Search PubMed⌕ Search

Biomedical subjects

A Baraldi

Publications and source records attributed to A Baraldi.

At least 19 recordsLinked to original sources

Carbon monoxide dissociation on Rh nanopyramids.

CO dissociation on rhomboidal faceted nanopyramids, produced on Rh(110) by fine-tuning of ion irradiation conditions, has been studied by high resolution core-level spectroscopy. We find that this morphology presents a large efficiency towards CO dissociation, a process which is inhibited on flat (110) terraces. We also measured the reactivity of nanostructures bound by different artificial step distributions identifying the sites responsible for the molecular bond disruption in the undercoordinated (n=6) edges running along the [11[over ]2] equivalent directions, with CO sitting in on-top configuration.

Journal Article↗

Monitoring super- and subsurface oxygen on Ag(210) by high energy resolution X-ray photoelectron spectroscopy: subsurface diffusion and segregation.

We report on a high energy resolution X-ray photoelectron spectroscopy plus supersonic molecular beam investigation of O/Ag(210). Two components are detected in the O1s spectra upon O2 adsorption, at binding energies EB=527.7 and 529.6 eV. The former peak persists up to 470 K, while the latter one decreases abruptly above 280 K. Comparison with a previous vibrational spectroscopy investigation on the same system (L. Vattuone, et al. Phys. Rev. Lett. 2003, 90, 228302) allows to assign both features to atomic oxygen. The low-energy peak is identified with adatoms, while the other is correlated to O atoms in subsurface sites. A minor contribution at the same binding energy, due to carbonates, is quantified by inspection of the C1s region and shows a different temperature behavior with respect to oxygen. Oxygen segregation into the subsurface region is observed when heating the crystal in the presence of supersurface oxygen.

Journal Article↗

The role of Oad in the decomposition of NH3 adsorbed on Ir(110): a combined TPD and high-energy resolution fast XPS study.

High energy resolution fast XPS combined with TPD experiments were used to study the effect of chemisorbed oxygen on the adsorption and dissociation of NH(3) on Ir(110). Below 250 K the presence of O(ad) does not influence NH(3) decomposition. Above 250 K O(ad) enhances NH(3) dissociation, which results in three times as much N(2) formation and less molecular NH(3) desorption compared to the experiments without O(ad). The effect of O(ad) can be attributed to destabilization of NH(ad) on the surface, resulting in a further dehydrogenation towards N(ad). The presence of O(ad) on the surface lowers the temperature at which the N(ad) combination reaction takes place by as much as 200 K, due to repulsive interaction between N(ad) and O(ad). NO is formed above 450 K if both N(ad) and O(ad) are present on the surface.

Adsorption↗

NH3 adsorption and decomposition on Ir(110): a combined temperature programmed desorption and high resolution fast x-ray photoelectron spectroscopy study.

The adsorption and decomposition of NH3 on Ir(110) has been studied in the temperature range from 80 K to 700 K. By using high-energy resolution x-ray photoelectron spectroscopy it is possible to distinguish chemically different surface species. At low temperature a NH3 multilayer, which desorbs at approximately 110 K, was observed. The second layer of NH3 molecules desorbs around 140 K, in a separate desorption peak. Chemisorbed NH3 desorbs in steps from the surface and several desorption peaks are observed between 200 and 400 K. A part of the NH3ad decomposes into NH(ad) between 225 and 300 K. NH(ad) decomposes into N(ad) between 400 K and 500 K and the hydrogen released in this process immediately desorbs. N2 desorption takes place between 500 and 700 K via N(ad) combination. The steady state decomposition reaction of NH3 starts at 500 K. The maximum reaction rate is observed between 540 K and 610 K. A model is presented to explain the occurrence of a maximum in the reaction rate. Hydrogenation of N(ad) below 400 K results in NH(ad). No NH2ad or NH3ad/NH3 were observed. The hydrogenation of NH(ad) only takes place above 400 K. On the basis of the experimental findings an energy scheme is presented to account for the observations.

Journal Article↗

Structural and kinetic effects on a simple catalytic reaction: oxygen reduction on Ni(110).

Oxygen hydrogenation at 100 K by gas phase atomic hydrogen on Ni(110) has been studied under ultrahigh vacuum conditions by temperature programmed desorption (TPD) and x-ray photoelectron spectroscopy (XPS). Formation of adsorbed water and hydroxyl species was observed and characterized. The coverage of the reaction products was monitored as a function of both temperature and initial oxygen precoverage. On the contrary, when high coverage oxygen overlayers were exposed to gas phase molecular hydrogen, no hydrogenation reaction took place. The results are compared to the inverse process, exposing the hydrogen covered surface to molecular oxygen. In this case, at 100 K, simple Langmuir-Hinshelwood modeling yields an initial sticking coefficient for oxygen adsorption equal to 0.26, considerably lower than for the clean surface. Moreover, formation of hydroxyl groups is found to be twice as fast as the final hydrogenation of OH groups to water. Assuming a preexponential factor of 10(13) s(-1), an activation barrier of 6.7 kcal/mol is obtained for OH formation, thus confirming the high hydrogenating activity of nickel with respect to other transition metals, for which higher activation energies are reported. However, oxygen is hardly removed by hydrogen on nickel: this is explained on the basis of the strong Ni-O chemical bond. The hydrogen residual coverage is well described including a contribution from the adsorption-induced H desorption process which takes place during the oxygen uptake and which is clearly visible from the TPD data.

Journal Article↗

Calorimetry at surfaces using high-resolution core-level photoemission.

We have developed a method to measure simultaneously the internal energy of bulk and the first layer atoms of a crystal. The internal energy of bulk and the surface atoms of lithium (110) have been evaluated from 22 K up to above the melting transition, applying the Debye model to the thermal broadening of the respective 1s photoemission lines. Our measurements clearly reveal two phase changes: the known liquid to solid transition and the surface melting, occurring 50 K below the bulk melting point.

Journal Article↗

Spectroscopic link between adsorption site occupation and local surface chemical reactivity.

In this Letter we show that sequences of adsorbate-induced shifts of surface core level (SCL) x-ray photoelectron spectra contain profound information on surface changes of electronic structure and reactivity. Energy shifts and intensity changes of time-lapsed spectral components follow simple rules, from which adsorption sites are directly determined. Theoretical calculations rationalize the results for transition metal surfaces in terms of the energy shift of the d-band center of mass and this proves that adsorbate-induced SCL shifts provide a spectroscopic measure of local surface reactivity.

Journal Article↗

Distinct reaction mechanisms in the catalytic oxidation of carbon monoxide on Rh(110): scanning tunneling microscopy and density functional theory studies.

By means of scanning tunneling microscopy measurements and density functional theory calculations, we identify the reaction mechanism for the oxidation of carbon monoxide to carbon dioxide on the Rh(110) surface at 160 K, which appears to be completely different than the one active at room temperature. The reasons for these different behaviors are determined. Our results demonstrate that even for a very simple catalytic reaction, the microscopic mechanism can dramatically change with temperature, following pathways that differ for nucleation sites and surface propagation and involve different surface moieties.

Journal Article↗

Liver and kidney foreign bodies granulomatosis in a patient with malocclusion, bruxism, and worn dental prostheses.

Granulomatous reactions caused by foreign bodies have been described in drug abusers, in subjects exposed to occupational pollutants, and more rarely, in association with the use of prosthetic devices. We describe a 62-year-old patient with multiorgan parenchymal granulomatosis caused by inorganic debris of unknown origin. The patient presented with fever, hepatosplenomegaly, progressive cholestasis, and acute renal failure. Liver and kidney biopsies showed the presence of noncaseating epithelioid giant-cell granulomas containing scattered polarizable particles. Similar particles were also present in stools. Studies by innovative scanning electron microscopy and energy-dispersive microanalytical techniques showed that the particles isolated in liver, kidney, and stools were made by feldspars, the main component of porcelain. No occupational or environmental exposure to these materials could be identified in this patient and the only reliable source of the porcelain debris turned out to be constituted by 2 dental bridges evidently worn because of a possible inappropriate construction, malocclusion, and bruxism. The porcelain of the dental prostheses had the same elemental spectrum of the particles isolated from stool specimens and liver-kidney granuloma. After identification of the dental prostheses as the most likely source of ceramic debris, and after their removal, the particles from stool specimens disappeared. The patient was then treated with steroids leading to a remission of the clinical symptoms and a decrease in granulomatous inflammatory reaction in both liver and kidney. This is the first report suggesting that a foreign body systemic granulomatosis can be associated with worn dental prostheses.

Bruxism↗

Chemical shift resolved photoionization cross sections of amorphous carbon nitride

The various components in the N 1s photoemission spectra of amorphous carbon nitride are identified by measuring their photon energy dependence and comparing the experimental results with ab initio multiple scattering calculations. The intensity modulations with photon energy are due to the extended x-ray absorption fine structure effects.

Journal Article↗

Acute renal failure of medical type in an elderly population.

One hundred and nine unselected patients with Acute Renal Failure (ARF) of medical aetiology were hospitalized at the Nephrological Unit of Policlinico University Hospital (Modena) during a 30-month period. ARF was considered as a rapid increase of serum creatinine > 2mg/dl over the baseline level or the doubling of pre-existing value in chronic renal failure. Mean age of patients was 67+/-17 years and median age was 72; 64.2% needing dialytic treatment. Four main causes of ARF were identified: 33 patients had reduced renal perfusion by dehydration, hypotension etc.; 20 multifactorial aetiology; 14 biopsy-investigated renal parenchymal diseases and 39 had drug-related acute renal failure (D-ARF). The clinical outcome was significantly worse in elderly patients as regard mortality (P < 0.02), chronic dialytic treatment (P < 0.04) and complete recovery (P < 0.004). The mean age of D-ARF patients was significantly greater than remaining ARF patients (72.6+/-12.8 vs 63.2+/-18.5: P < 0.004. Nonsteroidal antiinflammatory drugs (NSAIDs) and ACE-inhibitors (Ace-i) caused ARF in 24 and 8 patients respectively. Elderly age, vascular disease and monoclonal gammopathy represented the main risk factors and were significantly more frequent in D-ARF patients (P<001, <0.01, <0.04 respectively). Our data confirm the high susceptibility of ageing kidneys to nephrotoxic damage caused by drugs affecting glomerular autoregulation by microvascular mechanisms. Greater attention to renal changes in ageing and an increased dissemination of preventative measures among nephrologists, could reduce the incidence of these serious and potentially lethal diseases.

Acute Kidney Injury↗

Vascular access for haemodialysis: from surgical procedure to an integrated therapeutic approach.

During the past 10 years the type of vascular access for haemodialysis procedures have changed markedly in our centre: more elbow AV fistulae and more central venous catheters are now used. Nevertheless, early referral to nephrologists and availability of central venous catheters and peritoneal dialysis allow elderly people to be admitted for dialysis treatment. Since vascular access for haemodialysis plays a key role in patient well-being, it is mandatory to apply quality assurance criteria to vascular access for haemodialysis surgery. Based on the results of a national survey, in Italy this policy is still in its early stages: monitoring of vascular access differs amongst centres, interventional radiology is used in a differing way, planning of vascular access for haemodialysis in pre-dialysis patients often remains an unsolved problem. According to our initial experience, we propose the use and validation of a quality-index [(minimum success rate) in elective vascular access for haemodialysis surgery], allowing accreditation of a department and a single surgeon for access management. Prevalence of central venous catheters at first dialysis of chronic renal failure patients is also proposed to evaluate the efficiency in access planning. Better knowledge of vascular access management by different teams could eventually lead to definition of guidelines for this 'Cinderella of dialysis'.

Arteriovenous Shunt, Surgical↗

Protective effects of delapril, indapamide and their combination chronically administered to stroke-prone spontaneously hypertensive rats fed a high-sodium diet.

1. Stroke-prone spontaneously hypertensive rats (SHRsp) have been used widely to test agents putatively capable of vascular protection. These animals present an accelerated time course of hypertension and a reduced life-span. When fed a high-sodium diet from the eighth week of life, a further acceleration in blood pressure increase is obtained, and rats start to die after 5 weeks of diet as a consequence of cerebral haemorrhage. In this model, angiotensin-converting enzyme (ACE) inhibitors were repeatedly proved to prevent vascular lesions and death. Notably, this effect was independent of any hypotensive effect. On the contrary, diuretics were shown not to be equally effective. A combination of ACE inhibitors and diuretics, although known to have synergistic effects in the therapy of hypertension, has never previously been tested. 2. Our aim was to study the effects of long-term treatment with the ACE inhibitor delapril (12 mg day-1 kg-1), the thiazide-like diuretic indapamide (1 mg day-1 kg-1), and their combination (12 and 1 mg day-1 kg-1 respectively), on the survival of SHRsp rats fed a high-sodium diet from the eighth week of life onwards. The effects of the treatments on blood pressure, body weight, food and fluid intake, diuresis, proteinuria and the appearance of lesion signs and death were assessed weekly. When control rats reached 50% mortality, they were killed, together with some drug-treated rats, to compare lesions in brain and kidney. The other drug-treated rats continued treatments until 50% mortality was reached in two treatment groups. 3. All drug treatments were able to delay death significantly when compared with control rats, which reached 50% mortality after 6 weeks of salt loading. This event was preceded by a highly significant increase in proteinuria, diuresis and fluid intake that took place 3 weeks after the increase in blood pressure over the initial range. In delapril- or indapamide-treated SHRsp these changes were never seen, even when animals started to die. In the combination-treated group, a significant increase (P < 0.01) in fluid intake and diuresis, but not proteinuria, was observed from the third week of treatment onwards. 4. Treatment with delapril or indapamide did not block the progressive increase in blood pressure as observed in control animals. However, the increase in blood pressure was markedly retarded with respect to control rats. At variance with this, in combination-treated animals blood pressure levels were maintained until the end of the experiment within the 99% confidence interval initially observed in control animals. 5. Infarctual and haemorrhagic cerebral lesions were observed in 38% of control rats; no lesions were noted in brains of age-matched rats receiving a drug treatment. Kidneys from control animals presented major degenerative lesions of glomeruli and arteries, characterized by fibrinoid necrosis. This condition was absent in drug-treated animals, which presented minor signs of ischaemic lesion. Heart hypertrophy, when heart weight was expressed as a percentage of body weight, was similar in saline-, delapril- or indapamide-treated rats. At variance with this, in combination-treated animals the heart weight to body weight ratio was significantly (P < 0.01) lower than in the other groups. 6. In conclusion, the diuretic indapamide showed similar protective effects as the ACE inhibitor delapril on acute vascular lesions and survival of SHRsp. Moreover, their combination synergized in preventing heart hypertrophy consequent to longterm hypertension. This results is probably related to the enhanced diuresis and the better control of blood pressure levels selectively found in combination-treated animals.

Analysis of Variance↗