KFE activity was unaffected by trasylol (200 KIU/ml), soybean trypsin inhibitor (100 microgram/ml) and p-tosyl-L-lysine-chloromethyl ketone (10-3 M), but was inhibited by pepstatin A (10(-6) M) and chymostatin (1.5 x 10(-4) M). Each product from the rat plasma kininogen by the rat stomach KFE and the bovine spleen cathepsin D was eluated at the same retention time on the equilibrium chromatography on the SP-Sephadex C-25 column. The KFE activity in the rat stomach was considerably high compared with that in various regions of the intestine. These results suggest that the KFE is characteristically similar to cathepsin D, and the enzyme is probably relevant to the function of the stomach.

Animals↗

Ferrocyanide carbon-13 NMR line broadening as a probe of electron transfer reactions.

The electron transfer reaction between ferrocyanide ion and the blue copper protein, stellacyanin, has been investigated by means of 13C NMR line broadening of the inorganic oxidant. The temperature dependence of the ferrocyanide line broadening gives an activation energy for the electron transfer reaction of 17 +/- 3 kJ. The apparent rate constant decreases with increasing concentration of K4Fe(CN)6, a result which can be explained either by formation of a strong precursor ferrocyanide--stellacyanin [Cu(II)] complex or by increased formation of KFe(CN)3-6 ion pairs. The direct electron transfer between ferrocyanide and ferricyanide has also been studied by 13C NMR line broadening of the former species. The ferricyanide concentration dependence of the exchange line broadening yields a value for the apparent second-order rate constant at 25 degrees C of k = 1.65 . 10(3) M-1 . s-1, in agreement with previously reported values derived from 14N NMR and isotope exchange studies. This rate constant shows a linear dependence on the K+ concentration, independent of ionic strength, a result which confirms the importance of ion pair species such as KFe(CN)3-6 and KFe(CN)2-6 in the direct electron transfer mechanism. The general applications of the method are discussed, including the considerations which suggest that a wide range of electron transfer rates, from about 1 s-1 to 4 . 10(3) s-1, are, in principle, accessible to this technique. The potential utility of ferrocyanide 13C spin--lattice relaxation time measurements is decreasing the lower limit of this range is also discussed.

Electron Transport↗

Bioavailability of iron and cyanide from 59Fe- and 14C-labelled hexacyanoferrates(II) in rats.

"Soluble" (KFe(III)[Fe(II)(CN)6]) and "insoluble Prussian blue" (Fe(III)4[Fe(II)(CN)6]3 labelled with 59Fe either in the ferric (Fe(III)) or ferro (Fe(II)) position and 14C in the cyanide group were synthesized and administered intraperitoneally or orally to adult female rats with normal body iron stores. Following i.p. injection of KFe[Fe(CN)6], the colloidal complex is disintegrated into ferric iron and hexacyanoferrate(II) anion almost completely. About 96% of the ferric iron was retained in the body. Nearly 90% of both ferrous iron and cyanide were excreted with the urine within 7 days after i.p. injection, indicating that most of the undissociated hexacyanoferrate(II) anion ([Fe(CN)6]4-) was excreted through the kidney. Only 9% of the ferrous iron from [Fe(CN)6]4- was found mainly in carcass, liver and gut. As the 59Fe/14C-ratios in organs were found close to 1.0, the dissociation of the hexacyanoferrate(II) anion can only be small in vivo. No detectable 14CO2-activity (less than 0.01%) was monitored in the breath of rats after i.p. injection of the 14C-labelled KFe[Fe(CN)6], also indicating that no significant amounts of cyanide were released after parenteral administration. After oral administration of the soluble and insoluble Prussian blue, 0.3-0.7% of the ferric iron was absorbed and retained mainly in carcass, liver and blood. Only 0.06-0.18% of the ferrous iron was absorbed and mostly excreted with the urine (0.05-0.15%), so that only 0.01-0.03% of the oral ferrous 59Fe was retained in the body after 7-10 days. Very small fractions of 14C-label from the 14CN-group of the soluble and insoluble hexacyanoferrate(II) were observed in the exhaled air (0.04-0.08% of the oral dose). From the 14CO2-exhalation, the 14C-urine excretion and the distribution of iron in blood and organs it can be concluded that the hexacyanoferrate(II) moiety disintegrated only to a small extent in the intestinal tract after oral administration. From a dose of 36 mg hexacyanoferrate(II)/kg, an amount of free (non-complex bound) cyanide can be calculated which is in maximum two orders of magnitude below the LD100-level. Thus, the very low bioavailability of iron and cyanide from hexacyanoferrate(II) compounds after oral application is demonstrated in rats. In the case of a severe nuclear accident, appropriate doses of "soluble" and "insoluble" Prussian blue can be used as safe and effective antidote against radiocaesium contamination.

Animals↗

Reactivity patterns for redox reactions of monomer forms of myoglobin, hemocyanin and hemerythrin.

Electron-transfer reactions of myoglobin, hemocyanin and hemerythrin with the inorganic complexes [Fe(CN)6]3- (oxidant) and [Co(sep)]2+ (reductant) are considered. Rate constants kFe (25 degrees C) have been determined for the [Fe(CN)6]3- (410 mV) oxidation of horse deoxyMb, I = 0.100 M (NaCl). From the decrease in kFe over the range pH 5.5 to 9.0 a pKa of less than 6.2 is obtained, most likely due to the involvement of the heme propionate(s). At the higher pH values the rate constant is 1.2 x 10(6) M-1 s-1. Rate constants kCo (25 degrees C) for the [Co(sep)]2+ (-260 mV) reduction of metMb are also pH-dependent, pKa = 8.82, corresponding to acid dissociation of the H2O axially coordinated to the Fe(III). The rate constant for the aqua-met form is 2.8 x 10(3) M-1 s-1 at pH values less than 7.0. In contrast, no reaction is observed for the deoxy and met forms of P. interruptus hemocyanin monomer subunit a with the same two complexes (k less than 10(2) M-1 s-1). Comparisons are made with rate constants for hemerythrin, also as the monomer, which have been determined previously. Rate constants for the reactions of deoxy forms with the neutral small molecules, here O2 and H2O2, are also considered. Whereas the reactions of [Fe(CN)6]3- and [Co(sep)]2+ are at the protein surface, those of O2 and H2O2 are at the active site. Hemocyanin with the more buried (approximately 20 A) active site compared with myoglobin (3.8 A) and hemerythrin (6.3 A), does not readily undergo electron transfer with reagents at the surface. However, with the small molecules O2 and H2O2 penetration of the surrounding peptide occurs, with reaction at the active site. Rate constants for the three proteins are now of similar magnitude, and in the range (2.3-7.8) x 10(7) M-1 s-1 for O2, and 10.9 to 3600 M-1 s-1 for H2O2.

Animals↗

Assessment of isokinetic muscle strength in women who are obese.

STUDY DESIGN: Cross-sectional study of isokinetic trunk and knee muscle strength in women who are obese. OBJECTIVE: To provide reference values, to identify variables that affect peripheral muscle strength, and to provide recommendations for isokinetic testing of trunk and knee muscles in women who are obese and morbidly obese. BACKGROUND: The assessment of peripheral muscle strength is useful for the quantification of possible loss of strength, for exercise prescription, and for the evaluation of the effect of training programs in obese individuals. METHODS AND MEASURES: Isokinetic trunk and leg muscle strength was assessed in 241 women who were obese (18-65 years, body mass index (BMI) > or = 30 kg/m2). Trunk flexion and extension peak torque (PT) was measured using the Cybex TEF dynamometer; trunk rotation (TR) PT was measured using the Cybex TORSO dynamometer; and knee flexion/extension (KFE) PT was measured using the Cybex 350 dynamometer. Body composition was assessed using the bioelectrical impedance method; physical activity was assessed using the Baecke questionnaire; and peak VO2 was assessed using an incremental exercise capacity test on a bicycle ergometer. To identify variables related to muscle strength, Pearson correlations were computed and a stepwise multiple regression analysis was performed. RESULTS: Pearson correlation coefficients of all strength measurements at 60 degrees/s revealed low-to-moderate negative associations with age and positive associations with mass, height, fat free mass (FFM), and peak VO2 (P < 0.05), except for gravity-uncorrected trunk extension strength, which was not related to mass. The sports index of the Baecke questionnaire was associated with TR PT (r = 0.20, P < 0.01) and KFE PT (r = 0.18, P < 0.05). CONCLUSION: The weight of the trunk accounts largely for the measured trunk extensor and flexor strength in women who are obese. Contributing variables of isokinetic trunk flexion and extension strength in women who are obese are age, height, and FFM; whereas sports activities and aerobic fitness are contributing factors for trunk rotational and knee extension strength. Recommendations for measuring isokinetic muscle strength in individuals who are obese are provided.

Adult↗

Ultrastructure of the epidermal barrier after irritation.

The stratum corneum (SC) controls the diffusion and penetration of chemical substances and drugs into and through the skin. Surprisingly, knowledge of the SC structure and reaction to the various irritants is still poorly understood. Routine transmission electron microscopy has not been effective in demonstrating the epidermal lipids (EL) of SC which are believed to morphologically represent the water permeability barrier. To gain a better understanding of the interaction of chemically different irritants with the SC, we investigated the ultrastructural changes of epidermal lipids resulting from the topical application of sodium dodecyl sulfate (SDS 0.5% and 1% w/v) and absolute acetone. The disturbance of barrier function by these irritants was determined by the increase of transepidermal water loss (TEWL). Punch biopsies from the treated sites showed a maximum increase of TEWL. To visualize the EL which derive from lamellar body (LB) lipids (sheets), we used a special fixation method utilizing 0.5% ruthenium tetroxide/0.25% KFe(CN)6 as the postfixative. The 0.5% SDS caused cell damage to the nucleated cells of the epidermis with disturbance of LB lipid extrusion and the transformation into the lipid bilayers. However, the upper portions of SC displayed intact intercellular lipid layers. With the acetone treatment, the EL lamellae showed disruption and loss of cohesion between the lamellae at all levels of the SC. The more polar LB lipids appeared more resistant to acetone. The results of this study suggest that different irritants induce distinct and characteristic alterations to reflect the specific interaction with the epidermal permeability barrier.

Acetone↗

Complex stability of ferrous ascorbate in aqueous solution and its significance for iron absorption.

The greater absorption of iron in vivo from ferrous ascorbate [Fe(HL)2] as compared with ferrous sulfate has been ascribed both to retardation or prevention of Fe(II) oxidation by ascorbate and to the existence of Fe(II) as a chelate with ascorbate. The available literature and our own results demonstrate that Fe(HL)2 dissociates in aqueous solution into a monomeric cationic species Fe(HL)1+, Fe2+ and HL-. The HL anion acts as a monodentate. The low stability constant KFe(HL)1, about 20 l.mol-1 at mu = 0 and 25 degrees C, results in the conclusion that Fe(HL)2 is almost completely dissociated into Fe2+ and HL- at about pH = 5, so (chelate) complex formation does not contribute significantly to the increased iron absorption. Between pH = 6 and pH = 8 a solubility enhancing effect of ascorbate is observed which may be of relevance for the iron absorption from ferrous ascorbate.

Absorption↗

Prevention of enteral radiocesium absorption by hexacyanoferrates(II) in piglets.

The efficacy of different hexacyanoferrates(II) in preventing the enteral absorption of 134Cs was studied in piglets. As compared to the controls, oral application of 134Cs together with KFe[Fe(CN)6], NH4Fe[Fe(CN)6], or Fe4[Fe(CN)6]3 resulted in a strong reduction of the 134 Cs-uptake by more than 97%. The decrease in enteral absorption depends on the dose of administered hexacyanoferrate(II), whereas differences between the compounds under study were small. The biological half-life of 134Cs in non-hexacyanoferrate(II) treated piglets was 21.6 +/- 3.3 days (mean +/- SD).

Animals↗

Bioavailability of iron and cyanide from oral potassium ferric hexacyanoferrate(II) in humans.

After oral administration of 500 mg KFe[Fe(CN)6] labelled with 59Fe either in the ferric or ferrous position and with 14C in the cyanide group only 0.22% of the FeII and less than 0.04% of the FeIII were absorbed in three male volunteers. Only 2 mg non-complex bound 14C-labelled cyanide (0.03 mg CN-/kg body wt) were absorbed from 500 mg [14C]KFeHCF, which is about a factor of 20-100 below the lethal dose in humans (0.5-3.5 mg CN-/kg body wt). Therefore, iron(III) hexacyanoferrates(II) can be considered as safe antidotes, i.e. for inhibiting the intestinal absorption of radiocaesium or for accelerating the excretion of already absorbed 134/137Cs in the case of a severe nuclear accident.

Biological Availability↗

Inhibition of intestinal absorption and decorporation of radiocaesium in humans by hexacyanoferrates(II).

The effect of hexacyanoferrate(II) preparations, KFe[Fe(CN)6], (KFeHCF) anol Fe4[Fe(CN)6]3, (FeHCF) on intestinal radiocaesium absorption was studied in two male volunteers. The 134Cs absorption was decreased from 100 to 3-10% when 500-1000 mg KFeHCF or FeHCF were administered 10 min before the 134Cs-labelled test meal. However, when HCF was administered simultaneously with the test meal, the 134Cs absorption was decreased to only 38-63%. The biological half-time of previously absorbed 134Cs was reduced from 106 (73) to 44 (46) days by daily administration of 3 times 0.5 g KFeHCF. The 134Cs dose conversion factors lie below the values recommended by IRCP 30, indicating that the IRCP model represents a cautious description of the Cs biokinetics in our study.

Adult↗

Properties of hydrocarbon- and salt-contaminated flare pit soils in northeastern British Columbia (Canada).

Many contaminated sites in Canada are associated with flare pits generated during past petroleum extraction operations. Flare pits are located adjacent to well sites, compressor stations and batteries and are often subjected to the disposal of wastes from the flaring of gas, liquid hydrocarbons and brine water. This study was conducted to evaluate the physical, chemical, electrical and mineral properties of three flare pit soils as compared to adjacent control soils. Results showed that particle size distribution, pH, total N, cation exchange capacity, exchangeable Mg(2+), and sodium adsorption ratio were similar in soils from flare pits and control sites. Total C, exchangeable Ca(2+), K(+) and Na(+), soluble Ca(2+), Mg(2+), K(+) and Na(+) and electrical conductivity were higher in flare pit soils compared to control soils. X-ray diffraction and scanning electron microscopic analyses showed the presence of gypsum [CaSO(4).2H(2)O], dolomite [CaMg(CO(3))(2)], pyrite [FeS(2)], jarosite [KFe(3)(OH)(6)(SO(4))(2)], magnesium sulphate, oxides of copper and iron+copper in salt efflorescence observed in flare pit soils. Soils from both flare pits and control sites contained mica, kaolonite and 2:1 expanding clays. The salt-rich materials altered the ionic equilibria in the flare pit soils; K(Mg-Ca) selectivity coefficients in control soils were higher compared to contaminated soils. The properties of soils (e.g., high electrical conductivity) affected by inputs associated with oil and gas operations might render flare pit soils less conducive to the establishment and growth of common agricultural crops and forest trees.

British Columbia↗

(57)Fe Mössbauer isomer shifts of heme protein model systems: electronic structure calculations.

We report the results of density functional theory (DFT) calculations of the (57)Fe Mössbauer isomer shifts (delta(Fe)) for a series of 24 inorganic, organometallic, and metalloprotein/metalloporphyrin model systems in S = 0, (1)/(2), 1, (3)/(2), 2, and (5)/(2) spin states. We find an excellent correlation between calculation and experiment over the entire 2.34 mm s(-1) range of isomer shifts: a 0.07-0.08 mm s(-1) rms deviation between calculation and experiment (corresponding to 3-4% of the total delta(Fe) range, depending on the functionals used) with R(2) values of 0.973 and 0.981 (p < 0.0001). The best results are obtained by using the hybrid exchange-correlation functional B3LYP, used previously for (57)Fe Mössbauer quadrupole splittings and (57)Fe NMR chemical shifts and chemical shielding anisotropies. The relativistically corrected value of alpha, alpha(rel), converges with the large basis set used in this work, but the exact values vary somewhat with the methods used: -0.253 a(0)(3) mm s(-1) (Hartree-Fock; HF); -0.316 a(0)(3) mm s(-1) (hybrid HF-DFT; B3LYP), or -0.367 a(0)(3) mm s(-1) (pure DFT; BPW91). Both normal and intermediate spin state isomer shifts are well reproduced by the calculations, as is the broad range of delta(Fe) values: from [Fe(VI)O(4)](2-) (-0.90 mm s(-1) expt; -1.01 mm s(-1) calc) to KFe(II)F(3) (1.44 mm s(-1) expt; 1.46 mm s(-1) calc). Molecular orbital analyses of all inorganic solids as well as all organometallic and metalloporphyrin systems studied reveal that there are three major core MO contributions to rho(tot)(0), the total charge density at the iron nucleus (and hence delta(Fe)), that do not vary with changes in chemistry, while the valence MO contributions are highly correlated with delta(Fe) (R(2) = 0.915-0.938, depending on the functionals used), and the correlation between the valence MO contributions and the total MO contribution is even better (R(2) = 0.965-0.976, depending on the functionals used). These results are of general interest since they demonstrate that DFT methods now enable the accurate prediction of delta(Fe) values in inorganic, organometallic, and metalloporphyrin systems in all spin states and over a very wide range of delta(Fe) values with a very small rms error.

Electrochemistry↗

Efficacy of different hexacyanoferrates(II) in inhibiting the intestinal absorption of radiocaesium in rats.

The inhibitory effect of various oral doses of different hexacyanoferrate(II) compounds (HCF) and the influence of the time interval of HCF-administration on intestinal 134Cs-absorption was studied in rats. Optimum inhibition was obtained by administration of HCF together with or 2 min before oral 134Cs loading. Using appropriate low amounts (0.1-0.5 mg) of the different HCF compounds, the inhibitory effect increased in the sequence KZnHCF less than KCuHCF less than FeHCF less than KCoHCF = KNiHCF less than NH4FeHCF = KFeHCF. Oral administration of 5 mg (0.5 mg) of KFeHCF, together with 134CsCl loading, reduces 134Cs-absorption from 41% (control) to 0.8% (2.8%). Zinc-, copper-, cobalt, and nickel hexacyanoferrates(II), despite showing a high caesium sorption capacity in vitro, were less effective in rats and are not suited for in vivo application, also because they may produce toxic side effects. As a consequence, the orally administered colloidal-soluble iron(III) hexacyanoferrates(II) (NH4Fe[Fe(CN)6] and KFe[Fe(CN)6]) have to be considered as the most valuable countermeasure against radiocaesium absorption for humans and domestic animals in the case of a severe nuclear accident in the future. Manganese oxide, a non-hexacyanoferrate(II) compound with known in vitro caesium binding capacity, showed no inhibitory effect on radiocaesium absorption in rats.

Animals↗

The antibiotic tiamulin is a potent inducer and inhibitor of cytochrome P4503A via the formation of a stable metabolic intermediate complex. Studies in primary hepatocyte cultures and liver microsomes of the pig.

Tiamulin is a semisynthetic antibiotic frequently used in agricultural animals. The drug has been shown to produce clinically important--often lethal--interactions with other compounds that are simultaneously administered. To explain this, it has been suggested that tiamulin selectively inhibits oxidative drug metabolism via the formation of a cytochrome P450 metabolic intermediate complex. The aim of the present study was to provide further support for this hypothesis. When hepatic microsomes and cultured primary pig hepatocytes were incubated with tiamulin, a maximum in the absorbance spectrum at 455 nm was observed, which disappeared after adding KFe(CN)6. When hepatocytes were incubated with tiamulin for 72 hr, cytochrome P450 content and cytochrome P4503A apoprotein levels were increased. Tiamulin strongly inhibited and concentration dependently inhibited the hydroxylation rate of testosterone at the 6 beta-position in both microsomes and hepatocytes, and the microsomal N-demethylation rate of ethylmorphine. Other testosterone hydroxylations were inhibited to a lesser extent or not affected. The relative inhibition of the hydroxylation of testosterone at the 6 beta-position was more pronounced in microsomes from rifampicin- and triacetyloleandomycin-treated pigs. The results indicate that cytochrome P450 complex formation can at least partly explain the interactions observed with tiamulin. Tiamulin seems to be a strong, probably selective, inhibitor of the cytochrome P4503A subfamily and an interesting tool for further research.

Animals↗