Core-hole effects in fullerene molecules and small-diameter conducting nanotubes: a density functional theory study.

Core-hole induced electron excitations in fullerene molecules, and small-diameter conducting carbon nanotubes, are studied using density functional theory with minimal, split-valence, and triply-split-valence basis sets plus the generalized gradient approximation by Perdew-Burke-Ernzerhof for exchange and correlation. Finite-size computations are performed on the carbon atoms of a C(60) Bucky ball and a piece of (3, 3) armchair cylindrical network, terminated by hydrogen atoms, while periodically boundary conditions are imposed on a (3, 3) nanotube unit cell. Sudden creation of the core state is simulated by replacing a 1s electron pair, localized at a central site of the structures, with the effective pseudo-potentials of both neutral and ionized atomic carbon. Excited states are obtained from the ground-state (occupied and empty) electronic structure of the ionized systems, and their overlaps with the ground state of the neutral systems are computed. These overlaps enter Fermi's golden rule, which is corrected with lifetime and finite-temperature effects to simulate the many-electron response of the nanoobjects. A model based on the linked cluster expansion of the vacuum persistence amplitude of the neutral systems, in a parametric core-hole perturbation, is developed and found to be reasonably consistent with the density functional theory method. The simulated spectrum of the fullerene molecule is found to be in good agreement with x-ray photoemission experiments on thick C(60) films, reproducing the low energy satellites at excitation energies below 4 eV within a peak position error of ca. 0.3 eV. The nanotube spectra show some common features within the same experiments and describe well the measured x-ray photoelectron lineshape from nanotube bundles with an average diameter of 1.2 nm.

Role of many body shake-up in core-valence-valence electron emission from single wall carbon nanotubes.

Auger core-valence-valence transitions from single wall Carbon nanotubes are studied using a tight-binding calculational scheme with nearest neighbor overlap, hopping interactions, and a double-zeta basis set. The resulting Hamiltonian approximates the unperturbed pi and sigma bands of the nanomaterials coupled with the free electron states outside the solid and the core-hole. As a first step, the Fermi's golden rule is applied to determine the so called one-electron spectrum of emitted electrons from different tubes, in which either the neutralizing or the ejected electrons, in the initial state, lie within nearest neighboring atomic sites to the core-hole. Many-body corrections are effectively modeled using a broadening function, which accounts for dynamic screening effects involving the initial and final states. Particular attention is paid to the asymmetric component of the broadening function, responsible for the shake-up of pi electrons. Finally, the Cini-Sawatzky distortion function is used to describe the final state effect of the hole-hole interaction. A quantitative estimation of the interplay of shake-up processes is proposed by adjusting the asymmetric parameters of the broadening function to reproduce measurements of Auger electrons ejected from bundles of single wall Carbon nanotubes.

Secondary electron spectra of graphene on Ni(111) surface.

We report on kinetic energy distributions of electrons emitted during bombardment of graphene adsorbed on a Ni(111) surface by 0.5-0.9 keV electrons. The spectra reveal several peaks superimposed on the background of cascade electrons. The position of these peaks does not depend significantly on primary electron energy but show a remarkable angular dependence, indicating that they are directly related to the empty bands above the vacuum level of the sample.

Charge transfer in single and multiple scattering events at metal surfaces: a wavepacket study of the Na(+)/Cu(100) system.

Resonant neutralization of hyperthermal energy Na(+) ions impinging on Cu(100) surfaces is studied, focusing on two specific collision events: one in which the projectile is reflected off the surface, the other in which the incident atom penetrates the outer surface layers initiating a series of scattering processes, within the target, and coming out together with a single surface atom. A semi-empirical model potential is adopted that embeds: (i) the electronic structure of the sample, (ii) the central field of the projectile, and (iii) the contribution of the Cu atom ejected in multiple scattering events. The evolution of the ionization orbital of the scattered atom is simulated, backwards in time, using a wavepacket propagation algorithm. The output of the approach is the neutralization probability, obtained by projecting the time-reversed valence wavefunction of the projectile onto the initially filled conduction band states. The results are in agreement with available data from the literature (Keller et al 1995 Phys. Rev. Lett. 75 1654) indicating that the motion of surface atoms, exiting the targets with kinetic energies of the order of a few electronvolts, plays a significant role in the final charge state of projectiles.

Secondary electron emission spectra from clean and cesiated Al surfaces: the role of plasmon decay and data analysis for applications.

We report measurements of energy spectra of secondary electrons emitted from clean and cesiated aluminum surfaces under the impact of 130 eV electrons. Measurements show that the decay of bulk and surface plasmons dominates the electron emission. In contrast with theoretical calculations, our experiments indicate that the electron collision cascade inside the solid produced by electrons excited by plasmon decay do not contribute significantly to electron emission. A simple analysis of electron energy distributions measured as a function of Cs surface coverage allows separation of rediffused incident electrons from the continuum background of true secondary electrons. The result shows that yields of rediffused electrons used in several applications may have been significantly overestimated.

Effect of folic acid on homocysteine-induced trophoblast apoptosis.

In trophoblast cells exposed to homocysteine (Hcy) we observed cellular apoptosis and the inhibition of trophoblast functions. Because folate and Hcy, linked in the same metabolic pathway, are inversely related, we investigated the role of folic acid in reversing the Hcy effect in human placenta. In primary trophoblast cells we examined the cytosolic release of cytochrome c, both M30 and terminal deoxynucleotidyl transferase-mediated dUDP nick-end labelling (TUNEL) and DNA laddering. Hcy (20 micromol/l) treatment resulted in cytochrome c release from mitochondria to the cytosol, and an increased number of M30-positive trophoblast cells and TUNEL positive nuclei. Furthermore, DNA cleavage in agarose gel and the determination of histone-associated DNA fragments have been investigated. Homocysteine induced DNA fragmentation and significantly reduced hCG secretion. The addition of folic acid (20 nmol/l) resulted in inhibition of the effects of Hcy on human trophoblast. These results suggest a protective role of folic acid in the prevention of trophoblast apoptosis linked to Hcy.

Markedly reduced insulin-like growth factor-1 in the acute phase of myocardial infarction.

OBJECTIVES: We investigated whether insulin-like growth factor-1 (IGF-1) is reduced in the early phase of acute myocardial infarction (AMI) and whether such a decrease might influence prognosis. BACKGROUND: Insulin-like growth factor-1 protects against insulin resistance and apoptosis. Although insulin resistance has been reported in AMI, IGF-1 levels have not been investigated. METHODS: We measured serum IGF-1 in 23 patients with AMI within 24 h of symptom onset and in 11 matched controls. In the first 12 patients and controls, we also measured fasting insulin, diurnal growth hormone (GH) and insulin sensitivity (assessed as glucose disappearance or T/2 after an insulin bolus), and repeated IGF-1, insulin and GH after one year. In all patients, 90-day cardiovascular death, recurrent ischemia, reinfarction, revascularization and late malignant arrhythmias were assessed. RESULTS: The AMI patients versus controls showed markedly reduced IGF-1 (115 +/- 112 vs. 615 +/- 300 ng/ml, p < 0.0001) and slower T/2 (-0.98 +/- 1.5 vs. -2.57 +/- 1.0 mg/dl/min, p = 0.01). Low IGF-1 often preceded the rise of myocardial necrosis markers. Patients with 90-day events (n = 12) versus those without had lower IGF-1 (47 +/- 54 vs. 189 +/- 110 ng/ml, p < 0.0001). Acute phase GH and insulin concentrations did not differ significantly from controls. After one year, the patients' IGF-1 values had risen to 460 +/- 242 ng/ml (p = 0.1 vs. controls, p < 0.0005 vs. acute phase), whereas GH levels were lower (0.2 +/- 0.2 vs. 2.5 +/- 2.3 ng/ml, p = 0.01) and insulin levels higher (12.5 +/- 0.2 vs. 3.9 +/- 2.6 microU/ml, p < 0.0001) compared with controls. CONCLUSIONS: In the early phase of AMI, serum IGF-1 levels are markedly reduced and may contribute to adverse outcomes. Reduced IGF-1 preceding the rise of myocardial necrosis markers suggests a possible pathogenetic role. A compensatory increase in IGF-1 appears to occur by one year.

Six-minute walking performance in patients with moderate-to-severe heart failure; is it a useful indicator in clinical practice?

AIMS: The 6-min walk test has been incorporated into studies on the efficacy of new therapies and into prognostic stratification for chronic heart failure patients. Firm conclusions on the usefulness of the test in clinical practice are still lacking. The aim of this study was to investigate (1) the correlation between walk test performance and standard indices of cardiac function and exercise capacity, and (2) the prognostic value of the walk test with respect to peak VO2 and NYHA class. METHODS AND RESULTS: Three hundred and fifteen chronic heart failure patients (age: 53+/-9 years, NYHA class: II (182), III (133)) underwent a functional evaluation and a 6-min walk test. Of these, 270 were followed-up for a minimum of 6 months (mean 387+/-177 days). Walked distance was 396+/-92 m. There was no significant correlation between distance walked and central haemodynamic data. Functional capacity, as measured by ergometry, correlated moderately with distance walked (duration: r=0.48, peak VO2: r=0.59, anaerobic threshold: r=0.54; all P<0.001). During follow-up, 46 patients died from cardiovascular causes and 12 were urgently transplanted. Either of these events were considered end points of the study. Survival analysis was performed from a continuous walk test and peak VO2 measurements or after categorization of (a) quartile segmentation, (b) cut-off points from the literature and (c) thresholds from receiver operating characteristic curves. At univariate survival analysis (Cox regression), the association of the walk test with survival was of significance (P=0.03, continuous variable), or borderline significance (0.05< or =P< or =0.1, after categorization). Peak VO2 was always significant, independent of the scale used (0.005< or =P< or =0.03). The strongest association was found for NYHA class (P<0.001), which showed the highest sensitivity and specificity for the prediction of the event (0.64 and 0.65, respectively). When walk test performance, continuous or categorized, was entered into a multivariate model with NYHA class or peak VO2, it lost any significant association with survival (P>0.76 in all models with NYHA class and P>0.27 in all models with peak VO2). CONCLUSION: In moderate-to-severe chronic heart failure patients, the 6-min walk test is not related to cardiac function and only moderately related to exercise capacity. Walking performance does not provide prognostic information which can complement or substitute for that provided by peak VO2 or NYHA class. Hence the test is of limited usefulness as a decisional indicator in clinical practice.

Angular studies of potential electron emission in the interaction of slow ions with Al surfaces

We report energy distributions of electrons emitted from Al surfaces under impact by 1 keV Ar+ and 1-5 keV Ne+ ions. The variation of the energy distributions with the angle of incidence is different for both ions and provides information on the mechanism responsible for electron emission. For Ar+ electron emission results mainly from Auger neutralization, while for Ne+ an important emission mechanism is the decay of plasmon excitations. We find a transition between surface and bulk plasmon excitations as the energy of the ion is increased.

Does in-patient ECG monitoring have an impact on medical care in chronic heart failure patients?

BACKGROUND: Heart failure patients' management in non-intensive care units might be improved by telemetry monitoring. However, telemetry adds the cost and evidence of this effectiveness is not available. AIM: To evaluate the utility of the ECG monitoring in chronic heart failure patients admitted to a non-intensive care unit. METHODS: A prospective analysis of the utility of telemetry in 711 patients admitted to a Heart Failure Unit from March 1996 to September 1997. RESULTS: One hundred and ninety-nine patients underwent telemetry; 108 telemetry findings were recorded, in 35% of NYHA class II, in 46% in NYHA class III-IV and 43% in unstable patients. Reasons for telemetry were: known arrhythmia (n=82), electrolytes disturbances (n=20), atrial fibrillation (n=12), symptoms (n=48), i.v. dobutamine (n=13), drugs control (n=16), devices control (n=8). Crossing reasons for telemetry and detected events we had, respectively, 63, 11, 2, 17, 5, 6, and 0 telemetry findings. Treatment was guided by telemetry results in only 33 cases (respectively in 18, 0, 4, 5, 5, 1, and 0 cases). Physicians perceived telemetry as unhelpful in 30% of cases; as helpful in 70%. The percentage of inutility, usefulness with and without related medical intervention were similar between stable and unstable patients (30, 18, 51% and 31, 15, 54%, respectively). CONCLUSION: In a heart failure unit ECG monitoring is mostly used in severe and unstable patients. However, medical decisions are rarely guided by the telemetry findings. The usefulness of telemetry might be underestimated because one of the uncounted results might be the avoidance of inappropriate intervention.

[An analysis of the decision process in the pharmacological treatment of a patient with chronic heart failure by means of a therapy management information system: the experience of the Montescano Heart Failure Unit]. / Analisi del processo decisionale del trattamento farmacologico nel paziente con scompenso cardiaco cronico attraverso un sistema informatizzato di gestione della terapia: esperienza dell'Unità per lo Scompenso Cardiaco di Montescano.

A computer-based system integrated into the hospital information system for the pharmacological management of the chronic heart-failure patients admitted to the heart-failure unit of Montescano is presented. The major aims of the system involved monitoring the patients' treatment history and the related therapeutic decision-making. The treatment history of the first 151 consecutive CHF patients admitted after the system implementation is examined. The prescribed drug doses at admission and at discharge are compared, as well as the differences in etiology and NYHA class between patients discharged with or without each drug. Several considerations can be drawn from this analysis. First of all, in heart failure patients the choice of drugs is limited and optimal treatment is a result of individualized dosages. Secondly, time and trials are necessary to obtain optimal treatment. Consequently, continuity of care and in- and out-hospital networks are advisable. Third, a computer-based system offers advantages not only for the pharmacological management itself, but also for improving the quality of care through continuous analysis of the decision-making process.

Reproducibility of the six-minute walking test in patients with chronic congestive heart failure: practical implications.

This study assesses the reproducibility of the 6-minute walking test in patients with chronic heart failure using 2 different measurement protocols. Practical suggestions for the clinical setting are given.

Peak exercise oxygen consumption in chronic heart failure: toward efficient use in the individual patient.

OBJECTIVES: This study sought to 1) assess the short-, medium-and long-term prognostic power of peak oxygen consumption (VO2) in patients with heart failure; 2) verify the consistency of a nonmeasurable anaerobic threshold (AT) as a criterion of nonapplicability of peak VO2; 3) develop simple rules for the efficient use of peak VO2 in individualized prognostic stratification and clinical decision making. BACKGROUND: Peak VO2, when AT is identified, is among the indicators for heart transplant eligibility. However, in clinical practice the application of defined peak VO2 cutoff values to all patients could be inappropriate and misleading. METHODS: Six hundred fifty-three patients consecutively considered for eligibility for heart transplantation were followed up. Outcomes (cardiac death and urgent transplantation) were determined when all survivors had a minimum of 6 months of follow-up. RESULTS: Contraindication to the exercise test identified very high risk patients. The relatively small sample of women did not allow inferences to be drawn. In men, peak VO2 stratified into three levels (< or = 10, 10 to 18 and >18 ml/kg per min) identified groups at high, medium and low risk, respectively. The prognostic power of peak VO2 < or = 10 ml/kg per min was maintained even when the AT was not detected. In patients in New York Heart Association functional class III or IV, peak VO2 did not have prognostic power. In patients in functional class I or II, peak VO2 stratification was prognostically valuable, but less so at 6 than at 12 or 24 months. Age did not influence peak VO2 prognostic stratification. CONCLUSIONS: A contraindication to exercise testing should be considered a priority for listing patients for heart transplantation. Only in less symptomatic male patients does a peak VO2 < or = 10 ml/kg per min identify short-, medium- and long-term high risk groups. A peak VO2 >18 ml/kg per min implies good prognosis with medical therapy.

Age limits for heart transplantation: medical aspects.

OBJECTIVE: To contribute to the analysis of the medical issue of aging as a selection criteria for heart transplantation (HT) METHODS: Elderly candidates (52 subjects, aged > or = 60) were compared with younger patients (64 candidates, aged 50-55) in: clinical pattern (sex, etiology, duration of disease); laboratory and instrumental data (multiple organ function, hemodynamics, maximal and submaximal exercise capacity, nutritional status); follow-up (death, transplantation, status I, decompensation, complications) of at least 6 months. RESULTS: When compared with younger candidates, over 60 patients did not differ in clinical pattern, in all instrumental data, in end-organ function, in transplantation rate, in fatal and non-fatal cardiac events. In both groups the medical management was similarly complex. CONCLUSION: In regard to the medical issue, no reasons emerged to exclude older patients suitable from HT.

Sick euthyroid syndrome in patients with moderate-to-severe chronic heart failure.

BACKGROUND: Changes in peripheral thyroid hormone concentration and metabolism can occur in euthyroid patients suffering from severe non-thyroidal illnesses. Recently, sick euthyroid syndrome has been reported in patients suffering from advanced heart failure. AIM: This study was to evaluate prospectively the presence and pathophysiological implications of sick euthyroid syndrome in moderate-to-severe chronic heart failure patients. METHODS: The study population were 199 chronic heart failure patients admitted over a 2-year period to our heart failure unit for assessment of cardiac transplantation. They were closely followed up with clinical and instrumental examinations (including clinical, hormonal, nutritional and cardiac function evaluations). Sick euthyroid syndrome was defined as a serum total triiodothyronine value of less than the lowest normal limit (< 1.23 nmol.l-1) in the presence of a normal serum thyroid stimulating hormone concentration. RESULTS: Sick euthyroid syndrome was found in 36/199 patients (18%). According to the New York Heart Association (NYHA) classification of severity of heart failure, sick euthyroid syndrome patients appear in higher NYHA classes (31% of classes III and IV, vs 7% of class I and II). Such patients also weigh less and are more frequently malnourished. Alterations in cardiac index, ventricular filling pressures, functional impairment, and the liver function parameters, were more significant in sick euthyroid syndrome than in non-sick euthyroid syndrome patients. Serum norepinephrine and atrial natriuretic factor were significantly higher, and insulin significantly lower in the sick euthyroid syndrome group. During follow-up, deaths were significantly more frequent in sick euthyroid syndrome patients (13/27, 48%) than in non-sick euthyroid syndrome (30/141, 21%; P < 0.005). In six sick euthyroid syndrome patients who underwent heart transplantation, mean total triiodothyronine values increased from 0.9 +/- 0.1 before to 1.96 +/- 0.3 nmol.l(-1)post-transplantation (P < 0.05). CONCLUSIONS: In a large and representative population of patients with moderate-to-severe heart failure, sick euthyroid syndrome shows a prevalence of 18%. Its occurrence was related to the degree of functional cardiac impairment, but was not an independent negative prognostic factor. Preliminary results indicate that heart transplantation is associated with reversibility of sick euthyroid syndrome.

Concomitant factors of decompensation in chronic heart failure.

The concomitant factors implicated in 328 nonfatal decompensations of 304 patients with congestive heart failure were: arrhythmias in 24%, infections in 23%, poor compliance in 15%, angina in 14%, iatrogenic factors in 10%, and other causes in 5% of cases. New York Heart Association class and right atrial pressure significantly related to the occurrence of decompensation. Poor compliance and angina were unpredictable, infection was related to pulmonary wedge pressure, iatrogenic factors were predicted by the more advanced functional classes, whereas arrhythmias were more frequent in patients with renal failure.

Differences in membrane order between C3H 10 T1/2 cells and their transformed counterparts as measured by EPR.

Membrane order of mouse embryo fibroblasts and their ionizing radiation and chemically transformed counterparts was investigated using EPR spectroscopy after labeling the membrane of the cells with the fatty acid spin label, 5-nitroxy stearic acid. The EPR spectra were recorded at temperatures ranging from 18 to 38 degrees C for both control and transformed cells. The distance between the outer hyperfine splitting (2T' parallel), which is used as indicator of membrane order, varies in these two cell types. Below 28 degrees C. 2T' parallel is higher in transformed fibroblasts than in normal cells, whereas above this temperature membrane order is the same. Lipid analysis as carried out by the measurement of the cholesterol/membrane proteins and sphingomyelin/lecithin ratios, showed no difference in the amounts of the main membrane rigidifiers. These findings suggest that cell transformation of mouse fibroblasts induced by radiation or chemicals may produce alterations in the cell membrane, as evidenced by variations in its order at low temperature. These measured differences are presumably not attributable to its fatty acids composition but to its glycoproteins content, since changes in membrane rigidifiers were not observed between normal and transformed cells.

The use of amniotic fluid viscosity measurements to establish fetal lung maturity.

A Haake viscosimeter was used to determine the viscosity of amniotic fluid and this value correlated with fetal lung maturity. The results were evaluated along the weeks of pregnancy and compared to those obtained using Gluck's method (lecithin/sphingomyelin ratio (L/S). Using 91 separate amniotic fluid samples, free of meconium and blood contamination, we found that the new method was quick and easy to perform. Thirty-one neonates were delivered within 48 h of the amniotic fluid sampling and the percentage of correct prediction of respiratory distress syndrome (RDS) was 71% with a mature L/S ratio and 83% with viscosity less than 1.17 cP. In cases with an immature L/S ratio (value below 2) the correct prediction of RDS was 64%; with the fluorescence polarization (FP) technique it was 91%. We conclude that the amniotic fluid FP value is a reliable index of fetal lung maturity and risk for developing RDS and has also specific technical and diagnostic advantages over the L/S ratio.

2,3-diphosphoglycerate in normal and pathologic pregnancy: relationship to neonatal weight.

2,3-Diphosphoglycerate levels were assayed in 154 pregnant women in third trimester (61 normal, 52 diabetic, 19 with gestational hypertension, 7 with fetal macrosomia, and 15 with idiopathic fetal underdevelopment). A correlation was found between 2,3-diphosphoglycerate levels and birth weight (absolute and relative birth weight or birth weight expressed as percentile), which was negative in normal patients evaluated in the last 7 days before delivery (r = 0.38; p = 0.04) and positive in diabetic patients (evaluated in the third trimester and in the last 7 days before delivery) and in patients with gestational hypertension (evaluated in the third trimester) (r and p values differ according to whether birth weight is expressed as absolute, relative, or a percentile). No correlation was found between 2,3-diphosphoglycerate levels and birth weight in patients with neonatal underdevelopment or macrosomia of unknown origin. On the basis of these results we hypothesize that in some conditions the fetus can influence maternal 2,3-diphosphoglycerate levels and hence its own oxygen supply and growth in utero.