Temperature and concentration dependence of heat capacity of model aqueous solutions

Heat capacities of binary aqueous solutions of different concentrations of sucrose, glucose, fructose, citric acid, malic acid, and inorganic salts were measured with a differential scanning calorimeter in the temperature range from 5degreesC to 65degreesC. Heat capacity increased with increasing water content and increasing temperature. At low concentrations, heat capacity approached that of pure water, with a less pronounced effect of temperature, and similar abnormal behavior of pure water with a minimum around 30degreesC-40degreesC. Literature data, when available agreed relatively well with experimental values. A correction factor, based on the assumption of chemical equilibrium between liquid and gas phase in the Differential Scanning Calorimeter, was proposed to correct for the water evaporation due to temperature rise. Experimental data were fitted to predictive models. Excess molar heat capacity was calculated using the Redlich-Kister equation to represent the deviation from the additive ideal model.

Role of the surface state and structural feature in the thermoreversible sol-gel transition of a zirconyl aqueous precursor modified by sulfuric acid

The sols produced by admixture of ZrOCl2 acidified solutions to hot H2SO4 aqueous solutions were studied to clarify the effects of Cl- and SO42- ions on the kinetic stability of nanoparticles and to obtain some new evidence concerning the mechanism of a thermoreversible sol-gel transition observed in this system. The study of suspensions prepared with different molar ratios R-S = [Zr]/[SO42-] and R-Cl = [Zr]/[Cl-] revealed domains of composition of formation of thermoreversible gels, thermostable sols, and powder precipitation. The effects of R-S and R-Cl on the structural features of nanoparticles and on the particle solution interface were systematically analyzed for samples of thermoreversible and thermostable sol domains. Small-angle X-ray scattering measurements revealed the presence of small fractal aggregates in all samples of thermoreversible domains, while compact packing aggregates of primary particles are present in the thermostable sol. Extended X-ray absorption fine structure and elemental chemical analysis revealed that irrespective of the nominal value of R-S and R-Cl all studied samples of the thermoreversible domain are constituted by a well-defined compound possessing an inner core made of hydroxyl and oxo groups bridging together zirconium atoms surrounded on the surface by complexing sulfate ligands. zeta potentials of powders extracted by freeze-drying from the thermoreversible gel revealed a point of surface charge inversion attributed to the specific adsorption of SO42- ion. Thermoreversible gel formation is rationalized by considering the effect of the specific adsorption on the electrical double-layer repulsion together with the temperature dependency of the physical chemical properties of ions in solution.

Immobilization of humic acid in nanostructured layer-by-layer films for sensing applications

Humic acids (HAs), naturally occurring biomacromolecules, were incorporated into nanostructured polymeric films using the layer-by-layer (LbL) technique, in which HA layers were alternated with layers of poly(allylamine hydrochloride) (PAH). Atomic force microscopy (AFM) revealed very smooth films, with mean roughness varying from 0.89 to 1.19 nm for films containing 5 and 15 PAH/HA bilayers, respectively. The films displayed electroactivity, with the presence of only one reduction peak at ca. 0.675 V (vs Ag/AgCl). Such a well-defined electroactivity allowed the films to be used as highly sensitive pesticide sensors, with detection of pentachlorophenol (PCP) in solutions at concentrations as low as 10(-9) mol L(-1).

Aqueous solution behavior of thermosensitive (N-isopropylacrylamide-acrylic acid-ethyl methacrylate) terpolymers

A series of N-isopropylacrylamide (NIPAM)-acrylic acid-ethyl methacrylate terpolymers with varied monomer compositions was prepared by radical polymerization. The solution behavior of these polymers was studied in dilute aqueous solution using spectrophotometry, fluorescence spectroscopy and high-sensitivity differential scanning calorimetry. The results obtained revealed that the lower critical solution temperatures depend strongly on the copolymer composition, solution pH and ionic strength. At a high pH, the ionization of acrylic acid (AA) units leads to an increase in solution cloud points (T-c). Solutions of polymers containing 10% or less of AA display a constant T-c for pH above 5.5, with 15% there is a continuous increase in T-c with pH and, for higher AA contents, no clouding was observed within the studied temperature range. Fluorescence probe studies were conducted by following the I (1)/I (3) ratio of pyrene vibronic bands and the emission of anilinonaphtalene sulfonic acid, sodium salt (ANS), both approaches revealing the existence of hydrophobic domains for polymers with higher ethyl methacrylate content at temperatures lower than T-c, suggesting some extent of aggregation and/or a coil-to-globule transition. Scanning calorimetry measurements showed an endothermic transition at temperatures agreeing with the previously detected cloud points. Moreover, the transition curves became broader and with a smaller transition enthalpy, as both the AA content and the solution pH were increased. These broader transitions were interpreted to be the result of a wider molecular distribution upon polymer ionization, hence, displaying varied solution properties. The decrease in transition enthalpy was rationalized as a consequence of reminiscent hydration of NIPAM units, even after phase separation, owing to the presence of electric charges along the polymer chain.

Determination of cinnamic acid in human urine by differential-pulse polarography

The differential pulse polarographic behaviour of cinnamic acid was studied in acetate and phosphate buffer solutions (pH 3.5-7.5). The reduction mechanism is discussed. The drug can be determined at pH 5.0 over the concentration range 5 X 10(-5)-1 X 10(-3) mol l(-1). The effect of tetraalkylammonium salts on the electroanalytical determination of cinnamic acid was investigated, the direct determination of the drug (0.7-5.5 mu g ml(-1)) in urine samples diluted with acetate buffer (pH 5.0) can be effected in the presence of 1 x 10(-3) mol l(-1) cetyldimethylethylammonium bromide solution. The detection limit was found to be 0.1 mu g ml(-1). The relative standard deviation from six determinations at the 5.5 mu g ml(-1) level was 1%.

Effects of rooting media, indolbutyric acid and fertilization on the rooting of rose (Rosa sp. 'Dalas') leafy cuttings

The objectives of this study were to evaluate the effects of rooting media (vermiculite, carbonized rice bark, fenolic spume and sand), presence of IBA (indole-3-butyric acid) and presence of fertilization during the rooting of rose (Rosa sp.) leafy cuttings, Dalas cultivar. This investigation was carried out in Jaboticabal (Sao Paulo State - Brazil) during the period of March to April 1997. The experimental design was a randomized block in a factorial arrangement. It consisted of 16 treatments (the 4 rooting media combined with IBA concentrated solutions - 0 and 1.000 ppm and fertilizer - 0 and commercial product with macro and micronutrients, applied weekly) with 3 replicates. The evaluations were 30 days after cuttings showed that the best rooting percentage occurs in sand (98%), followed by vermiculite (90%) and fenolic spume (87%) and cuttings treated with IBA (95%), while the fertilization showed no promoting effects. The number of cuttings roots wasn't affected with rooting media or DBA treatment, while the fertilization showed effective.

Photodegradation of dichloroacetic acid and 2,4-dichlorophenol by ferrioxalate/H2O2 system

The photo-Fenton process using potassium ferrioxalate as a mediator in the photodegradation reaction of organochloride compounds in an aqueous medium was investigated. The influence of parameters such as hydrogen peroxide and ferrioxalate concentrations and initial pH, was evaluated using dichloroacetic acid (DCA) as a model compound under black-light lamp irradiation. An upflow annular photoreactor, operating in a single pass or recirculating mode was used during photodegradation experiments with artificial light. The extent of the release of chloride ions was used to evaluate the photodegradation reaction. The optimum pH range observed was 2.5-2.8. The efficiency of DCA dechlorination increased with increasing concentrations of H2O2 and potassium ferrioxalate, reaching a plateau after the addition of 6 and 1.5 mmol/L of those reagents, respectively. The total organic carbon (TOC) content in DCA and 2,4-dichlorophenol (DCP) solutions was compared with the chloride released after photodegradation. The influence of natural solar light intensity, measured at 365 nm, was evaluated for the dechlorination of DCA on typical summer's days showing a linear dependency. The photodegradation of DCA using black-light lamp and solar irradiation was compared.

Coil to extended coil transition in polygalacturonic acid: Conductometric titration and monte carlo simulations

The conformational transition from coil to extended coil for polygalacturonic acid has been studied by conductometric titrations and Monte Carlo simulations. The results of conductometric titrations at different polymer concentrations have been analyzed using the model proposed by Manning,1 which describes the conductivity of polyelectrolitic solutions. This experimental approach provides the transport factor and the average distance between charged groups at different degrees of ionization (α). The mean distances between charged groups have been compared with the values obtained by Monte Carlo simulations. In these simulations the polymer chain is modeled as a self-avoiding random walk in a cubic lattice. The monomers interact through the unscreened Coulombic potential. The ratio between the end-to-end distance and the number of ionized beads provides the average distance between charged monomers. The experimental and theoretical values are in good agreement for the whole range of ionization degrees accessed by conductometric titrations. These results suggest that the electrostatic interactions seem to be the major contribution for the coil to extended coil conformational change. The small deviations for α ≤ 0.5 suggests that the stiffness of the chain, associated with local interactions, becomes increasingly significant as the fraction of charged groups is decreased. © 2000 American Chemical Society.

Smear layer removal capacity of disinfectant solutions used with and without EDTA for the irrigation of canals: a SEM study.

The purpose of this study was to carry out a scanning electron microscopic (SEM) analysis of the cleaning qualities and smear layer removal from root canal walls, instrumented and irrigated with 2.5% NaOCl, 2.0% chlorhexidine and saline solutions. Fifty extracted teeth were used in this study. All teeth were radiographed to determine the existence of a single canal. The crowns were cut at the cervical limit and the root canals were instrumented with K-type files up to size 45. During root canal preparation, irrigations were made with the different solutions being evaluated: Group 1: 2.5% NaOCl (10 roots); Group 2: 2.5% NaOCl and 17% EDTA for 2 minute (10 roots); Group 3: 2.0% chlorhexidine (10 roots); Group 4: 2.0% chlorhexidine and 17% EDTA for 2 minutes (10 roots); Group 5: saline solution (5 roots); Group 6: saline solution and 17% EDTA for 2 minutes (5 roots). After instrumentation, the canals were irrigated with each one of the solutions and the roots were cut in the buccolingual direction for SEM analysis, at the cervical, middle and apical thirds, to ascertain the presence or absence of smear layer and debris. SEM analysis was performed by three calibrated examiners and scores were submitted to Kruskal-Wallis test at the significance level of p = 5%. Results showed that the use of 17% EDTA decreased the smear layer significantly (p < 0.05) for all evaluated solutions in all thirds. When EDTA was not used, a significantly higher quantity of smear layer on the apical third was observed only in the NaOCl groups. The use of 17% EDTA was significant for debris removal except for the chlorhexidine groups. The following conclusion could be drawn: the use of 17% EDTA was necessary to enhance cleanness of the root canals.

Influence of IBA and boric acid on rooting of stem-cuttings of Aloysia triphylla (L'Hérit) Britton

Aloysia triphylla (L'Hérit) Britton is a perennial and bushy plant, with simple, entire, lanceolate and whorl shaped leaves and originally from South America. It is used as medicinal plant in Brazil with stomatic and sedative properties. The employment of stem cuttings for propagation of pre-selected plants, acquired great importance, because it eliminates the juvenile phase of seedlings, which can be produced in a shorter period of time. The rooting of stem cuttings is stimulated by auxin and, boric acid supply is essential for growth and development of initial rootlets. This micronutrient is required 48 hours after plant segments have been placed into auxin solution and it can be supplied any time, including the seedling growth period. The experiment was carried out in the Department of Plant Production, UNESP-Botucatu-SP-Brazil, with stem-cuttings of Aloysia triphylla (L'Hérit) Britton, Verbenaceae obtained from the Medicinal and Aromatic Plant Garden. The aim of the work was to verify the influence of growth regulators and boric acid on stem cutting rooting of this species. The 15 cm-stem cuttings, without leaves, were submerged during 24 hs in the following solutions: water; 150 mg.L-1 of IBA; 150 mg.L-1 of IBA+ Boric acid; 250 mg.L-1 of IBA; 250 mg.L-1 of IBA + Boric acid. The statistical design was entirely randomized with 5 treatments and 3 replications, totalizing 15 plots with 10 stem cuttings each. They were planted on propylene trays with vermiculite and kept under spraying condition during twenty five days. The best results were observed in treatment 250 mg.L -1 of IBA+ Boric acid on number of roots, length of roots, rooting percentage, fresh and dry weight of leaves when compared with all other treatments. We can conclude that this treatment is the most suitable for stem cutting rooting of this species.

Water relations of cut inflorescences of Alpinia purpurata treated with seven pulsing solutions

Alpinia purpurata (Vieill) K. Schum, common name red ginger belongs to Zingiberaceae family, and is a perennial, with nice inflorescences composed of layers of bracts arranged in spirals. The utilization of keeping-quality solutions seeks to prolong vase-life and to maintain the quality of cut flowers. This research was performed to evaluate the effect of seven pulsing solutions (during 24 hours) on water relations, quality (turgor, browning and curvature) and the longevity of cut red ginger. The experiment followed complete randomized design, in factorial arrangement. The following treatments were studied: 1) distilled water (control), 2) sucrose 2% + 8-hidroxyquinoline citrate 200 ppm, 3) sucrose 2%, 4) sucrose 2% + citric acid, 5) benzyladenine 10 μM, 6) benzyladenine 10 μmol + sucrose 2%, 7) quaternary ammonia 0,5 mL/L. There was no significant (P>0.05) reduction of the relative water content (RWC) of the inflorescence bracts, among solutions, in the first period (7 days) and in the second period (14 days) and, between the two periods for all treatments. Significant differences among RWC of some treatments were recorded after 16 days of vase life. The utilization of benzyladenine, benzyladenine plus sucrose and sucrose plus citric acid, in the pulsing solution, allowed to keep the flowers quality for longer periods than the other treatments.

Influence of brush type as a carrier of adhesive solutions and paper points as an adhesive-excess remover on the resin bond to root dentin

Purpose: To evaluate the influence of the brush type as a earner of priming adhesive solutions and the use of paper points as a remover of the excess of these solutions on the push-out bond strength of resin cement to bovine root dentin. The null hypotheses were that brush type and the use of paper points do not affect the bond strength. Materials and Methods: The canals of 80 single-root bovine roots (16 mm in length) were prepared at 12 mm using the preparation drill (FRC Postec Plus, Ivoclar). Half of each root was embedded in acrylic resin and the specimens were divided into 8 groups, considering the factors brush type (4 levels) and paper point (2 levels) (n = 10): Gr 1: small microbrush (Cavi-Tip, SDI); Gr 2: Microbrush (Dentsply); Gr 3: Endobrush (Bisco); Gr 4: conventional brush (Bisco); Gr 5: Cavi-Tip (SDI) + paper points; Gr 6: Microbrush (Dentsply) + paper points; Gr 7: Endobrush (Bisco) + paper points; Gr 8: conventional brush (Bisco) + paper points. The root dentin was treated with a multistep total-etch adhesive system (All Bond 2). The adhesive system was applied using each microbrush, with and without using paper points. One fiber post was molded with addition silicon and 80 posts were made of resin cement (Duolink), The resin posts were luted (Duolink resin cement), and the specimens were stored for 24 h in water at 37°C. Each specimen was cut into 4 disk-shaped samples (1.8 mm in thickness), which were submitted to the push-out test. Results: The brush type (p < 0.0001) (small microbrush > microbrush = endobrush = conventional brush) and the use of paper points (p = 0.0001) (with > without) influenced the bond strength significantly (two-way ANOVA). The null hypotheses were rejected. Conclusion: The smallest brush (Cavi-Tip) and the use of paper points significantly improved the resin bond to bovine root dentin.

Calcium hydroxide intracanal dressing removal with different rotary instruments and irrigating solutions: A scanning electron microscopy study

This study evaluated the efficacy of 2 types of rotary instruments employed in association with sodium hypochlorite (NaOCl) or EDTA in removing calcium hydroxide (CH) residues from root canals dentin walls. Forty-two mandibular human incisors were instrumented with the ProTaper System up to F2 instrument, irrigated with 2.5% NaOCl followed by 17% EDTA and filled with a CH intracanal dressing. After 7 days, the CH dressing was removed using 4 techniques: NiTi rotary instrument size 25, 0.06 taper (K3 Endo) and irrigation with 17% EDTA (Group 1), NiTi rotary F1 instrument (ProTaper) and irrigation with 17% EDTA (Group 2), NiTi rotary instrument size 25, 0.06 taper and irrigation with 2.5% NaOCl (Group 3) and NiTi rotary F1 instrument and irrigation with 2.5% NaOCl (Group 4). Two roots without intracanal dressing were used as negative controls. Teeth were evaluated by scanning electron microscopy, in the cervical and apical canal thirds. None of the techniques removed the CH dressing completely. In the apical and cervical thirds, F1 instrument was better than instrument size 25, 0.06 taper in removing CH residues (p<0.05), regardless of the final irrigating solution. No difference was found between the irrigating solutions in the groups of F1 instrument and of instrument size 25, 0.06 taper (p>0.05). The negative controls had no CH residues on the dentin walls. In conclusion, the ProTaper F1 instrument was better than K3 Endo instrument size 25, 0.06 taper in the removal of CH intracanal medication, regardless of irrigating solution used.

Effect of disinfectant solutions on a denture base acrylic resin.

The aim of this study was to evaluate the hardness, roughness and mass loss of an acrylic denture base resin after in vitro exposure to four disinfectant solutions. Forty specimens (Clássico, Brazil) were prepared and randomly assigned to 4 groups n = 10) according to the disinfectant solution: G1: control, stored in distilled water at 37 degrees C; G2: 1% sodium hypochlorite; G3: 2% glutaraldehyde; G4: 4% chlorhexidine. G2 to G4 were immersed for 60 minutes in the disinfectant solution. Measurements were carried out both before and after immersion in the solution. The surface was analyzed with a surface roughness tester (Surfcorder SE 1700 KOZAKALAB), a microdurometer FM-700 (Future Tech) and a scanning electron microscope (DSM 962-ZEISS). Loss of mass was determined with a digital weighing scale. After disinfection procedures, values were analyzed statistically. The acrylic denture base resin may be vulnerable to surface changes after in vitro immersion in the disinfectant solutions studied.

Osmotic Dehydration of Pineapple with Impregnation of Sucrose, Calcium, and Ascorbic Acid

Mass transfer was evaluated during osmotic dehydration of pineapple in solutions with until four components aiming to investigate the solutes concentration influence on impregnation. In the first step, the experimental trials for optimization of solution concentration were based on 23 factorial design. In the second step, effective diffusion coefficients were determined. Equations representing the influence of the concentration of sucrose, calcium lactate, and ascorbic acid in osmotic solutions on water loss and gains of sucrose, calcium, and vitamin C were found. Results showed that both calcium lactate and sucrose concentration affected calcium and sucrose gain. On the other hand, only vitamin C gain was significantly affected by the ascorbic acid concentration in the studied concentration range. However, when comparing diffusivities in pineapple immersed in sucrose solutions, with and without calcium lactate, with and without ascorbic acid, it was possible to verify that diffusivities of water, sugar, and calcium increased in presence of ascorbic acid in solution. Calcium in solution diminished the water and sucrose diffusivities. High calcium and vitamin C contents were obtained in 1 h immersion in the solutions studied. © 2013 Springer Science+Business Media New York.