Spectrophotometric determination of glucosamine and its analogous amino sugars with o-hydroxyhydroquinonephthalein and palladium(II).
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A simple and highly sensitive spectrophotometric method for the determination of glucosamine and its analogous amino sugars was established based on fading of the palladium(II)-o-hydroxyhydroquinonephthalein-hexadecyltrimethylammonium complex. In the determination of glucosamine, Beer's law is obeyed in the range of 0.02 - 0.18 microg ml(-1), with an effective molar absorptivity at 630 nm and the relative standard deviation being 8.4 x 10(5) dm3 mol(-1) cm(-1) and 1.08% (n = 10). This method is about 70-times more sensitive than the Elson-Morgan method. The method was successfully applied to the assay of glucosamine in actual samples. (+info)
Evaluation of the adaptation interface of one-piece implant-supported superstructures obtained in Ni-Cr-Ti and Pd-Ag alloys.
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Several formulations of alternative alloys have been proposed for the substitution of gold-based alloys used in Dentistry. Recently, a Ni-Cr-Ti-based alloy has been introduced. The purpose of this work was to verify the marginal adaptation obtained with one-piece superstructures for implant-supported prostheses obtained in Ni-Cr-Ti alloy, compared to a semi-noble alloy Pd-Ag. Eight superstructures for each alloy were produced over 4 implants in the anterior region of the mandible. The superstructures were placed in a torquemeter and the fixation screw of implant #1 was tightened with a 20 Ncm load with the others loosened (Sheffield test). The unfitness (in mm) was measured using a three-dimensional optical measurer in each implant, in the buccal and lingual aspects. The obtained data were submitted to statistical analysis by the analysis of variance and Tukey's test at 5% level. Significant differences were found for the factors material (p< or =0.05), with Ni-Cr-Ti pieces better than Pd-Ag ones, and implants (p< or =0.01). There were no significant differences for the factor position and interactions among factors (p>0.05). Based on the analysis of the data, it is possible to conclude that the Ni-Cr-Ti alloy makes possible the obtainment of one-piece implant-supported superstructures with a smaller misfit compared to the one obtained in Pd-Ag alloy, traditionally indicated for this situation. Additional tests may verify the superiority of the Ni-Cr-Ti alloy. (+info)
RNA-mediated metal-metal bond formation in the synthesis of hexagonal palladium nanoparticles.
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RNA sequences have been discovered that mediate the growth of hexagonal palladium nanoparticles. In vitro selection techniques were used to evolve an initial library of approximately 10(14) unique RNA sequences through eight cycles of selection to yield several active sequence families. Of the five families, all representative members could form crystalline hexagonal palladium platelets. The palladium particle growth occurred in aqueous solution at ambient temperature, without any endogenous reducing agent, and at low concentrations of metal precursor (100 micromolar). Relative to metal precursor, the RNA concentration was significantly lower (1 micromolar), yet micrometer-size crystalline hexagonal palladium particles were formed rapidly (7.5 to 1 minutes). (+info)
Bond durability of resin cements to Au-Pd-Ag alloy under cyclic impact load.
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The bond durability of resin cements to a 12% Au-Pd-Ag alloy was studied through cyclic impact tests with different loads. A piece of casting alloy was bonded to a cast block with two types of resin cements, Super Bond C&B and Bistite II. A shear load was applied onto a small piece of alloy until debonding of the specimen, using different weights of plungers, 130 g, 230 g, 330 g and 430 g. The specimen bonded with Super Bond exhibited a higher resistance than that with Bistite II. The fracture modes of the debonded cements were completely different from each other. That is, Bistite II showed a bulk fracture of cement by the crack penetrating through the cement layer. On the other hand, Super Bond showed damages limited to the surface and no bulk fracture. The mode of fracture was dependent not on the loading weight but the types of resin cements used. (+info)
Elucidating the significance of beta-hydride elimination and the dynamic role of acid/base chemistry in a palladium-catalyzed aerobic oxidation of alcohols.
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The mechanistic details of aerobic alcohol oxidation with catalytic Pd(IiPr)(OAc)(2)(H(2)O) (IiPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) are disclosed. Under optimal conditions, beta-hydride elimination is rate-limiting supported by kinetic studies including a high primary kinetic isotope effect (KIE) value of 5.5 +/- 0.1 and a Hammett rho value of -0.48 +/- 0.04. On the basis of these studies, a late transition state is proposed for beta-hydride elimination, which is further corroborated by theoretical calculations using density functional theory. Additive acetic acid modulates the rates of both the alcohol oxidation sequence and regeneration of the Pd catalyst. With no additive [HOAc], turnover-limiting reprotonation of intermediate palladium peroxo is kinetically competitive with beta-hydride elimination, allowing for reversible oxygenation and decomposition of Pd(0). With additive [HOAc] (>2 mol %), reprotonation of the palladium peroxo is fast and beta-hydride elimination is the single rate-controlling step. This proposal is supported by an apparent decomposition pathway modulated by [HOAc], a change in alcohol concentration dependence, a lack of [O(2)] dependence at high [HOAc], and significant changes in the KIE values at different HOAc concentrations. (+info)
Selective reduction of N-oxides to amines: application to drug metabolism.
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Phase I oxidative metabolism of nitrogen-containing drug molecules to their corresponding N-oxides is a common occurrence. There are instances where liquid chromatography/tandem mass spectometry techniques are inadequate to distinguish this pathway from other oxidation processes, including C-hydroxylations and other heteroatom oxidations, such as sulfur to sulfoxide. Therefore, the purpose of the present study was to develop and optimize an efficient and practical chemical method to selectively convert N-oxides to their corresponding amines suitable for drug metabolism applications. Our results indicated that efficient conversion of N-oxides to amines could be achieved with TiCl(3) and poly(methylhydrosiloxane). Among them, we found TiCl(3) to be a facile and easy-to-use reagent, specifically applicable to drug metabolism. There are a few reports describing the use of TiCl(3) to reduce N-O bonds in drug metabolism studies, but this methodology has not been widely used. Our results indicated that TiCl(3) is nearly as efficient when the reductions were carried out in the presence of biological matrices, including plasma and urine. Finally, we have shown a number of examples where TiCl(3) can be successfully used to selectively reduce N-oxides in the presence of sulfoxides and other labile groups. (+info)
Dental devices; dental noble metal alloys and dental base metal alloys; designation of special controls. Final rule.
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The Food and Drug Administration is amending the identification and classification regulations of gold-based alloys and precious metal alloys for clinical use and base alloys devices in order to designate a special control for these devices. FDA is also exempting these devices from premarket notification requirements. The agency is taking this action on its own initiative. This action is being taken under the Federal Food, Drug, and Cosmetic Act (the act), as amended by the Safe Medical Devices Act of 1990 (SMDA), and the Food and Drug Administration Modernization Act of 1997 (FDAMA). Elsewhere in this issue of the Federal Register, FDA is announcing the availability of the draft guidance documents that would serve as special controls for these devices. (+info)
A new synthetic method for an indolizidine skeleton by C-N bond formation via a pi-allylpalladium complex.
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Pd(0)-catalyzed intramolecular cyclic reaction via a pi-allylpalladium complex provided an indolizidine skeleton in satisfactory high and reproducible yields by using allylic compound having an acetoxyl group as a leaving group. These results must be available for syntheses of various functional indolizidine alkaloids. (+info)