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Biomedical subjects

M Toscano

Publications and source records attributed to M Toscano.

At least 19 recordsLinked to original sources
PubMed2007

On the copper(II) ion coordination by prion protein HGGGW pentapeptide model.

The interaction of the octapeptide domain of the prion protein with the transition-metal-ion Cu2+ was studied at the DFT level by using the HGGGW pentapeptide as a model to mimic the PHGGGWGQ octarepeat sequence. Ten complexes, in which the metal ion exhibits different coordinations, were considered. Our results indicate that the lowest-energy structure is characterized by a tetracoordinated metal center and that this tendency of the ion to assume the square planar geometry is strong enough to prevent the addition of a further water molecule in its coordination sphere. The role of tryptophan was found to cause a lowering of the system energy due to the stabilizing effect of the electrostatic interaction between the Trp aromatic indole and histidine imidazole rings.

Circular Dichroism↗
PubMed2005

Interaction of cysteine with Cu2+ and group IIb (Zn2+, Cd2+, Hg2+) metal cations: a theoretical study.

The structure and energetics of complexes obtained upon interaction between cysteine and Zn2+, Cd2+, Hg2+ and Cu2+ cations were studied using quantum chemical density functional theory calculations with the 6-311++G** orbital basis set and relativistic pseudopotentials for the cations. Different coordination sites for metal ions on several cysteine conformers were considered. In their lowest energy complexes with the amino acid, the Zn2+ and Cd2+ cations appear to be three-coordinated to carbonyl oxygen, nitrogen and sulfur atoms, whereas the Cu2+ and Hg2+ ions are coordinated to both the carbonyl oxygen and sulfur atoms of one of the zwitterion forms of the amino acid. Bonds of metal cations with the coordination sites are mainly ionic except those established with sulfur, which show a small covalent character that become most significant when Cu2+ and Hg2+ are involved. The order of metal ion affinity proposed is Cu>Zn>Hg>Cd.

Cadmium↗
PubMed2001

Potential energy surfaces for the gas-phase interaction between alpha-alanine and alkali metal Ions (Li+, Na+, K+). A density functional study.

The conformations of alpha-alanine and those of the eight most stable adducts that it forms with lithium, sodium, and potassium cations were studied by means of the density functional theory using the hybrid B3LYP exchange correlation potential and the 6-311++G basis set. Minima and transition states characterizing the energetic paths for the interaction of the three metal ions with the free amino acid were explored in detail, and the results show that they are almost the same in the cases of lithium and sodium ions. At the absolute minimum, the Li+ and Na+ cations appear to be contemporaneously linked to the carbonyl oxygen and nitrogen atoms of alpha-alanine. Slight differences were found for potassium; the most stable adduct has the cation coordinated to both oxygen atoms of carboxyl function. The influence of the low-energy conformers in the determination of the gas-phase absolute affinities is demonstrated.

Alanine↗
PubMed2001

Bond energies and attachments sites of sodium and potassium cations to DNA and RNA nucleic acid bases in the gas phase.

Gas-phase metal affinities of DNA and RNA bases for the Na(+) and K(+) ions were determined at density functional level employing the hybrid B3LYP exchange correlation potential in connection with the 6-311+G(2df,2p) basis set. All the molecular complexes, obtained by the interaction between several low-lying tautomers of nucleic acid bases and the alkali ions on the different binding sites, were considered. Structural features of the sodium and potassium complexes were found to be similar except in some uracil and thymine compounds in which the tendency of potassium ion toward monocoordination appeared evident. B3LYP bond energies for both metal ions were in agreement with the available experimental results in the cases of uracil and thymine for which the most stable complex was obtained starting from the most stable tautomer of the free nucleic acid base. For adenine, although the interaction of the ions with the most stable free tautomer generated the least stable molecular complex, the best agreement with experiment was found in just this case. For the remaining cytosine and guanine bases, our calculations indicated that the metal ion affinity value closest to experiment should be determined taking into account the role played by the different tautomers of the free bases with similar energy and all the possible complexes obtained by them.

Adenine↗
PubMed2001

Density functional computations of proton affinity and gas-phase basicity of proline.

The proton affinity and gas-phase basicity of proline were evaluated by using density functional theory coupling the B3-LYP hybrid functional with the extended 6--311++G** basis set. Cis and trans conformations of the carboxyl moiety for both exo and endo ring structures were considered for the neutral proline. The results show that the most stable structure of proline has the endo ring conformation with the carboxyl group in the cis position. The structure at the global minimum is stabilized by an intramolecular hydrogen bond. The nitrogen of the ring in the exo form is the preferred protonation site. The calculated proton affinity (924.3 kJ mol(-1)) and gas-phase basicity (894.4 kJ mol(-1)) are in very good agreement with the experimental counterparts.

Gases↗
PubMed2001

Hormone metabolism in the pulmonary circulation.

We measured hormonal levels in blood samples from pulmonary and radial arteries in 117 patients undergoing aorto-coronary by-pass surgery with the aim of investigating the role of the pulmonary vessel endothelium in hormone metabolism. Insulin and glucagon concentrations were significantly higher in pulmonary artery blood with respect to radial artery blood (73 +/- 65 vs. 65 +/- 47 pmol/l, p < 0.005, and 80 +/- 49 vs. 73 +/- 51 ng/l, p < 0.01, respectively), while no difference was found for growth hormone, prolactin, C peptide, insulin-like growth factor I, follicle stimulating hormone, luteinizing hormone, thyroid stimulating hormone, parathyroid hormone, thyroglobulin, triiodothyronine, thyroxine, free triiodothyronine, and free thyroxine. Moreover, prolactin concentrations were more than twice the normal levels, this being an effect of propafol and the opiate fentanyl used for the general anesthesia. Assuming that the arteriovenous differences observed are a marker of peptide hormone degradation, our study has demonstrated that with similar kinetics insulin and glucagon secreted into portal circulation and escaping from hepatic extraction undergo further homeostatic removal of about 9-10 % in the pulmonary circulation before entering the general circulation.

Aged↗
PubMed2001

A primary intracavitary right atrial neurilemoma.

Primary cardiac neurilemoma, a benign tumor, is extremely uncommon. To our knowledge only eight cases have been reported in the literature. We report a case of a 72-year-old man who presented with complaints of progressive shortness of breath and chest pain, seven years after a right nephrectomy for renal adenocarcinoma. An intra-right atrial tumor was surgically removed; the lesion was found to be a neurilemoma of the right atrium. This case report describes the surgical removal and rarity of neurilemomas, their predisposition to be right-sided in the heart and their coincidental association with other types of cancer.

Adenocarcinoma↗
PubMed2000

Gas-phase metal ion (Li+, Na+, Cu+) affinities of glycine and alanine.

The gas-phase metal affinities of glycine and alanine for Li+, Na+ and Cu+ ions have been determined theoretically employing the hybrid B3LYP exchange-correlation functional and using extended basis sets. All computations indicate that the metal ion affinity (MIA) decreases on going from Cu+ to Li+ and Na+ for both the considered amino acids. The absolute MIA values are close to the experimental counterparts with the exception of lithium for which a deviation of about 7 kcal/mol at the B3LYP level is obtained. The optimized structures indicate that Li+, Na+ and Cu+ prefer a bidentate coordination, bonding with both nitrogen and oxygen atoms of amino acids.

Alanine↗
PubMed2000

Semiempirical molecular modeling into quercetin reactive site: structural, conformational, and electronic features.

The conformational behavior, molecular geometry and electronic structure of quercetin were investigated using the semiempirical AM1 and PM3 methods. Results reveal that quercetin has a nonplanar molecular structure, with cross-conjugation occurring at the C ring. Calculations were also performed for quercetin radical species at the OH groups, showing the presence of three radicals in a narrow range of energy. An interpretation of the antioxidative process mechanism, exerted by quercetin as a free radical scavenger, relies on two isoenergetic radicals with extended electronic delocalization between adjacent rings, also having cross-conjugated systems and being affected by the experimental environment influencing their relative order.

Electrons↗
PubMed1999

Cardiac growth factors in human hypertrophy. Relations with myocardial contractility and wall stress.

The aim of the present study was to investigate whether and which cardiac growth factors are involved in human hypertrophy, whether growth factor synthesis is influenced by overload type and/or by the adequacy of the hypertrophy, and the relationships between cardiac growth factor formation and ventricular function. Cardiac growth factor formation was assessed by measuring aorta-coronary sinus concentration gradient in patients with isolated aortic stenosis (n=26) or regurgitation (n=15) and controls (n=12). Gene expression and cellular localization was investigated in ventricular biopsies using reverse transcriptase-polymerase chain reaction and in situ hybridization. Cardiac hypertrophy with end-systolic wall stress <90 kdyne/cm2 was associated with a selective increased formation of insulin-like growth factor (IGF)-I in aortic regurgitation and of IGF-I and endothelin (ET)-1 in aortic stenosis. mRNA levels for IGF-I and preproET-1 were elevated and mainly expressed in cardiomyocytes. At stepwise analysis, IGF-I formation was correlated to the mean velocity of circumferential fiber shortening (r=0.86, P<0.001) and ET-1 formation to relative wall thickness (r=0.82, P<0. 001). When end-systolic wall stress was >90 kdyne/cm2, IGF-I and ET-1 synthesis by cardiomyocytes was no longer detectable, and only angiotensin (Ang) II was generated, regardless of the type of overload. The mRNA level for angiotensinogen was high, and the mRNA was exclusively expressed in the interstitial cells. Ang II formation was positively correlated to end-systolic stress (r=0.89, P<0.001) and end-diastolic stress (r=0.84, P<0.001). Multivariate stepwise analysis selected end-systolic stress as the most predictive variable and left ventricular end-diastolic pressure as the independent variable for Ang II formation (r=0.93, P<0.001). In conclusion, the present results indicate that the course of human left ventricular hypertrophy is characterized by the participation of different cardiac growth factors that are selectively related both to the type of hemodynamic overload and to ventricular function.

Aged↗
PubMed1999

Interleukin 10 production in patients undergoing cardiopulmonary bypass: evidence of inhibition of Th-1-type responses.

The cardiopulmonary bypass (CPB) procedure has long been associated with a generalized immunosuppression. To understand further the cytokine-mediated regulation of the complex physiological and immunological changes induced by CPB, the authors decided to investigate whether CPB affects the release of interleukin (IL)-10, as well as other cytokines, in correlation to the inhibition of T cell responses. Using phytohaemagglutinin (PHA) as mitogen and peripheral blood mononuclear cells (PBMC) isolated from patients undergoing CPB, we investigated whether this procedure has an effect on the secretion of different patterns of cytokines (Th1- and Th2-type) and PBMC proliferation. In all patients, CPB significantly enhances IL-10 and IL-6 production in resting and PHA-stimulated PBMC. On the other hand, IL-2 production, in response to PHA, was significantly diminished. Reduced IL-2 and enhanced IL-10 production were associated with a significant decrease in PBMC proliferation. Immunosuppression was also associated to lymphopenia, while neutrophil counts were significantly enhanced. These results show that after CPB there is a transient but clear unbalanced immune response demonstrated by a differentiated production of Th1- and Th2-type cytokines. The release of different patterns of cytokines observed after CPB may be helpful in understanding and preventing the development of infectious and immune complications in surgical procedure employing CPB.

Aged↗
PubMed1999

Antinociceptive and uterine relaxant activities of Viburnum toronis alive (Caprifoliaceae).

Petroleum ether, ethyl acetate and methanolic leaf extracts of Viburnum toronis Killip et Smith were studied. From the petroleum ether extract, fatty acids of methyl esters such as methyl myristate, methyl palmitate, methyl stearate and methyl araquidonate were identified by means of GC-MS. From the ethyl acetate extract, 2-methylbutanoic, 2-methyl-2-butenoic, 3-methylbutanoic acids and 4-hydroxy-4-methylpentanone were identified by means of GC-MS. Through the isolated organ technique, uterine relaxant was verified; and through the method of writhings induced by acetic acid, the antinociceptive activity of methanolic extracts and the extract in ethyl acetate were verified. It was found that the extract in ethyl acetate showed the greatest in both uterine relaxant and antinociceptive activity at doses of 250 mg/kg.

Analgesics↗
PubMed1999

Theoretical calculations of glycine and alanine gas-phase acidities.

The gas-phase acidities of glycine and alanine were determined by using a variety of high level theoretical methods to establish which of these would give the best results with accessible computational efforts. MP2, MP4, QCISD, G2 ab initio procedures, hybrid Becke3-LYP (B3LYP) and gradient corrected Becke-Perdew (BP) and Perdew-Wang and Perdew (PWP) nonlocal density functionals were used for the calculations. A maximum deviation of approximately 13 and 18 kJ/mol from experimental data was observed for the computed delta Hacid and delta Gacid values, respectively. The best result was obtained at G2 level, but comparable reliability was reached when the considerably less time consuming B3LYP, BP, and PWP density functional approaches were employed.

Alanine↗
PubMed1999

The diagnostic and prognostic value of cardiac Troponin T in bypass surgery.

BACKGROUND: The purpose of this study was to verify the utility of serum Troponin T (TnT) in the diagnosis of myocardial damage after coronary surgery performed using different methods of myocardial protection. The prognostic value of TnT peak for a poor postoperative course was also investigated. METHODS: Forty-three patients were enrolled and randomised in 2 group: Group A (n. 22) receiving warm blood cardioplegia and Group B (n. 21) receiving cold blood cardioplegia. According to TnT peak levels 3 subgroups were identified: Subgroup 1 (TnT peak < than 1 ng/ml); Subgroup 2 (TnT peak between 1 and 3 ng/ml), Subgroup 3 (TnT peak >3 ng/ml). A comparison with the standard criteria for diagnosis of myocardial ischemia was performed for each subgroup of patients. A 12 months follow-up for the patients of subgroups 1 and 2 was also completed in order to evaluate the prognostic value of a higher TnT peak. RESULTS: The overall patients subdivision in subgroup 1, 2 and 3 was 20 (46.5%), 14 (32.5%) and 9 (20.9%) respectively with no statistical difference for Group A or B. Only 7 of the patients of subgroup 3 (87%) matched the WHO diagnostic criteria for myocardial infarction. At the overall follow-up, 2 (14.28%) patients of subgroup 2, and 4 (20.0%) of subgroup 3, revealed a residual ischemia at the ECG-stress test even if none of these needed reoperation. CONCLUSIONS: Our data confirmed the high sensitivity and specificity of TnT measurement in the diagnosis of myocardial infarction and minor myocardial damage. This study, however, failed to show any statistically significant difference of the TnT peak when using different strategies of myocardial protection. The late prognostic value of the TnT increase in the early post-operative course has to be confirmed from a further study.

Aged↗
PubMed1999

Siena's experience with pulmonary autograft operations: clinical and echocardiographic follow-up.

As there is no perfect aortic valve substitute, there is a need to find out which one is the best option to replace the diseased aortic valve. Any type of mechanical or biological stented device has a residual gradient and does not reproduce the extremely sophisticated normal aortic valve function. This may influence the short- and long-term outcome, especially in dilated and poorly contracting left ventricles which do not tolerate even a mild stenosis. Thus, the potentially ideal valve to replace the aortic valve is either an aortic valve (aortic homograft) or a pulmonary autograft in aortic position. These grafts are also less subject to endocarditis. It has been demonstrated that pulmonary autografts can grow when implanted in children and as they remain viable, they maintain their dynamic behavior and possibly the internal innervation of the cusps. Unfortunately, pulmonary autograft surgery is more demanding and lasts longer, which may increase the risk of the operation. In addition, the exact indications and applications of the operation, particularly in patients with poor left ventricles or additional lesions, have not been clearly defined. Here we report our experience with this technique in 11 patients with severe aortic valve disease, including those with poor left ventricle function and/or associated disease. We describe our short- and medium-term follow-up, which shows optimal left ventricle recovery with no perioperative or postoperative complications, thus supporting a wider application of the operation.

Adult↗