Crystallographic and spectroscopic studies on palladium(II) complexes containing pyrazole and thiocyanate ligands

Mononuclear palladium(II) complexes containing both pyrazole-type ligands and thiocyanate, of general formula [Pd(SCN) 2(L) 2] {L = pyrazole (HPz) and l-phenyl-3-methylpyrazole (phmPz)} have been prepared and characterized by elemental analysis, i.r. and n.m.r. spectroscopy and by single crystal X-ray diffraction methods. The Pd atom in these structures lies on the crystallographic inversion center; in a square-planar coordination geometry made by two sulfur and two nitrogen atoms of the ligands, both in trans positions.

Cariostatic effect of fluoride-containing restorative systems associated with dentifrices on root dentin

Objective. The aim of this in vitro study was to evaluate the interaction between two sources of fluoride (restorative systems and dentifrices) in inhibiting artificial root caries development. Methods. One hundred and eighty tooth segments were embedded in polyester resin, and sanded flat. Cylindrical cavities 1.0 mm-deep and 1.5 mm-diameter were prepared in root dentin and randomly restored by fluoride-containing restorative systems: Ketac-fil/Espe (Ke), Fuji II LC/GC Corp (Fj), F2000/3M (F2), Surefil/Dentsply (Su) or a control: Filtek Z250/3M (Z2). Ten experimental groups were made to test the association among the five restorative systems and two dentifrices: with F - (Sensodyne Baking Soda) or without F- (Sensodyne Original) (n = 18). After surface polishing, a 1 mm-wide margin around the restorations was demarcated and initial dentin surface Knoop microhardness values (KHNi) were obtained. The specimens were submitted to a pH-cycling model, and to applications of slurries of dentifrice. Afterwards the final dentin surface Knoop microhardness values (KHNf) were measured. Results. The differences between KHNi and KHNf, and the covariate KHNi were considered by the ANCOVA and Tukey's test (α = 0.05). The interaction between restorative system and dentifrice was statistically significant (p = 0.0026). All restorative systems provided some protection against artificial caries challenge when associated with the fluoride-containing dentifrice treatment. The means (standard deviation) of reductions in Knoop hardness values for systems associated with the fluoride-containing dentifrice were: Ke: 40.0(1.02)a, Fj: 41.9(1.02)b, F2: 43.3(1.04)c, Su: 43.5(1.00)c, Z2: 44.0(1.02)c; and with the non-fluoride-containing dentifrice were: Ke: 42.9(1.02)a, Fj: 44.7(1.01)b, F2: 45.2(1.09)bc, Su: 46.0(0.99)c, Z2: 46.6(0.99)c (statistical differences were expressed by different letters). Conclusion. The cariostatic effect shown by the fluoride-containing dentifrice could enhance that shown by Ketac-fil and Fuji II LC, and could mask that shown by F2000. © 2002 Elsevier Science Ltd. All rights reserved.

Infrared-to-visible frequency upconversion in transparent glass ceramics containing trivalent-rare-earth-doped nanocrystals

In this work we report on visible upconversion emission in Er 3+-, and Ho3+-doped PbGeO3-PbF 2-CdF2-based transparent glass ceramics under 980 nm infrared excitation. In erbium-doped vitroceramic samples, blue(410 ran), green(530, and 550 nm) and red(660 nm) emission signals were generated, which were identified as due to the 2H9/2, 2H 11/2, 4S3/2, and 4F9/2 transitions to the 4I15/2 ground-state, respectively. Intense red(650 nm) upconversion emission corresponding to the 5F5 - 5I8 transition and very small blue(490 nm) and green(540 nm) signals assigned to the 5F 2,3 - 5I8 and 4S2, 5F4 - 5I8 transitions, respectively, were observed in the holmium-doped samples. The 540 nm is the dominant upconversion signal in Ho3+-doped vitroceramics under 850 nm excitation. The dependence of the upconversion processes upon pump power and doping concentration are also investigated, and the main routes for the upconversion excitation processes are also identified. The comparison of the upconversion process in transparent glass ceramics and the precursor glass was also examined and the results revealed that the former present higher upconversion efficiencies.

Preconcentration and determination of mercury(II) at a chemically modified electrode containing 3-(2-thioimidazolyl)propyl silica gel

A mercury-sensitive chemically modified graphite paste electrode was constructed by incorporating modified silica gel into a conventional graphite paste electrode. The functional group attached to the (3-chloropropyl) silica gel surface was 2-mercaptoimidazole, giving a new product denoted by 3-(2-thioimidazolyl)propyl silica gel, which is able to complex mercury ions. Mercury was chemically adsorbed on the modified graphite paste electrode containing 3-(2-thioimidazolyl)propyl silica (TIPSG GPE) by immersion in a Hg(II) solution, and the resultant surface was characterized by cyclic and differential pulse anodic stripping voltammetry. One cathodic peak at 0.1 V and other anodic peak at 0.34 V were observed on scanning the potential from -0.1 to 0.8 V (0.01 M KNO3; ν = 2.0 mV s-1 νs. Ag/AgCl). The anodic peak at 0.34 V show an excellent sensitivity for Hg(II) ions in the presence of several foreign ions. A calibration graph covering the concentration range from 0.02 to 2 mg L-1 was obtained. The detection limit was estimated to be 5 μg L-1. The precision for six determinations of 0.05 and 0.26 mg L-1 Hg(II) was 3.0 and 2.5% (relative standard deviation), respectively. The method can be used to determine the concentration of mercury(II) in natural waters contaminated by this metal. 2005 © The Japan Society for Analytical Chemistry.

Study of the thermo-mechanical and electrical properties of conducting composites containing natural rubber and carbon black

This work shows the preparation and characterization of composites obtained by mixing natural rubber (NR) and carbon black (CB) in different percentages aiming suitable mechanical properties, processability and electrical conductivity for future applications as transducers in pressure sensors. The composites NR/CB are characterized through dc conductivity, thermal analysis using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMA), thermogravimetry (TGA) and stress-strain test. The electrical conductivity changed from 10-9 to 10 Sm-1 depending on the percentage of CB in the composite. Besides, it was found a linear (and reversible) dependence of the conductivity on the applied pressure in the range from 0 to 1.6 MPa for the sample 80/20 (NR/CB wt%).

Electrooptic proprieties of layer-by-layer films of a azobenzene containing copolymer

The methacrylic copolymer functionalized with the azo chromophore 4-[N-ethyl-N-(2-hydroxiethyl)]-amino-2′-chloro-4-nitroazobenzene (MMADR13), in its polyelectrolyte form, can be used to fabricate thin films by the layer-by-layer (LbL) technique just if one alternates this anionic polyelectrolyte with a cationic polyelectrolyte such as poly(allylamine hydrochloride) (PAH). Since PAH does not present any particular optical functionality, the main final film feature will came from the side chain DR13 azo-chromophore group due to its large nonlinear optical properties and photoisomerization capabilities. This work reports the electrooptic activity of MMADR13/DR13 LBL films, which arises from the high hiperpolarizability about the azo side chain group.

Ethylcelullose microspheres containing sodium diclofenac: Development and characterization

The objective of the present study was the development and characterization of ethylcellulose microspheres containing diclofenac and the determination of the in vitro drug release profile. Microspheres were prepared by emulsification/solvent evaporation method using ethyl acetate as solvent for the polymer and water as non solvent. The microspheres were characterized by morphologic and granulometric analyses. The amount of encapsulated drug as well as its release profile in vitro were also determined. The product obtained was microparticles with smooth surface and narrow size distribution, about 50% of the particles being smaller than 5 μm. The methodology used allowed drug encapsulation with a good yield and the system provided a controlled release of diclofenac.

Comparison between polyurethanes containing castor oil (Soft Segment) and cancellous bone autograft in the treatment of segmental bone defect induced in rabbits

The aim of this study is to compare polyurethanes containing castor oil (soft segment) in granular form compared to cancellous bone autograft applied to a segmental bone defect. Norfolk adult female rabbits - approximately 13 months of age with a mean body weight of 4.5 kg - are used. In both radial diaphyses, 1 cm osteoperiosteal segmental defects are created. The defect in the left radius is filled with the castor-oil-based polyurethane, and the right one, filled with cancellous bone autograft, collected from the left proximal humerus. The rabbits are euthanazed at 15, 30, 60, and 120 days postsurgery (5 animals/ period), for histological analyses. By radiographic analyses, at these time points, the bone regeneration is more evident and accelerated in the bone defects treated with the cancellous bone autograft. At 120 days postsurgery, the segmental bone defects treated with the cancellous bone autograft are totally reconstituted and remodeled, while the bone defects treated with polyurethane polymer have bone formation of 79%. Histological study shows that the polyurethane acts as a space filler, minimizing the local production of fibrous tissue. No granule degradation, resorption or any inflammatory reaction is detected. Thus, it is possible to conclude that the castor-oil-plant-based polyurethane - in the granule presentation - is biocompatible and osteointegrated, but does not show the same bone regeneration capacity as the cancellous bone autograft. © 2007 SAGE Publications.

In vitro antimicrobial efficiency of a mouthwash containing triclosan/gantrez and sodium bicarbonate

Several antiseptic substances have been used as adjuncts to routine mechanical procedures of oral hygiene, based on their antimicrobial effects. The objective of this study was to assess in vitro the antimicrobial efficiency of 2 mouthwash containing Triclosan/Gantrez and sodium bicarbonate in comparison to both positive and negative controls. Standard strain samples of Escherichia coli, Pseudomonas aeruginosa, Actinomyces viscosus and Bacillus subtilis were used. Samples of Streptococcus mutans and Gram-negative bacilli were collected from 20 volunteers (10 with a clinically healthy periodontium and 10 presenting biofilm-associated gingivitis). Evaluation of the antimicrobial activity was performed by determining the minimal inhibitory concentration (MIC). The results indicated that the test solution inhibited the growth of both Gram-negative and Gram-positive microorganisms from the volunteers' saliva as well as that of the standard strains at the MIC dilution of 1:20, whereas the MIC dilution of 0.12% chlorhexidine against the same bacteria was 1:80. Thus, even though the tested mouthrinse solution presented an in-vitro antimicrobial activity superior to that of a placebo, it was inferior to that of chlorhexidine.

In vitro evaluation of the abrasiveness of a commercial low-abrasive dentifrice and an experimental dentifrice containing vegetable oil

Toothpastes usually contain detergents, humectants, water colorant, fluoride and thickeners (e.g. silica). Tooth wear has a multi-factorial etilology and the use of abrasive dentifrices is related to abrasion of dental tissues during toothbrushing. This study evaluated in vitro the abrasiveness of a commercial silica gel low-abrasive dentrifice compared to an experimental dentifrice containing vegetable (almond) oil. Distilled water served as a control group. Acrylic specimens (8 per group) were submitted to simulated toothbrushing with slurries of the commercial dentifrice experimental dentifrice, almond oil and water in an automatic brushing machine programmed to 30,000 brush strokes for each specimen which is equivalent to 2 years of manual toothbrushing. Thereafter, surface roughness (Ra) of the specimens was analyzed with a Surfcorder SE 1700 profilometer. Data were analyzed statistically by ANOVA and Tukey's test at 5% significance level. There was no statistically significant differences (p>0.05) in the surface roughness after brushing with water almond oil experimental dentifrice. The commercial dentifrice produced rougher surfaces compared to the control and abrasive free products (p<0.05). Further studies are necessary in confirm the potential benefits of using vegetable oil in toothpaste as an alternative in abrasives in an attempt to minimize the tooth wear caused by toothbrushing.

Crystal and molecular structure of dinuclear palladium(II) complex containing nitrogen and phosphorus donor ligands, [Pd2(N3)4(PPh3)2(μ-ted)]

The dinuclear azido-palladium(II) complex [Pd2(N3)4(PPh3)2(μ-ted)], where PPh3 = triphenylphosphine and ted = triethylenediamine, was synthesized and characterized by single-crystal X-ray diffraction. The title compound was crystallized in a triclinic system, space group P1 with a = 11.5875(2)Å, b = 13.0817(3)Å, c = 15.2618(3)Å, α = 93.306(2)°, β =110.040(1)°, γ = 98.486(1)°, V = 2134.95(8)Å3, Z = 2. Each Pd(II) center displays a distorted squareplanar coordination environment formed by two N atoms from two trans terminally coordinated azido groups, one P atom from the phosphine and one N atom from the bridging ted ligand. 2008 © The Japan Society for Analytical Chemistry.

DNA vaccine containing the mycobacterial hsp65 gene prevented insulitis in MLD-STZ diabetes

Background: Our group previously demonstrated that a DNA plasmid encoding the mycobacterial 65-kDa heat shock protein (DNA-HSP65) displayed prophylactic and therapeutic effect in a mice model for tuberculosis. This protection was attributed to induction of a strong cellular immunity against HSP65. As specific immunity to HSP60 family has been detected in arthritis, multiple sclerosis and diabetes, the vaccination procedure with DNA-HSP65 could induce a cross-reactive immune response that could trigger or worsen these autoimmune diseases. Methods: In this investigation was evaluated the effect of a previous vaccination with DNA-HSP65 on diabetes development induced by Streptozotocin (STZ). C57BL/6 mice received three vaccine doses or the corresponding empty vector and were then injected with multiple low doses of STZ. Results: DNA-HSP65 vaccination protected mice from STZ induced insulitis and this was associated with higher production of IL-10 in spleen and also in the islets. This protective effect was also concomitant with the appearance of a regulatory cell population in the spleen and a decreased infiltration of the islets by T CD8+ lymphocytes. The vector (DNAv) also determined immunomodulation but its protective effect against insulitis was very discrete. Conclusion: The data presented in this study encourages a further investigation in the regulatory potential of the DNA-HSP65 construct. Our findings have important implications for the development of new immune therapy strategies to combat autoimmune diseases. © 2009 Santos et al; licensee BioMed Central Ltd.

Radiopacity evaluation of root canal sealers containing calcium hydroxide and MTA

The purpose of this study was to evaluate the radiopacity of root canal sealers containing calcium hydroxide and MTA (Acroseal, Sealer 26, Sealapex, Endo CPM Sealer, Epiphany and Intrafill). Five disc-shaped specimens (10 x 1 mm) were fabricated from each material, according to the ISO 6876/2001 standard. After setting of the materials, radiographs were taken using occlusal film and a graduated aluminum stepwedge varying from 2 to 16 mm in thickness. The dental X-ray unit (GE1000) was set at 50 kVp, 10 mA, 18 pulses/s and distance of 33.5 cm. The radiographs were digitized and the radiopacity compared to that of the aluminum stepwedge using VIXWIN-2000 software (Gendex). The data (mmAl) were analyzed statistically by ANOVA and Tukey's test at the 5% significance level. Epiphany and Intrafill presented the highest radiopacity values (8.3 mmAl and 7.5 mmAl respectively, p < 0.05) followed by Sealer 26 (6.3 mmAl), Sealapex (6.1 mmAl) and Endo CPM Sealer (6 mmAl). Acroseal was the least radiopaque material (4 mmAl, p < 0.05). In conclusion, the calcium hydroxide- and MTA-containing root canal sealers had different radiopacities. However, all materials presented radiopacity values above the minimum recommended by the ISO standard. © 2009 Sociedade Brasileira de Pesquisa Odontológica.

Clinical and microbiological evaluation of the use of toothpaste containing 1% chlorhexidine and the influence of motivation on oral hygiene in patients with motor deficiency

Patients with motor deficiency have variable difficulties with mechanical plaque control, and as a consequence, the incidence of dental caries and periodontal disease can be higher in these patients. The objective of this study was to evaluate the clinical and microbiological efficacy of a toothpaste containing 1% chlorhexidine, which was used by patients with motor deficiency for 14 days. The reduction in plaque and gingival index and the impact on salivary microorganisms was evaluated. We conclude that the motivation of caregivers to carry out oral hygiene for patients with mental and motor deficiency is of great importance and is effective in reducing the formation of plaque as long as it is continuously reinforced. The use of chlorhexidine- containing toothpaste significantly reduced the plaque index and microorganism count between days 0 and 14. A reduction was also observed in the group that used a dentifrice without the chlorhexidine, but this difference was not significant. © 2010 Special Care Dentistry Association and Wiley Periodicals, Inc.

Hardness evaluation of prosthetic silicones containing opacifiers following chemical disinfection and accelerated aging

We evaluated the effects of disinfection and aging on the hardness of silicones containing opacifiers and intended for use in facial prosthetics. A total of 90 samples were produced using a cylindrical metal mold 3 mm in height and 30 mm in diameter. The samples were fabricated from Silastic MDX 4-4210 silicone in three groups: GI contained no opacifier, GII contained barium sulfate (Ba), and GIII contained titanium dioxide (Ti). The samples were disinfected using effervescent tablets (Ef), neutral soap (Ns), or 4% chlorhexidine (Cl) 3 times a week for 60 days. After this period the samples underwent 1,008 hours of accelerated aging. The hardness was measured using a durometer immediately following the disinfection period and after 252, 504, and 1,008 hours of aging. The data were statistically analyzed using 3-way ANOVA and the Tukey test (p < .05). The GIII group exhibited the greatest variation in hardness regardless of elapsed time. All groups displayed greater hardness after 1,008 hours of accelerated aging independent of disinfectant type. All of the hardness values were within the clinically acceptable range.