Biomedical subjects

Z Szabó

Publications and source records attributed to Z Szabó.

At least 19 recordsLinked to original sources

PubMed2004

Ileocolic anastomotic ulcer after surgery in adulthood: case report and review of the literature.

Anastomotic ulcer is a rare complication after ileocolic resection, especially in adults without evidence of inflammatory bowel disease or tumor recurrence. We report the case of a 63-year-old male patient who presented 6 years after ileocolic resection, and also review the data of six similar cases described in the literature. The markedly reduced bile acid absorption found in our case raises the possibility of an etiological role of bile acids in the development of ileocolic anastomotic ulcers.

Anastomosis, Surgical↗

PubMed2003

High-dose glucose-insulin-potassium after cardiac surgery: a retrospective analysis of clinical safety issues.

BACKGROUND: Metabolic treatment with insulin or glucose-insulin-potassium (GIK) has received attention in association with myocardial infarction, cardiac surgery and critical care. As a result of insulin resistance during neuroendocrine stress, doses of insulin up to 1 IU kg-1 b.w.*h are required to achieve maximal metabolic effects after cardiac surgery. The clinical experience with regard to safety issues of such a high-dose GIK regime in critically ill patients after cardiac surgery is reported. METHODS: Retrospective, observational study involving all patients treated with high-dose GIK after cardiac surgery during one year in a cardiovascular center at a University Hospital. RESULTS: Eighty-nine patients out of 854 adult patients undergoing cardiac surgery were treated with high-dose GIK. Mean age was 69 +/- 1 years, Higgins score 5.3 +/- 0.3. Preoperatively 31.4% had left ventricular function EF< or =0.35 and 32.5% had sustained a myocardial infarct during surgery. Mortality was 5.6% and the average ICU stay was 3.7 +/- 0.5 days. The main indication for GIK was intraoperative heart failure (69.7%). The average glucose infusion rate during the first 6 h was 4.22 +/- 0.15 and 4.91 +/- 0.14 mg kg-1 b.w.*min, respectively, in diabetic and non-diabetic patients (P = 0.023). Blood glucose and s-potassium control was acceptable. CONCLUSIONS: The high-dose GIK regime allowed substantial amounts of glucose to be infused both in diabetic and critically ill patients with maintenance of acceptable blood glucose control. Provided careful monitoring, this regime can be safely used in clinical practice and deserves further evaluation for treatment of critically ill patients following cardiac surgery.

Aged↗

PubMed2003

A simple method to pass a pulmonary artery flotation catheter rapidly into the pulmonary artery in anaesthetized patients.

BACKGROUND: In some patients passage of a pulmonary artery flotation catheter (PAFC) into the pulmonary artery may be difficult and time consuming and the prolonged manipulation can cause ventricular arrhythmias. A simple clinical method used during general anaesthesia is presented to allow rapid passage of a PAFC into the pulmonary artery. METHODS: The operating table is positioned head up and slightly right side down to position the pulmonary valve at the highest level possible. When the balloon catheter is in the right ventricular outflow tract (indicated by premature ventricular contractions) the ventilator is paused in inspiration and the balloon catheter simultaneously passed into the pulmonary artery. RESULTS: The manoeuvre shortens the time necessary to pass the catheter into the pulmonary artery and may reduce ventricular arrhythmias. Over 5 yr, 105 PAFCs were inserted with this method without major complications. CONCLUSION: This method may reduce the risk of ventricular arrhythmias, and could be particularly useful in high-risk critically ill patients.

Anesthesia, General↗

PubMed2002

Structure-function analysis of lipopeptide pheromones from the plant pathogen Ustilago maydis.

Mating of two haploid cells is a prerequisite for the successful infection of corn by the pathogenic fungus Ustilago maydis. Cell-cell recognition is mediated by small lipopeptide pheromones. Genes encoding pheromone precursors as well as pheromone receptors are located in the a mating type locus. Two pheromones are known, the tridecapeptide a1 and the nonapeptide a2, both of which contain an S-prenylated cysteine methyl ester at the C-terminus. It has previously been shown that synthetic pheromones are active in a biological test system. Here, we used the same assay to perform a detailed analysis of synthetic a1 and a2 pheromones. Testing of truncated derivatives of a1 and a2 revealed that in both cases the pheromone function is less sensitive to N-terminal than to C-terminal truncations. Replacement of each amino acid in the a1 pheromone by either alanine or the corresponding D-amino acids revealed that four positions are important for function: the two central glycines (positions 5 and 9), proline at position 7 and tyrosine at position 10. By introducing different naturally occurring as well as synthetic amino acids at position 10, we demonstrate that the presence of an aromatic side chain at this position is necessary for function. We propose a model in which a cis peptide bond at proline 7 favours the formation of a type II' beta turn of the a1 pheromone backbone with glycine 9 in position i+1 (where i refers to the first position of the beta turn). As a result, tyrosine 10, at position i+2 of the turn, would be highly exposed and could be inserted into a structurally well-defined binding pocket of the receptor. The latter may represent an important facet of receptor specificity.

Amino Acid Sequence↗

PubMed2002

Synaptic reorganization of calbindin-positive neurons in the human hippocampal CA1 region in temporal lobe epilepsy.

The distribution, morphology, synaptic coverage and postsynaptic targets of calbindin-containing interneurons and afferent pathways have been analyzed in the control and epileptic CA1 region of the human hippocampus. Numerous calbindin-positive interneurons are preserved even in the strongly sclerotic CA1 region. The morphology of individual cells is altered: the cell body and dendrites become spiny, the radially oriented dendrites disappear, and are replaced by a large number of curved, distorted dendrites. Even in the non-sclerotic epileptic samples, where pyramidal cells are present and calbindin-immunoreactive interneurons seem to be unchanged, some modifications could be observed at the electron microscopic level: they received more inhibitory synaptic input, and the calbindin-positive excitatory afferents - presumably derived from the CA1, the CA2 and/or the dentate gyrus - are sprouted. In the strongly sclerotic tissue, with the death of pyramidal cells, calbindin-positive terminals (belonging to interneurons and the remaining excitatory afferents) change their targets. Our data suggest that an intense synaptic reorganization takes place in the epileptic CA1 region, even in the non-sclerotic tissue, before the death of considerable numbers of pyramidal cells. Calbindin-positive interneurons participate in this reorganization: they show plastic changes in response to epilepsy. The enhanced inhibition of inhibitory interneurons may result in the disinhibition of pyramidal cells or in an abnormal synchrony in the output region of the hippocampus.

Adult↗

PubMed2002

Diagnosis, prevention and treatment of aspirin-induced asthma and rhinitis.

Bronchial asthma is not a homogenous disease. Several variants of asthma can be distinguished. One of them is aspirin-induced asthma. In this distinct clinical syndrome, aspirin and most other nonsteroidal anti-inflammatory drugs that inhibit cyclooxygenase-1 precipitate rhinitis and asthma attacks. This type of asthma affects 5-10% of adult asthmatics, but remains largely underdiagnosed. The natural history of aspirin-induced asthma (AIA) has been described, based on an extensive pan-European survey. Aspirin provocation tests with improved diagnostic accuracy have been developed, although no in-vitro tests has been found to be of diagnostic value. Recent interest in AIA has been stirred by the finding of alterations in arachidonate metabolic pathways, leading to cysteinyl-leukotriene overproduction. LTC4 synthase is overexpressed in bronchi and its mRNA is upregulated in peripheral blood eosinophils. The gene coding for LTC4 synthase exists in two common alleles, one of which appears to be associated with a severe, steroid-dependent type of asthma. New highly specific COX-2 inhibitors appear to be a safe alternative for patients with aspirin-induced asthma.

Aspirin↗

PubMed2001

The mechanism for water exchange in [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-), as studied by quantum chemical methods.

The mechanisms for the exchange of water between [UO(2)(H(2)O)(5)](2+), [UO(2)(oxalate)(2)(H(2)O)](2)(-)(,) and water solvent along dissociative (D), associative (A) and interchange (I) pathways have been investigated with quantum chemical methods. The choice of exchange mechanism is based on the computed activation energy and the geometry of the identified transition states and intermediates. These quantities were calculated both in the gas phase and with a polarizable continuum model for the solvent. There is a significant and predictable difference between the activation energy of the gas phase and solvent models: the energy barrier for the D-mechanism increases in the solvent as compared to the gas phase, while it decreases for the A- and I-mechanisms. The calculated activation energy, Delta U(++), for the water exchange in [UO(2)(H(2)O)(5)](2+) is 74, 19, and 21 kJ/mol, respectively, for the D-, A-, and I-mechanisms in the solvent, as compared to the experimental value Delta H(++) = 26 +/- 1 kJ/mol. This indicates that the D-mechanism for this system can be ruled out. The energy barrier between the intermediates and the transition states is small, indicating a lifetime for the intermediate approximately 10(-10) s, making it very difficult to distinguish between the A- and I-mechanisms experimentally. There is no direct experimental information on the rate and mechanism of water exchange in [UO(2)(oxalate)(2)(H(2)O)](2-) containing two bidentate oxalate ions. The activation energy and the geometry of transition states and intermediates along the D-, A-, and I-pathways were calculated both in the gas phase and in a water solvent model, using a single-point MP2 calculation with the gas phase geometry. The activation energy, Delta U(++), in the solvent for the D-, A-, and I-mechanisms is 56, 12, and 53 kJ/mol, respectively. This indicates that the water exchange follows an associative reaction mechanism. The geometry of the A- and I-transition states for both [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-) indicates that the entering/leaving water molecules are located outside the plane formed by the spectator ligands.

Journal Article↗

PubMed2001

Solvent effects on uranium(VI) fluoride and hydroxide complexes studied by EXAFS and quantum chemistry.

The structures of the complexes UO(2)F(n)(H(2)O)(5-n)(2-n), n = 3-5, have been studied by EXAFS. All have pentagonal bipyramid geometry with U-F of and U-H(2)O distances equal to 2.26 and 2.48 A, respectively. On the other hand the complex UO(2)(OH)(4)(2-) has a square bipyramid geometry both in the solid state and in solution. The structures of hydroxide and fluoride complexes have also been investigated with wave function based and DFT methods in order to explore the possible reasons for the observed structural differences. These studies include models that describe the solvent by using a discrete second coordination sphere, a model with a spherical, or shape-adapted cavity in a conductor-like polarizable continuum medium (CPCM), or a combination of the two. Solvent effects were shown to give the main contribution to the observed structure variations between the uranium(VI) tetrahydroxide and the tetrafluoride complexes. Without a solvent model both UO(2)(OH)(4)(H(2)O)(2-) and UO(2)F(4)(H(2)O)(2-) have the same square bipyramid geometry, with the water molecule located at a distance of more than 4 A from uranium and with a charge distribution that is very near identical in the two complexes. Of the models tested, only the CPCM ones are able to describe the experimentally observed square and pentagonal bipyramid geometry in the tetrahydroxide and tetrafluoride complexes. The geometry and the relative energy of different isomers of UO(2)F(3)(H(2)O)(2-) are very similar, indicating that they are present in comparable amounts in solution. All calculated bond distances are in good agreement with the experimental observations, provided that a proper model of the solvent is used.

Journal Article↗

PubMed2001

Preservation of perisomatic inhibitory input of granule cells in the epileptic human dentate gyrus.

Temporal lobe epilepsy is known to be associated with hyperactivity that is likely to be generated or amplified in the hippocampal formation. The majority of granule cells, the principal cells of the dentate gyrus, are found to be resistant to damage in epilepsy, and may serve as generators of seizures if their inhibition is impaired. Therefore, the parvalbumin-containing subset of interneurons, known to provide the most powerful inhibitory input to granule cell somata and axon initial segments, were examined in human control and epileptic dentate gyrus. A strong reduction in the number of parvalbumin-containing cells was found in the epileptic samples especially in the hilar region, although in some patches of the granule cell layer parvalbumin-positive terminals that form vertical clusters characteristic of axo-axonic cells were more numerous than in controls. Analysis of the postsynaptic target elements of parvalbumin-positive axon terminals showed that they form symmetric synapses with somata, dendrites, axon initial segments and spines as in the control, but the ratio of axon initial segment synapses was increased in the epileptic tissue (control: 15.9%, epileptic: 31.3%). Furthermore, the synaptic coverage of granule cell axon initial segments increased more than three times (control: 0.52, epileptic: 2.10 microm synaptic length/100 microm axon initial segment membrane) in the epileptic samples, whereas the amount of somatic symmetric synapses did not change significantly. Although the number of parvalbumin-positive interneurons is decreased, the perisomatic inhibitory input of dentate granule cells is preserved in temporal lobe epilepsy. Basket and axo-axonic cell terminals - whether positive or negative for parvalbumin - are present, moreover, the axon collaterals targeting axon initial segments sprout in the epileptic dentate gyrus. We suggest that perisomatic inhibitory interneurons survive in epilepsy, but their somadendritic compartment and partly the axon loses parvalbumin or immunoreactivity for parvalbumin. The hyperinnervation of axon initial segments might be a compensatory change in the inhibitory network, but at the same time may lead to a more effective synchronization of granule cell firing that could contribute to the generation or amplification of epileptic seizures.

Adolescent↗

PubMed2001

Neurological injury after surgery for ischemic heart disease: risk factors, outcome and role of metabolic interventions.

OBJECTIVES: Neurological complication remains a feared and increasing problem in association with cardiac surgery. The aim of this study was to analyze risk factors for neurological complications in a cohort of patients in whom inotropes for weaning from cardiopulmonary bypass was gradually replaced by metabolic treatment. METHODS: The records of 775 consecutive patients undergoing coronary artery bypass grafting (CABG) or combined CABG+valve procedures were examined. Forward stepwise multiple logistic regression analysis was used for statistical evaluation of independent risk factors. RESULTS: The incidence of neurological injury was 1.8% in patients undergoing isolated CABG and 5.4% after combined CABG+valve procedures. After cross-validation multivariate analysis identified history of cerebrovascular disease, advanced age and aortic cross-clamp time as independent risk factors for postoperative cerebral complications. Chronic obstructive pulmonary disease and number of bypasses also emerged as risk factors in the primary analysis. CONCLUSIONS: In general, markers for advanced atherosclerosis, with history of cerebrovascular disease as the most important, emerged as predictors for neurological injury. Although it did not enter the final risk model, the results also suggest that postoperative heart failure deserves further surveillance as a potential risk factor for neurological complications. However, no evidence for untoward neurological effects associated with glutamate or glucose-insulin-potassium treatment was found.

Cardioplegic Solutions↗

PubMed2001

Immunohistochemical analysis of atypical ductular reaction in the human liver, with special emphasis on the presence of growth factors and their receptors.

AIMS/BACKGROUND: The objective of this study was to characterize the expression of transforming growth factor-alpha/epidermal growth factor receptor, hepatocyte growth factor/c-met, transforming growth factor-beta/Type I-II transforming growth factor-beta receptors, stem cell factor, urokinase plasminogen activator, smooth muscle actin, CD34 and alpha-fetoprotein in human liver samples with (sub)massive necrosis of different etiology containing atypical ductular reaction. METHODS: Their presence was studied by immunohistochemistry on paraffin-embedded tissue sections. RESULTS: Transforming growth factor-alpha and -beta, hepatocyte growth factor and their receptors were demonstrated in the ductules; additionally stem cell factor and urokinase plasminogen activator were also expressed. The atypical ductules were surrounded by smooth muscle actin-positive activated stellate cells. CONCLUSION: These phenotypic similarities confirm that the atypical ductules in the human liver may be equivalent of oval cells in the rat liver, which are regarded as the progeny of stem cells. That is, the atypical ductular proliferation may correspond to a stem cell-fed regenerative process.

Adolescent↗

PubMed2001

Malignant fibrous histiocytoma of the kidney.

Malignant fibrous histiocytoma (MFH) is extremely rare in the kidney. We present a case of primary renal MFH in a 55-year-old male and briefly review the disease. It is essential to differentiate MFH from more frequent renal cell carcinomas, because MFH represents a worse prognosis and requires different treatment.

Histiocytoma, Benign Fibrous↗

PubMed2001

Myocardial uptake and release of substrates in type II diabetics undergoing coronary surgery.

OBJECTIVE: Knowledge about myocardial metabolism in diabetic patients is limited, and even more so in association with myocardial ischaemia and cardiac surgery. This study investigates myocardial substrate utilization in type II diabetic patients after elective coronary artery bypass graft surgery (CABG). DESIGN: Myocardial substrate utilization in 10 type II diabetic patients was assessed during the first hours after elective CABG with the coronary sinus catheter technique. RESULTS: No significant myocardial uptake of carbohydrates was observed. Free fatty acids were extracted throughout the study period but uptake was not related to arterial levels. As arterial levels of beta-hydroxybutyric acid tended to increase a significant myocardial uptake emerged. The average extraction rate of beta-hydroxybutyric acid was 31% with a peak of 42%. A comparable extraction rate of glutamate was also found whereas alanine was released from the heart. CONCLUSION: Free fatty acids were the main source of energy for the heart whereas uptake of carbohydrates was restricted. The high extraction rates of beta-hydroxybutyric acid and glutamate suggest an adaptive role for these substrates during this unfavourable metabolic state for the post-ischaemic diabetic heart.

3-Hydroxybutyric Acid↗

PubMed2001

Hepatocyte proliferation and cell cycle phase fractions in chronic viral hepatitis C by image analysis method.

OBJECTIVE: Chronic hepatitis is characterized by necrosis of liver cells, accompanied by an inflammatory reaction and compensatory cell proliferation. The interaction of the core and non-structural proteins of hepatitis C virus (HCV) with several cellular factors suggests that cell proliferation may be influenced by HCV. The aim of this study was to investigate hepatocyte proliferation and DNA ploidy patterns in patients with chronic viral hepatitis C (CH-C) compared with chronic non-viral hepatitis (CH-N), using a TV image analysis method. METHODS: The DNA index (DI) and cell phase fractions (G1, S, G2) were measured by means of digital picture analysis method on nuclear suspensions of Feulgen stained hepatocytes. Cells were taken from the liver biopsy specimens of 71 patients with CH-C and 24 patients with CH-N. Twenty-six normal liver samples were used as controls. RESULTS: Significantly higher G1 (94 +/- 4) and lower S (3.56 +/- 3.16) phase fractions were measured in CH-C compared with CH-N (G1, 90 +/- 6; S, 6.4 +/- 5.99). The DI of moderate (1.12 +/- 0.05) and severe (1.12 +/- 0.05) CH-C showed near-aneuploid DNA content, while diploidy (DI < 1.10) was detected in cases of CH-N. CONCLUSION: The higher G1 and lower S cell cycle phase fractions in CH-C reflect decreased hepatocyte proliferation compared with CH-N. The near-aneuploid DNA content of the HCV-infected liver samples may be a sign of increased genetic instability, which may contribute to the carcinogenic potential of HCV.

Adult↗

PubMed2001

Effects of high-dose glucose-insulin-potassium on myocardial metabolism after coronary surgery in patients with Type II diabetes.

The effects of glucose-insulin-potassium (GIK) on cardiac metabolism have been studied previously in non-diabetic patients after cardiac surgery. Although patients with diabetes mellitus can be expected to benefit most from such treatment, the impact of GIK in diabetic patients undergoing cardiac surgery remains unexplored. Therefore the present study investigates the effects of high-dose GIK on myocardial substrate utilization after coronary surgery in patients with Type II diabetes. A total of 20 patients with Type II diabetes undergoing elective coronary surgery were randomly allocated to either post-operative high-dose GIK or standard post-operative care, including insulin infusion if necessary to keep blood glucose below 10 mmol/l. Myocardial substrate utilization was studied using the coronary sinus catheter technique. Haemodynamic state was assessed with the aid of Swan-Ganz catheters. High-dose GIK caused a shift towards carbohydrate utilization, with significant lactate uptake throughout the study period and significant uptake of glucose after 4 h. Arterial levels of non-esterified fatty acids and beta-hydroxybutyric acid decreased, and after 1 h no significant uptake of these substrates was found. Increases in the cardiac index and stroke volume index were found in patients treated with high-dose GIK. A decrease in systemic vascular resistance was found both in the control group and in the high-dose GIK group. We conclude that high-dose GIK can be used in diabetic patients after cardiac surgery to promote carbohydrate uptake at the expense of non-esterified fatty acids and beta-hydroxybutyric acid. This could have implications for treatment of the diabetic heart in association with surgery and ischaemia.

3-Hydroxybutyric Acid↗

PubMed2000

Differences in the changes of allergen-specific IgE serum levels and the chemiluminescence of peripheral blood phagocytes in patients with allergic rhinoconjunctivitis during the ragweed season.

The objective of this study was to compare the changes in the values of allergen-specific serum IgE levels and zymosan-induced whole blood chemiluminescence (CL) in 41 patients who had exclusively only ragweed allergy in the season of acute symptoms of disease in July, August and September. All patients had allergic rhinitis or rhinoconjunctivitis. Each patient was investigated as a self-control. The ragweed-specific IgE levels were measured by enzyme immunoassay (EIA). The luminol amplified zymosan-induced CL of whole human blood was detected. The allergen-specific serum IgE levels showed slight, but not significant, gradually increasing elevations during the whole season. On the other hand, significant increases were found in the values of the basal but especially in the zymosan-stimulated CL of peripheral blood phagocytes during the acute phase of allergy. Both the basal and the zymosan-induced CL reflected significantly the activated state of the immune system. These observations clearly show that there are well detectable signs of the systemic activation of the immune system in allergic rhinoconjunctivitis beside the local alterations. In addition, the measurements of the basal and zymosan-induced CL of peripheral phagocytes could clearly reflect the clinical state of disease in vitro.

Adult↗

PubMed2000

Potentiometric and multinuclear NMR study of the binary and ternary uranium(VI)-L-fluoride systems, where L is alpha-hydroxycarboxylate or glycine.

Equilibria, structures, and ligand-exchange dynamics in binary and ternary U(VI)-L-F- systems, where L is glycolate, alpha-hydroxyisobutyrate, or glycine, have been investigated in 1.0 M NaClO4 by potentiometry and 1H, 17O, and 19F NMR spectroscopy. L may be bonded in two ways: either through the carboxylate end or by the formation of a chelate. In the glycolate system, the chelate is formed by proton dissociation from the alpha-hydroxy group at around pH 3, indicating a dramatic increase, a factor of at least 10(13), of its dissociation constant on coordination to uranium(VI). The L exchange in carboxylate-coordinated UO2LF3(2-) follows an Eigen-Wilkins mechanism, as previously found for acetate. The water exchange rate, k(aq) = 4.2 x 10(5) s(-1), is in excellent agreement with the value determined earlier for UO2(2+)(aq). The ligand-exchange dynamics of UO2(O-CH2-COO)2F3- and the activation parameters for the fluoride exchange in D2O (k(obs) = 12 s(-1), deltaH(double dagger) = 45.8 +/- 2.2 kJ mo(-1), and deltaS(double dagger) = -55.8 +/- 3.6 J K(-1) mol(-1)) are very similar to those in the corresponding oxalate complex, with two parallel pathways, one for fluoride and one for the alpha-oxocarboxylate. The same is true for the L exchange in UO2(O-CH2-COO)2(2-) and UO2(oxalate)2(2-). The exchange of alpha-oxocarboxylate takes place by a proton-assisted chelate ring opening followed by dissociation. Because we cannot decide if there is also a parallel H+-independent pathway, only an upper limit for the rate constant, k1 < 1.2 s(-1), can be given. This value is smaller than those in previously studied ternary systems. Equilibria and dynamics in the ternary uranium(VI)-glycine-fluoride system, investigated by 19F NMR spectroscopy, indicate the formation of one major ternary complex, UO2LF3(2-), and one binary complex, UO2L2 (L = H2N-CH2COO-), with chelate-bonded glycine; log beta(9) = 13.80 +/- 0.05 for the equilibrium UO2(2+) + H2N-CH2COO- + 3F- = UO2(H2N-CH2COO)F3(2-) and log beta(11) = 13.0 +/- 0.05 for the reaction UO2(2+) + 2H2N-CH2COO- = UO2(H2N-CH2COO)2. The glycinate exchange consists of a ring opening followed by proton-assisted steps. The rate of ring opening, 139 +/- 9 s(-1), is independent of both the concentration of H+ and the solvent, H2O or D2O.

Journal Article↗

PubMed2000

19F NMR study of the equilibria and dynamics of the Al3+/F- system.

A careful reinvestigation by high-field 19F NMR (470 MHz) spectroscopy has been made of the Al3+/F- system in aqueous solution under carefully controlled conditions of pH, concentration, ionic strength (I), and temperature. The 19F NMR spectra show five distinct signals at 278 K and I = 0.6 M (TMACl) which have been attributed to the complexes AlFi(3-i)+(aq) with i < or = 5. There was no need to invoke AlFi(OH)j(3-i-j)+ mixed complexes in the model under our experimental conditions (pH < or = 6.5), nor was any evidence obtained for the formation of AlF6(3-)(aq) at very high ratios of F-/Al3+. The stepwise equilibrium constants obtained for the complexes by integration of the 19F signals are in good agreement with literature data given the differences in medium and temperature. In I = 0.6 M TMACl at 278 K and in I = 3 M KCl at 298 K the log Ki values are 6.42, 5.41, 3.99, 2.50, and 0.84 (for species i = 1-5) and 6.35, 5.25, and 4.11 (for species i = 1-3), respectively. Disappearance of the 19F NMR signals under certain conditions was shown to be due to precipitation. Certain 19F NMR signals exhibit temperature- and concentration-dependent exchange broadening. Detailed line shape analysis of the spectra and magnetization transfer measurements indicate that the kinetics are dominated by F- exchange rather than complex formation. The detected reactions and their rate constants are AlF2(2+) + *F- reversible AlF*F2+ + F- (k02 = (1.8 +/- 0.3) x 10(6) M-1 s-1), AlF3(0) + *F- reversible AlF2*F0 + F- (k03 = (3.9 +/- 0.9) x 10(6) M-1 s-1), and AlF3(0) + H*F reversible AlF2*F0 + HF (kH03 = (6.6 +/- 0.5) x 10(4) M-1 s-1). The rates of these exchange reactions increase markedly with increasing F- substitution. Thus, the reactions of AlF2+(aq) were too inert to be detected even on the T1 NMR time scale, while some of the reactions of AlF3(0)(aq) were fast, causing large line broadening. The ligand exchange appears to follow an associative interchange mechanism. The cis-trans isomerization of AlF2+(aq), consistent with octahedral geometry for that complex, is slowed sufficiently to be observed at temperatures around 270 K. Difference between the Al3+/F- system and the much studied Al3+/OH- system are briefly commented on.

Journal Article↗