Quantum chemical topological analysis of hydrogen bonding in HX…HX and CH3X…HX dimers (X = Br, Cl, F)

We present a systematic investigation of the nature and strength of the hydrogen bonding in HX···HX and CH3X…HX (X = Br, Cl and F) dimers using ab initio MP2/aug-cc-pVTZ calculations in the framework of the quantum theory of atoms in molecules (QTAIM) and electron localisation functions (ELFs) methods. The electron density of the complexes has been characterised, and the hydrogen bonding energy, as well as the QTAIM and ELF parameters, is consistent, providing deep insight into the origin of the hydrogen bonding in these complexes. It was found that in both linear and angular HX…HX and CH3X…HX dimers, F atoms form stronger HB than Br and Cl, but they need short (∼2 Å) X…HX contacts.

Bioconversion of Cellulose to Hydrogen by dark fermentation

Hydrogen is known as a clean energy resource. The biological production of hydrogen has been attracting attention as an environmentally friendly processs that does not consume fossil fuels. Cellulosic plant and waste materials are potential resources for fermentative hydrogen production. Cellulose is a linear biopolymer of glucose molecules, connected by β-1,4-glycosidic bonds. Enzymatic hydrolysis of cellulose requires the presence of cellulase. The present study aimed to investigate the efficiency of acid pretreatment on ruminal fluid in order to enrich H2 producing bacteria consortia to enhance biohydrogen rate and substrate removal efficiency. In this study, fermentative hydrogen producers were enriched on cellulose (2g/L) in a modificated Del Nery medium (DNM) at 37ºC and initial pH 7.0 using rumen fluid (10% v/v) as inoculum. To increase the hydrogen production it was added cellulose (10mL) to the medium. The gas products (mainly H2 and CO2) was analyzed by gas chromatography (Shimadzu GC 2010) using a thermal conductivity detector. The volatile fatty acids and ethanol were also detected by GC using a flame ionization detector. Cellulose degradation was quantified by using the phenolsulfuric acid method. Analysis showed that the biogas produced from the anaerobic fermentation contained only hydrogen and carbon dioxide, without detectable methane after acid pretreatment test. On DNM the hydrogen production started with 4 h (5,3 x 105 mmol H2/L) of incubation, and the maximum H2 concentration was observed with 34 h (7,1 x 106 mmol H2/L) of incubation. During the process, it was observed a predominance of acetic acid and butyric acid as well as a low production of acetone, ethanol and nbutanol in all experimental phases. Butyrate accounted for more than 77% of total. As a result of the accumulation of volatile fatty acids (VFAs), the pH value in anaerobic digestion system was reduced to 4,0. On microscopy analyses there were observed rods with endospores. The batch anaerobic fermentation assays performed on anaerobic mixed inoculum from rumen fluid demonstrated the feasibility of H2 generation utilizing cellulose as substrate. Based on the results, it can be concluded that the acid treatment was efficient to inhibit the methanogenic archaea cells present in rumen fluid. The rumen fluid cells present a potential route in converting renewable biomass such as cellulose into hydrogen energy.

Biological Hydrogen production from environmental sample in tropical countries

The hydrogen gas is regarded as clean and renewable energy source, since it generates only water during combustion when used as fuel. It shows 2.75 times more energy content than any hydrocarbon and it can be converted into electrical, mechanical energy or heat. Inoculum sources have been successfully tested for hydrogen biological production in temperate climate countries as sludge treatment plants sewage, sludge treatment plant wastewater, landfill sample, among others. However, hydrogen biologic production with inoculum from environmental samples such as sediment reservoirs, especially in tropical countries like Brazil, is rarely investigated. Reservoirs and fresh water lake sediment may contain conditions for the survival of a wide variety of microorganisms which use different carbon sources mainly glucose and xylose, in the fermentation. Glucose is an easily biodegradable, present in most of the industrial effluents and can be obtained abundantly from agricultural wastes. A wide variety of wastewater resulting from agriculture, industry and pulp and paper processed from wood may contain xylose in its constitution. Such effluent contains glucose and xylose concentrations of about 2 g/L. In this sense, this work verified hydrogen biological production in anaerobic batch reactor (1L), at 37 ° C, initial pH 5.5, headspace with N2 (100%), Del Nery medium, vitamins and peptone (1 g/L), fed separately with glucose (2g/L) and xylose (2 g/L). The inoculum was taken from environmental sample (sediment reservoir Itupararanga - Ibiúna - SP-Brazil). It was previously purified in serial dilutions at H2 generation (10-5, 10-7, 10-10), and heat treated (90º C - 10 min) later to inhibited the H2 consumers. The maximum H2 generations obtained in both tests were observed at 552 h, as described below. At the reactors fed with glucose and xylose were observed, respectively, 9.1 and 8.6 mmol H2/L, biomass growth (0.2 and 0.2 nm); consumption of sugar concentrations 53.6% (1.1 glucose g/L) and 90.5% (1.8 xylose g/L); acetic acid generation (124.7 mg/L and 82.7 mg/L), butyric acid (134.0 mg/L and 230.4 mg/L) and there wasn’t methane generation in the reactors. Microscopic analysis of biomass in anaerobic reactors showed the predominance of Gram positive rods and rods with endospores, whose morphology is characteristic of H2-generating bacteria, in both tests. These species were selected from the natural environment. In DGGE analysis performed difference were observed between populations from inoculum and in tests. This analysis confirmed that some species of bacteria were selected which remained under the conditions imposed on the experiment. The efficiency of the pre-treatment of inoculum and the imposition of pH 5.5 inhibited methane-producing microorganisms and the consumers of H2. Therefore, the experimental conditions imposed allowed the attainment of bacterial consortium of producer H2 taken from an environmental sample with concentration of xylose and glucose similar to the ones of the industrial effluents.

The effect of biomass immobilization support material and bed porosity on hydrogen production in an upflow anaerobic packed-bed bioreactor

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Performance and composition of bacterial communiies in anaerobic fluidized bed reactors for hydrogen production: Effects of organic loading rate and alkalinity

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Indirect cytocompatibility of a low-concentrated hydrogen peroxide bleaching gel to odontoblast-like cells

Aim To assess the initial cytotoxicity and the late phenotype marker expression of odontoblast-like cells (MDPC-23) subjected to less aggressive in-office bleaching therapies. Methodology A 17.5% hydrogen peroxide (H2O2) gel was applied for 45, 15 or 5 min to enamel/dentine discs adapted to trans-wells positioned over cultured MDPC-23 cells. No treatment was performed on the negative control. Immediately after bleaching, the cell viability, gene expression of inflammatory mediators and quantification of H2O2 diffusion were evaluated. The ALP activity, DSPP and DMP-1 gene expression and mineralized nodule deposition (MND) were assessed at 7, 14 or 21 days post-bleaching and analysed statistically with Mann–Whitney U-tests (α = 5%). Results H2O2 diffusion, proportional to treatment time, was observed in all bleached groups. Reductions of approximately 31%, 21% and 13% in cell viability were observed for the 45-, 15- and 5-min groups, respectively. This reduction was significant (P < 0.05) for the 45- and 15-min groups, which also presented significant (P < 0.05) over-expression of inflammatory mediators. The 45-min group was associated with significant (P < 0.05) reductions in DMP-1/DSPP expression at all periods, relative to control. The ALP activity and MND were reduced only in initial periods. The 15-min group had less intense reduction of all markers, with no difference to control at 21 days. Conclusions The 17.5% H2O2 applied to tooth specimens for 5 min caused no alteration in the odontoblast-like cells. When this gel was applied for 45 or 15 min, a slight cytotoxicity, associated with alterations in phenotypic markers, was observed. However, cells were able to recover their functions up to 21 days post-bleaching.

Effect of hydrogen-peroxide-mediated oxidative stress on human dental pulp cells

To evaluate the effect of the oxidative stress on human dental pulp cells (HDPCs) promoted by toxic concentrations of hydrogen peroxide (H2O2) on its odontoblastic differentiation capability through time. Methods HDPCs were exposed to two different concentrations of H2O2 (0.1 and 0.3 μg/ml) for 30 min. Thereafter, cell viability (MTT assay) and oxidative stress generation (H2DCFDA fluorescence assay) were immediately evaluated. Data were compared with those for alkaline phosphatase (ALP) activity (thymolphthalein assay) and mineralized nodule deposition (alizarin red) by HDPCs cultured for 7 days in osteogenic medium. Results A significant reduction in cell viability and oxidative stress generation occurred in the H2O2-treated cells when compared with negative controls (no treatment), in a concentration-dependent fashion. Seven days after H2O2 treatment, the cells showed significant reduction in ALP activity compared with negative control and no mineralized nodule deposition. Conclusion Both concentrations of H2O2 were toxic to the cells, causing intense cellular oxidative stress, which interfered with the odontogenic differentiation capability of the HDPCs. Clinical significance The intense oxidative stress on HDPCs mediated by H2O2 at toxic concentrations promotes intense reduction on odontoblastic differentiation capability in a 7-day evaluation period, which may alter the initial pulp healing capability in the in vivo situation.

Color alteration, hydrogen peroxide diffusion, and cytotoxicity caused by in-office bleaching protocols

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Hydrogen peroxide attenuates the dipsogenic, renal and pressor responses induced by cholinergic activation of the medial septal area

Cholinergic activation of the medial septal area (MSA) with carbachol produces thirst, natriuresis, antidiuresis and pressor response. In the brain, hydrogen peroxide (H2O2) modulates autonomic and behavioral responses. In the present study, we investigated the effects of the combination of carbachol and H2O2 injected into the MSA on water intake, renal excretion, cardiovascular responses and the activity of vasopressinergic and oxytocinergic neurons in the hypothalamic paraventricular (PVN) and supraoptic (SON) nuclei. Furthermore, the possible modulation of carbachol responses by H2O2 acting through K+ATP channels was also investigated. Male Holtzman rats (280–320 g) with stainless steel cannulas implanted in the MSA were used. The pre-treatment with H2O2 in the MSA reduced carbachol-induced thirst (7.9 ± 1.0, vs. carbachol: 13.2 ± 2.0 ml/60 min), antidiuresis (9.6 ± 0.5, vs. carbachol: 7.0 ± 0.8 ml/120 min,), natriuresis (385 ± 36, vs. carbachol: 528 ± 46 μEq/120 min) and pressor response (33 ± 5, vs. carbachol: 47 ± 3 mmHg). Combining H2O2 and carbachol into the MSA also reduced the number of vasopressinergic neurons expressing c-Fos in the PVN (46.4 ± 11.2, vs. carbachol: 98.5 ± 5.9 c-Fos/AVP cells) and oxytocinergic neurons expressing c-Fos in the PVN (38.5 ± 16.1, vs. carbachol: 75.1 ± 8.5 c-Fos/OT cells) and in the SON (57.8 ± 10.2, vs. carbachol: 102.7 ± 7.4 c-Fos/OT cells). Glibenclamide (K+ATP channel blocker) into the MSA partially reversed H2O2 inhibitory responses. These results suggest that H2O2 acting through K+ATP channels in the MSA attenuates responses induced by cholinergic activation in the same area.

Endogenous and exogenous teeth whitening through gel-based bleaching hydrogen peroxide (35%) with the aid of silicon guide

The aim of this study is to demonstrate through a case report, a proposed treatment for discolored teeth, with and without pulp vitality, by the technique of external and internal tooth bleaching with hydrogen peroxide to 35% Lase Peroxide Sensy (DMC) using Whitening Lase II Device (DMC), and a silicone guide (3M ESPE) in the palatine portion of the upper teeth. In this clinical case, the patient had darkened dental elements 11 and 22, and dissatisfaction with the coloring of other elements. It was observed that the techniques used and the materials chosen allowed for an excellent aesthetic result, with technical simplicity and low cost, and minimal occurrence of signs and symptoms

Effects of coronal leakage on concentration of hydrogen ions and calcium hydroxide release of several calcium hydroxide pastes over different periods of time

Purpose: To evaluate the effects of coronal leakage on concentration of hydrogen ions (pH) and calcium release of several calcium hydroxide pastes, over different periods of time. Material and Methods: Fifty extracted human mandibular central incisors (n=10) were instrumented up to the F2 instrument and assigned to the following intracanal dressing: G1- Calen, G2- Calen with 0.4% chlorhexidine (CHX), G3- Calcium hydroxide with camphorated paramonochlorophenol (CPMC) and glycerin, G4- Calen, but temporary filling material maintained during all test (positive control) and G5- Root canal without intracanal dressing (negative control). All groups were immersed in distilled water for 7 days. In sequence, the temporary filling materials were removed, except in controls groups. All specimens were individually mounted on a specific device and only its root again immersed in distilled water. Concentration of hydrogen ions and calcium release by calcium hydroxide pastes in distilled water were evaluated in 24h, 7, 14 and 28 days. The results were submitted to ANOVA test (p = 0.05). After 28 days, root canals from experimental groups were examined in SEM. Results: G1, G2, G3 and G4 presented similar pH values and calcium release and did not differ from each other (p>0.05), up to 7 days. After this time G1, G2 and G3 presented values lower values than G4 (p<0.05). In SEM analysis, calcium hydroxide residues were observed in all experimental groups. Conclusions: After 7 days, coronal leakage decreased the concentration of hydrogen ions and calcium ion release provided by all calcium hydroxide pastes.

Effect of two formulations of 10% sodium ascorbate on fracture resistance of endodontically treated tooth submitted to dental bleaching with hydrogen peroxide associated titanium dioxide nanoparticles

Purpose: This study evaluated the effect of 10% sodium ascorbate (10SA), in gel (10SAg) or aqueous solution (10SAs) formulations, on fracture resistance of endodontically treated tooth submitted to dental bleaching procedures with 15% hydrogen peroxide associated with titanium dioxide (15HP-TiO2) nanoparticles and photoactivated by LED-laser. Material and methods: Forty maxillary premolars were endodontically-treated and embedded in acrylic resin up to the cement-enamel junction. The specimens were divided into four groups (n=10): G1 (negative control): no bleaching, coronal access restored with composite resin; G2 (positive control): three dental bleaching sessions using 15HP-TiO2 and LED-laser photoactivation and restored with composite resin (positive control); G3 (10SAg): similar procedures to G2, but applied 10SA, in gel formulation, for 24 hours before restoration; G4 (10SAs): similar procedures to G3, but applied 10SA, in aqueous solution formulation. The 15HP-TiO2 was applied on buccal and lingual surfaces of the crown tooth and inside the pulp chamber and photoactivated by LED-laser. Between each bleaching session, the teeth were maintained in artificial saliva, at 37oC, for 7 days. In sequence, the teeth were submitted to fracture resistance testing using an eletromechanical machine test. The data was analyzed using Kruskal Wallis test (p = 0.05) Results: There are no differences significant among the groups in relation to fracture resistance of endodontically treated teeth (p>0.05). Conclusions: The use of 10% sodium ascorbate, in gel or aqueous solution formulations, did not interfered on the fracture resistance teeth after dental bleaching using 15HP-TiO2 and LED-laser photoactivation.

Hydrogen ion and calcium releasing of MTA Fillapex® and MTA-based formulations

MTA is composed of various metal oxides, calcium oxide and bismuth. It has good biological properties and is indicated in cases of endodontic complications. Several commercial formulations are available and further studies are necessary to evaluate these materials. Objective: To evaluate pH and calcium releasing of MTA Fillapex® compared with gray and white MTA. Material and methods: Gray and white MTA (Angelus) and MTA Fillapex® (Angelus) were manipulated and placed into polyethylene tubes and immersed in distilled water. The pH of these solutions was measured at 24 hours, 7 days and 14 days. Simultaneously, at these same aforementioned periods, these materials' calcium releasing was quantified, through atomic absorption spectrophotometry. The results were submitted to ANOVA, with level of significance at 5%. Results: Concerning to pH, the materials present similar behaviors among each other at 24 hours (p > 0.05). At 7 and 14 days, MTA Fillapex® provided significantly lower pH values than the other materials (p < 0.05). Regarding to calcium releasing, at 24 hours and 7 days, MTA Fillapex® provided lower releasing than the other materials (p < 0.05). After 14 days, differences were found between MTA Fillapex® and gray MTA (p < 0.05). Conclusion: All materials showed alkaline pH and calcium releasing, with significantly lower values for MTA Fillapex® sealer.

Can an LED-laser hybrid light help to decrease hydrogen peroxide concentration while maintaining effectiveness in teeth bleaching?

The aim of this study was to compare the bleaching efficacy of 35% hydrogen peroxide and 15% hydrogen peroxide with nitrogen-doped titanium dioxide catalysed by an LED-laser hybrid light. We studied 70 patients randomized to two groups. Tooth shade and pulpal sensitivity were registered. Group 1: 15% hydrogen peroxide with nitrogen-doped titanium dioxide. Group 2: 35% hydrogen peroxide. Both groups were activated by an LED-laser light. No significant differences were seen in shade change immediately, one week or one month after treatment (p > 0.05). Differences were seen in pulpal sensitivity (p < 0.05). The use of an LED-laser hybrid light to activate 15% hydrogen peroxide gel with N_TiO2 permits decreasing the peroxide concentration with similar aesthetic results and less pulpal sensitivity than using 35% hydrogen peroxide for bleaching teeth.

Fracture resistance of endodontically-treated teeth submitted to bleaching treatment with hydrogen peroxide and titanium dioxide nanoparticles photoactivated by LED-laser

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)