The nature of Ru-NO bonds in ruthenium tetraazamacrocycle nitrosyl complexes-a computational study

Ruthenium complexes including nitrosyl or nitrite complexes are particularly interesting because they can not only scavenge but also release nitric oxide in a controlled manner, regulating the NO-level in vivo. The judicious choice of ligands attached to the [RuNO] core has been shown to be a suitable strategy to modulate NO reactivity in these complexes. In order to understand the influence of different equatorial ligands on the electronic structure of the Ru-NO chemical bonding, and thus on the reactivity of the coordinated NO, we propose an investigation of the nature of the Ru-NO chemical bond by means of energy decomposition analysis (EDA), considering tetraamine and tetraazamacrocycles as equatorial ligands, prior to and after the reduction of the {RuNO}(6) moiety by one electron. This investigation provides a deep insight into the Ru-NO bonding situation, which is fundamental in designing new ruthenium nitrosyl complexes with potential biological applications.

Diametral tensile strength and film thickness of an experimental dental luting agent derived from castor oil

The need to develop new dental luting agents in order to improve the success of treatments has greatly motivated research. Objective: The aim of this study was to evaluate the diametral tensile strength (DTS) and film thickness (FT) of an experimental dental luting agent derived from castor oil (COP) with or without addition of different quantities of filler (calcium carbonate - CaCO3). Material and Methods: Eighty specimens were manufactured (DTS N=40; FT N=40) and divided into 4 groups: Pure COP; COP 10%; COP 50% and zinc phosphate (control). The cements were mixed according to the manufacturers' recommendations and submitted to the tests. The DTS test was performed in the MTS 810 testing machine (10 KN, 0.5 mm/min). For FT test, the cements were sandwiched between two glass plates (2 cm(2)) and a load of 15 kg was applied vertically on the top of the specimen for 10 min. The data were analyzed by means of one-way ANOVA and Tukey's test (alpha=0.05). Results: The values of DTS (MPa) were: Pure COP- 10.94 +/- 1.30; COP 10%- 30.06 +/- 0.64; COP 50%- 29.87 +/- 0.27; zinc phosphate- 4.88 +/- 0.96. The values of FT (pm) were: Pure COP- 31.09 +/- 3.16; COP 10%- 17.05 +/- 4.83; COP 50%- 13.03 +/- 4.83; Zinc Phosphate- 20.00 +/- 0.12. One-way ANOVA showed statistically significant differences among the groups (DTS - p=1.01E-40; FT - p=2.4E-10). Conclusion: The experimental dental luting agent with 50% of filler showed the best diametral tensile strength and film thickness.

Rationale, study design, and analysis plan of the Alveolar Recruitment for ARDS Trial (ART): Study protocol for a randomized controlled trial

Background: Acute respiratory distress syndrome (ARDS) is associated with high in-hospital mortality. Alveolar recruitment followed by ventilation at optimal titrated PEEP may reduce ventilator-induced lung injury and improve oxygenation in patients with ARDS, but the effects on mortality and other clinical outcomes remain unknown. This article reports the rationale, study design, and analysis plan of the Alveolar Recruitment for ARDS Trial (ART). Methods/Design: ART is a pragmatic, multicenter, randomized (concealed), controlled trial, which aims to determine if maximum stepwise alveolar recruitment associated with PEEP titration is able to increase 28-day survival in patients with ARDS compared to conventional treatment (ARDSNet strategy). We will enroll adult patients with ARDS of less than 72 h duration. The intervention group will receive an alveolar recruitment maneuver, with stepwise increases of PEEP achieving 45 cmH(2)O and peak pressure of 60 cmH2O, followed by ventilation with optimal PEEP titrated according to the static compliance of the respiratory system. In the control group, mechanical ventilation will follow a conventional protocol (ARDSNet). In both groups, we will use controlled volume mode with low tidal volumes (4 to 6 mL/kg of predicted body weight) and targeting plateau pressure <= 30 cmH2O. The primary outcome is 28-day survival, and the secondary outcomes are: length of ICU stay; length of hospital stay; pneumothorax requiring chest tube during first 7 days; barotrauma during first 7 days; mechanical ventilation-free days from days 1 to 28; ICU, in-hospital, and 6-month survival. ART is an event-guided trial planned to last until 520 events (deaths within 28 days) are observed. These events allow detection of a hazard ratio of 0.75, with 90% power and two-tailed type I error of 5%. All analysis will follow the intention-to-treat principle. Discussion: If the ART strategy with maximum recruitment and PEEP titration improves 28-day survival, this will represent a notable advance to the care of ARDS patients. Conversely, if the ART strategy is similar or inferior to the current evidence-based strategy (ARDSNet), this should also change current practice as many institutions routinely employ recruitment maneuvers and set PEEP levels according to some titration method.

Mixed-valence state of symmetric diruthenium complexes: synthesis, characterization, and electron transfer investigation

Complexes of the type {[(pyS)Ru(NH3)(4)](2)-mu-L}(n), where pyS = 4-mercaptopyridine, L = 4,4'-dithiodipyridine (pySSpy), pyrazine (pz) and 1,4-dicyanobenzene (DCB), and n = +4 and +5 for fully reduced and mixed-valence complexes, respectively, were synthesized and characterized. Electrochemical data showed that there is electron communication between the metal centers with comproportionation constants of 33.2, 1.30 x 10(8) and 5.56 x 10(5) for L = pySSpy, pz and DCB, respectively. It was also observed that the electronic coupling between the metal centers is affected by the p-back-bonding interaction toward the pyS ligand. Raman spectroscopy showed a dependence of the intensity of the vibrational modes on the exciting radiations giving support to the assignments of the electronic transitions. The degree of electron communication between the metal centers through the bridging ligands suggests that these systems can be molecular wire materials.

Implant Stability Measurements of Two Immediate Loading Protocols for the Edentulous Mandible: Rigid and Semi-rigid Splinting of the Implants

Aim: Primary and secondary stabilities of immediately loaded mandibular implants restored with fixed prostheses (FP) using rigid or semirigid splinting systems were clinically and radiographically evaluated. Methods: Fifteen edentulous patients were rehabilitated using hybrid FP; each had 5 implants placed between the mental foramens. Two groups were randomly divided: group 1-FP with the conventional rigid bar splinting the implants and group 2-semi-rigid cantilever extension system with titanium bars placed in the 2 distal abutment cylinders. Primary stability was evaluated using resonance frequency analysis after installation of the implant abutments. The measurements were made at 3 times: T0, at baseline; T1, 4 months after implant placement; and T2, 8 months after implant placement. Presence of mobility and inflammation in the implant surrounding regions were checked. Stability data were submitted to statistical analysis for comparison between groups (P, 0.05). Results: Implant survival rate for the implants was of 100% in both groups. No significant differences in the mean implant stability quotient values were found for both groups from baseline and after the 8-month follow-up. Conclusion: The immediate loading of the implants was satisfactory, and both splinting conditions (rigid and semi-rigid) can be successfully used for the restoration of edentulous mandibles. (Implant Dent 2012;21:486-490)

Systematic position of the monotypic Azorean genus Falbouria Dyte with notes on the definition of Chrysotus Meigen (Diptera: Dolichopodidae)

The systematic position and the generic status of the monotypic genus Falbouria Dyte (Dolichopodidae: Diaphorinae) are evaluated. The type-species of the genus, F. acorensis (Parent), endemic to the Azores, is re-described, and hypopygial and oviscapt morphology illustrated in detail for the first time. Falbouria is kept as a separate genus, but close to Chrysotus Meigen, which is certainly paraphyletic (or even polyphyletic) in its present composition. A brief discussion on the delimitation of Chrysotus is provided and its laesus-group of species is suggested as the core clade of the genus.

Spironolactone prevents alterations associated with cardiac hypertrophy produced by isoproterenol in rats: involvement of serum- and glucocorticoid-regulated kinase type 1

Persistent beta-adrenergic receptor stimulation with isoproterenol is associated with cardiac hypertrophy as well as cardiac synthesis of angiotensin II. Serum- and glucocorticoid-regulated kinase type 1 (SGK-1) is a key mediator in structural, functional and molecular cardiac effects of aldosterone in rats. This study was designed to investigate the cardiac effects of the mineralocorticoid receptor antagonist spironolactone on the response to isoproterenol treatment in rats, as well as the involvement of the main mediator of cellular aldosterone action, SGK-1, in the heart. Male Wistar rats received isoproterenol (3 mg kg-1 day-1) or vehicle for 15 days. Half of the animals in each group were simultaneously treated with spironolactone (200 mg kg-1 day-1). Systolic and diastolic blood pressures were not significantly different among groups. Treatment with spironolactone normalized the increased left ventricular end-diastolic pressure observed in isoproterenol-treated rats. Isoproterenol treatment induced cardiac hypertrophy and increased collagen content, both of which were normalized by spironolactone treatment. The mRNA levels of transforming growth factor beta, connective tissue growth factor, matrix metalloprotease 2, matrix metalloprotease inhibitor 2, tumour necrosis factor a, interleukin 1 beta, p22phox and xanthine dehydrogenase were increased (P < 0.05) in isoproterenol-treated rats, and this effect was prevented by spironolactone (P < 0.05). Spironolactone also reduced the elevated SGK-1 expression in isoproterenol-treated rats. The observed reduction of the principal mediator of aldosterone cellular actions, SGK-1, by spironolactone in hearts from isoproterenol-treated rats suggests a role of mineralocorticoids in the cardiac hypertrophy, fibrosis, inflammation, oxidation and diastolic dysfunction induced by isoproterenol treatment in rats.

Effect of the vanadium(V) concentration on the spectroscopic properties of nanosized europium-doped yttrium phosphates

Nanosized rare earth phosphovanadate phosphors (Y(P,V)O-4:Eu3+) have been prepared by applying the organic-inorganic polymeric precursors methodology. Luminescent powders with tetragonal structure and different vanadate concentrations (0%, 1%, 5%, 10%, 20%, 50%, and 100%, with regard to the phosphate content) were then obtained for evaluation of their structural and spectroscopic properties. The solids were characterized by scanning electron microscopy, X-ray diffractometry, vibrational spectroscopy (Raman and infrared), and electronic spectroscopy (emission, excitation, luminescence lifetimes, chromaticity, quantum efficiencies, and Judd-Ofelt intensity parameters). The solids exhibited very intense D-5(0) -> F-7(J) Eu3+ transitions, and it was possible to control the luminescent characteristics, such as excitation maximum, lifetime and emission colour, through the vanadium(V) concentration. The observed luminescent properties correlated to the characteristics of the chemical environments around the Eu3+ ions with respect to the composition of the phosphovanadates. The Eu3+ luminescence spectroscopy results indicated that the presence of larger vanadium(V) amounts in the phosphate host lattice led to more covalent and polarizable chemical environments. So, besides allowing for control of the luminescent properties of the solids, the variation in the vanadate concentration in the obtained YPO4:Eu3+ phosphors enabled the establishment of a strict correlation between the observable spectroscopic features and the chemical characteristics of the powders.

Two New Species of Stenophragma Skuse from Western Australia (Diptera, Mycetophilidae, Sciophilinae)

Stenophragma Skuse was originally described for S. meridianum (Skuse), from Australia. Since then seventeen species have been added to the genus-from Brazil, Ecuador, Peru, Bolivia, Paraguay, Chile, Argentina, and Canada. We add two new species to the genus Stenophragma-S. bickeli n.sp. and S. collessi n.sp.-from Western Australia. An identification key for the Australian species of Stenophragma is provided. Comments are made about possible relationships among these new species and the remaining Australasian species of the genus. OLIVEIRA, SARAH SIQUEIRA, AND DALTON DE SOUZA AMORIM. 2012. Two new species of Stenophragma Skuse from Western Australia (Diptera, Mycetophilidae, Sciophilinae). Records of the Australian Museum 64(2): 149-158.

Early transplantation of human immature dental pulp stem cells from baby teeth to golden retriever muscular dystrophy (GRMD) dogs: Local or systemic?

Background:The golden retriever muscular dystrophy (GRMD) dogs represent the best available animal model for therapeutic trials aiming at the future treatment of human Duchenne muscular dystrophy (DMD). We have obtained a rare litter of six GRMD dogs (3 males and 3 females) born from an affected male and a carrier female which were submitted to a therapeutic trial with adult human stem cells to investigate their capacity to engraft into dogs muscles by local as compared to systemic injection without any immunosuppression. Methods Human Immature Dental Pulp Stem Cells (hIDPSC) were transplanted into 4 littermate dogs aged 28 to 40 days by either arterial or muscular injections. Two non-injected dogs were kept as controls. Clinical translation effects were analyzed since immune reactions by blood exams and physical scores capacity of each dog. Samples from biopsies were checked by immunohistochemistry (dystrophin markers) and FISH for human probes. Results and Discussion We analyzed the cells' ability in respect to migrate, engraftment, and myogenic potential, and the expression of human dystrophin in affected muscles. Additionally, the efficiency of single and consecutive early transplantation was compared. Chimeric muscle fibers were detected by immunofluorescence and fluorescent in situ hybridisation (FISH) using human antibodies and X and Y DNA probes. No signs of immune rejection were observed and these results suggested that hIDPSC cell transplantation may be done without immunosuppression. We showed that hIDPSC presented significant engraftment in GRMD dog muscles, although human dystrophin expression was modest and limited to several muscle fibers. Better clinical condition was also observed in the dog, which received monthly arterial injections and is still clinically stable at 25 months of age. Conclusion Our data suggested that systemic multiple deliveries seemed more effective than local injections. These findings open important avenues for further researches.

Oral health as a predictive factor for oral mucositis

OBJECTIVES: Oral mucositis is a complication frequently associated with hematopoietic stem cell transplantation, decreasing a patient’s quality of life and increasing the occurrence of opportunistic infections. The purpose of this study was to determine the incidence and severity of oral mucositis and to assess the correlation of this disease with the oral health of an individual at the time of hematopoietic stem cell transplantation. METHODS: Before transplantation, patients’ oral health and inflammatory conditions were determined using the gingival index and the plaque index, which are based on gingival bleeding and the presence of dental plaque, respectively. Additionally, the dental health status was determined using the decayed, missing, and filled teeth index. The monitoring of oral mucositis was based on the World Health Organization grading system and was performed for five periods: from Day 0 to D+5, from D+6 to D+10, from D+11 to D+15, from D+16 to D+20, and from D+21 to D+30. RESULTS: A total of 97 patients (56% male and 44% female) who underwent hematopoietic stem cell transplantation at the Hospital das Clinicas da Faculdade de Medicina da Universidade de Sao Paulo between January 2008 and July 2009 were prospectively examined. The incidence of ulcerative mucositis was highest from days +6 to +10 and from days +11 to +15 in the patients who underwent autologous and allogeneic hematopoietic stem cell transplantation, respectively. CONCLUSION: The data, including the dental plaque and periodontal status data, showed that these oral health factors were predictive of the incidence and severity of oral mucositis in a cohort of patients with similar conditioning regimens before hematopoietic stem cell transplantation

Oxidative stress and inflammatory response increase during coronary artery bypass grafting with extracorporeal circulation

INTRODUCTION: Thiobarbituric acid-reactive substance is a marker of oxidative stress and has cytotoxic and genotoxic actions. C- reactive protein is used to evaluate the acute phase of inflammatory response. OBJECTIVES: To assess the thiobarbituric acid-reactive substance and C-reactive protein levels during extracorporeal circulation in patients submitted to cardiopulmonary bypass. METHODS: Twenty-five consecutive surgical patients (16 men and nine women; mean age 61.2 ± 9.7 years) with severe coronary artery disease diagnosed by angiography scheduled for myocardial revascularization surgery with extracorporeal circulation were selected. Blood samples were collected immediately before initializing extracorporeal circulation, T0; in 10 minutes, T10; and in 30 minutes, T30. RESULTS: The thiobarbituric acid-reactive substance levels increased after extracorporeal circulation (P=0.001), with average values in T0=1.5 ± 0.07; in T10=5.54 ± 0.35; and in T30=3.36 ± 0.29 mmoles/mg of serum protein. The C-reactive protein levels in T0 were negative in all samples; in T10 average was 0.96 ± 0.7 mg/dl; and in T30 average was 0.99 ± 0.76 mg/dl. There were no significant differences between the dosages in T10 and T30 (P=0.83). CONCLUSIONS: C-reactive protein and thiobarbituric acid-reactive substance plasma levels progressively increased during extracorporeal circulation, with maximum values of thiobarbituric acid-reactive substance at 10 min and of Creactive protein at 30 min. It suggests that there are an inflammatory response and oxidative stress during extracorporeal circulation.

Frequency of human platelet antigens in oncohematological patients with thrombocytopenia and the probability of incompatibility to platelet transfusions

OBJECTIVE: The objective of this study was to evaluate the frequencies of human platelet antigens in oncohematological patients with thrombocytopenia and to analyze the probability of their incompatibility with platelet transfusions. METHODS: Platelet antigen genotyping was performed by sequence-specific primer polymerase chain reaction (SSP-PCR) for the HPA-1a, HPA-1b, HPA-2a, HPA-2b, HPA-3a, HPA-3b, HPA-4a, HPA-4b, HPA-5a, HPA-5b; HPA-15a, HPA-15b alleles in 150 patients of the Hematology Service of the Hospital das Clínicas (FMUSP). RESULTS: The allele frequencies found were: HPA-1a: 0.837; HPA-1b: 0.163; HPA-2a: 0.830; HPA-2b: 0.170; HPA-3a: 0.700; HPA-3b: 0.300; HPA-4a: 1; HPA-4b: 0; HPA-5a: 0.887; HPA-5b: 0.113; HPA-15a: 0.457 and HPA-15b: 0.543. CONCLUSIONS: Data from the present study showed that the A allele is more common in the population than the B allele, except for HPA-15. This suggests that patients homozygous for the B allele are more predisposed to present alloimmunization and refractoriness to platelet transfusions by immune causes. Platelet genotyping could be of great value in the diagnosis of alloimmune thrombocytopenia and to provide compatible platelet concentrates for these patients.

Prevalence of celiac disease among blood donors in São Paulo: the most populated city in Brazil

OBJECTIVE: Celiac disease is a permanent enteropathy caused by the ingestion of gluten, which leads to an immunemediated inflammation of the small intestine mucosa. The prevalence of celiac disease varies among different nations and ethnic backgrounds, and its diversity is determined by genetic and environmental factors. São Paulo city is one of the largest cities in the world, with a vast population and an important history of internal migratory flow from other Brazilian regions, as well as immigration from other, primarily European, countries, resulting in significant miscegenation. The aim of the present study was to estimate the prevalence of adults with undiagnosed celiac disease among blood donors of São Paulo by collecting information on the ancestry of the population studied. METHODS: The prevalence of celiac disease was assessed by screening for positive IgA transglutaminase and IgA endomysium antibodies in 4,000 donors (volunteers) in the Fundação Pró-Sangue Blood Center of São Paulo, São Paulo, Brazil. The antibody-positive subjects were asked to undergo a small bowel biopsy. RESULTS: Of the 4,000 subjects, twenty-four had positive tests, although both antibody tests were not always concordant. For example, ten subjects were positive for IgA tissue transglutaminase only. In twenty-one positive patients, duodenal biopsies were performed, and the diagnosis of celiac disease was confirmed in fourteen patients (Marsh criteria modified by Oberhuber). In this group, 67% claimed to have European ancestry, mainly from Italy, Portugal and Spain. CONCLUSION: The prevalence of celiac disease is at least 1:286 among supposedly healthy blood bank volunteers in São Paulo, Brazil.

Pyloric Brunner’s gland hamartoma with atypical hyperplasia

Brunner’s gland hamartoma (BGH) is an extremely rare benign digestive tumor, generally located in the duodenal bulb. We report the case of a 51-year-old asymptomatic man with a large pedunculated BGH arising from the pylorus. It was successfully removed en bloc by endoscopic resection.