Reactivity of unactivated peroxymonosulfate and peroxyacetic acid with thioether micropollutants: Mechanisms and rate prediction.

Thioether compounds, prevalent in pharmaceuticals, are of growing environmental concern due to their prevalence and potential toxicity. Peroxy chemicals, including peroxymonosulfate (PMS) and peroxyacetic acid (PAA), hold promise for selectively attacking specific thioether moieties. Still, it has been unclear how chemical structures affect the interactions between thioethers and peroxy chemicals. This study addresses this knowledge gap by quantitatively assessing the relationship between the structure of thioethers and intrinsic reaction rates. First, the results highlighted the adverse impact of electron-withdrawing groups on reactivity. Theoretical calculations were employed to locate reactive sites and investigate structural characteristics, indicating a close relationship between thioether charge and reaction rate. Additionally, we established a SMILES-based model for rapidly predicting PMS reactivity with thioether compounds. With this model, we identified 147 thioether chemicals within the high production volume (HPV) and Food and Drug Administration (FDA) approved drug lists that PMS could effectively eliminate with the toxicity (-lg LC50) decreasing. These findings underscore the environmental significance of thioether compounds and the potential for their selective removal by peroxides.

Doped Cu0 and sulfidation induced transition from R-O• to •OH in peracetic acid activation by sulfidated nano zero-valent iron-copper.

Peracetic acid (PAA) has emerged as a new effective oxidant for various contaminants degradation through advanced oxidation process (AOP). In this study, sulfidated nano zero-valent iron-copper (S-nZVIC) with low Cu doping and sulfidation was synthesized for PAA activation, resulting in more efficient degradation of sulfamethoxazole (SMX, 20 µM) and other contaminants using a low dose of catalyst (0.05 g/L) and oxidant (100 µM). The characterization results suggested that S-nZVIC presented a more uniform size and distribution with fewer metal oxides, as the agglomeration and oxidation were inhibited. More significantly, doped Cu0 and sulfidation significantly enhanced the generation and contribution of •OH but decreased that of R-O• in S-nZVIC/PAA/SMX system compared with that of nZVIC and S-nZVI, accounting for the relatively high degradation efficiency of 97.7% in S-nZVIC/PAA/SMX system compared with 85.7% and 78.9% in nZVIC/PAA/SMX and S-nZVI/PAA/SMX system, respectively. The mechanisms underlying these changes were that (i) doped Cu° could promote the regeneration of Fe(Ⅱ) for strengthened PAA activation through mediating Fe(Ⅱ)/Fe(Ⅲ) cycle by Cu(Ⅰ)/Cu(Ⅱ) cycle; (ii) S species might consume part of R-O•, resulting in a decreased contribution of R-O• in SMX degradation; (iii) sulfidation increased the electrical conductivity, thus facilitating the electron transfer from S-nZVIC to PAA. Consequently, the dominant reactive oxygen species transited from R-O• to •OH to degrade SMX more efficiently. The degradation pathways, intermediate products and toxicity were further analyzed through density functional theory (DFT) calculations, liquid chromatography-mass spectrometry (LC-MS) and T.E.S.T software analysis, which proved the environmental friendliness of this process. In addition, S-nZVIC exhibited high stability, recyclability and degradation efficiency over a wide pH range (3.0∼9.0). This work provides a new insight into the rational design and modification of nano zero-valent metals for efficient wastewater treatment through adjusting the dominant reactive oxygen species (ROS) into the more active free radicals.

Formation of Halogenated Byproducts upon Water Treatment with Peracetic Acid.

Peracetic acid has quickly gained ground in water treatment over the last decade. Specifically, its disinfection efficacy toward a wide spectrum of microorganisms in wastewater is accompanied by the simplicity of its handling and use. Moreover, peracetic acid represents a promising option to achieve disinfection while reducing the concentration of typical chlorination byproducts in the final effluent. However, its chemical behavior is still amply debated. In this study, the reactivity of peracetic acid in the presence of halides, namely, chloride and bromide, was investigated in both synthetic waters and in a real contaminated water. While previous studies focused on the ability of this disinfectant to form halogenated byproducts in the presence of dissolved organic matter and halides, this work indicates that peracetic acid also contributes itself as a primary source in the formation of these potentially carcinogenic compounds. Specifically, this study suggests that 1.5 mM peracetic acid may form around 1-10 µg/L of bromoform when bromide is present. Bromoform formation reaches a maximum at near neutral pH, which is highly relevant for wastewater management.

The use of peracetic acid for estrogen removal from urban wastewaters: E2 as a case study.

17ß-Estradiol (E2) is a natural estrogen produced by the feminine endocrine system. It is excreted mainly through urine and feces. Exposure to E2 may affect the reproductive system of both animals and humans, especially since the removal of E2 in conventional processes and technologies present in the wastewater treatment plants is not sufficient. Chlorine is one of the most studied and used oxidant worldwide. Although there are studies that demonstrate the endocrine disrupting compounds removal like E2, its reaction with organic matter can originate by-products, namely, trihalomethanes, which are known to have high toxic potential. The main aim of the present study was to evaluate the removal of E2 (50 µg E2 L-1-maximum concentration) using peracetic acid (PAA), a seeming cleaner and innocuous alternative to chlorine. To this end, a series of jar tests were performed, using different peracetic acid concentrations (1, 5, 10, and 15 mg L-1) and contact times (10, 15, and 20 min). The results obtained showed that a peracetic acid concentration of 15 mg L-1 with a contact time of 20 min had a removal efficacy of approximately 100%. The second main goal of this study was to evaluate the ecotoxicological potential of the tested treatments on the zebrafish Danio rerio. Several oxidative stress biomarkers were evaluated, namely glutathione S-transferase, lipid peroxidation, and catalase, besides vitellogenin. Both peracetic acid and E2 caused significant increases in the oxidative stress biomarkers, although this did not lead to increased lipid peroxidation levels. In addition, peracetic acid significantly decreased the estrogenic activity of E2, as indicated by decreased vitellogenin levels. Peracetic acid demonstrated to have great potential as an alternative disinfectant for chlorine treatments, and indications for future research are discussed.

Efficacy assessment of peracetic acid in the removal of synthetic 17α-ethinyl estradiol contraceptive hormone in wastewater.

Increasing concerns have been raised on endocrine disrupting chemicals like the sex hormone 17α-ethinylestradiol (EE2), the more since traditional wastewater (WW) treatments appear to be ineffective for their removal. The efficacy of the relatively novel disinfectant peracetic acid (PAA) in EE2 removal was evaluated, as well as its potential effects on WW quality parameters. The treatments tested for EE2 removal were also evaluated in terms of toxicity, through the determination of biochemical responses (antioxidant enzymes, lipid peroxidation and vitellogenin induction) using zebrafish (Danio rerio) as a biological model. PAA contact times less than 20 min appeared insufficient regardless of the PAA dose tested, but a 100% EE2 removal was attained at a PAA concentration of 15 mg/L with a contact time of 20 min. Total suspended solids, chemical oxygen demand and pH in PAA treatments remained well within levels set in European legislation for WW discharge. EE2 induced significant increased vitellogenin (VTG) levels in both female and male fish, indicating increased estrogenic activity, especially in males suggesting an endocrine disruption effect. With the addition of PAA (15 mg/L), however, VTG levels in both sexes returned to control values. Although this PAA treatment showed increased levels of the antioxidant enzyme catalase, the lipid peroxidation levels were similar or even lower than in controls. Overall the results suggest that the use of PAA appears a promising way forward as a less toxic alternative to chlorine disinfection with high efficiency in the removal of EDC like EE2.

Effect of peracetic acid used as single irrigant on the smear layer, adhesion, and penetrability of AH Plus

Abstract The aim of this study was to evaluate the effect of peracetic acid (PAA) as a single irrigant on the smear layer, on the intraradicular dentinal bond strength, and on the penetrability of an epoxy-based resin sealer into the dentinal tubules. A total of 120 roots were distributed into 4 groups according to the irrigant used in root canal preparation: 1% PAA (PAA); 2.5% NaOCl followed by final irrigation with 17% EDTA and 2.5% NaOCl (NaOCl-EDTA-NaOCl); 2.5% NaOCl (NaOCl); and saline solution (SS). The smear layer was evaluated using scanning electron microscopy. The bond strength of an epoxy-based resin sealer (AH Plus) to root dentin was evaluated by the push-out test and penetrability of the sealer into dentinal tubules was observed by confocal laser microscopy. The results were analyzed by the Kruskal-Wallis and the Dunn post-test (α = 0.05). The use of 1% PAA as single root canal irrigant provided smear layer removal and improved the penetrability and bond strength of AH Plus to root dentin in a manner similar to that of the NaOCl-EDTA-NaOCl group (p > 0.05). The NaOCl and SS groups had higher values of smear layer and lower values of sealer penetrability and dentin bond strength than the PAA and NaOCl-EDTA-NaOCl groups (p < 0.05). Thus, 1% PAA has the potential to be used as a single irrigant in root canals.

Effects of different irrigation regimes in physico-chemical properties of dentin and consequences of changes in the adhesion of microorganisms and AH Plus sealer / Efeitos de diferentes regimes de irrigação nas propriedades físicoquímicas da dentina e consequências das alterações na adesão de microrganismos e do cimento endodôntico AH Plus

Besides of the desired effects, the chemical solutions used to assist the endodontic instruments in the cleanliness and disinfection of the root canal system can also cause changes in the physicochemical properties of dentin, and consequently affect the adhesion of endodontic sealers and microorganisms to the root canal walls. However, the effects of new irrigators and irrigation protocols remain unknown. The objectives of this thesis were to verify the alterations in the properties of some irrigants when used combined in mixtures, to define the time necessary for the smear layer removal by a new irrigant, to determine the organic matter dissolution capacity and the effects in the physicochemical properties of dentin of some irrigation solutions and protocols, and to evaluate the adhesion of microorganisms and AH Plus sealer to dentin after its submission to different irrigation sequences. In all experiments with dentin, the samples used were obtained from bovine teeth. In the analysis performed in this thesis, the following solutions were tested isolated and combined in different irrigation protocols: saline solution (control), sodium hypochlorite (NaOCl), trisodium (EDTAHNa3), alkaline ethylenediaminetetraacetic acid tetrasodium (EDTANa4), chlorhexidine (CHX), peracetic acid (PAA), and etidronic acid (HEDP). The EDTAHNa3 and EDTANa4 were tested in relation to their effects on the free chlorine content of NaOCl. The solutions were mixed in a 1:1 ratio and the iodometric titration of the mixtures performed in different time intervals. The time necessary for smear layer removal from dentin samples by solutions of EDTAHNa3 and different concentrations of EDTANa4 isolated and mixed with NaOCl was determined with the aid of the scanning electron microscope (SEM). The capacity of NaOCl to dissolve organic matter was determined by weighting fragments of bovine muscle before and after immersion in solutions of 1%, 2.5%, and 5% of NaOCl in different periods of time. Also, the effects of EDTAHNa3, EDTANa4 and HEDP on the organic matter dissolution by NaOCl were evaluated. The alterations produced by all solutions isolated and some irrigation protocols in the organic and inorganic components of the dentin surface were analysed by the attenuated total reflectance of Fourier transform infrared spectroscopy (ATR-FTIR) technique. Absorbance spectra were collected from the dentin surface before and after immersion of samples in the irrigants and the ratios of the amide III/phosphate and carbonate/phosphate bands were calculated. To quantify the adhesion of CHX to mineralized dentin and to dentin demineralized by different irrigation protocols, the areas of the band associated with CHX with the peak in 1492 cm−1 were determined in spectra obtained by ATR-FTIR. The effects of different irrigation protocols in the roughness and wettability of dentin surface were measured with a benchtop roughness tester and the sessile drop technique, respectively. For the assays of microorganisms' adhesion, samples were prepared and treated the same way and with the same irrigation protocols used in the roughness and wettability tests. Following, Candida albicans and Enterococcus faecalis were maintained in contact with the dentin for 2 hours and the samples were analyzed on the confocal laser scanning microscope (CLSM). Tests of push-out were performed to determine the impact of different irrigation protocols on the dentin bonding strength of AH Plus sealer over time. Canals of bovine incisors teeth were instrumented, irrigated and following obturated using only the sealer AH Plus. Half of the samples were submitted to pushout assessment 7 days after the obturation and the other half 20 months later. The results of the experiments showed that the EDTAHNa3 caused an almost complete and immediate loss of free available chlorine from NaOCl, whilst EDTANa4 promoted a slow and concentration-dependent decline. The smear layer was removed only by decalcifying solutions and in about 1 min by the 17% EDTAHNa3 and 5 min by the EDTANa4, both isolated or mixed with NaOCl. The increase in NaOCl concentration and contact time with the samples intensified the dissolution of organic matter. The mixtures of NaOCl with EDTANa4 and HEDP were able to dissolve the fragments of bovine muscle over-time, however, the EDTAHNa3 strongly affected the NaOCl dissolution capacity when they were mixed. The results of ATR-FTIR experiments showed that the increase in the NaOCl concentration intensified the deproteination of the dentin collagen with a reduction in the amide III/phosphate ratio. For the same decalcifying agent, the higher the concentration and immersion time the greater the removal of phosphate, exposure of the collagen matrix and consequently the increases in amide III/phosphate ratio. The PAA caused greater increases in amide III/phosphate ratio, followed by EDTAHNa3, EDTANa4 and HEDP and this order was maintained in the protocols in which NaOCl was used before the decalcifying agents. NaOCl required approximately 0.5 min to deproteinate the collagen matrix exposed after phosphate removal by EDTAHNa3 and PAA. The carbonate/phosphate ratio decreased after 30 s of samples immersion in solutions of NaOCl at 1%, 2.5% and 5% with no more alterations over time. The carbonate of the dentine was removed faster than phosphate by all decalcifying agents employed alone and in the irrigation protocols in which the use of the NaOCl was followed by the use of the EDTAHNa3, PAA and HEDP. For irrigation protocols that associate NaOCl with chelating solutions, the last irrigant used defined the final dentine amide III/phosphate and carbonate/phosphate ratios. For the ATR-FTIR analysis of CHX adhesion, the results showed that the adsorption of this irrigant to the dentin was potentiated when chelating agents were used prior to the CHX. In relation to the experiments of surface roughness, the saline solution, NaOCl, HEDP and CHX did not alter the roughness of the dentin, but EDTAHNa3 and PAA increased it. The wettability of the surface increased after the use of all irrigants, being the HEDP to cause the greater increases. In the assays of microorganisms' adhesion, the smear layer and collagen exposed by the chelating agents favored the adhesion of E. faecalis. The C. albicans adhesion was major in surfaces with smear layer and more mineral. The use of CHX as the final irrigant reduced the adhesion of both microorganisms. The wettability did not influence the microorganisms' adhesion, while increases in roughness seems to potentiate the adherence of E. faecalis. The experiments of bond strength of AH Plus to the dentin showed that the irrigation with NaOCl and mixture of NaOCl + EDTANa4 produced the lowest push-out bond strength values in 7 days compared to NaOCl + EDTAHNa3, NaOCl + EDTAHNa3 + NaOCl, NaOCl + EDTAHNa3 + CHX and the mixture of NaOCl + HEDP. After 20 months the lowest values were obtained in the groups irrigated with NaOCl and NaOCl + EDTAHNa3. The groups of NaOCl + EDTAHNa3 + NaOCl, mixture NaOCl + HEDP, and mixture NaOCl + EDTANa4 presented values of push-out bond strength in 20 months similar to the values in 7 days. It was possible to conclude that the irrigation solutions tested in this study have different effects in the organic and inorganic matter and some of them can affect the action of each other when mixed. Independent of being used isolated or combined in irrigation protocols, these irrigants cause modifications in the dentin physicochemical properties that influence the adhesion of AH Plus sealer in short and long term and the microorganisms' adherence to the surface in cases of recontaminations.(AU)

Além dos efeitos desejados, as soluções químicas utilizadas para auxiliar os instrumentos endodônticos na limpeza e desinfecção do sistema radiculares podem causar alterações nas propriedades físico-químicas da dentina e consequentemente afetar a adesão de cimentos endodônticos e microrganismos às paredes do canal radicular. Contudo, os efeitos de novos irrigantes e protocolos de irrigação ainda são desconhecidos. Os objetivos desta tese foram verificar as alterações nas propriedades de alguns irrigantes quando utilizados combinados em misturas, definir o tempo necessário para a remoção da camada de smear layer por um novo irrigante, determinar a capacidade de dissolução de matéria orgânica e os efeitos de algumas soluções e protocolos de irrigação nas propriedades físico-químicas de dentina e avaliar a adesão de microrganismos e cimento AH Plus à dentina após a submissão desta a diferentes sequências de irrigação. Em todos os experimentos com dentina as amostras utilizadas foram obtidas a partir de dentes bovinos. Nas análise realizadas nesta tese as seguintes soluções foram testadas isoladas e combinadas em diferentes protocolos de irrigação: solução salina (controle), hipoclorito de sódio (NaOCl), ácido etilenodiaminotetraacético trisódico (EDTAHNa3), ácido etilenodiaminotetracético tetrassódico alcalino (EDTANa4), clorexidina (CHX), ácido peracético (PAA) e ácido etidrônico (HEDP). O EDTAHNa3 e o EDTANa4 foram testados em relação aos seus efeitos sobre o teor de cloro livre do NaOCl. As soluções foram misturadas em uma proporção de 1:1 e a titulação iodométrica das misturas realizada em diferentes intervalos de tempo. O tempo necessário para a remoção da smear layer de amostras de dentina pela solução de EDTAHNa3 a 17% e diferentes concentrações de EDTANa4 isoladas e misturadas com NaOCl foi determinado com o auxílio do microscópio eletrônico de varredura (SEM). A capacidade de dissolução de matéria orgânica pelo NaOCl foi determinada pesando fragmentos de músculo bovino antes e depois da imersão em soluções de 1%, 2,5% e 5% de NaOCl em diferentes períodos de tempo. Além disso, os efeitos do EDTAHNa3, EDTANa4 e HEDP na dissolução de matéria orgânica pelo NaOCl foram avaliados. As alterações produzidas por todas as soluções isoladas e alguns protocolos de irrigação nos componentes orgânicos e inorgânicos da superfície da dentina foram analisadas pela técnica de reflexão total atenuada em espectroscopia no infravermelho por transformação de Fourier (ATRFTIR). Espectros de absorbância foram coletados da superfície da dentina antes e após a imersão das amostras nos irrigantes, e foram calculadas as razões das bandas de amida III/fosfato e carbonato/fosfato. Para quantificar a adesão da CHX à dentina mineralizada e à dentina desmineralizada por diferentes protocolos de irrigação, foram determinadas as áreas da banda associada a CHX com pico em 1492 cm−1 em espectros obtidos por ATR-FTIR. Os efeitos de diferentes protocolos de irrigação na rugosidade e molhabilidade da superfície da dentina foram medidos com um rugosímetro de bancada e a técnica de gota séssil, respectivamente. Para os ensaios de adesão de microrganismos, amostras foram preparadas e tratadas da mesma maneira e com os mesmos protocolos de irrigação utilizados nos testes de rugosidade e molhabilidade. Em seguida, Candida albicans e Enterococcus faecalis foram mantidos em contato com a dentina por 2 horas e as amostras foram analisadas no microscópio confocal de varredura laser (CLSM). Testes de push-out foram realizados para determinar o impacto de diferentes protocolos de irrigação na resistência de união à dentina do cimento AH Plus ao longo do tempo. Canais de dentes incisivos de bovinos foram instrumentados, irrigados e em seguida obturados utilizando apenas o cimento AH Plus. Metade das amostras foi submetida a avaliação de push-out 7 dias após a obturação e a outra metade após 20 meses. Os resultados dos experimentos mostraram que o EDTAHNa3 causou uma perda quase completa e imediata do cloro livre do NaOCl, enquanto o EDTANa4 promoveu um declínio lento e concentração dependente. A smear layer foi removida apenas por soluções descalcificantes e em cerca de 1 min pelo EDTAHNa3 a 17% e em 5 min pelo EDTANa4, tanto isolados ou misturados com o NaOCl. O aumento da concentração de NaOCl e do tempo de contato com os fragmentos de músculo bovino intensificou a dissolução da matéria orgânica. As misturas de NaOCl com EDTANa4 e HEDP foram capazes de dissolver as amostras de músculo ao longo do tempo, no entanto, o EDTAHNa3 afetou fortemente a capacidade de dissolução do NaOCl quando eles foram misturados. Os resultados dos experimentos com ATR-FTIR mostraram que o aumento da concentração do NaOCl intensificou a desproteinização do colágeno da dentina com redução da relação amida III/fosfato. Para o mesmo agente de descalcificação, quanto maior a concentração e o tempo de imersão, maior a remoção de fosfato, exposição da matriz de colágeno e consequentemente o aumento da proporção amida III/fosfato. O PAA causou os maiores aumentos na relação amida III/fosfato, seguido de EDTAHNa3, EDTANa4 e HEDP e esta ordem foi mantida nos protocolos em que o NaOCl foi usado antes dos agentes descalcificantes. O NaOCl necessitou aproximadamente 0,5 min para desproteinizar a matriz de colágeno exposta após a remoção de fosfato pelo EDTAHNa3 e o PAA. A relação carbonato/fosfato diminuiu após 30 s de imersão das amostras em soluções de NaOCl a 1%, 2,5% e 5%, sem mais alterações ao longo do tempo. O carbonato da dentina foi removido mais rápido do que o fosfato por todos os agentes descalcificantes empregados sozinhos e nos protocolos de irrigação em que o uso do NaOCl foi seguido pelo uso do EDTAHNa3, PAA e HEDP. Para os protocolos de irrigação que associam o NaOCl com soluções quelantes, o último irrigante utilizado definiu as proporções finais de amida II/fosfato e carbonato/fosfato da dentina. Para as análises da adesão da CHX em ATR-FTIR, os resultados mostraram que a adsorção deste irrigante à dentina foi potencializada quando agentes quelantes foram utilizados antes da CHX. Em relação aos experimentos de rugosidade da superfície, a solução salina, o NaOCl, o HEDP e a CHX não alteraram a rugosidade da dentina, mas o EDTAHNa3 e o PAA a aumentaram. A molhabilidade da superfície aumentou após o uso de todos os irrigantes, sendo que o HEDP causou os maiores aumentos. Nos ensaios de adesão dos microrganismos, a smear layer e o colágeno exposto pelos agentes quelantes favoreceram a adesão de E. faecalis. A adesão da C. albicans foi maior em superfícies com smear layer ou mais mineral. O uso de CHX como irrigante final reduziu a adesão de ambos os microrganismos. A molhabilidade não influenciou a adesão dos microrganismos, enquanto o aumento da rugosidade parece potencializar a adesão do E. faecalis. Os experimentos de resistência de união do AH Plus à dentina mostraram que a irrigação com NaOCl e a mistura de NaOCl + EDTANa4 produziram valores de resistência de união em 7 dias mais baixos em comparação com NaOCl + EDTAHNa3, NaOCl + EDTAHNa3 + NaOCl, NaOCl + EDTAHNa3 + CHX e a mistura de NaOCl + HEDP. Após 20 meses, os valores mais baixos foram obtidos nos grupos irrigados com NaOCl e NaOCl + EDTAHNa3. Os grupos de NaOCl + EDTAHNa3 + NaOCl, mistura de NaOCl + HEDP e mistura de NaOCl + EDTANa4 apresentaram valores de força de união por push-out em 20 meses semelhante aos valores em 7 dias. Foi possível concluir que as soluções de irrigação testadas neste estudo têm diferentes efeitos na matéria orgânica e inorgânica e elas podem afetar as ações umas das outras quando misturadas. Independentemente de serem utilizadas isoladas ou combinadas em protocolos de irrigação, os irrigantes causam modificações nas propriedades físico-químicas dentinárias que influenciam na adesão do cimento AH Plus a curto e longo prazo e na adesão de microrganismos à superfície em casos de recontaminação.(AU)

Variability of Listeria monocytogenes strains in biofilm formation on stainless steel and polystyrene materials and resistance to peracetic acid and quaternary ammonium compounds.

Listeria monocytogenes is a foodborne pathogen able to tolerate adverse conditions by forming biofilms or by deploying stress resistant mechanisms, and thus manages to survive for long periods in food processing plants. This study sought to investigate the correlation between biofilm forming ability, tolerance to disinfectants and cell surface characteristics of twelve L. monocytogenes strains. The following attributes were evaluated: (i) biofilm formation by crystal violet staining method on polystyrene, and by standard cell enumeration on stainless steel and polystyrene; (ii) hydrophobicity assay using solvents; (iii) minimum inhibitory concentration (MIC) and biofilm eradication concentration (BEC) of peracetic acid (PAA) and quaternary ammonium compounds (QACs), and (iv) resistance to sanitizers (PAA 2000ppm; QACs 500ppm) of biofilms on polystyrene and stainless steel. After 72h of incubation, higher biofilm levels were formed in TSB at 20°C, followed by TSB at 37°C (P=0.087) and diluted TSB 1/10 at both 20 (P=0.005) and 37°C (P=0.004). Cells grown at 30°C to the stationary phase had significant electron donating nature and a low hydrophobicity, while no significant correlation of cell surface properties to biofilm formation was observed. Strains differed in MICPAA and BECPAA by 24- and 15-fold, respectively, while a positive correlation between MICPAA and BECPAA was observed (P=0.02). The MICQACs was positively correlated with the biofilm-forming ability on stainless steel (P=0.03). Regarding the impact of surface type, higher biofilm populations were enumerated on polystyrene than on stainless steel, which were also more tolerant to disinfectants. Among all strains, the greatest biofilm producer was a persistent strain with significant tolerance to QACs. These results may contribute to better understanding of L. monocytogenes behavior and survival on food processing surfaces.

Delignification outperforms alkaline extraction for xylan fingerprinting of oil palm empty fruit bunch.

Enzyme hydrolysed (hemi-)celluloses from oil palm empty fruit bunches (EFBs) are a source for production of bio-fuels or chemicals. In this study, after either peracetic acid delignification or alkaline extraction, EFB hemicellulose structures were described, aided by xylanase hydrolysis. Delignification of EFB facilitated the hydrolysis of EFB-xylan by a pure endo-ß-1,4-xylanase. Up to 91% (w/w) of the non-extracted xylan in the delignified EFB was hydrolysed compared to less than 4% (w/w) of that in untreated EFB. Alkaline extraction of EFB, without prior delignification, yielded only 50% of the xylan. The xylan obtained was hydrolysed only for 40% by the endo-xylanase used. Hence, delignification alone outperformed alkaline extraction as pretreatment for enzymatic fingerprinting of EFB xylans. From the analysis of the oligosaccharide-fingerprint of the delignified endo-xylanase hydrolysed EFB xylan, the structure was proposed as acetylated 4-O-methylglucuronoarabinoxylan.

Effects of Peracetic Acid on the Corrosion Resistance of Commercially Pure Titanium (grade 4)

The aim of this study was to evaluate the corrosion resistance of pure titanium grade 4 (cp-Ti-4), subjected to disinfection with 0.2% and 2% peracetic acid during different immersion periods using anodic potentiodynamic polarization test in acid and neutral artificial saliva. Cylindrical samples of cp-Ti-4 (5 mm x 5 mm) were used to fabricate 24 working electrodes, which were mechanically polished and divided into eight groups (n=3) for disinfection in 2% and 0.2% peracetic acid for 30 and 120 min. After disinfection, anodic polarization was performed in artificial saliva with pH 4.8 and 6.8 to assess the electrochemical behavior of the electrodes. A conventional electrochemical cell, constituting a reference electrode, a platinum counter electrode, and the working electrode (cp-Ti specimens) were used with a scanning rate of 1 mV/s. Three curves were obtained for each working electrode, and corrosion was characterized by using scanning electron microscopy (SEM) and energy dispersive x-ray spectrometry (EDS). Data of corrosion potential (Ecorr) and passive current (Ipass) obtained by the polarization curves were analyzed statistically by Student's t-test (a=0.05). The statistical analysis showed no significant differences (p>0.05) between artificial saliva types at different concentrations and periods of disinfection, as well as between control and experimental groups. No surface changes were observed in all groups evaluated. In conclusion, disinfection with 0.2% and 2% peracetic acid concentrations did not cause corrosion in samples manufactured with cp-Ti-4.

Resumo O objetivo deste estudo foi avaliar a resistência à corrosão de titânio puro grau 4 (cp-Ti-4) submetido à desinfecção com ácido peracético a 0,2% e 2% durante diferentes períodos de imersão por meio do teste de polarização potenciodinâmica anódica em saliva artificial ácida e neutra. Amostras cilíndricas de cp-Ti-4 (5 mm x 5 mm) foram usadas para confeccionar 24 eletrodos de trabalho, os quais foram polidos mecanicamente e divididos em oito grupos (n=3) para desinfecção com ácido peracético a 2% e 0,2% por 30 e 120 minutos. Após a desinfecção, foi realizado o teste de a polarização anódica em saliva artificial com pH 4,8 e 6,8 para avaliar o comportamento eletroquímico dos eletrodos. Uma célula electroquímica convencional, composta por eletrodo de referência, contra-eletrodo de platina, e eletrodo de trabalho (amostras de cp-Ti) foi usada com taxa de varredura de 1 mV/s. Foram obtidas três curvas para cada eletrodo de trabalho e a corrosão foi analisada por microscopia eletrônica de varredura (MEV) e espectrometria de energia dispersiva de raios-X (EEDX). Os dados de potencial de corrosão (Ecorr) e corrente passiva (Ipass) obtidos com as curvas de polarização foram analisados estatisticamente pelo teste t de Student (=0,05). A análise estatística não mostrou diferenças significantes (p>0,05) entre os tipos de saliva artificial nas diferentes concentrações e períodos de desinfecção, bem como entre os grupos controle e experimental. Não foram observadas alterações nas superfícies das amostras de todos os grupos avaliados. Conclui-se que a desinfecção com ácido peracético nas concentrações de 0,2% e 2% não provocou corrosão nas amostras confeccionadas com cp-Ti-4.

Inactivation of Protein Tyrosine Phosphatases by Peracids Correlates with the Hydrocarbon Chain Length.

BACKGROUND/AIMS: Protein tyrosine phosphatases are crucial enzymes controlling numerous physiological and pathophysiological events and can be regulated by oxidation of the catalytic domain cysteine residue. Peracids are highly oxidizing compounds, and thus may induce inactivation of PTPs. The aim of the present study was to evaluate the inhibitory effect of peracids with different length of hydrocarbon chain on the activity of selected PTPs. METHODS: The enzymatic activity of human CD45, PTP1B, LAR, bacterial YopH was assayed under the cell-free conditions, and activity of cellular CD45 in human Jurkat cell lysates. The molecular docking and molecular dynamics were performed to evaluate the peracids binding to the CD45 active site. RESULTS: Here we demonstrate that peracids reduce enzymatic activity of recombinant CD45, PTP1B, LAR, YopH and cellular CD45. Our studies indicate that peracids are more potent inhibitors of CD45 than hydrogen peroxide (with an IC50 value equal to 25 nM for peroctanoic acid and 8 µM for hydrogen peroxide). The experimental data show that the inactivation caused by peracids is dependent on hydrocarbon chain length of peracids with maximum inhibitory effect of medium-chain peracids (C8-C12 acyl chain), which correlates with calculated binding affinities to the CD45 active site. CONCLUSION: Peracids are potent inhibitors of PTPs with the strongest inhibitory effect observed for medium-chain peracids.

Stability of antimicrobial activity of peracetic acid solutions used in the final disinfection process

The instruments and materials used in health establishments are frequently exposed to microorganism contamination, and chemical products are used before sterilization to reduce occupational infection. We evaluated the antimicrobial effectiveness, physical stability, and corrosiveness of two commercial formulations of peracetic acid on experimentally contaminated specimens. Stainless steel specimens were contaminated with Staphylococcus aureus, Escherichia coli, Candida albicans, blood, and saliva and then immersed in a ready peracetic acid solution: 2% Sekusept Aktiv (SA) or 0.25% Proxitane Alpha (PA), for different times. Then, washes of these instruments were plated in culture medium and colony-forming units counted. This procedure was repeated six times per day over 24 non-consecutive days. The corrosion capacity was assessed with the mass loss test, and the concentration of peracetic acid and pH of the solutions were measured with indicator tapes. Both SA and PA significantly eliminated microorganisms; however, the SA solution was stable for only 4 days, whereas PA remained stable throughout the experiment. The concentration of peracetic acid in the SA solutions decreased over time until the chemical was undetectable, although the pH remained at 5. The PA solution had a concentration of 500-400 mg/L and a pH of 2-3. Neither formulation induced corrosion and both reduced the number of microorganisms (p = 0.0001). However, the differences observed in the performance of each product highlight the necessity of establishing a protocol for optimizing the use of each one.

Effect of endodontic chelating solutions on the bond strength of endodontic sealers

The purpose of this in vitro study was to evaluate the effect of various chelating solutions on the radicular push-out bond strength of calcium silicate-based and resin-based root canal sealers. Root canals of freshly-extracted single-rooted teeth (n = 80) were instrumented by using rotary instruments. The specimens were randomly divided into 4 groups according to the chelating solutions being tested: (1) 17% ethylenediaminetetraacetic acid (EDTA); (2) 9% etidronic acid; (3) 1% peracetic acid (PAA); and (4) distilled water (control). In each group, the roots were further assigned into 2 subgroups according to the sealer used: (1) an epoxy resin-based sealer (AH Plus) and (2) a calcium silicate-based sealer (iRoot SP). Four 1 mm-thick sections were obtained from the coronal aspect of each root (n = 40 slices/group). Push-out bond strength test was performed at a crosshead speed of 1 mm/min., and the bond strength data were analyzed statistically with two-way analysis of variance (ANOVA) with Bonferroni’s post hoc test (p < 0.05). Failure modes were assessed quantitatively under a stereomicroscope. Irrespective of the irrigation regimens, iRoot SP exhibited significantly higher push-out bond strength values than AH Plus (p < 0.05). For both the sealers, the use of chelating solutions increased the bond strength, but to levels that were not significantly greater than their respective controls (p > 0.05). iRoot SP showed higher resistance to dislocation than AH Plus. Final irrigation with 17% EDTA, 9% Etidronic acid, and 1% PAA did not improve the bond strength of AH Plus and iRoot SP to radicular dentin.

Spectroscopic and kinetic investigation of the reactions of peroxyacetic acid with Burkholderia pseudomallei catalase-peroxidase, KatG.

Catalase-peroxidases or KatGs can utilize organic peroxyacids and peroxides instead of hydrogen peroxide to generate the high-valent ferryl-oxo intermediates involved in the catalase and peroxidase reactions. In the absence of peroxidatic one-electron donors, the ferryl intermediates generated with a low excess (10-fold) of peroxyacetic acid (PAA) slowly decay to the ferric resting state after several minutes, a reaction that is demonstrated in this work by both stopped-flow UV-vis absorption measurements and EPR spectroscopic characterization of Burkholderia pseudomallei KatG (BpKatG). EPR spectroscopy showed that the [Fe(IV)═O Trp330(•+)], [Fe(IV)═O Trp139(•)], and [Fe(IV)═O Trp153(•)] intermediates of the peroxidase-like cycle of BpKatG ( Colin, J. Wiseman, B. Switala, J. Loewen, P. C. Ivancich, A. ( 2009 ) J. Am. Chem. Soc. 131 , 8557 - 8563 ), formed with a low excess of PAA at low temperature, are also generated with a high excess (1000-fold) of PAA at room temperature. However, under high excess conditions, there is a rapid conversion to a persistent [Fe(IV)═O] intermediate. Analysis of tryptic peptides of BpKatG by mass spectrometry before and after treatment with PAA showed that specific tryptophan (including W330, W139, and W153), methionine (including Met264 of the M-Y-W adduct), and cysteine residues are either modified with one, two, or three oxygen atoms or could not be identified in the spectrum because of other undetermined modifications. It was concluded that these oxidized residues were the source of electrons used to reduce the excess of PAA to acetic acid and return the enzyme to the ferric state. Treatment of BpKatG with PAA also caused a loss of catalase activity towards certain substrates, consistent with oxidative disruption of the M-Y-W adduct, and a loss of peroxidase activity, consistent with accumulation of the [Fe(IV)═O] intermediate and the oxidative modification of the W330, W139, and W153. PAA, but not H2O2 or tert-butyl hydroperoxide, also caused subunit cross-linking.

Direct and simultaneous determination of trace-level carbon tetrachloride, peroxyacetyl nitrate, and peroxypropionyl nitrate using gas chromatography-electron capture detection.

Gas chromatography equipped with electron capture detector (GC-ECD) has been widely used for detecting atmospheric peroxyacetyl nitrate (PAN) and peroxypropionyl nitrate (PPN). However, to the best of our knowledge, only a few capillary columns have been adopted for separation to achieve the direct and simultaneous analysis of the two atmospheric pollutants. This paper demonstrates a novel method for directly and simultaneously measuring atmospheric carbon tetrachloride (CCl(4)), PAN, and PPN using GC-ECD with a DB-1 separation column. The responses of the GC-ECD to PAN, PPN, and CCl(4) were individually calibrated by using gas mixtures prepared via volatilization of synthesized solutions of PAN and PPN or high-purity CCl(4) reagent in a Teflon Bag. The concentrations of PAN and PPN in the synthesized solutions were quantified by ion chromatography (IC). Further calibration of the GC-ECD for PAN was conducted by in situ photochemical formation of gaseous PAN which was quantified by a NO(x) analyzer. The two calibration methods agreed well with each other, and the overall uncertainties for measuring atmospheric PAN were estimated to be ± 13% and ± 15% based on the calibrations of IC and NO(x), respectively. The detection limits (three times the signal to noise ratio) for PAN, PPN, and CCl(4) were estimated to be 22, 36, and 5 pptv (parts per trillion by volume), respectively. The atmospheric concentrations of these compounds were measured for several days in August in Beijing, and the values obtained in this study were found to be in good agreement with the data reported in the literature for Beijing using other GC-ECD methods.

Consequences of ineffective decellularization of biologic scaffolds on the host response.

Biologic scaffold materials composed of extracellular matrix (ECM) are routinely used for a variety of clinical applications. Despite known variations in tissue remodeling outcomes, quantitative criteria by which decellularization can be assessed were only recently described and as a result, the amount of retained cellular material varies widely among commercial products. The objective of this study was to evaluate the consequences of ineffective decellularization on the host response. Three different methods of decellularization were used to decellularize porcine small intestinal ECM (SIS-ECM). The amount of cell remnants was quantified by the amount and fragmentation of DNA within the scaffold materials. The M1/M2 phenotypic polarization profile of macrophages, activated in response to these ECM scaffolds, was assessed in vitro and in vivo using a rodent model of body wall repair. The results show that, in vitro, more aggressive decellularization is associated with a shift in macrophage phenotype predominance from M1 to M2. While this shift was not quantitatively apparent in vivo, notable differences were found in the distribution of M1 vs. M2 macrophages within the various scaffolds. A clear association between macrophage phenotype and remodeling outcome exists and effective decellularization remains an important component in the processing of ECM-based scaffolds.

Surface detail reproduction and dimensional accuracy of stone models: influence of disinfectant solutions and alginate impression materials

This study compared the surface detail reproduction and dimensional accuracy of stone models obtained from molds disinfected with 2% sodium hypochlorite, 2% chlorhexidine digluconate or 0.2% peracetic acid to models produced using molds which were not disinfected, with 3 alginate materials (Cavex ColorChange, Hydrogum 5 and Jeltrate Plus). The molds were prepared over matrix containing 20-, 50-, and 75-µm lines, performed under pressure with perforated metal tray. The molds were removed following gelation and either disinfected (using one of the solutions by spraying followed by storage in closed jars for 15 min) or not disinfected. The samples were divided into 12 groups (n=5). Molds were filled with dental gypsum Durone IV and 1 h after the start of the stone mixing the models were separated from the tray. Surface detail reproduction and dimensional accuracy were evaluated using optical microscopy on the 50-µm line with 25 mm in length, in accordance with the ISO 1563 standard. The dimensional accuracy results (%) were subjected to ANOVA. The 50 µm-line was completely reproduced by all alginate impression materials regardless of the disinfection procedure. There was no statistically significant difference in the mean values of dimensional accuracy in combinations between disinfectant procedure and alginate impression material (p=0.2130) or for independent factors. The disinfectant solutions and alginate materials used in this study are no factors of choice regarding the surface detail reproduction and dimensional accuracy of stone models.

Este estudo comparou a reprodução de detalhes da superfície e alteração dimensional de modelos de gesso obtidos a partir de moldes desinfetados com hipoclorito de sódio 2%, digluconato de clorexidina 2%, ou ácido peracético 0,2% a modelos confeccionados utilizando moldes que não foram desinfetados com três alginatos (Cavex ColorChange, Hydrogum 5, Jeltrate Plus). Os moldes foram preparados sobre matriz contendo linhas de 20, 50 e 75 µm realizado sob pressão com moldeira de metal perfurada. Os moldes foram removidos após a geleificação e desinfetados (utilizando uma das soluções por pulverização, armazenados em frascos fechados durante 15 min) ou não desinfetados. Assim, as amostras foram divididas em 12 grupos (n=5). Os moldes foram preenchidos com gesso dental Durone IV e uma hora após a manipulação do gesso os modelos foram separados da moldeira. A reprodução de detalhes da superfície e a precisão dimensional foram avaliadas usando microscopia óptica na linha 50 µm com 25 mm de comprimento, de acordo com a norma ISO 1563. Os resultados de precisão dimensional (%) foram submetidos à ANOVA. A linha de 50 µm foi completamente reproduzida por todos os alginatos, independentemente do processo de desinfecção. Não houve diferença estatisticamente significativa nos valores médios de precisão dimensional nas combinações entre procedimento de desinfecção e alginato (p=0,2130), ou para fatores independentes. Soluções desinfetantes e alginatos utilizados neste estudo não são fatores de escolha em relação à reprodução de detalhes da superfície e alteração dimensional de modelos de gesso.

Hypochlorous and peracetic acid induced oxidation of dairy proteins.

Hypochlorous and peracetic acids, both known disinfectants in the food industry, were compared for their oxidative capacity toward dairy proteins. Whey proteins and caseins were oxidized under well controlled conditions at pH 8 as a function of the sanitizing concentration. Different markers for protein oxidation were monitored. The results established that the protein carbonyl content was a rather unspecific marker for protein oxidation, which did not allow one to differentiate the oxidant used especially at the lower concentrations. Cysteine, tryptophan, and methionine were proven to be the most vulnerable amino acids for degradation upon hypochlorous and peracetic acid treatment, while tyrosine was only prone to degradation in the presence of hypochlorous acid. Hypochlorous acid induced oxidation gave rise to protein aggregation, while during peracetic acid induced oxidation, no high molecular weight aggregates were observed. Protein aggregation upon hypochlorous acid oxidation could primarily be linked to tryptophan and tyrosine degradation.

Oxidation of proteins adsorbed on hemodialysis membranes and model materials.

The cleaning of cellulosic hemodialysis membrane Cuprophan and model materials (glass; polystyrene and polypropylene, as such and surface-oxidized), conditioned by adsorption of blood plasma proteins (HSA, fibrinogen, IgG) was investigated in vitro. Sodium hypochlorite (NaClO) and Renalin, a product containing hydrogen peroxide and peroxyacetic acid, were used as cleaning reagents. X-ray photoelectron spectroscopy and the use of radiolabeled fibrinogen demonstrated the presence of varying amounts of a polypeptidic residue, with sulfur brought to a high oxidation stage (sulfonate-like). The trends were the same for the three proteins regarding the effectiveness of the oxidizer and the influence of the surface properties. NaClO was much more effective than Renalin to remove the adsorbed proteins. The proteins adsorbed on Cuprophan were more sensitive to the oxidizers, when compared with proteins adsorbed on other materials. This may be due to both the lower protein-surface affinity, as indicated by radiochemical measurements, and the sensitivity of the material itself to the oxidizer, as revealed by weight loss measurements. These results support the attribution of hemocompatibility improvement after regeneration of Cuprophan with Renalin to the masking of the activating surface by a residue from previously adsorbed proteins.

Studies on the epoxidation of mahua oil (Madhumica indica) by hydrogen peroxide.

Mahua oil (Madhumica indica) with an iodine value of 88 g/100 g, and containing 46% oleic acid and 12.74% linoleic acid, was epoxidised in situ with hydrogen peroxide as oxygen donor and glacial acetic acid as active oxygen carrier in presence of catalytic amount of an inorganic acid. Catalytic loading of two different acids, i.e., H2SO4 and HNO3 were studied, and H2SO4 was found to be more effective in terms of conversion to oxirane. The effects of various parameters, such as temperature, hydrogen peroxide-to-ethylenic unsaturation mole ratio, acetic acid-to-ethylenic unsaturation mole ratio, and stirring speed, on the epoxidation rate as well as on the oxirane ring stability and iodine value of the epoxidised mahua oil (EMO) were studied. The effects of these parameters on the conversion to the epoxidised oil were studied and the optimum conditions were established. The rate constant and activation energy for epoxidation of MO was found to be of the order of 10(-6) l mol(-1) s(-1) and 14.5 kcal mol(-1), respectively. Thermodynamic parameters such as enthalpy, entropy and free energy of activation were found to be of 13.8 kcal mol(-1), -51.1 cal mol(-1) K(-1) and 30.6 kcal mol(-1), respectively. Relative conversion data showed that it was possible to develop epoxides from locally available natural renewable resources such as mahua oil.