New Pd(II) and Pt(II) complexes with N,S-chelated pyrazolonate ligands: Molecular and supramolecular structure and preliminary study of their in vitro antitumoral activity

New Pd(II) and Pt(II) complexes [ML2] (HL = a substituted 2,5-dihydro-5-oxo-1H-pyrazolone-1-carbothioamide) have been synthesized by reacting K2MCl4 (M = Pd, Pt) or Pd(OAc)(2) with beta-ketoester thiosemicarbazones. The structures of seven of these complexes were determined by X-ray diffraction. Although all exhibit a distorted square-planar coordination with trans- or (in one case) cis-[MN2S2] kernels, their supramolecular arrangements vary widely from isolated molecules to 3D-networks. The in vitro antitumoral assays performed with two HL ligands and their metal complexes showed significant cytostatic activity for the latter, with the most active [ML2] derivative (a palladium complex) being about sixteen times more active than cis-DDP against the cis-platinum-resistant cell line A2780cisR. (c) 2007 Elsevier Inc. All rights reserved.

Dithiocarbazate complexes with the [M(PPh(3))](2+) (M=Pd or Pt) moiety Synthesis, characterization and anti-Tripanosoma cruzi activity

New neutral Pd(II) and Pt(II) complexes of the type [M(L)(PPh(3))] (M Pd or Pt) were prepared in crystalline form in high-yield synthesis with the S-benzyldithiocarbazates and S-4-nitrobenzyldithiocarbazates derivatives from 2-hydroxyacetophenone, H(2)L(1a) and H(2)L(1b), and benzoylacetone, H(2)L(2a) and H(2)L(2b). The new complexes [Pt(L(1a))(PPh(3))] (1), [Pd(L(1a))(PPh(3))] (2), [Pt(L(1b))(PPh(3))] (3), [Pd(L(1b))(PPh(3))] (4), [Pt(L(2a))(PPh(3))] (5), [Pd(L(2a))(PPh(3))] (6), [Pt(L(2b))(PPh(3))] (7) and [Pd(L(2b))(PPh(3))] (8) were characterized on the basis of elemental analysis, conductivity measurements, UV-visible, IR, electrospray ionization mass spectrometry (ESI-MS), NMR ((1)H and (31)P) and by X-ray diffraction studies. The studies showed that differently from what was observed for the H(2)L(1a) and H(2)L(1b) ligands, H(2)L(2a) and H(2)L(2b) assume cyclic forms as 5-hydroxypyrazolinic. Upon coordination, H2L2a and H2L2b suffer ring-opening reaction, coordinating in the same manner as H(2)L(1a) and H(2)L(1b), deprotonated and in O,N,S-tridentate mode to the (MPPh(3))(2+) moiety. All complexes show a quite similar planar fourfold environment around the M(II) center. Furthermore, these complexes exhibited biological activity on extra and intracellular forms of Trypanosoma cruzi in a time- and concentration-dependent manner with IC(50) values ranging from 7.8 to 18.7 mu M, while the ligand H(2)L(2a) presented a trypanocidal activity on trypomastigote form better than the standard drug benznidazole. (C) 2010 Elsevier Inc. All rights reserved.

Antimycobacterial and antitumor activities of Palladium(II) complexes containing isonicotinamide (isn): X-ray structure of trans-[Pd(N(3))(2)(isn)(2)]

Complexes of the type trans-[PdX(2)(isn)(2)] {X = Cl (1), N(3) (2), SCN (3), NCO (4); isn = isonicotinamide} were synthesized and evaluated for in vitro antimycobacterial and antitumor activities. The coordination mode of the isonicotinamide and the pseudohalide ligands was inferred by IR spectroscopy. Single crystal X-ray diffraction determination on 2 showed that coordination geometry around Pd(II) is nearly square planar, with the ligands in a trans configuration. All the compounds demonstrated better in vitro activity against Mycobacterium tuberculosis than isonicotinamide and pyrazinamide. Among the complexes, compound 2 was found to be the most active with MIC of 35.89 mu M. Complexes 1-4 were also screened for their in vitro antitumor activity towards LM3 and LP07 murine cancer cell lines. (C) 2010 Elsevier Masson SAS. All rights reserved.

First dynamic kinetic resolution of selenium-containing chiral amines catalyzed by palladium (Pd/BaSO(4)) and Candida antartica lipase (CAL-B)

An efficient method for chemoenzymatic dynamic kinetic resolution of selenium-containing chiral amines (organoselenium-1-phenylethanamines) has been developed, leading to the corresponding amides in excellent enantioselectivities and high isolated yields. This one-pot procedure employs two different types of catalysts: Pd on barium sulphate (Pd/BaSO(4)) as racemization catalyst and lipase (CAL-B) as the resolution catalyst. (C) 2009 Elsevier Ltd. All rights reserved.

Synthesis of L1(0) Fe-Pd films by electrodeposition and thermal annealing

Fe-Pd alloy films have been prepared by electrochemical deposition from an alkaline electrolyte containing Fe sulfate, Pd chloride and 5-sulfosalicylic acid onto polycrystalline titanium substrates. The as-deposited films were nanocrystalline and magnetically soft (coercivity similar to 25 Oe). L1(0) Fe-Pd films with a (111) preferred orientation were obtained by post-deposition thermal annealing of films with composition about 37 at% Fe in an (Ar + 5% H-2) gas flow at 500 degrees C. Such films exhibit hard magnetic properties, with a coercivity up to 1880 Oe, and a slightly anisotropic magnetic response, with a larger in-plane remanence. Preliminary magnetic investigations support magnetization switching through pinning of domain walls. (c) 2008 Elsevier B.V. All rights reserved.

Nitrate reduction on Pt single crystals with Pd multilayer

Nitrate reduction on palladium multilayers deposited on platinum single crystal electrodes was studied by cyclic voltammetry and FTIR spectroscopy in acid and alkaline media. The results are compared with those obtained with bulk palladium single crystals. The reaction is sensitive to the electrode surface structure, the reactivity depending on the solution pH. In acid solution nitrate was reduced at potentials below the potential of zero total charge (pztc), when the electrode is negatively charged. Competition between nitrate, hydrogen and anion adsorption and NO formation and accumulation at the surface are proposed as the main reasons for the slow reaction rate. On the bulk palladium single crystal electrodes, NO formation leads to a fast blockage of the surface resulting in a very low activity for nitrate reduction. In alkaline solution, nitrate is reduced at more positive potentials with significantly higher current being measured on the Pd multilayer on Pt(100) electrode. (C) 2008 Elsevier Ltd. All rights reserved.

Potential oscillations in a proton exchange membrane fuel cell with a Pd-Pt/C anode

We report in this paper the occurrence of potential oscillations in a proton exchange membrane fuel cell (PEMFC) with a Pd-Pt/C anode, fed with H(2)/100 ppm CO, and operated at 30 degrees C. We demonstrate that the use of Pd-Pt/C anode enables the emergence of dynamic instabilities in a PEMFC. Oscillations are characterized by the presence of very high oscillation amplitude, ca. 0.8 V. which is almost twice that observed in a PEMFC with a Pt-Ru/C anode under similar conditions. The effects of the H(2)/CO flow rate and cell current density on the oscillatory dynamics were investigated and the mechanism rationalized in terms of the CO oxidation and adsorption processes. We also discuss the fundamental aspects concerning the operation of a PEMFC under oscillatory regime in terms of the benefit resulting from the higher average power output. (c) 2010 Elsevier B.V. All rights reserved.

Synthesis and characterization of mono and polymeric cyclopalladated compounds: Crystal and molecular structure of [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (pz = pyrazine)

In the treatment of cyclometallated dimer [Pd(dmba)(mu-Cl)](2) (dmba = N,N-dimethylbenzylamine) with AgNO(3) and acetonitrile the result was the monomeric cationic precursor [Pd(dmba)(NCMe)(2)](NO(3)) (NCMe=acetonitrile) (1). Compound 1 reacted with m-nitroaniline (m-NAN) and pirazine (pz), originating [Pd(dmba)(ONO(2))(m-NAN)] (2) and [{Pd(dmba)(ONO(2))}(2)(mu-pz)] center dot H(2)O (3), respectively. These compounds were characterized by elemental analysis, IR and NMR spectroscopy. The IR spectra of (2-3) display typical bands of monodentade O-bonded nitrate groups, whereas the NMR data of 3 are consistent with the presence of bridging pyrazine ligands. The structure of compound 3 was determined by Xray diffraction analysis. This packing consists of a supramolecular chain formed by hydrogen bonding between the water molecule and nitrato ligands of two consecutive [Pd(2)(dmba)(2)(ONO(2))2(mu-pz)] units. (c) 2008 Elsevier Ltd. All rights reserved.

The influence of residual salivary fluoride from dentifrice on enamel erosion: an in situ study

The objective of this study was to assess the salivary residual effect of fluoride dentifrice on human enamel subjected to an erosive challenge. This crossover in situ study was performed in two phases (A and B), involving ten volunteers. In each phase, they wore acrylic palatal appliances, each containing 3 human enamel blocks, during 7 days. The blocks were subjected to erosion by immersion of the appliances in a cola drink for 5 minutes, 4 times a day. Dentifrice was used to brush the volunteers’ teeth, 4 times a day, during 1 minute, before the appliance was replaced into the mouth. In phases A and B the dentifrices used had the same formulation, except for the absence (PD) or presence (FD) of fluoride, respectively. Enamel alterations were determined using profilometry, microhardness (%SMHC), acid- and alkali-soluble F analysis. The data were tested using ANOVA (p < 0.05). The concentrations (mean ± SD) of alkali- and acid-soluble F (µgF/cm²) were, respectively, PD: 1.27ª ± 0.70/2.24A ± 0.36 and FD: 1.49ª ± 0.44/2.24A ± 0.67 (p > 0.05). The mean wear values (± SD, µm) were PD: 3.63ª ± 1.54 and FD: 3.54ª ± 0.90 (p > 0.05). The mean %SMHC values (± SD) were PD: 89.63ª ± 4.73 and FD: 87.28ª ± 4.01 (p > 0.05). Thus, we concluded that the residual fluoride from the fluoride-containing dentifrice did not protect enamel against erosion.

Periodontal treatment during pregnancy decreases the rate of adverse pregnancy outcome: a controlled clinical trial

OBJECTIVES: The aim of this study was to evaluate the effects of non-surgical treatment of periodontal disease during the second trimester of gestation on adverse pregnancy outcomes. MATERIAL AND METHODS: Pregnant patients during the 1st and 2nd trimesters at antenatal care in a Public Health Center were divided into 2 groups: NIG - "no intervention" (n=17) or IG- "intervention" (n=16). IG patients were submitted to a non-surgical periodontal treatment performed by a single periodontist consisting of scaling and root planning (SRP), professional prophylaxis (PROPH) and oral hygiene instruction (OHI). NIG received PROPH and OHI during pregnancy and were referred for treatment after delivery. Periodontal evaluation was performed by a single trained examiner, blinded to periodontal treatment, according to probing depth (PD), clinical attachment level (CAL), plaque index (PI) and sulcular bleeding index (SBI) at baseline and 35 gestational weeks-28 days post-partum. Primary adverse pregnancy outcomes were preterm birth (<37 weeks), low birth weight (<2.5 kg), late abortion (14-24 weeks) or abortion (<14 weeks). The results obtained were statistically evaluated according to OR, unpaired t test and paired t test at 5% signifcance level. RESULTS: No signifcant differences were observed between groups at baseline examination. Periodontal treatment resulted in stabilization of CAL and PI (p>0.05) at IG and worsening of all periodontal parameters at NIG (p<0.0001), except for PI. Signifcant differences in periodontal conditions of IG and NIG were observed at 2nd examination (p<0.001). The rate of adverse pregnancy outcomes was 47.05% in NIG and 6.25% in IG. Periodontal treatment during pregnancy was associated to a decreased risk of developing adverse pregnancy outcomes [OR=13.50; CI: 1.47-123.45; p=0.02]. CONCLUSIONS: Periodontal treatment during the second trimester of gestation contributes to decrease adverse pregnancy outcomes.

Short-Term effect of COX-2 selective inhibitor as an adjunct for the treatment of periodontal disease: a clinical double-blind study in humans

Adjunctive therapeutic strategies that modulate the inflammatory mediators can play a significant role in periodontal therapy. In this double-blind, placebo-controlled study, 60 subjects diagnosed as periodontitis patients were evaluated for 28 days after periodontal treatment combined with selective cyclooxygenase-2 (COX-2) inhibitor. The experimental group received scaling and root planning (SRP) combined with the Loxoprofen antiinflammatory drug (SRP+Loxoprofen). The control group received SRP combined with placebo (SRP+placebo). Plaque index (PI), probing pocket depth (PD) and bleeding on probing (BOP) were monitored with an electronic probe at baseline and after 14 and 28 days. Both groups displayed clinical improvement in PD, PI and BOP. They also showed statistically similar values (p>0.05) of PD reduction on day 14 (0.4 mm) and on day 28 (0.6 mm). At the baseline, few deeper sites (>7 mm) from SRP+Loxoprofen group were responsible and most PD reduction was observed after 14 days (p<0.05). The percentage of remaining deep pockets (>7 mm) after 14 days in the SRP+Loxoprofen group was significantly lower (p<0.05) than in the SRP+placebo group. Loxoprofen presents potential effect as an adjunct of periodontal disease treatment, but long-term clinical trials are necessary to confirm its efficacy.

Relationship between periodontitis and rheumatoid arthritis and the effect of non-surgical periodontal treatment

This study analyzed the association of periodontal disease (PD) and rheumatoid arthritis (RA). Seventy-five 35-60-year-old patients were assigned to 5 groups according to the presence (+) or not (-) of PD and RA and the treatment received (TR+) or not (TR-) for PD. Group 3 uses total prosthesis (TP). Clinical and laboratory evaluations were performed at baseline, 3 and 6 months of follow-up by probing pocket depth, bleeding on probing and plaque index for PD, HAQ, DAS28, SF-36 and laboratory: AAG, ESR, CRP for RA. Statistically significant differences for PD after 3 (p=0.0055) and after 6 months (p=0.0066) were obtained in Group 1 (RA+PD+TR+) and 2(RA+PD+TR-); significant reduction in the % of BOP after 6 months (p=0.0128) and significant reduction in the % of Pl after 3 (p=0.0128) and 6 months (p=0.0002) in Group 1. Statistically significant differences between Groups 1 and 3 (RA+TP) for DAS28 at baseline and after 3 months were observed, but not after 6 months. No other parameters for RA were significantly affected. The relationship between RA and PD disease activities is not clear, but the importance of periodontal treatment in the control of inflammation to avoid tooth extraction is evident.

Correlation between metal-ceramic bond strength and coefficient of linear thermal expansion difference

The purpose of this study was to evaluate the metal-ceramic bond strength (MCBS) of 6 metal-ceramic pairs (2 Ni-Cr alloys and 1 Pd-Ag alloy with 2 dental ceramics) and correlate the MCBS values with the differences between the coefficients of linear thermal expansion (CTEs) of the metals and ceramics. Verabond (VB) Ni-Cr-Be alloy, Verabond II (VB2), Ni-Cr alloy, Pors-on 4 (P), Pd-Ag alloy, and IPS (I) and Duceram (D) ceramics were used for the MCBS test and dilatometric test. Forty-eight ceramic rings were built around metallic rods (3.0 mm in diameter and 70.0 mm in length) made from the evaluated alloys. The rods were subsequently embedded in gypsum cast in order to perform a tensile load test, which enabled calculating the CMBS. Five specimens (2.0 mm in diameter and 12.0 mm in length) of each material were made for the dilatometric test. The chromel-alumel thermocouple required for the test was welded into the metal test specimens and inserted into the ceramics. ANOVA and Tukey's test revealed significant differences (p=0.01) for the MCBS test results (MPa), with PI showing higher MCBS (67.72) than the other pairs, which did not present any significant differences. The CTE (10-6 oC-1) differences were: VBI (0.54), VBD (1.33), VB2I (-0.14), VB2D (0.63), PI (1.84) and PD (2.62). Pearson's correlation test (r=0.17) was performed to evaluate of correlation between MCBS and CTE differences. Within the limitations of this study and based on the obtained results, there was no correlation between MCBS and CTE differences for the evaluated metal-ceramic pairs.

Analysis of the periodontal status of patients with mandibular-bonded retainers

PURPOSE: This clinical study evaluated the periodontal status of patients with bonded retainers as compared to a non-treated control group. METHODS: Forty dental students were included in the sample and divided into the following two groups: 1) a test group of 20 subjects that, after orthodontic treatment, have been bonded retainer users for at least 2 years and 2) a control group of 20 patients that never experienced orthodontic treatment nor used any bonded retainer. The region associated with the retainer in the test group and the lower canine-to-canine region in the control group were examined according to the following clinical parameters: plaque index (PI), bleeding on probing (BOP), gingival recession (GR), clinical attachment level (CAL) and probing depth (PD). RESULTS: No differences were observed for GR or BOP (P>0.05). In contrast, the test group showed higher values of CAL and PD at proximal sites when compared to controls (P<0.05). In addition, IP was significantly increased at buccal and lingual sites (P<0.05). CONCLUSION: The placement of orthodontic bonded retainers negatively affected periodontal health, resulting in increased PI, PD and CAL.

Exposição repetida à cafeína aumenta a atividade locomotora induzida pelo femproporex em ratos adolescentes e adultos

A cafeína e o femproporex são substâncias psicoestimulantes. O femproporex é muito utilizado no Brasil como anorexígeno enquanto a cafeína é amplamente consumida como constituinte regular da dieta. A administração repetida de psicoestimulantes induz sensibilização comportamental que se caracteriza pelo aumento progressivo dos seus efeitos locomotores. Pode ocorrer ainda sensibilização cruzada entre essas substâncias. Investigamos se a administração repetida de cafeína aumenta a locomoção induzida pelo femproporex em ratos adolescentes e adultos. Quarenta e oito ratos adolescentes (dia pós-natal 27) e 32 adultos (dia pós-natal 60) foram distribuídos em dois grupos que receberam injeção intra-peritoneal de 10,0 mg/kg de cafeína (CAF) (adolescentes N = 24; adultos N = 16) ou salina (SAL) (adolescentes N = 24; adultos N = 16) diariamente durante 10 dias. Três dias após a última injeção, cada grupo CAF ou SAL foi subdividido em dois subgrupos que receberam injeção i.p. de salina (SAL) (1 mL/kg) ou femproporex (FEM) (2,0 mg/kg). Após as injeções, a atividade locomotora foi avaliada automaticamente em intervalos de 5 minutos durante 1 hora. Nossos resultados demonstraram que em ratos adolescentes e adultos o pré-tratamento com CAF aumenta a atividade locomotora induzida pela administração aguda de FEM, sugerindo que a cafeína causa sensibilização aos efeitos locomotores desse derivado anfetamínico.