A kinetic model for the ultrasound catalyzed hydrolysis of solventless TEOS-water mixtures and the role of the initial additions of ethanol

The acid and ultrasound catalyzed hydrolysis of solventless TEOS-water mixtures are studied, as a function of the initial additions of ethanol to the mixtures, by means of flux calorimetry measurements. A device was specially designed for this purpose. Under acid conditions, our proposed method has been able to resolve hydrolysis from other condensation reactions, by detecting the exothermal hydrolysis reaction heat. The process has been explained by a dissolution and reaction mechanism. Ultrasound forces the dissolution process to start the reaction. The alcohol produced in the reaction helps the dissolution process to further enhance the hydrolysis. Initial amounts of pure ethanol added to the mixtures shorten the start time of the reaction, due to an additional effect of dissolution, and diminish the reaction rate, as a result of the solvent dilution effect. Our dissolution and reaction mechanism modeling describes the main points arising from the experimental data and yields k(H) = 0.24 M(-1) min(-1) for the second-order hydrolysis rate constant at 39 degrees C.

Study of the hydrolysis of TEOS-TMOS mixtures under ultrasound stimulation

Pure and mixed tetramethoxysilane (TMOS) and tetraethoxysilane (TEOS) were hydrolyzed at 35 degrees C, using oxalic acid as a catalyst and ultrasound stimulation. The hydrolysis reaction was carried out in a specially designed device, in which a heat flow steady state, between the ultrasound source and an external thermostatic bath, was maintained, in the absence of reactions. The exothermic hydrolysis causes a time dependent thermal peak. An induction time is apparent in pure TEOS before the hydrolysis peaks starts, which has been explained by the initial immiscibility gap of the TEOS-water system. The induction time was found to be approximately of the same magnitude as in the HCl catalyzed hydrolysis, in spite of the uncertainty accompanying the peak definition. No induction period is apparent in pure TMOS, so that the hydrolysis starts with its maximum rate. Two independent thermal peaks in the mixed TMOS-TEOS samples were found, both associated to the respective hydrolyses of the pure component. The induction time for the TEOS hydrolysis is decreased as more alcohol (and silanol) is produced in the earlier TMOS hydrolysis. This effect is explained by improvement of homogenization by alcohol.

Effects of the water quantity on the solventless TEOS hydrolysis under ultrasound stimulation

The acid hydrolysis under ultrasound stimulation of solventless tetraethoxysilane(TEOS)-water mixtures was studied at 40 degrees C, by means of a heat flux calorimetric method, as a function of the initial water/TEOS molar ratio (r) ranging from 2 to 10. The method is based on the time record of the exothermic heat peak of hydrolysis, arising after an induction time under ultrasound stimulation, which is a measure of the reaction rate. The hydrolysed quantity was found to be approximately independent of the water/TEOS molar ratio, even for r < 4. Polycondensation reaction takes place mainly for low water/TEOS molar ratio in order to supply water to allow almost complete hydrolysis. The overall process of dissolution and hydrolysis has reasonably been described by a previous modelling. The dissolution process of water in TEOS, under ultrasound stimulation and acid conditions, was found to be rather dependent of the alcohol produced in the hydrolysis reaction instead of the initial water quantity present in the mixture.

Isolation and sequence determination of peptides in the venom of the spider wasp (Cyphononyx dorsalis) guided by matrix-assisted laser desorption/ionization time of flight (MALDI-TOF) mass spectrometry

Micro-scale (sub-pmol) isolation and sequence determination of three peptides from the venom of the solitary spider wasp Cyphononyx dorsalis is described. We isolated two novel peptides Cd-125 and Cd-146 and a known peptide Thr(6)-bradykinin from only two venom sacs of solitary spider wasp Cyphononyx dorsalis without bioassay-guided fractionation. but instead guided by MALDI-TOF MS. The MALDI-TOF MS analysis of each fraction showed the purity and molecular weight of the components, which led to the isolation of the peptides virtually without loss of sample amount. The sequences of the novel peptides Cd-125 (Asp-Thr-Ala-Arg-Leu-Lys-Trp-His) and Cd-146 (Ser-Glu-Thr-Gly-Asn-Thr-Val-Thr-Val-Lys-Gly-Phe-Ser-Pro-Leu-Arg) were determined by Edman degradation together with mass spectrometry. and finally corroborated by solid-phase synthesis. The known peptide Thr(6)-bradykinin (Arg-Pro-Pro-Gly-Phe-Thr-Pro-Phe-Arg) was identified by comparison with the synthetic authentic specimen. This is the first example for any kinins to be found in Pompilidae wasp venoms. The procedure reported here can be applicable to studies on many other components of solitary wasp venoms with limited sample availability. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

A dissolution and reaction modeling for hydrolysis of TEOS in heterogeneous TEOS-water-HCl mixtures under ultrasound stimulation

A simplified dissolution and reaction modeling was employed to study the hydrolysis of heterogeneous tetraethoxysilane (TEOS)-water-HCl mixtures under ultrasound stimulation. The nominal pH was changed from 0.8 to 2.0. The acid specific hydrolysis rate constant was determined as k = 6.1 mol(-1) 1 min(-1) [H+](-1) at 39 degreesC, in good agreement with the literature. Along the heterogeneous step of the reaction, the ultrasound maintains an additional quantity of water under a virtual state of dissolution besides the water dissolved due to the homogenizing effect of the alcohol produced in the reaction. The forced virtually dissolved water is probably represented by water at the TEOS-water interface during the heterogeneous step of the reaction. The mean radius of the heterogeneity represented by water dispersed in TEOS phase, while hydrolysis has not started yet, was evaluated as about 290 A. The HCl concentration accordingly increases the hydrolysis rate constant but its fundamental role on the immiscibility gap of the TEOS-water-ethanol system has not been unequivocally established. (C) 2002 Elsevier B.V. B.V. All rights reserved.

New attachment achieved by guided tissue regeneration using a bioresorbable polylactic acid membrane in dogs

Created periodontal defects in dogs were randomly assigned for experimental (Guidor bioresorbable membranes) or control (conventional therapy) treatment the results showed that the new connective issue attachment was significantly greater in test sites than in controls. This new attachment averaged 2.79 +/- 0.74 mm and 1.47 +/- 0.20 mm at test and control sites, respectively (P < 0.05). Epithelial downgrowth was also reduced in the test sites (P < 0.05). No differences in bone response were found. The bioresorbable barrier was effective in blocking gingival epithelial downgrowth and connective tissue proliferation, promoting new attachment according to the principles of guided tissue regeneration.

A CALORIMETRIC STUDY OF THE ULTRASOUND-STIMULATED HYDROLYSIS OF SOLVENTLESS TEOS-WATER MIXTURES

The kinetics of ultrasound-stimulated and HCl-catalyzed hydrolysis of solventless TEOS-water mixtures was studied as a function of temperature ranging from 10 degrees C up to 65 degrees C by means of flux calorimetry measurements. A specially designed device was utilized for this purpose. The exothermic peak arising few minutes after sonication began has been attributed mainly to the hydrolysis reaction. The overall hydrolysis process, which was measured through the irradiation time up to the hydrolysis peak, was found to be thermally activated, with an apparent activation energy Delta E = 36.4 kJ/mol. The alcohol produced at the early hydrolysis due to sonication seems to further enhance the reaction, via a parallel autocatalytic path, which is controlled by a faster pseudo second order rate constant (k'). Our modeling yielded k' = 6.3 x 10(-2) M(-1) min(-1) at 20 degrees C, which is in a reasonable agreement with the literature, and an activation energy Delta E = 40.4 kJ/mol for the specific process of hydrolysis in presence of alcohol.

Predicting beef carcass retail products of Mediterranean buffaloes by real-time ultrasound measures

Twenty eight Mediterranean buffaloes bulls were scanned with real-time ultrasound (RTU), slaughtered, and fabricated into retail cuts to determine the potential for ultrasound measures to predict carcass retail yield. Ultrasound measures of fat thickness, ribeye area and rump fat thickness were recorded three to five days prior to slaughter. Carcass measurements were taken, and one side of each carcass was fabricated into retail cuts. Stepwise regression analysis was used to compare possible models for prediction of either kilograms or percent retail product from carcass mesaurements and ultrasound measures. Results indicate that possible prediction models for percent or kilograms of retail products using RTU measures were similar in their predictive power and accuracy when compared to models derived from carcass measurements. Both fat thickness and ribeye area were over-predicted when measured ultrasonically compared to measurements taken on the carcass in the cooler. The mean absolute differences for both traits are larger than the mean differences, indicating that some images were interpreted to be larger and some smaller than actual carcass measurements. Ultrasound measurements of REA and FT had positive correlations with carcass measures of the same traits (r=.96 for REA and r=.99 for FT). Standard errors of prediction currently are being used as the standard to certify ultrasound technicians for accuracy. Regression equations using live weight (LW), rib eye area (REAU) and subcutaneous fat thickness (FTU) between 12(th) and 13 (th) ribs and also over the biceps femoris muscle (FTP8) by ultrasound explained 95% of the variation in the hot carcass weight when measure immediately before slaughter.

Correlations among carcass traits taken by ultrasound and after slaughter in Mediterranean (Bubalus bubalis) young bulls

The objective of this work was to estimate the correlations among measurements taken in vivo with ultrasound equipment with some carcass traits measured after slaughter. Twenty eight Mediterranean bulls, with average shrunk body weight of 330 kg and 14 months of age, were fed by 120 days with high concentrate diets. The shrunk body weight, the ribeye area (REAU), the back fat thickness (FTU) over the Longissimus dorsi muscle between 12(a) and 13(a) ribs and rump fat (EGP8U), were measured at 28 days intervals. Real-time ultrasound equipment Piemedical Scanner 200 VET, with 18 cm linear array transducer was utilized. After the slaughter, the hot carcass weight (PCQ) and the kidney, pelvic and inguinal fat (GRPI) were weighted and the dressing percentage (DP) calculated. After 24 hours of cooling the ribeye area (REAC), backfat thickness (FTC) and rump fat (EGP8C) were measured. Both the REAC, FTC and EGP8C were underestimated by ultrasound measurements. The Pearson correlation coefficients for ribeye area, backfat thickness and rump fat measured in the carcass and with ultrasound, were 0.96, 0.99 and 0.91, respectively. The coefficient between DP and REAU was 0.47; 0.45 between DP and REAC, 0.56 between DP and FTU and 0.58 between DP and FTC. DP presented a 0.59 correlation coefficient with EGP8U. The Spearman correlation was estimated between REAU and REAC, FTU and FTC, EGP8U and EGP8C, and the values were 0.96, 0.99 and 0.91,respectively. The ultrasound measures could be used to estimate carcass traits in buffaloes with good accuracy.

Treatment of ligature-induced peri-implantitis by lethal photosensitization and guided bone regeneration: A preliminary histologic study in dogs

Background: the purpose of this pilot study was to evaluate the healing potential and reosseointegration in ligature-induced peri-implantitis defects adjacent to various dental implant surfaces following lethal photosensitization.Methods: A total of 36 dental implants with 4 different surface coatings (9 commercially pure titanium surface [CPTi]; 9 titanium plasma-sprayed [TPS]; 9 hydroxyapatite [HA]; and 9 acid-etched [AE]) were inserted in 6 male mongrel dogs 3 months after extraction of mandibular premolars. After a 2-month period of ligature-induced peri-implantitis and 12 months of natural peri-implantitis progression, only 19 dental implants remained. The dogs underwent surgical debridement of the remaining dental implant sites and lethal photosensitization by combination of toluidine blue O (100 mug/ml) and irradiation with diode laser. All exposed dental implant surfaces and bone craters were meticulously cleaned by mechanical means, submitted to photodynamic therapy, and guided bone regeneration (GBR) using expanded polytetrafluoroethylene (ePTFE) membranes. Five months later, biopsies of the implant sites were dissected and prepared for ground sectioning and analysis.Results: the percentage of bone fill was HA: 48.28 +/- 15.00; TPS: 39.54 +/- 12.34; AE: 26.88 +/- 22.16; and CPTi: 26.70 +/- 16.50. The percentage of reosseointegration was TPS: 25.25 +/- 11.96; CPTi: 24.91 +/- 17.78; AE: 17.30 +/- 15.41; and HA: 15.83 +/- 9.64.Conclusion: These data suggest that lethal photosensitization may have potential in the treatment of peri-implantitis.

Uterine evaluation and gestation diagnosis in owl monkey (Aotus azarai infulatus) using the B mode ultrasound

Background Gynecological and obstetrical ultrasonography has become an indispensable tool in the routine management, health evaluation and research on captive non-human primates.Methods Ultrasound was used to evaluate the uterus and estimate the gestation of owl monkeys. Twelve couples were selected, where five were primiparous and seven multiparous females from the National Primate Center reproductive colony, Ananindeua-PA, Brazil. The procedures were carried out using the GE (R) Logiq 100 MP, equipped with a 7.5 MHz linear probe.Results the females showed a simple uterus, of elongated shape, regular outline and homogeneous echogenic texture. In the uterine measurements craniocaudal diameter, dorsoventral diameter and uterine volume (UV), significant differences were identified (P < 0.05) between ultrasound examinations of primiparous and multiparous females. The UV showed a positive correlation with the number of births. The gestational sac and the embryonic echo were visible between 28 and 38 days after mating. Between 48 and 68 days after mating, embryonic death was identified in all the gestations.Conclusions the chemical (use of tranquilizers) and husbandry factors (capture stress) may be related to the prenatal death. The establishing methods of conditioning the female to the ultrasonographic exam may offer a solution to this problem.