RESUMO

Attrition-enhanced chiral symmetry breaking in crystals, known as Viedma deracemization, is a promising method for converting racemic solid phases into enantiomerically pure ones under non-equilibrium conditions. However, many aspects of this process remain unclear. In this study, we present a new investigation into Viedma deracemization using a comprehensive kinetic rate equation continuous model based on classical primary nucleation theory, crystal growth, and Ostwald ripening. Our approach employs a fully microreversible kinetic scheme with a size-dependent solubility following the Gibbs-Thomson rule. To validate our model, we use data from a real NaClO3 deracemization experiment. After parametrization, the model shows spontaneous mirror symmetry breaking (SMSB) under grinding. Additionally, we identify a bifurcation scenario with a lower and upper limit of the grinding intensity that leads to deracemization, including a minimum deracemization time within this window. Furthermore, this model uncovers that SMSB is caused by multiple instances of concealed high-order autocatalysis. Our findings provide new insights into attrition-enhanced deracemization and its potential applications in chiral molecule synthesis and understanding biological homochirality.

RESUMO

Perchlorate is a widespread drinking water contaminant with regulatory standards ranging from 2 to 18 µg/L. The hydrogen-based membrane-biofilm reactor (MBfR) can effectively reduce perchlorate, but it is challenging to achieve low-µg/L levels. We explored chlorate addition to increase the abundance of perchlorate-reducing bacteria (PRB) and improve removals. MBfR reactors were operated with and without chlorate addition. Results show that chlorate doubled the abundance of putative PRB (e.g., Rhodocyclales) and improved perchlorate reduction to 23 ± 17 µg/L, compared to 53 ± 37 µg/L in the control. Sulfate reduction was substantially inhibited during chlorate addition, but quickly recovered once suspended. Our results suggest that chlorate addition can enhance perchlorate reduction by providing a selective pressure for PRB. It also decreases net sulfate reduction. KEY POINTS: • Chlorate increased the abundance of perchlorate-reducing bacteria • Chlorate addition improved perchlorate removal • Chlorate appeared to suppress sulfate reduction.

Assuntos

Cloratos , Percloratos , Bactérias , Biofilmes , Hidrogênio , Oxirredução , Sulfatos

RESUMO

Contamination of natural water (NW) by emerging contaminants has been widely pointed out as one of the main challenges to ensure high-quality drinking water. Thus, the effectiveness of a solar-driven free chlorine advanced oxidation process simultaneously investigating the elimination of six organic microcontaminants (OMCs) and three bacteria from NW at a pilot-scale was evaluated in this study. Firstly, the solar/free chlorine process was studied at lab-scale using a solar simulator to evaluate the effect of free chlorine concentration (0.5-10 mg L-1) on OMC degradation and generation of toxic oxyanions (e.g., ClO3- ions). Thus, the best free chlorine concentration observed was applied for the simultaneous removal of OMCs and pathogens under natural solar light at pilot scale. At lab-scale, the solar/free chlorine (2.5 mg L-1) process achieved 80% of total degradation in 5 min (1.4 kJ L-1 of accumulative UV energy) with an oxidant consumption of 0.3 mg L-1 and without ClO3- generation. Similar results were attained under natural solar irradiation at a pilot-scale. For all bacteria strains, the legally required detection limit (DL = 1 CFU 100 mL-1) for reclaimed water reuse was attained in a short contact time. Still, more importantly, the solar/free chlorine (2.5 mg L-1) process effectively avoided the possible bacterial regrowth in the post-treated sample after six days. Finally, the combination of free chlorine with solar irradiation provided a simple and energy-efficient process for OMC and bacteria removal in NW at a pilot-scale.

Assuntos

Cloro , Água

RESUMO

Natural chlorate (ClO3-) is widely distributed in terrestrial and extraterrestrial environments. To improve understanding of the origins and distribution of ClO3-, we developed and tested methods to determine the multi-dimensional isotopic compositions (δ18O, Δ17O, δ37Cl, 36Cl/Cl) of ClO3- and then applied the methods to samples of natural nitrate-rich caliche-type salt deposits in the Atacama Desert, Chile, and Death Valley, USA. Tests with reagents and artificial mixed samples indicate stable-isotope ratios were minimally affected by the purification processes. Chlorate extracted from Atacama samples had δ18O = +7.0 to +11.1‰, Δ17O = +5.7 to +6.4‰, δ37Cl = -1.4 to +1.3‰, and 36Cl/Cl = 48 × 10-15 to 104 × 10-15. Chlorate from Death Valley samples had δ18O = -6.9 to +1.6‰, Δ17O = +0.4 to +2.6‰, δ37Cl = +0.8 to +1.0‰, and 36Cl/Cl = 14 × 10-15 to 44 × 10-15. Positive Δ17O values of natural ClO3- indicate that its production involved reaction with O3, while its Cl isotopic composition is consistent with a tropospheric or near-surface source of Cl. The Δ17O and δ18O values of natural ClO3- are positively correlated, as are those of ClO4- and NO3- from the same localities, possibly indicating variation in the relative contributions of O3 as a source of O in the formation of the oxyanions. Additional isotopic analyses of ClO3- could provide stronger constraints on its production mechanisms and/or post-formational alterations, with applications for environmental forensics, global biogeochemical cycling of Cl, and the origins of oxyanions detected on Mars.

Assuntos

Cloratos , Nitratos , Chile , Nitratos/análise

RESUMO

Chlorate has been described as an emerging pollutant that compromises water sources. In this study, bioelectrochemical reactors (BERs) using Dechloromonas agitata CKB, were evaluated as a sustainable alternative for chlorate removal. BERs were operated under flow-recirculation and batch modes with an applied cell-voltage of 0.44 V over a resistance of 1 kΩ. Results show chlorate removal up to 607.288 mg/L. After 115 days, scanning electron microscopy showed biofilm development over the electrodes, and electrochemical impedance spectroscopy confirmed the biocatalytic effect of CKB. The theoretical chlorate bioreduction potential (ε° = 0.792 V) was proven, and a kinetic study indicated that 6 electrons were involved in the reduction mechanism. Finally, a hypothetical bioelectrochemical mechanism for chlorate reduction in a BER was proposed. This research expands upon current knowledge of novel electrochemically active microorganisms and widens the scope of BER applications for chlorate removal.

Assuntos

Cloratos , Elétrons , Betaproteobacteria , Eletrodos , Oxirredução

RESUMO

The influence of sodium chlorate (SC), ferulic acid (FA), and essential oils (EO) was examined on the survivability of two porcine diarrhetic enterotoxigenic Escherichia coli (ETEC) strains (F18 and K88) and populations of porcine fecal bacteria. Fecal bacterial populations were examined by denaturing gradient gel electrophoresis (DGGE) and identification by 16S gene sequencing. The treatments were control (no additives), 10 mM SC, 2.5 mg FA /mL, a 1.5% vol/vol solution of an EO mixture as well as mixtures of EO + SC, EO + FA, and FA + SC at each of the aforementioned concentrations. EO were a commercial blend of oregano oil and cinnamon oil with water and citric acid. Freshly collected porcine feces in half-strength Mueller Hinton broth was inoculated with E. coli F18 (Trial 1) or E. coli K88 (Trial 2). The fecal-E. coli suspensions were transferred to crimp top tubes preloaded with the treatment compounds. Quantitative enumeration was at 0, 6, and 24 h. All treatments reduced (P < 0.05) the counts of E. coli F18 at 6 and 24 h. With the exception of similarity coefficient (%SC), all the other treatments reduced (P < 0.05) the K88 counts at 24 h. The most effective treatments to reduce the F18 and K88 CFU numbers were those containing EO. Results of DGGE revealed that Dice percentage similarity coefficients (%SC) of bacterial profiles among treatment groups varied from 81.3% to 100%SC. The results of gene sequencing showed that, except for SC at 24 h, all the other treatments reduced the counts of the family Enterobacteriaceae, while Lactobacillaceae and Ruminococcaceae increased and Clostridiaceae decreased in all treatments. In conclusion, all treatments were effective in reducing the ETEC, but EO mixture was the most effective. The porcine microbial communities may be influenced by the studied treatments.

Assuntos

Bactérias/efeitos dos fármacos , Cloratos/farmacologia , Ácidos Cumáricos/farmacologia , Fezes/microbiologia , Óleos Voláteis/farmacologia , Suínos , Animais , Bactérias/classificação , Cinnamomum zeylanicum , Microbiota , Origanum , Óleos de Plantas/farmacologia

RESUMO

Potassium chlorate is a powerful oxidizer salt that, when mixed with a fuel source, has been used as a homemade explosive (HME). As an inorganic salt, potassium chlorate has no appreciable vapor pressure under ambient conditions and requires temperatures exceeding 300 °C for decomposition. However, detection of potassium chlorate by trained canines has been demonstrated, implying that it exudes a vapor signature with one or more volatile compounds, although no such species have been confirmed to date. In this work, solid-phase microextraction with a novel on-fiber derivatization reaction was used to interrogate the headspace of several potassium chlorate samples of varying purity, as well as that of related chlorinated salts and explosive mixtures. This analysis showed the presence of few volatile species in the headspace of potassium chlorate other than vaporous chlorine, detected as the derivatized product, chloro-2-propanol. Relative amounts of chloro-2-propanol could be compared between potassium chlorate variants, and could be detected in the presence of other volatile species associated with the fuels.

RESUMO

Androgens induce rat prostate induction from the urogenital sinus epithelium at embryonic day 17.5. Subsequent morphogenesis, including epithelial cord growth, branching, and canalization, results from concerted paracrine interactions with the stroma. A significant number of paracrine factors bind heparan sulfate (HS). We hypothesized that interfering with overall sulfation could disrupt the signaling mediated by HS-binding factors and that the undersulfated environment would allow investigation of individual exogenous morphogens. First, we investigated whether acinar morphogenesis involved HS-proteoglycan expression and found that syndecans 1 and 3 were upregulated in RWPE1 cells in the transition from two- to three-dimensional (3D) Matrigel, capable of promoting spheroid formation. We then investigated whether sodium chlorate, a general sulfation inhibitor, interfered with spheroid formation by RWPE1 cells and acinar morphogenesis in ex vivo ventral prostate (VP) organ culture. As expected, treatment with sodium chlorate inhibited spheroid formation by RWPE1 cells in 3D culture. Chlorate also inhibited ex vivo VP epithelial branching and canalization, resulting in long branchless epithelial structures. We then investigated whether the HS-binding factors, FGF10, TGFß1, and SDF1, could reverse the effect of sodium chlorate. Although no effect was seen in the FGF10- and TGFß1-treated samples, SDF1 promoted epithelial canalization in the low sulfated environment, highlighting its specific role in lumen formation. Altogether, the results show that sodium chlorate perturbed prostate morphogenesis and allowed investigation of factors involved in branching and/or canalization, implicating SDF1 signaling in epithelial canalization.

Assuntos

Quimiocina CXCL12/metabolismo , Células Epiteliais/metabolismo , Morfogênese/fisiologia , Próstata/metabolismo , Próstata/fisiologia , Animais , Linhagem Celular , Colágeno/metabolismo , Combinação de Medicamentos , Células Epiteliais/fisiologia , Epitélio/metabolismo , Epitélio/fisiologia , Fator 10 de Crescimento de Fibroblastos/metabolismo , Regulação da Expressão Gênica no Desenvolvimento/fisiologia , Proteoglicanas de Heparan Sulfato/metabolismo , Heparitina Sulfato/metabolismo , Humanos , Laminina/metabolismo , Masculino , Técnicas de Cultura de Órgãos/métodos , Organogênese/fisiologia , Proteoglicanas/metabolismo , Ratos , Ratos Wistar , Transdução de Sinais/fisiologia , Fator de Crescimento Transformador beta1/metabolismo

RESUMO

ETHNOPHARMACOLOGICAL RELEVANCE: Petiveria alliacea L. (Phytolaccaceae) is a perennial shrub native to the Amazon region and other tropical areas such as Central America and the Caribbean. Popularly known as mucuracaá, P. alliacea is used in the folk medicine for a broad variety of therapeutic purpose and also in religious ceremonies by slaves as a sedative, which highlights its properties on the Central Nervous System (CNS). AIM OF THE STUDY: The present study evaluated the effects of the P. alliacea leaves hydroalcoholic extract (PaLHE) on the cognition, including learning and memory. MATERIAL AND METHODS: Three-month-old male and female Wistar rats (n=8-10/group) were administered with 900mg/kg of PaLHE. The behavioral assays included Step-down Inhibitory avoidance (IA) and Morris Water Maze (MWM) tests. RESULTS: Consistent with our previous reports, P. alliacea improved long-term memory. It also exerted previously unreported effects on short-term and spatial memory improvement, and increased learning in the tasks. CONCLUSIONS: The P. alliacea extract elicited mnemonic effects and improved the learning process in both IA and MWM tests. Our results highlight the importance of further studies in order to identify the active substances of the PaLHE and investigate the pharmacological mechanisms that underlies the reported effects.

Assuntos

Aprendizagem da Esquiva/efeitos dos fármacos , Aprendizagem em Labirinto/efeitos dos fármacos , Phytolaccaceae , Extratos Vegetais/farmacologia , Animais , Aprendizagem da Esquiva/fisiologia , Feminino , Masculino , Aprendizagem em Labirinto/fisiologia , Extratos Vegetais/isolamento & purificação , Folhas de Planta , Ratos , Ratos Wistar

RESUMO

Advances in technologies to enable water reuse in industry have been the objective of many research efforts, mainly due to the need to reduce the use of natural resources and due to factors related to their availability. This paper evaluates the crystallization of salts from petrochemical saline waste to achieve zero water discharge by the recovery of water and dissolved salts as a solid mixture. In line with process symbiosis, the recovered water should be suitable for use as cooling water in heat exchangers. Vacuum evaporative crystallization, at the batch scale, was used to remove the salts present in the concentrated stream from reverse electrodialysis of pretreated wastewater by a biological process. The partition of organic compounds in the feed solution between the condensate and the mother liquor was obtained from measurements of the total organic carbon and total nitrogen in the solutions. The solid phases formed experimentally are compared with those predicted by chemical modelling by PHREEQC. The recovered water presented almost 50 times less total dissolved solids than the feed stream (from 2100 to 44 mg/L). Calcium sulphate hydrate, calcium sulphate and sodium chloride were the majority crystalline phases formed, in accordance with the modelling by PHREEQC.

Assuntos

Conservação de Recursos Energéticos/métodos , Diálise/instrumentação , Eletroquímica/instrumentação , Sais/isolamento & purificação , Purificação da Água/instrumentação , Água/química , Diálise/métodos , Eletroquímica/métodos , Desenho de Equipamento , Análise de Falha de Equipamento , Sais/química , Purificação da Água/métodos

RESUMO

We aimed her mainly to evaluate the contribution of newly employed bromate selection system, in obtaining new Aspergillus niger nitrate/nitrite assimilation defective mutants, through Ultraviolet treatment (UV), 1, 2, 7, 8-Diepoxyoctane (DEO), phenols mixture (Phx)) and spontaneous treatments. The newly employed bromate selection system was able to specify only two putative novel mutant types designated brn (bromate resistant but chlorate sensitive (RS) strain, which may specify nitrite specific transporter) and cbrn mutants (bromate resistant and chlorate resistant strain, which may specify nitrate/nitrite bispecific system). The most relevant and innovative findings of this research work involve the isolation of the RR (cbrn) mutants (a new type of nitrate assimilation defective mutants), that could be useful for studying the bispecific nitrate /nitrite transporter system. The majority of obtained bromate resistant mutants (93.3 percent of the total mutants obtained by all treatments) were of the brn type, whereas the remaining percentage (6.76 percent) was given to cbrn strains. The highest percentages of brn mutant strains (48 percent and 58.6 percent of the total RS strains) were obtained with UA after spontaneous and Phx treatment, whereas Trp has generated 29 percent and 42 percent of RS strains after UV and DEO treatments, respectively. The obtained ratios of cbrn mutants were higher (i.e. in the range of 8.4 percent-11.64 percent of the total bromate mutants) with chemical treatments, especially when U.A or Pro was serving as sole N-sources at 25ºC rather than 37ºC. A 69 percent mutants' yield of Aspergillus niger mutant strains representing nine gene loci (niaD, cnx-6 loci, nrt and nirA) were selected on the bases of chlorate (600 mM) toxicity. All chlorate resistant mutants were completely sensitive to bromate (250 mM). The niaD mutants showed the highest percentage (73.97 percent) of chlorate resistant mutants obtained with all tested treatments. The UV treatment has generated the highest ratio (86.9 percent) of niaD mutants, whereas, the least (61 percent) was obtained with Phx treatment. The highest percentage of cnx mutants (32 percent) was obtained with Phx treatment. The DEO treatment as compared to other tested treatments was the best to use for obtaining the highest ratios of either nrt (13.8 percent) mutants or nirA (1.9 percent) mutants.

RESUMO

We aimed her mainly to evaluate the contribution of newly employed bromate selection system, in obtaining new Aspergillus niger nitrate/nitrite assimilation defective mutants, through Ultraviolet treatment (UV), 1, 2, 7, 8-Diepoxyoctane (DEO), phenols mixture (Phx)) and spontaneous treatments. The newly employed bromate selection system was able to specify only two putative novel mutant types designated brn (bromate resistant but chlorate sensitive (RS) strain, which may specify nitrite specific transporter) and cbrn mutants (bromate resistant and chlorate resistant strain, which may specify nitrate/nitrite bispecific system). The most relevant and innovative findings of this research work involve the isolation of the RR ( cbrn) mutants (a new type of nitrate assimilation defective mutants), that could be useful for studying the bispecific nitrate /nitrite transporter system. The majority of obtained bromate resistant mutants (93.3% of the total mutants obtained by all treatments) were of the brn type, whereas the remaining percentage (6.76%) was given to cbrn strains. The highest percentages of brn mutant strains (48% and 58.6% of the total RS strains) were obtained with UA after spontaneous and Phx treatment, whereas Trp has generated 29% and 42% of RS strains after UV and DEO treatments, respectively. The obtained ratios of cbrn mutants were higher (i.e. in the range of 8.4%-11.64% of the total bromate mutants) with chemical treatments, especially when U.A or Pro was serving as sole N-sources at 25ºC rather than 37ºC. A 69% mutants` yield of Aspergillus niger mutant strains representing nine gene loci ( niaD, cnx-6 loci , nrt and nirA) were selected on the bases of chlorate (600 mM) toxicity. All chlorate resistant mutants were completely sensitive to bromate (250 mM). The niaD mutants showed the highest percentage (73.97%) of chlorate resistant mutants obtained with all tested treatments. The UV treatment has generated the highest ratio (86.9%) of niaD mutants, whereas, the least (61%) was obtained with Phx treatment. The highest percentage of cnx mutants (32%) was obtained with Phx treatment. The DEO treatment as compared to other tested treatments was the best to use for obtaining the highest ratios of either nrt (13.8%) mutants or nirA (1.9%) mutants.

RESUMO

We aimed her mainly to evaluate the contribution of newly employed bromate selection system, in obtaining new Aspergillus niger nitrate/nitrite assimilation defective mutants, through Ultraviolet treatment (UV), 1, 2, 7, 8-Diepoxyoctane (DEO), phenols mixture (Phx)) and spontaneous treatments. The newly employed bromate selection system was able to specify only two putative novel mutant types designated brn (bromate resistant but chlorate sensitive (RS) strain, which may specify nitrite specific transporter) and cbrn mutants (bromate resistant and chlorate resistant strain, which may specify nitrate/nitrite bispecific system). The most relevant and innovative findings of this research work involve the isolation of the RR (cbrn) mutants (a new type of nitrate assimilation defective mutants), that could be useful for studying the bispecific nitrate /nitrite transporter system. The majority of obtained bromate resistant mutants (93.3% of the total mutants obtained by all treatments) were of the brn type, whereas the remaining percentage (6.76%) was given to cbrn strains. The highest percentages of brn mutant strains (48% and 58.6% of the total RS strains) were obtained with UA after spontaneous and Phx treatment, whereas Trp has generated 29% and 42% of RS strains after UV and DEO treatments, respectively. The obtained ratios of cbrn mutants were higher (i.e. in the range of 8.4%-11.64% of the total bromate mutants) with chemical treatments, especially when U.A or Pro was serving as sole N-sources at 25ºC rather than 37ºC. A 69% mutants' yield of Aspergillus niger mutant strains representing nine gene loci (niaD, cnx-6 loci, nrt and nirA) were selected on the bases of chlorate (600 mM) toxicity. All chlorate resistant mutants were completely sensitive to bromate (250 mM). The niaD mutants showed the highest percentage (73.97%) of chlorate resistant mutants obtained with all tested treatments. The UV treatment has generated the highest ratio (86.9%) of niaD mutants, whereas, the least (61%) was obtained with Phx treatment. The highest percentage of cnx mutants (32%) was obtained with Phx treatment. The DEO treatment as compared to other tested treatments was the best to use for obtaining the highest ratios of either nrt (13.8%) mutants or nirA (1.9%) mutants.