Antileishmanial activity of ruthenium(II)tetraammine nitrosyl complexes

The complexes trans-[Ru(NO)(NH(3))(4)L](X)(3) (X = BF(4)(-), PF(6)(-) or Cl(-) and L = N-heterocyclic ligands, P (OEt)(3), SO(3)(-2)), and [Ru(NO)Hedta)] were shown to exhibit IC(50pro) in the range of 36 (L = imN) to 5000 mu M (L = imC). The inhibitory effects of trans-[Ru(NO)(NH(3))(4)imN](BF(4))(3) and of the Angeli`s salt on the growth of the intramacrophage amastigote form studied were found to be similar while the trans-[Ru(NH(3))(4)imN(H(2)O)](2+) complex was found not to exhibit any substantial antiamastigote effect. The trans-[Ru(NO)(NH(3))(4)imN](BF(4))(3) compound, administered (500 nmol kg(-1) day(-1)) in BALB/c mice infected with Leishmania major, was found to exhibit a 98% inhibition on the parasite growth. Furthermore, this complex proved to be at least 66 times more efficient than glucantime in in vivo experiments. (C) 2010 Elsevier Masson SAS. All rights reserved.

Effects of type II pyrethroid cyhalothrin on rat innate immunity: A flow cytometric study

Synthetic type II pyrethroids induce anxiety, immunosuppresion or, alternatively, immunostimulatory effects in laboratory animals. Macrophages and neutrophils are known to be key elements in cellular immune responses. The present study was designed to investigate the in vivo effects of cyhalothrin (1.0 and 3.0 mg/kg/once daily for 7 days) on macrophage and neutrophil activities, using a flow cytometry method. Results showed that cyhalothrin treatment decreased the percentage and intensity of phagocytosis performed by macrophages, but did not alter these parameters in neutrophils: and also decreased basal neutrophil oxidative burst and increased S. aureus-induced neutrophil oxidative burst, but did not alter these responses in macrophages. The present results are discussed in the light of a possible indirect action of cyhalothrin on macrophage and neutrophil activities via hypothalamic pituitary adrenal (HPA) axis activation. A possible direct effect of cyhalothrin on macrophage and neutrophil activities is also considered. (C) 2008 Elsevier B.V. All rights reserved.

Fracture resistance of Class II glass-ionomer cement restorations

Purpose: To investigate in vitro the effect of retentive grooves, GIC type and insertion method on the fracture resistance of Class II glass-ionomer cement (GIC) restorations. Methods: Premolars were divided into 12 groups (n=10) according to three variables: retentive grooves [presence (PR) or absence AR)], GICs type [Ketac-Molar (KM), Fuji VIII (F8) and RelyX Luting (RX)], and insertion method [syringe injector (SI) or spoon excavator (SE)]. The specimens were subjected to fracture resistance test. Data were submitted to three-way ANOVA and multiple comparisons were performed using a Tukey test (P < 0.05). Results: Mean fracture resistance values (Kgf) +/- standard deviations (SD) were: KM (PR+SI) 65.66 +/- 2.5; KM (PR+SE) = 62.58 +/- 2.1; KM (AR+SI) = 57.11 +/- 1.9; KM (AR+SE) = 51.94 +/- 2.3; F8 (PR+SI) = 63.05 +/- 2.1; F8 (PR+SE) = 60.12 +/- 2.3; F8 (AR+SI) = 55.11 +/- 1.9; F8(AR+SE)=49.20 +/- 1.6; RX (PR+SI)=50.99 +/- 2.4; RX (PR+SE)=48.81 +/- 2.5; RX (AR+SI)=45.53 +/- 2.6; RX (AR+SE)=41.88 +/- 3.0. Statistically significant differences were observed among all the groups tested (P=0.001). There was significant difference when pooled means for GIC type were compared with retentive grooves (P=0.01) and when pooled means for retentive grooves were compared with insertion method (P=0.01).

Long-term stability of Class II malocclusion treated with 2-and 4-premolar extraction protocols

Introduction: The objective of this study was to cephalometrically compare the stability of complete Class II malocclusion treatment with 2 or 4 premolar extractions after a mean period of 9.35 years. Methods: A sample of 57 records from patients with complete Class II malocclusion was selected and divided into 2 groups. Group 1 consisted of 30 patients with an initial mean age of 12.87 years treated with extraction of 2 maxillary premolars. Group 2 consisted of 27 patients with an initial mean age of 13.72 years treated with extraction of 4 premolars. T tests were used to compare the groups` initial cephalometric characteristics and posttreatment changes. Pearson correlation coefficients were calculated to determine the correlation between treatment and posttreatment dental-relationship changes. Results: During the posttreatment period, both groups had similar behavior, except that group 1 had a statistically greater maxillary forward displacement and a greater increase in the apical-base relationship than group 2. On the other hand, group 2 had a statistically greater molar-relationship relapse toward Class II. There were significant positive correlations between the amounts of treatment and posttreatment dentoalveolar-relationship changes. Conclusions: Treatment of complete Class II malocclusions with 2 maxillary premolar extractions or 4 premolar extractions had similar long-term posttreatment stability. (Am J Orthod Dentofacial Orthop 2009;136:154.e1-154.e10)

Comparative efficiency of Class II malocclusion treatment with the pendulum appliance or two maxillary premolar extractions and edgewire appliances

The objective of this study was to compare, on study models and initial cephalograms, the efficiency of Class II malocclusion treatment with the pendulum appliance, and with two maxillary premolar extraction protocol. The sample consisted of 48 treated Class II malocclusion patients: group 1 comprised 22 patients (7 males, 15 females) treated with the pendulum appliance, with an initial mean age of 14.44 years and group 2, 26 patients (14 males, 12 females) treated with two maxillary premolar extractions at an initial mean age of 13.66 years. To compare the efficiency of each treatment protocol, the occlusal outcomes were evaluated on dental casts using the Peer Assessment Rating (PAR) Index and the treatment time (TT) of each group was calculated on clinical charts. The degree of treatment efficiency was calculated as the ratio between the percentage of occlusal improvement, evaluated through the PAR index, and TT. Statistical analysis was undertaken by means of t-tests. The findings demonstrated that the two maxillary premolar extraction protocol provided the occlusal outcomes in a shorter time (group 1: 45.7 months, group 2: 23.01 months) and, therefore, demonstrated greater treatment efficiency than the pendulum appliance.

Influence of cephalometric characteristics on the occlusal success rate of Class II malocclusions treated with 2-and 4-premolar extraction protocols

Introduction: The objectives of this investigation were to compare the initial cephalometric characteristics of complete Class II Division 1 malocclusions treated with 2 or 4 premolar extractions and to verify their influence on the occlusal success rate of these treatment protocols. Methods: A sample of 98 records from patients with complete Class II Division 1 malocclusion was divided into 2 groups with the following characteristics: group 1 consisted of 55 patients treated with 2 maxillary first premolar extractions at an initial mean age of 13.07 years; group 2 included 43 patients treated with 4 premolar extractions, with an initial mean age of 12.92 years. Initial and final occlusal statuses were evaluated on dental casts with Grainger`s treatment priority index (TPI), and the initial cephalometric characteristics were obtained from the pretreatment cephalograms. The initial cephalometric characteristics and the initial and final occlusal statuses of the groups were compared with the t test. A multiple regression analysis was used to evaluate the influence of all variables in the final TPI. Results: The 2-premolar extraction protocol provided a statistically smaller TPI and consequently a better occlusal success rate than the 4-premolar extraction protocol. The 4-premolar extraction group had statistically smaller apical base lengths, more vertical facial growth patterns, and greater hard- and soft-tissue convexities at pretreatment than the 2-premolar extraction group. However, the multiple regression analysis showed that only the extraction protocol was significantly associated with the final occlusal status. Conclusions: The initial cephalometric characteristics of the groups did not influence the occlusal success rate of these 2 treatment protocols.

Occlusal outcomes and efficiency of 1-and 2-phase protocols in the treatment of Class II Division 1 malocclusion

Introduction: The purpose of this study was to compare the occlusal outcomes and the efficiency of 1-phase and 2-phase treatment protocols in Class II Division 1 malocclusions. Treatment efficiency was defined as a change in the occlusal characteristics in a shorter treatment time. Methods: Class II Division 1 subjects ( n = 139) were divided into 2 groups according to the treatment protocol for Class II correction. Group 1 comprised 78 patients treated with a 1-phase treatment protocol at initial and final mean ages of 12.51 and 14.68 years. Group 2 comprised 61 patients treated with a 2-phase treatment protocol at initial and final mean ages of 11.21 and 14.70 years. Lateral cephalometric radiographs were taken at the pretreatment stage to evaluate morphological differences in the groups. The initial and final study models of the patients were evaluated by using the peer assessment rating index. Chi-square tests were used to test for differences between the 2 groups for categorical variables. Variables regarding occlusal results were compared by using independent t tests. A linear regression analysis was completed, with total treatment time as the dependent variable, to identify clinical factors that predict treatment length for patients with Class II malocclusions. Results: Similar occlusal outcomes were obtained between the 1-phase and the 2-phase treatment protocols, but the duration of treatment was significantly shorter in the 1-phase treatment protocol group. Conclusions: Treatment of Class II Division 1 malocclusions is more efficient with the 1-phase than the 2-phase treatment protocol.

Cephalometric evaluation of Class II malocclusion treatment with cervical headgear and mandibular fixed appliances

The present study aimed to evaluate the cephalometric changes in Class II patients treated exclusively with cervical headgear (CHG) in the maxillary arch and fixed appliances in the mandibular arch as compared with a control group. The sample comprised 82 lateral cephalograms obtained pre- (T1) and post- (T2) treatment/observation of 41 subjects, divided into two groups: group 1-25 Class II division 1 patients (20 females and five males), with a mean pre-treatment age of 10.4 years, treated for a mean period of 2.5 years and group 2-16 Class II untreated subjects (12 females and four males), with a mean initial age of 9.9 years, followed for a mean period of 2.2 years. Treatment changes between the groups were compared by means of t-tests. The results showed restriction of maxillary forward displacement and also a restriction in maxillary length growth, improvement in the maxillomandibular relationship, restriction of mandibular incisor vertical development, reduction in overjet and overbite, and improvement in molar relationship. It was concluded that this treatment protocol corrected the Class II malocclusion characteristics primarily through maxillary forward growth restriction.

Separation of mercury (II), lead (II), and silver (I) from aqueous solution using an aminopolycarboxylate silica

A quartz crystal microbalance modified by the attachment of silica particles derivatized with the aminopolycarboxylate ligand N-[(3-trimethoxysilyl)propyl]ethylenediamine-N,N',N'-triacetic acid has been employed to assess conditions under which mercury (II), lead (II), and silver (I) nitrates may be separated in aqueous solution. The separation protocol, which involved removal of Hg(II), as [HgI4](2-), and Pb(II) with H+ was successfully applied to a batchwise separation of the 3 metal ions.

Cardiostimulant effects of urotensin-II in human heart in vitro

The effects of the recently identified human peptide urotensin-II (hU-II) were investigated on human cardiac muscle contractility and coronary artery tone. In right atrial trabeculae from non-failing hearts, hU-II caused a concentration-dependent increase in contractile force (pEC(50)=9.5+/-0.1; E-max= 31.3+/-4.8% compared to 9.25 mM Ca2+; n = 9) with no change in contraction duration. In right ventricular trabeculae from explanted hearts, 20 nM hU-II caused a small increase in contractile force (7.8+/-1.4% compared to 9.25 mM Ca2+; n= 3/6 tissues from 2 out of 4 patients). The peptide caused arrhythmic contractions in 3/26 right atrial trabeculae from 3/9 patients in an experimental model of arrhythmia and therefore has less potential to cause arrhythmias than ET-1. hU-II (20 nM) increased tone (17.9% of the response to 90 mM KCI) in 7/7 tissues from 1 patient, with no response detected in 8/8 tissues from 2 patients. hU-II is a potent cardiac stimulant with low efficacy.

The preparation of zinc(II) and cadmium(II) complexes of the pentadentate N3S2 ligand formed from 2,6-diacetylpyridine and S-benzyldithiocarbazate (H2SNNNS) and the X-ray crystal structure of the novel dimeric [Zn2(SNNNS)2] complex

The pentadentate chelating agent, 2,6-diacetylpyridinebis(S-benzyldithiocarbazate) (H2SNNNS) reacts with zinc(II) and cadmium(II) ions forming stable complexes of empirical formula, [M(SNNNS)] (M=Zn2+, Cd2+; SNNNS2 =doubly deprotonated anionic form of the Schiff base). These complexes have been characterized by a variety of physico-chemical techniques. IR and H-1 NMR spectral evidence indicate that the Schiff base coordinates to the zinc(II) and cadmium(II) ions via the pyridine nitrogen atoms, the azomethine nitrogen atoms and the mercaptide sulfur atoms. The crystal and molecular structure of the zinc(II) complex has been determined by X-ray diffraction. The complex is a dimer in which the pyridine nitrogen atom,the azomethine nitrogen atom and the thiolate sulfur atom from one ligand coordinate to one of the zinc(II) ions whereas the azomethine and thiolate sulfur atoms from another ligand complete pentacoordination around the zinc(II) ion, the ligands being coordinated in their deprotonated forms. The coordination geometry about each zinc(II) can be considered as intermediate between a square-pyramid and trigonal-bipyramid. The cadmium(II) complex is also assigned with a dimeric structure. (C) 2003 Elsevier Ltd. All rights reserved.

Studies of the Antiproliferative Activity of Ruthenium (II) Cyclopentadienyl-Derived Complexes with Nitrogen Coordinated Ligands

Four cationic ruthenium(II) complexes with the formula [Ru(eta(5)-C5H5)(PPh3)(2)](+), with L = 5-phenyl-1H-tetrazole (TzH) 1, imidazole (ImH) 2, benzo[1,2-b; 4,3-b'] dithio-phen-2-carbonitrile (Bzt) 3, and [5-(2-thiophen-2-yl)-vinyl]-thiophene-2-carbonitrile] (Tvt) 4 were prepared and characterized in view to evaluate their potentialities as antitumor agents. Studies by Circular Dichroism indicated changes in the secondary structure of ct-DNA. Changes in the tertiary structure of pBR322 plasmid DNA were also observed in gel electrophoresis experiment and the images obtained by atomic force microscopy (AFM) suggest strong interaction with pBR322 plasmid DNA; the observed decreasing of the viscosity with time indicates that the complexes do not intercalate between DNA base pairs. Compounds 1, 2, and 3 showed much higher cytotoxicity than the cisplatin against human leukaemia cancer cells (HL-60 cells).

Synthesis and Coordination Chemistry of a New N-4-Polydentate Class of Pyridyl-Functionalized Scorpionate Ligands: Complexes of Fe-II, Zn-II, V-IV, Pd-II and Use for Heterobimetallic Systems

The new potentially N-4-multidentate pyridyl-functionalized scorpionates 4-((tris-2,2,2-(pyrazol-1-ypethoxy)methyl)pyridine (TpmPy, (1)) and 4-((tris-2,2,2-(3-phenylpyrazol-1-yl)ethoxy)methyl)pyridine (TpmPy(Ph), (2)) have been synthesized and their coordination behavior toward Fe-II, Ni-II, Zn-II, Cu-II, Pd-II, and V-III centers has been studied. Reaction of (1) with Fe(BF4)(2)center dot 6H(2)O yields [Fe(TpmPy)(2)](BF4)(2) (3), that, in the solid state, shows the sandwich structure with trihapto ligand coordination via the pyrazolyl arms, and is completely low spin (LS) until 400 K. Reactions of 2 equiv of (1) or (2) with Zn-II or Ni-II chlorides give the corresponding metal complexes with general formula [MCl2(TpmPy*)(2)] (M = Zn, Ni; TpmPy* = TpmPy, TpmPy(Ph)) (4-7) where the ligand is able to coordinate through either the pyrazolyl rings (in case of [Ni(TpmPy)(2)Cl-2 (5)) or the pyridyl-side (for [ZnCl2(TpmPy)(2)] (4), [ZnCl2(TpmPy(Ph))(2)] (6) and [NiCl2(TpmPy(Ph))(2)] (7)). The reaction of (1) with VCl3 gives [VOCl2(TpmPy)] (8) that shows the N-3-pyrazolyl coordination-mode. Moreover, (1) and react with cis-[PdCl2(CH3CN)(2)] to give the disubstituted complexes [PdCl2(TprnPy)(2)] (9) and [PdCl2(TpmPy(Ph))(2)] (10), respectively, bearing the scorpionate coordinated via the pyridyl group. Compounds (9) and (10) react with Fe(BF4)(2) to give the heterobimetallic Pd/Fe systems [PdCl2(mu-TpmPy)(2)-Fe](BF4)(2) (11) and [PdCl2(mu-TpmPy(Ph))(2)Fe-2(H2O)(6)]BF4)(4) (13), respectively. Compound (11) can also be formed from reaction of (3) with cis-[PdCl2(CH3CN)(2)], while reaction of (3) with Cu(NO3)(2).2.5H(2)O generates [Fe(mu-TpmPy)(2)-Cu(NO3)(2)](BF4)(2) (12), confirming the multidentate ability of the new chelating ligands. The X-ray diffraction analyses of compounds (1), (3), (4), (5), and (9) are also reported.

Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions.

Voltammetric oxidation of drugs of abuse II. Codeine and metabolites

The oxidation of codeine on glassy carbon electrodes has been studied in detail using differential pulse voltammetry. The results obtained using a glassy carbon electrode clearly show a much more complex oxidation mechanism than that previously reported when platinum and gold electrodes were used. To clarify the codeine oxidative profile, several metabolites and analogues of this alkaloid, codeine N-oxide, norcodeine, dihydrocodeine, acetylcodeine and 6- chlorodesoxycodeine, were synthesized and studied. It was deduced that the anodic waves observed in codeine oxidation are related to the presence of methoxy, hydroxy and tertiary amine groups. Due to the similarity of potentials at which these oxidative processes take place, at some pHs an overlap of peaks occurs and only one anodic wave is observed.