Correlation between the mobility of spin-labeled peptide chains and resin solvation: An approach to optimize the synthesis of aggregating sequences

Resin solvation properties affect the efficiency of the coupling reactions in solid-phase peptide synthesis. Here we report a novel approach to evaluate resin solvation properties, making use of spin label electron paramagnetic resonance (EPR) spectroscopy. The aggregating VVLGAAIV and ING sequences were assembled in benzhydrylamine-resin with different amino group contents (up to 2.6 mmol/g) to examine the extent of chain association within the beads. These model peptidyl-resins were first labeled at their N-terminus with the amino acid spin label 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (Toac). Their solvation properties in different solvents were estimated, either by bead swelling measurement or by assessing the dynamics of their polymeric matrixes through the analysis of Toac EPR spectra, and were correlated with the yield of the acylation reaction. In most cases the coupling rate was found to depend on bead swelling. Comparatively, the EPR approach was more effective. Line shape analysis allowed the detection of more than one peptide chain population, which influenced the reaction. The results demonstrated the unique potential of EPR spectroscopy not only for improving the yield of peptide synthesis, even in challenging conditions, but also for other relevant polymer-supported methodologies in chemistry and biology.

Estudo Comparativo de Juntas Soldadas a TIG e Laser Empregando-se Ti com Pureza Comercial Utilizado em Prótese sobre Implantes

Welding in the dentistry has been used for great part of the specialized dentist-surgeons in the implants area to solve prosthesis supported by implant adaptation problems. The development of new equipments Laser and TIG allowed a larger use of these processes in the prosthesis production. In this work, it was studied welded joints made by Laser and TIG, using commercial purity titanium, cpTi, applied in prosthesis supported by implants. The weld characterizations were carried out by light microscopy, EDS_elementary mapping, microhardness and tensile test. Through metallographic characterization, the weld bead presented a martensitic microstructure in the Laser welding process, originated from shear provoked by deformations in the lattice. This caused structural changes of the transformed area, which determines a fine plate-like morphology. In the weld bead from TIG, besides presenting higher hardness, was observed formation of Widmansttaten structure, which is characteristic of a geometric model, resulted of new phase formation along of the crystallographic plans. The martensitic structure is more refined than Widmansttaten structure, due to the high-speed cooling (10(3)degrees C/s) imposed by the Laser process.

Evaluation of autogenous bone grafts, particulate or collected during osteotomy with implant burs: Histologic and histomorphometric analysis in rabbits

Purpose: the aim of this study was to evaluate bone regeneration in bone cavities filled with particulate autogenous bone either harvest in blocks and subjected to milling procedures or collected during osteotomy with implant burs. Materials and Methods: In 12 rabbits, 3 noncritical unicortical cavities 7 mm in diameter were prepared with a trephine drill on the right tibia. The cavities were filled respectively with particulate autogenous bone achieved with a manual bone crusher ( particulate group), with particulate autogenous bone obtained using bone collector during osteotomy ( collected group), and with blood clot ( control group). Animals were sacrificed at 7, 15, and 30 days after surgery ( 4 animals for each time period). The sections were examined by histologic and histomorphometric analysis. Results: At 7 days, the samples were filled by coagulum, and bone particles were observed only in the collected (24%) and particulate groups (44.75%). At 15 days, there was connective differentiation in all groups, with presence of grafted bone particles and onset of newly formed bone in the collected (38.88%) and particulate groups (46.0%). At 30 days, there was bone fill ( immature trabecular bone) of the cavities in the control (50%), collected (64.63%) and particulate groups (66%). Conclusion: No significant difference was demonstrated between noncritical unicortical bone defects in rabbit tibiae filled with particulate bone harvested as a block and subjected to milling and those filled with bone collected during osteotomy with implant drills when the defects were observed up to 30 days following their creation.

The nature of the photo luminescence in amorphized PZT

The polymeric precursor method was used to synthesize lead zirconate titanate powder (PZT). The crystalline powder was then amorphized by a high-energy ball milling process during 120h. A strong photoluminescence emission was observed at room temperature for the amorphized PZT powder. The powders were characterized by XRD and the percentage of amorphous phase was calculated through Rietveld refinement. The microstructure for both phases was investigated by TEM. The optical gap was calculated through the Wood and Tauc method using the UV-Vis. data. Quantum mechanical calculations were carried out to give an interpretation of the photoluminescence in terms of electronic structure. (C) 2004 Elsevier B.V. All rights reserved.

PZT ceramics obtained from mechanochemically synthesized powders

PZT ceramics were obtained from the mechanochemically synthesized powders. Milling and sintering conditions were optimized based on results of density measurements, as well as on microstructural and electrical characterization. As a result, highly dense and homogeneous ceramics were obtained. Excellent microstructural properties resulted in good electrical properties. Samples showed values of dielectric constants reaching 12800 at the Curie temperature, as well as low dielectric loss under the optimal processing conditions. High values of remanent polarization, reaching 60 muC cm(-2), indicate high internal polarizability. (C) 2003 Kluwer Academic Publishers.

Dielectric and piezoelectric properties of the mechanochemically prepared PZT ceramics

Mechanochemical synthesis was applied to obtain nanocrystalline powders of composition Pb(Zr0.52Ti0.48)O-3 (PZT). Milling was performed in a planetary ball mill using vials and balls made of zirconia or steel-in order to investigate influence of milling media on the electrical properties of resulting ceramics. PZT ceramics showed high values for dielectric constant (epsilon(r)), reaching 970 at room temperature, as well as low dielectric loss (tandelta) under the optimal processing conditions. High values of remanent polarization (P-r) indicate high internal polarizability. The best samples showed piezoelectric strain constant d(33) = 347 pC/N and planar coupling factor k(P) = 0.44. Milling in ZrO2 medium prevents powder contamination and provides reproducibility of milling process. Also, PZT obtained from the powders milled in ZrO2 exhibited lower values of dielectric loss, in comparison with the PTZ obtained from the powders milled in Fe. This suggests that contamination of the powder with Fe could result in an increase of conductivity in final product. (C) 2004 Kluwer Academic Publishers.

Properties and in vivo investigation of nanocrystalline hydroxyapatite obtained by mechanical alloying

Mechanical alloying has been used successfully to produce nanocrystalline powders of hydroxyapatite (HA) using three different procedures. The milled HA was studied by X-ray diffraction, Infrared, Raman scattering spectroscopy and Scanning Electron Microscopy (SEM). We obtained HA with different degrees of crystallinity and time of milling. The grain size analysis through SEM and XRD shows particles with dimensions of 36.9, 14.3 and 35.5 nm (for (R1), (R2) and (R3), respectively) forming bigger units with dimensions given by 117.2, 110.8 and 154.4 nm (for (R1), (R2) and (R3), respectively). The Energy-Dispersive Spectroscopy (EDS) analysis showed that an atomic ratio of Ca/P= 1.67, 1.83 and 1.50 for reactions (R1), (R2) and (R3), respectively. These results suggest that the R1 nanocrystalline ceramic is closer to the expected value for the ratio Ca/P for hydroxyapatite, which is 513 congruent to 1.67. The bioactivity analysis shows that all the samples implanted into the rabbits can be considered biocompatible, since they had been considered not toxic, bad not caused inflammation and reject on the part of the organisms of the animals, during the period of implantation. The samples implanted in rabbits had presented new osseous tissue formation with the presence of osteoblasts cells. (C) 2004 Elsevier B.V. All rights reserved.

Determination of site-site distance and site concentration within polymer beads: A combined swelling-electron paramagnetic resonance study

[GRAPHICS]This work proposes a combined swelling-electron paramagnetic resonance (EPR) approach aiming at determining some unusual polymer solvation parameters relevant for chemical processes occurring inside beads. Batches of benzhydrylamine-resin (BHAR), a copolymer of styrene-1% divinylbenzene containing phenylmethylamine groups were, labeled with the paramagnetic amino acid 2,2,6,6-tetramethylpiperidine-1-oxyl-4-amine-4-carboxylic acid (TOAC), and their swelling properties and EPR spectra were examined in DCM and DMF. By taking into account the BHARs labeling degrees, the corresponding swelling values, and some polymer structural characteristics, it was possible to calculate polymer swelling parameters, among them, the volume and the number of sites per bead, site-site distances and site concentration. The latter values ranged from 17 to 170 angstrom and from 0.4 to 550 mM, respectively. EPR spectroscopy was applied to validate the multistep calculation strategy of these swelling parameters. Spin-spin interaction was detected in the labeled resins at site-site distances less than approximately 60 A or probe concentrations higher than approximately 1 x 10(-2) M, in close agreement with the values obtained for the spin probe free in solution. Complementarily, the yield of coupling reactions in different resins indicated that the greater the inter-site distance or the lower the site concentration, the faster the reaction. The results suggested that the model and the experimental measurements developed for the determination of solvation parameters represent a relevant step forward for the deeper understanding and improvement of polymer-related processes.

Mechanochemical synthesis of barium titanate

A powder mixture of BaO and TiO2, was mechanochemically treated in a planetary ball mill in an air atmosphere for up to 4 h, using zirconium oxide vial and zirconium oxide balls as the milling medium. Mechanochemical reaction leads to the gradual formation of BaTiO3 phase. Phase evolution during synthesis and changes in powder size and morphology were monitored by XRD, DSC, IR and TEM analysis and it was shown that the formation of BaTiO3 phase was initiated after 60 min. Extended time of milling directed to formation of higher amount of BaTiO3 perovskite phase. Barium titanate with good crystallinity was formed after 240 min sintering without pre-calcination step was performed at 1330 degrees C for 2 It within heating rate 10 degrees C/min. (c) 2005 Elsevier Ltd. All rights reserved.

Mechanochemical synthesis of PZT powders

PZT ceramic powders were successfully prepared from the mixture of PbO, ZrO2 and TiO2 by mechanochemical synthesis in a planetary ball mill, under different milling conditions. Phase evolution during synthesis was monitored by X-ray diffraction analysis. Intensive milling resulted in formation of the nanocrystalline, perovskite PZT powders after 1 h of milling. This is a significant improvement in comparison to milling conditions reported by other authors. Depending on milling parameters the presence of some other phases, such as unreacted ZrO2, was also detected in some samples. The changes in powder size and morphology due to intensive milling, were determined by SEM and TEM, while BET analysis was used to determine specific surface area of the powders. Conclusions about processes taking place during mechanochemical synthesis of PZT powders were made based on the results of characterization. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Ferroelectric properties of mechanically synthesized nanosized barium titanate

Barium titanate ceramics were prepared through mechanochemical synthesis starting from fresh prepared barium oxide and titanium oxide in rutile form. Mixture of oxides was milled in zirconia oxide jar in the planetary ball-mill during 30, 60, 120 and 240 min. Extended time of milling directed to formation of higher amount of barium titanate perovskite phase. Barium titanate with good crystallinity was formed after 240 min. Sintering without pre-calcinations step was performed at 1330 degrees C for 2 hours with heating rate of 10 degrees C/min. The XRD, DSC, IR and TEM analyses were performed. Electric and ferroelectric properties were studied. Very well defined hysteresis loop was obtained.

Experimental and theoretical investigation of the room-temperature photoluminescence of amorphized Pb(ZrTi)O-3

Ultrafine PbZr0.20Ti0.80O3 was omorphized through high-energy mechanical milling. The structural evolution through the omorphization process was accompanied by various characterization techniques, such as X-ray diffraction, Fourier-transformed IR spectroscopy (FTIR), high-resolution transmission electron microscopy (HR-TEM), and Raman spectroscopy. A strong photoluminescence was measured at room temperature for amorphized PbZr0.20Ti0.80O3, and interpreted by means of high-level quantum mechanical calculations in the density functional theory frame-work. Three periodic models were used to represent the crystalline and amorphized PbZr0.20Ti0.80O3, and they allowed the calculation of electronic properties that are consistent with the experimental data and that explain the appearance of photoluminescence.

Investigation on possibility of mechanochemical synthesis of CaTiO3 from different precursors

Recently, mechanochemical synthesis was widely used in preparation of perovskite type of materials, such as BaTiO3, PbTiO3, PZT, etc. In this work, the possibility of mechanochemical synthesis of CaTiO3 from different precursors, such as CaCO3 or CaO and TiO2 was investigated. Intensive milling of mixture of CaO and TiO2, under optimal milling conditions, resulted in synthesis of single phase CaTiO3. It was also found that intensive milling of powder mixture containing CaCO3 and TiO2 only activate the powders for the sintering process; hence the CaTiO3 could be obtained at lower temperatures of sintering. To complete reaction of CaTiO3 formation during milling it is necessary to reduce CO2 partial pressure, i.e. it is necessary to change the atmosphere inside the vials during milling. In this work, an explanation for difference in milling behavior of different precursors was proposed and discussed. (c) 2006 Elsevier Ltd. All rights reserved.

Influence of processing conditions on the thermal decomposition of SrTiO3 precursors

The present work investigates the influence of milling and calcination atmosphere on the thermal decomposition of SrTiO3 powder precursors. Both pure and neodymium-modified SrTiO3 samples were studied. Milling did not significantly influence numerical mass loss value, but reduced the number of decomposition steps, modifying the profiles of the TG and DTA curves. on the other hand, milling increases the amount of energy liberated by the system upon combustion of organic matter. It was also observed that the milling process, associated to the calcination in an oxygen atmosphere, considerably decreases the amount of organic matter and increases the final mass loss temperature.

Barium titanate screen-printed thick films

Barium titanate (BT) thick films were prepared from mechanically activated powders based on BaCO(3) and TiO(2). After homogenization and milling in a high-energy vibro mill, the powders were calcined at 700 degreesC for 2 h by slow heating and cooling rates. A thick film paste was prepared by mixing BT fine powders with small amount of low temperature sintering aid and organic binder. The thick films were screen-printed on alumina substrates electroded with Ag-Pd. The BT films were sintered at 850 degreesC for 1 h. The thickness was 25-75 mum depending of number of layers. The microstructure of thick films and the compatibility between BT layers and substrate were investigated by SEM Results of dielectric property measurements are also reported. (C) 2002 Elsevier B.V. Ltd and Techna S.r.l. All rights reserved.