5-AIQ inhibits H2O2-induced apoptosis through reactive oxygen species scavenging and Akt/GSK-3β signaling pathway in H9c2 cardiomyocytes.

PubMed

Park, Eun-Seok; Kang, Jun Chul; Kang, Do-Hyun; Jang, Yong Chang; Yi, Kyu Yang; Chung, Hun-Jong; Park, Jong Seok; Kim, Bokyung; Feng, Zhong-Ping; Shin, Hwa-Sup

2013-04-01

Poly(adenosine 5'-diphosphate ribose) polymerase (PARP) is a nuclear enzyme activated by DNA strand breaks and plays an important role in the tissue injury associated with ischemia and reperfusion. The aim of the present study was to investigate the protective effect of 5-aminoisoquinolinone (5-AIQ), a PARP inhibitor, against oxidative stress-induced apoptosis in H9c2 cardiomyocytes. 5-AIQ pretreatment significantly protected against H2O2-induced cell death, as determined by the XTT assay, cell counting, terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling assay, and Western blot analysis of apoptosis-related proteins such as caspase-3, Bax, and Bcl-2. Upregulation of antioxidant enzymes such as manganese superoxide dismutase and catalase accompanied the protective effect of 5-AIQ on H2O2-induced cell death. Our data also showed that 5-AIQ pretreatment protected H9c2 cells from H2O2-induced apoptosis by triggering activation of Akt and glycogen synthase kinase-3β (GSK-3β), and that the protective effect of 5-AIQ was diminished by the PI3K inhibitor LY294002 at a concentration that effectively abolished 5-AIQ-induced Akt and GSK-3β activation. In addition, inhibiting the Akt/GSK-3β pathway by LY294002 significantly attenuated the 5-AIQ-mediated decrease in cleaved caspase-3 and Bax activation and H9c2 cell apoptosis induction. Taken together, these results demonstrate that 5-AIQ prevents H2O2-induced apoptosis in H9c2 cells by reducing intracellular reactive oxygen species production, regulating apoptosis-related proteins, and activating the Akt/GSK-3β pathway. Copyright © 2013 Elsevier Inc. All rights reserved.

Antioxidative potential of Duranta repens (Linn.) fruits against H2O2 induced cell death in vitro.

PubMed

Khan, Md Asaduzzaman; Rahman, Mohammad Mijanur; Tania, Mousumi; Shoshee, Nusrat Fatima; Xu, Ai-hua; Chen, Han-chun

2013-01-01

The effects of Duranta repens fruits were investigated on H2O2 induced oxidative cell death to evaluate its antioxidative potential in vitro. HEK293T cells were treated with different concentrations [0-1000 µg/ ml] of ethanol extract (E-Ex) and methanol extract (M-Ex) of D. repens for 24h, and then treated with 100 µM H2O2 for 24h. Cell viability, antioxidant parameters of cells, and antioxidant constituents of the extracts were determined. Treatment with limited dose of E-Ex or M-Ex increased the survival rate of H2O2-treated HEK293T cells, however the extra-high dose showed growth inhibitory effect. Treatment with E-Ex or M-Ex protected cellular lipid per-oxidation. In vitro analyses showed the 2,2-diphenyl-1-picrylhydrazyl and H2O2 scavenging activities as well as reducing potential of the extracts. We report here that the limited dose of E-Ex and M-Ex possess antioxidative potential, which can protect H2O2-induced oxidative cell damage.

Silymarin versus Silibinin: Differential Antioxidant and Neuroprotective Effects against H2O2-induced Oxidative Stress in PC12 Cells.

PubMed

Jiang, Hui-Hui; Yan, Fa-Shun; Shen, Liang; Ji, Hong-Fang

2016-05-01

The present study assessed comparatively the antioxidant activities of silymarin and its major active component silibinin and their neuroprotective effects against hydrogen peroxide (H2O2)-induced oxidative stress in rat pheochromocytoma PC12 cells. It was found that despite newly prepared silymarin and silibinin solution possessing comparable superoxide anion (O2*-)-scavenging activities, with time the activity of silymarin lowered slightly, but that of silibinin decreased dramatically. Both silymarin and silibinin suppressed H2O2-induced oxidative stress and apoptosis, and the neuroprotective effect of silymarin was overall relatively stronger than that of silibinin. The findings provided clues for future studies on therapeutic potentials of the whole silymarin or purified silibinin for neurodegenerative diseases.

Antioxidant ameliorating effects against H2O2-induced cytotoxicity in primary endometrial cells.

PubMed

Zal, F; Khademi, F; Taheri, R; Mostafavi-Pour, Z

2018-02-01

Oxidative stress and a disrupted antioxidant system are involved in a variety of pregnancy complications. In the present study, the role of vitamin E (Vit E) and folate as radical scavengers on the GSH homeostasis in stress oxidative induced in rat endometrial cells was investigated. Primary endometrial stromal cell cultures treated with 50 and 200 µM of H 2 O 2 and evaluated the cytoprotective effects of Vit E (5 µM) and folate (0.01 µM) in H 2 O 2 -treated cells for 24 h. Following the exposure of endometrial cells to H 2 O 2 alone and in the presence of Vit E and/or folate, cell survival, glutathione peroxidase (GPx) and glutathione reductase activities and the level of reduced glutathione (GSH) were measured. Cell adhesions comprise of cell attachment and spreading on collagen were determined. Flow cytometric analysis using annexin V was used to measure apoptosis. H 2 O 2 treatment showed a marked decrease in cell viability, GPx and GR activities and the level of GSH. Although Vit E or folate had some protective effect, combination therapy with Vit E and folate attenuated all the changes due to H 2 O 2 toxicity. An increasing number of alive cells was showed in the cells exposed to H 2 O 2 (50 µM) accompanied by co-treatment with Vit E and folic acid. The present findings indicate that co-administration of Vit E and folate before and during pregnancy may maintain a viable pregnancy and contribute to its clinical efficacy for the treatment of some idiopathic infertility.

5-AIQ inhibits H{sub 2}O{sub 2}-induced apoptosis through reactive oxygen species scavenging and Akt/GSK-3β signaling pathway in H9c2 cardiomyocytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Park, Eun-Seok; Kang, Jun Chul; Kang, Do-Hyun

2013-04-01

Poly(adenosine 5′-diphosphate ribose) polymerase (PARP) is a nuclear enzyme activated by DNA strand breaks and plays an important role in the tissue injury associated with ischemia and reperfusion. The aim of the present study was to investigate the protective effect of 5-aminoisoquinolinone (5-AIQ), a PARP inhibitor, against oxidative stress-induced apoptosis in H9c2 cardiomyocytes. 5-AIQ pretreatment significantly protected against H{sub 2}O{sub 2}-induced cell death, as determined by the XTT assay, cell counting, terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling assay, and Western blot analysis of apoptosis-related proteins such as caspase-3, Bax, and Bcl-2. Upregulation of antioxidant enzymes such as manganese superoxidemore » dismutase and catalase accompanied the protective effect of 5-AIQ on H{sub 2}O{sub 2}-induced cell death. Our data also showed that 5-AIQ pretreatment protected H9c2 cells from H{sub 2}O{sub 2}-induced apoptosis by triggering activation of Akt and glycogen synthase kinase-3β (GSK-3β), and that the protective effect of 5-AIQ was diminished by the PI3K inhibitor LY294002 at a concentration that effectively abolished 5-AIQ-induced Akt and GSK-3β activation. In addition, inhibiting the Akt/GSK-3β pathway by LY294002 significantly attenuated the 5-AIQ-mediated decrease in cleaved caspase-3 and Bax activation and H9c2 cell apoptosis induction. Taken together, these results demonstrate that 5-AIQ prevents H{sub 2}O{sub 2}-induced apoptosis in H9c2 cells by reducing intracellular reactive oxygen species production, regulating apoptosis-related proteins, and activating the Akt/GSK-3β pathway. - Highlights: ► 5-AIQ, a PARP inhibitor, decreased H{sub 2}O{sub 2}-induced H9c2 cell death and apoptosis. ► 5-AIQ upregulated antioxidant Mn-SOD and catalase, while decreasing ROS production. ► 5-AIQ decreased H{sub 2}O{sub 2}-induced increase in cleaved caspase-3 and Bax and decrease in Bcl2. ► 5-AIQ activated Akt and

Interpreting activity in H(2)O-H(2)SO(4) binary nucleation.

PubMed

Bein, Keith J; Wexler, Anthony S

2007-09-28

Sulfuric acid-water nucleation is thought to be a key atmospheric mechanism for forming new condensation nuclei. In earlier literature, measurements of sulfuric acid activity were interpreted as the total (monomer plus hydrate) concentration above solution. Due to recent reinterpretations, most literature values for H(2)SO(4) activity are thought to represent the number density of monomers. Based on this reinterpretation, the current work uses the most recent models of H(2)O-H(2)SO(4) binary nucleation along with perturbation analyses to predict a decrease in critical cluster mole fraction, increase in critical cluster diameter, and orders of magnitude decrease in nucleation rate. Nucleation rate parameterizations available in the literature, however, give opposite trends. To resolve these discrepancies, nucleation rates were calculated for both interpretations of H(2)SO(4) activity and directly compared to the available parameterizations as well as the perturbation analysis. Results were in excellent agreement with older parameterizations that assumed H(2)SO(4) activity represents the total concentration and duplicated the predicted trends from the perturbation analysis, but differed by orders of magnitude from more recent parameterizations that assume H(2)SO(4) activity represents only the monomer. Comparison with experimental measurements available in the literature revealed that the calculations of the current work assuming a(a) represents the total concentration are most frequently in agreement with observations.

A unique polysaccharide purified from Hericium erinaceus mycelium prevents oxidative stress induced by H2O2 in human gastric mucosa epithelium cell

PubMed Central

Kanako, Nakajima; Zhang, Yanqiu; Xiao, Xulang; Gao, Qipin; Tetsuya, Konishi

2017-01-01

Hericium erinaceus (HE) has been used both as a traditional Chinese medicine and home remedy for treatment of gastric and duodenal ulcers and gastritis. EP-1, a purified polysaccharide isolated from HE mycelium, has recently been identified as the active component responsible for HE anti-gastritis activity. Because oxidative stress has been implicated as a pathogenic cause of gastritis and gastric ulcers, EP-1 antioxidant properties were systematically examined in vitro using the human gastric mucosal epithelial cell line, GES-1. Results showed that EP-1 possessed higher oxygen radical absorbance capacity (ORAC) and 2–3 times higher ability to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH), superoxide and hydroxyl radicals than a hot water extract of commercially available HE fruiting body. A crude mycelial polysaccharide (CMPS) extract of HE, from which EP-1 was purified, showed slightly stronger radical scavenging activity and ORAC than EP-1, with the exception of DPPH-scavenging activity. Antioxidant activities of these extracts were further studied using hydrogen peroxide (H2O2)-abused GES-1 cells; EP-1 dose-dependently preserved cell viability of abused cells as assessed via MTT assay. Moreover, FACS analysis revealed that EP-1 prevented H2O2-induced apoptotic cell death by inhibiting activation of apoptotic cellular signals within mitochondria-dependent apoptotic pathways. CMPS also prevented H2O2-induced oxidative stress, but to a lesser degree than did EP-1, even though CMPS exhibited comparable or stronger in vitro antioxidant activity than did EP-1. PMID:28742114

A unique polysaccharide purified from Hericium erinaceus mycelium prevents oxidative stress induced by H2O2 in human gastric mucosa epithelium cell.

PubMed

Wang, Mingxing; Kanako, Nakajima; Zhang, Yanqiu; Xiao, Xulang; Gao, Qipin; Tetsuya, Konishi

2017-01-01

Hericium erinaceus (HE) has been used both as a traditional Chinese medicine and home remedy for treatment of gastric and duodenal ulcers and gastritis. EP-1, a purified polysaccharide isolated from HE mycelium, has recently been identified as the active component responsible for HE anti-gastritis activity. Because oxidative stress has been implicated as a pathogenic cause of gastritis and gastric ulcers, EP-1 antioxidant properties were systematically examined in vitro using the human gastric mucosal epithelial cell line, GES-1. Results showed that EP-1 possessed higher oxygen radical absorbance capacity (ORAC) and 2-3 times higher ability to scavenge 2,2-diphenyl-1-picrylhydrazyl (DPPH), superoxide and hydroxyl radicals than a hot water extract of commercially available HE fruiting body. A crude mycelial polysaccharide (CMPS) extract of HE, from which EP-1 was purified, showed slightly stronger radical scavenging activity and ORAC than EP-1, with the exception of DPPH-scavenging activity. Antioxidant activities of these extracts were further studied using hydrogen peroxide (H2O2)-abused GES-1 cells; EP-1 dose-dependently preserved cell viability of abused cells as assessed via MTT assay. Moreover, FACS analysis revealed that EP-1 prevented H2O2-induced apoptotic cell death by inhibiting activation of apoptotic cellular signals within mitochondria-dependent apoptotic pathways. CMPS also prevented H2O2-induced oxidative stress, but to a lesser degree than did EP-1, even though CMPS exhibited comparable or stronger in vitro antioxidant activity than did EP-1.

Defining the chemical role of H2O in mantle melts: Effect of melt composition and H2O content on the activity of SiO2

NASA Astrophysics Data System (ADS)

Moore, G.; Roggensack, K.

2007-12-01

Quantifying the influence of volatiles (H2O, CO2) on the chemistry of mantle melts is a critical aspect of understanding the petrogenesis of arc magmas. A significant amount of experimental work done on the effect of H2O on the solidii of various mantle compositions, as well as on multiple saturation points of various primitive melts, has shown that H2O stabilizes olivine with respect to orthopyroxene. Or, in other words, at constant activity of SiO2, the presence of H2O decreases the activity coefficient of SiO2 in the melt, potentially leading to mantle melts that have suprisingly high SiO2 contents (Carmichael, 2002). Quantification and modelling of this behavior in hydrous silicate melts in equilibrium with the mantle have proven problematic, due mainly to a relatively small set of experiments that allow this type of thermodynamic analysis, and because of the experimental and analytical difficulties of dealing with hydrous high P-T samples (e.g. quench to a glass, rapid melt-solid reaction on quench, electron beam sensitivity of resulting glass, volatile content determination, etc). A further complication in the existing data includes co-variance of important experimental parameters (e.g. T and H2O content), making robust statistical regression analysis difficult and potentially misleading. We present here results of high P-T experiments conducted at a single pressure and temperature (1.0 GPa, 1200 deg C) that have the specific goal of quantifying the effect of H2O, as well as other melt components, on the activity coefficient of SiO2 in mantle melts. Using a "sandwich" type experiment, basaltic melts are saturated with an olivine plus orthopyroxene mineral assemblage with varying H2O and CO2 contents. The resulting samples have their bulk solid phase and glass compositions determined using EPMA, and the volatile content of the glass is determined by FTIR. The activity of SiO2 is then calculated using the olivine and orthopyroxene compositions. This value is

Removal of pharmaceutically active compounds from synthetic and real aqueous mixtures and simultaneous disinfection by supported TiO2/UV-A, H2O2/UV-A, and TiO2/H2O2/UV-A processes.

PubMed

Bosio, Morgana; Satyro, Suéllen; Bassin, João Paulo; Saggioro, Enrico; Dezotti, Márcia

2018-05-01

Pharmaceutically active compounds are carried into aquatic bodies along with domestic sewage, industrial and agricultural wastewater discharges. Psychotropic drugs, which can be toxic to the biota, have been detected in natural waters in different parts of the world. Conventional water treatments, such as activated sludge, do not properly remove these recalcitrant substances, so the development of processes able to eliminate these compounds becomes very important. Advanced oxidation processes are considered clean technologies, capable of achieving high rates of organic compounds degradation, and can be an efficient alternative to conventional treatments. In this study, the degradation of alprazolam, clonazepam, diazepam, lorazepam, and carbamazepine was evaluated through TiO 2 /UV-A, H 2 O 2 /UV-A, and TiO 2 /H 2 O 2 /UV-A, using sunlight and artificial irradiation. While using TiO 2 in suspension, best results were found at [TiO 2 ] = 0.1 g L -1 . H 2 O 2 /UV-A displayed better results under acidic conditions, achieving from 60 to 80% of removal. When WWTP was used, degradation decreased around 50% for both processes, TiO 2 /UV-A and H 2 O 2 /UV-A, indicating a strong matrix effect. The combination of both processes was shown to be an adequate approach, since removal increased up to 90%. H 2 O 2 /UV-A was used for disinfecting the aqueous matrices, while mineralization was obtained by TiO 2 -photocatalysis.

Electrocatalytic activity of LaNiO3 toward H2O2 reduction reaction: Minimization of oxygen evolution

NASA Astrophysics Data System (ADS)

Amirfakhri, Seyed Javad; Meunier, Jean-Luc; Berk, Dimitrios

2014-12-01

The catalytic activity of LaNiO3 toward H2O2 reduction reaction (HPRR), with a potential application in the cathode side of fuel cells, is studied in alkaline, neutral and acidic solutions by rotating disk electrode. The LaNiO3 particles synthesised by citrate-based sol-gel method have sizes between 30 and 70 nm with an active specific surface area of 1.26 ± 0.05 m2 g-1. LaNiO3 shows high catalytic activity toward HPRR in 0.1 M KOH solution with an exchange current density based on the active surface area (j0A) of (7.4 ± 1) × 10-6 A cm-2 which is noticeably higher than the j0A of N-doped graphene. The analysis of kinetic parameters suggests that the direct reduction of H2O2, H2O2 decomposition, O2 reduction and O2 desorption occur through HPRR on this catalyst. In order to control and minimize oxygen evolution from the electrode surface, the effects of catalyst loading, bulk concentration of H2O2, and using a mixture of LaNiO3 and N-doped graphene are studied. Although the mechanism of HPRR is independent of the aforementioned operating conditions, gas evolution decreases by increasing the catalyst loading, decreasing the bulk concentration of H2O2, and addition of N-doped graphene to LaNiO3.

Synthesis of Nanoscale CaO-Al2O3-SiO2-H2O and Na2O-Al2O3-SiO2-H2O Using the Hydrothermal Method and Their Characterization

PubMed Central

Yang, Jingbin; Li, Dongxu; Fang, Yuan

2017-01-01

C-A-S-H (CaO-Al2O3-SiO2-H2O) and N-A-S-H (Na2O-Al2O3-SiO2-H2O) have a wide range of chemical compositions and structures and are difficult to separate from alkali-activated materials. Therefore, it is difficult to analyze their microscopic properties directly. This paper reports research on the synthesis of C-A-S-H and N-A-S-H particles with an average particle size smaller than 300 nm by applying the hydrothermal method. The composition and microstructure of the products with different CaO(Na2O)/SiO2 ratios and curing conditions were characterized using XRD, the RIR method, FTIR, SEM, TEM, and laser particle size analysis. The results showed that the C-A-S-H system products with a low CaO/SiO2 ratio were mainly amorphous C-A-S-H gels. With an increase in the CaO/SiO2 ratio, an excess of Ca(OH)2 was observed at room temperature, while in a high-temperature reaction system, katoite, C4AcH11, and other crystallized products were observed. The katoite content was related to the curing temperature and the content of Ca(OH)2 and it tended to form at a high-temperature and high-calcium environment, and an increase in the temperature renders the C-A-S-H gels more compact. The main products of the N-A-S-H system at room temperature were amorphous N-A-S-H gels and a small amount of sodalite. An increase in the curing temperature promoted the formation of the crystalline products faujasite and zeolite-P. The crystallization products consisted of only zeolite-P in the high-temperature N-A-S-H system and its content were stable above 70%. An increase in the Na2O/SiO2 ratio resulted in more non-bridging oxygen and the TO4 was more isolated in the N-A-S-H structure. The composition and microstructure of the C-A-S-H and N-A-S-H system products synthesized by the hydrothermal method were closely related to the ratio of the raw materials and the curing conditions. The results of this study increase our understanding of the hydration products of alkali-activated materials. PMID

Catalase-like activity of horseradish peroxidase: relationship to enzyme inactivation by H2O2.

PubMed Central

Hernández-Ruiz, J; Arnao, M B; Hiner, A N; García-Cánovas, F; Acosta, M

2001-01-01

H2O2 is the usual oxidizing substrate of horseradish peroxidase C (HRP-C). In the absence in the reaction medium of a one-electron donor substrate, H2O2 is able to act as both oxidizing and reducing substrate. However, under these conditions the enzyme also undergoes a progressive loss of activity. There are several pathways that maintain the activity of the enzyme by recovering the ferric form, one of which is the decomposition of H2O2 to molecular oxygen in a similar way to the action of catalase. This production of oxygen has been kinetically characterized with a Clark-type electrode coupled to an oxygraph. HRP-C exhibits a weak catalase-like activity, the initial reaction rate of which is hyperbolically dependent on the H2O2 concentration, with values for K(2) (affinity of the first intermediate, compound I, for H2O2) and k(3) (apparent rate constant controlling catalase activity) of 4.0 +/- 0.6 mM and 1.78 +/- 0.12 s(-1) respectively. Oxygen production by HRP-C is favoured at pH values greater than approx. 6.5; under similar conditions HRP-C is also much less sensitive to inactivation during incubations with H2O2. We therefore suggest that this pathway is a major protective mechanism of HRP-C against such inactivation. PMID:11171085

Effect of matrix components on UV/H2O2 and UV/S2O8(2-) advanced oxidation processes for trace organic degradation in reverse osmosis brines from municipal wastewater reuse facilities.

PubMed

Yang, Yi; Pignatello, Joseph J; Ma, Jun; Mitch, William A

2016-02-01

When reverse osmosis brines from potable wastewater reuse plants are discharged to poorly-flushed estuaries, the concentrated organic contaminants are a concern for receiving water ecosystems. UV/hydrogen peroxide (UV/H2O2) and UV/persulfate (UV/S2O8(2-)) advanced oxidation processes (AOPs) may reduce contaminant burdens prior to discharge, but the effects of the high levels of halide, carbonate and effluent organic matter (EfOM) normally present in these brines are unclear. On the one hand, these substances may reduce process efficiency by scavenging reactive oxygen species (ROS), hydroxyl (OH) and sulfate (SO4(-) radicals. On the other, the daughter radicals generated by halide and carbonate scavenging may themselves degrade organics, offsetting the effect of ROS scavenging. UV/H2O2 and UV/S2O8(2-) AOPs were compared for degradation of five pharmaceuticals spiked into brines obtained from two reuse facilities and the RO influent from one of them. For UV/H2O2, EfOM scavenged ∼75% of the OH, reducing the degradation efficiency of the target contaminants to a similar extent; halide and carbonate scavenging and the reactivities of associated daughter radicals were less important. For UV/S2O8(2-), anions (mostly Cl(-)) scavenged ∼93% of the SO4(-). Because daughter radicals of Cl(-) contributed to contaminant degradation, the reduction in contaminant degradation efficiency was only ∼75-80%, with the reduction driven by daughter radical scavenging by EfOM. Conversion of SO4(-) to more selective halogen and carbonate radicals resulted in a wider range of degradation efficiencies among the contaminants. For both AOPs, 250 mJ/cm(2) average fluence achieved significant removal of four pharmaceuticals, with significantly better performance by UV/S2O8(2-) treatment for some constituents. Accounting for the lower brine flowrates, the energy output to achieve this fluence in brines is comparable to that often applied to RO permeates. However, much higher fluence was

Using in vivo oxidation status of one- and two-component redox relays to determine H2O2 levels linked to signaling and toxicity.

PubMed

Domènech, Alba; Ayté, José; Antunes, Fernando; Hidalgo, Elena

2018-06-01

Hydrogen peroxide (H 2 O 2 ) is generated as a by-product of metabolic reactions during oxygen use by aerobic organisms, and can be toxic or participate in signaling processes. Cells, therefore, need to be able to sense and respond to H 2 O 2 in an appropriate manner. This is often accomplished through thiol switches: Cysteine residues in proteins that can act as sensors, and which are both scarce and finely tuned. Bacteria and eukaryotes use different types of such sensors-either a one-component (OxyR) or two-component (Pap1-Tpx1) redox relay, respectively. However, the biological significance of these two different signaling modes is not fully understood, and the concentrations and peroxides driving those types of redox cascades have not been determined, nor the intracellular H 2 O 2 levels linked to toxicity. Here we elucidate the characteristics, rates, and dynamic ranges of both systems. By comparing the activation of both systems in fission yeast, and applying mathematical equations to the experimental data, we estimate the toxic threshold of intracellular H 2 O 2 able to halt aerobic growth, and the temporal gradients of extracellular to intracellular peroxides. By calculating both the oxidation rates of OxyR and Tpx1 by peroxides, and their reduction rates by the cellular redoxin systems, we propose that, while Tpx1 is a sensor and an efficient H 2 O 2 scavenger because it displays fast oxidation and reduction rates, OxyR is strictly a H 2 O 2 sensor, since its reduction kinetics are significantly slower than its oxidation by peroxides, and therefore, it remains oxidized long enough to execute its transcriptional role. We also show that these two paradigmatic H 2 O 2 -sensing models are biologically similar at pre-toxic peroxide levels, but display strikingly different activation behaviors at toxic doses. Both Tpx1 and OxyR contain thiol switches, with very high reactivity towards peroxides. Nevertheless, the fast reduction of Tpx1 defines it as a scavenger

The properties of ZnO nanofluids and the role of H2O2 in the disinfection activity against Escherichia coli.

PubMed

Zhang, Lingling; Li, Yu; Liu, Xiaoming; Zhao, Lihua; Ding, Yulong; Povey, Malcolm; Cang, Daqiang

2013-08-01

This work investigates the disinfection property of ZnO nanofluids, focusing on H2O2 production and the disinfection activities of ZnO suspensions with different particles/aggregates. The possible disinfection mechanisms of ZnO suspensions are analysed. In this work, a medium mill was used to produce ZnO suspensions with different sizes of particles/aggregates. During the milling process, five ZnO suspension samples (A-E) were produced. X-ray Diffraction (XRD) and Dynamic Light Scattering (DLS) analyses revealed that after milling, the size of ZnO particles/aggregates in the suspensions decreased. Disinfection tests, H2O2 detection assays and fluorescent analyses were used to explore the disinfection activities and mechanism of ZnO suspensions. Disinfection tests results showed that all the produced ZnO suspension exhibited disinfection activity against Escherichia coli. ZnO suspensions with smaller particles/aggregates showed better disinfection activities. The presence of H2O2 in ZnO suspension was analysed. The H2O2 detection assay suggested that there is 1 μM H2O2 in 0.2 g/l ZnO Sample A, while there was no H2O2 present in ZnO Sample E. Though results showed that there was no H2O2 present in ZnO Sample E, Sample E with a size of 93 nm showed the best disinfection activities. Fluorescence tests detected that the interaction between E. coli lipid vesicles and ZnO Sample E was much faster and more efficient. This study firstly demonstrated that ZnO suspensions with different particles/aggregates produced different amount of H2O2. Results suggested that H2O2 is responsible for the disinfection activity of larger ZnO particles/aggregates while the interaction between smaller ZnO particles/aggregates and vesicle lipids is responsible for the disinfection activity of smaller ZnO particles/aggregates. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Nonlinear feedback drives homeostatic plasticity in H2O2 stress response

PubMed Central

Goulev, Youlian; Morlot, Sandrine; Matifas, Audrey; Huang, Bo; Molin, Mikael; Toledano, Michel B; Charvin, Gilles

2017-01-01

Homeostatic systems that rely on genetic regulatory networks are intrinsically limited by the transcriptional response time, which may restrict a cell’s ability to adapt to unanticipated environmental challenges. To bypass this limitation, cells have evolved mechanisms whereby exposure to mild stress increases their resistance to subsequent threats. However, the mechanisms responsible for such adaptive homeostasis remain largely unknown. Here, we used live-cell imaging and microfluidics to investigate the adaptive response of budding yeast to temporally controlled H2O2 stress patterns. We demonstrate that acquisition of tolerance is a systems-level property resulting from nonlinearity of H2O2 scavenging by peroxiredoxins and our study reveals that this regulatory scheme induces a striking hormetic effect of extracellular H2O2 stress on replicative longevity. Our study thus provides a novel quantitative framework bridging the molecular architecture of a cellular homeostatic system to the emergence of nonintuitive adaptive properties. DOI: http://dx.doi.org/10.7554/eLife.23971.001 PMID:28418333

Bleaching of cotton fabric with tetraacetylhydrazine as bleach activator for H2O2.

PubMed

Liu, Kai; Zhang, Xuan; Yan, Kelu

2018-05-15

Tetraacetylhydrazine (TH) as bleach activator for H 2 O 2 cotton bleaching was synthesized and characterized by 1 H NMR, 13 C NMR and MS spectra. TH has better solubility than that of TAED. The CIE whiteness index (WI), H 2 O 2 decomposition rate and bursting strength were employed to investigate the performance of H 2 O 2 /TH bleaching system. By addition of TH, WI and H 2 O 2 decomposition rate increased significantly at 70 °C. Bleaching temperature, NaHCO 3 concentration and bleaching time were also discussed in detail and the loss of bursting strength is not clear. By using benzenepentacarboxylic acid (BA) as a fluorescent probe for hydroxyl radical detection, the bleaching process of H 2 O 2 /TH system was investigated. Acetylhydrazine and diacetylhydrazine were also utilized to further confirm the process. In addition, bimolecular decomposition was investigated by using 9,10-dimethylanthracene (DMA) as fluorescent probe of 1 O 2 . Based on these experimental results, the bleaching mechanism of H 2 O 2 /TH system was proposed. Copyright © 2018 Elsevier Ltd. All rights reserved.

UV-activated ZnO films on a flexible substrate for room temperature O2 and H2O sensing.

PubMed

Jacobs, Christopher B; Maksov, Artem B; Muckley, Eric S; Collins, Liam; Mahjouri-Samani, Masoud; Ievlev, Anton; Rouleau, Christopher M; Moon, Ji-Won; Graham, David E; Sumpter, Bobby G; Ivanov, Ilia N

2017-07-20

We demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2 O. We propose that the distinctive responses to O 2 and H 2 O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2 O adsorption energy on ZnO surfaces were performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). These simulations suggest that the adsorption mechanisms differ for O 2 and H 2 O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2 O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2 O at low temperature.

Comparative study of CO2 and H2O activation in the synthesis of carbon electrode for supercapacitors

NASA Astrophysics Data System (ADS)

Taer, E.; Apriwandi, Yusriwandi, Mustika, W. S.; Zulkifli, Taslim, R.; Sugianto, Kurniasih, B.; Agustino, Dewi, P.

2018-02-01

The physical activation for the comparative study of carbon electrode synthesized for supercapacitor applications made from rubber wood sawdust has been performed successfully. Comparison of physical activation used in this research is based on the different gas activation such as CO2 and H2O. The CO2 and H2O activation are made by using an integrated carbonization and activation system. The carbonization process is performed in N2 atmosphere followed by CO2 and H2O activation process. The carbonization process at temperature of 600°C, the CO2 and H2O activation process at a temperature of 900°C and maintained at this condition for 2 h and 3 h. The electrochemical properties were analyzed using cyclic voltammetric (CV) method. The CV results show that the carbon electrode with CO2 activation has better capacitive properties than H2O, the highest specific capacitance obtained is 93.22 F/g for 3 h of activation time. In addition, the analysis of physical properties such as surface morphology and degree of crystallinity was also performed.

Transgenic Centipedegrass (Eremochloa ophiuroides [Munro] Hack.) Overexpressing S-Adenosylmethionine Decarboxylase (SAMDC) Gene for Improved Cold Tolerance Through Involvement of H2O2 and NO Signaling.

PubMed

Luo, Jianhao; Liu, Mingxi; Zhang, Chendong; Zhang, Peipei; Chen, Jingjing; Guo, Zhenfei; Lu, Shaoyun

2017-01-01

Centipedegrass ( Eremochloa ophiuroides [Munro] Hack.) is an important warm-season turfgrass species. Transgenic centipedgrass plants overexpressing S-adenosylmethionine decarboxylase from bermudagrass ( CdSAMDC1 ) that was induced in response to cold were generated in this study. Higher levels of CdSAMDC1 transcript and sperimidine (Spd) and spermin (Spm) concentrations and enhanced freezing and chilling tolerance were observed in transgenic plants as compared with the wild type (WT). Transgenic plants had higher levels of polyamine oxidase (PAO) activity and H 2 O 2 than WT, which were blocked by pretreatment with methylglyoxal bis (guanylhydrazone) or MGBG, inhibitor of SAMDC, indicating that the increased PAO and H 2 O 2 were a result of expression of CdSAMDC1 . In addition, transgenic plants had higher levels of nitrate reductase (NR) activity and nitric oxide (NO) concentration. The increased NR activity were blocked by pretreatment with MGBG and ascorbic acid (AsA), scavenger of H 2 O 2 , while the increased NO level was blocked by MGBG, AsA, and inhibitors of NR, indicating that the enhanced NR-derived NO was dependent upon H 2 O 2 , as a result of expression CdSAMDC1 . Elevated superoxide dismutase (SOD) and catalase (CAT) activities were observed in transgenic plants than in WT, which were blocked by pretreatment with MGBG, AsA, inhibitors of NR and scavenger of NO, indicating that the increased activities of SOD and CAT depends on expression of CdSAMDC1 , H 2 O 2 , and NR-derived NO. Our results suggest that the elevated cold tolerance was associated with PAO catalyzed production of H 2 O 2 , which in turn led to NR-derived NO production and induced antioxidant enzyme activities in transgenic plants.

UV-activated ZnO films on a flexible substrate for room temperature O 2 and H 2O sensing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobs, Christopher B.; Maksov, Artem B.; Muckley, Eric S.

Here, we demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2O. We also propose that the distinctive responses to O 2 and H 2O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2O adsorption energy on ZnO surfaces weremore » performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). Furthermore, these simulations suggest that the adsorption mechanisms differ for O 2 and H 2O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2O at low temperature.« less

UV-activated ZnO films on a flexible substrate for room temperature O 2 and H 2O sensing

DOE PAGES

Jacobs, Christopher B.; Maksov, Artem B.; Muckley, Eric S.; ...

2017-07-20

Here, we demonstrate that UV-light activation of polycrystalline ZnO films on flexible polyimide (Kapton) substrates can be used to detect and differentiate between environmental changes in oxygen and water vapor. The in-plane resistive and impedance properties of ZnO films, fabricated from bacteria-derived ZnS nanoparticles, exhibit unique resistive and capacitive responses to changes in O 2 and H 2O. We also propose that the distinctive responses to O 2 and H 2O adsorption on ZnO could be utilized to statistically discriminate between the two analytes. Molecular dynamic simulations (MD) of O 2 and H 2O adsorption energy on ZnO surfaces weremore » performed using the large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) with a reactive force-field (ReaxFF). Furthermore, these simulations suggest that the adsorption mechanisms differ for O 2 and H 2O adsorption on ZnO, and are governed by the surface termination and the extent of surface hydroxylation. Electrical response measurements, using DC resistance, AC impedance spectroscopy, and Kelvin Probe Force Microscopy (KPFM), demonstrate differences in response to O 2 and H 2O, confirming that different adsorption mechanisms are involved. Statistical and machine learning approaches were applied to demonstrate that by integrating the electrical and kinetic responses the flexible ZnO sensor can be used for detection and discrimination between O 2 and H 2O at low temperature.« less

Novel Process of Simultaneous Removal of Nitric Oxide and Sulfur Dioxide Using a Vacuum Ultraviolet (VUV)-Activated O2/H2O/H2O2 System in A Wet VUV-Spraying Reactor.

PubMed

Liu, Yangxian; Wang, Qian; Pan, Jianfeng

2016-12-06

A novel process for NO and SO 2 simultaneous removal using a vacuum ultraviolet (VUV, with 185 nm wavelength)-activated O 2 /H 2 O/H 2 O 2 system in a wet VUV-spraying reactor was developed. The influence of different process variables on NO and SO 2 removal was evaluated. Active species (O 3 and ·OH) and liquid products (SO 3 2- , NO 2 - , SO 4 2- , and NO 3 - ) were analyzed. The chemistry and routes of NO and SO 2 removal were investigated. The oxidation removal system exhibits excellent simultaneous removal capacity for NO and SO 2 , and a maximum removal of 96.8% for NO and complete SO 2 removal were obtained under optimized conditions. SO 2 reaches 100% removal efficiency under most of test conditions. NO removal is obviously affected by several process variables. Increasing VUV power, H 2 O 2 concentration, solution pH, liquid-to-gas ratio, and O 2 concentration greatly enhances NO removal. Increasing NO and SO 2 concentration obviously reduces NO removal. Temperature has a dual impact on NO removal, which has an optimal temperature of 318 K. Sulfuric acid and nitric acid are the main removal products of NO and SO 2 . NO removals by oxidation of O 3 , O·, and ·OH are the primary routes. NO removals by H 2 O 2 oxidation and VUV photolysis are the complementary routes. A potential scaled-up removal process was also proposed initially.

Characterization of the activity of L-ascorbic acid 2-[3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H-1-be nzopyran-6-yl-hydrogen phosphate] potassium salt in hydroxyl radical elimination.

PubMed

Tomita, T; Kashima, M; Tsujimoto, Y

2000-03-01

The effect of L-ascorbic acid 2-[3,4-dihydro-2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-2H -1-benzopyran-6-yl-hydrogen phosphate] potassium salt (EPC-K1) on hydroxyl radical (*OH) elimination was studied using electron spin resonance (ESR) and spectrophotometric experiments. The addition of EPC-K, and *OH scavengers eliminated the *OH generated from Cu2+/H2O2, Fe2+/H2O2 and H2O2/UV-irradiation reaction systems. However, in competitive reactions using different concentrations of a spin-trap agent, the addition of the *OH scavenger altered the IC50 values, whereas the addition of EPC-K1 and a metal chelater did not change the value in the Cu2+/H2O2 and Fe2+/H2O2 reaction systems. The addition of EPC-K1 and metal chelater changed the ESR signal for free Cu2+. The spectrophotometric experiments confirmed that the addition of EPC-K1 and metal chelater altered the absorption spectra due to CuCl2 and FeSO4, whereas the *OH scavenger did not alter the spectra. Therefore, it was demonstrated that EPC-K, has the ability both to scavenge *OH directly and to inhibit the generation of *OH by the chelation of Cu2+ and Fe2+.

Fermented Acanthopanax koreanum Root Extract Reduces UVB- and H2O2-Induced Senescence in Human Skin Fibroblast Cells.

PubMed

Park, Min-Ja; Bae, Young-Seuk

2016-07-28

The present study assessed the effects of an aqueous extract of Acanthopanax koreanum root (AE) and of AE following fermentation by lactic acid bacteria (Lactobacillus plantarum and Bifidobacterium bifidum) (AEF) on human skin fibroblast HS68 cells exposed to ultraviolet B (UVB) irradiation and oxidative stress. AEF effectively antagonized the senescence-associated β-galactosidase staining and upregulation of p53 and p21(Cip1/WAF1) induced by UVB or H2O2 treatment in HS68 cells. It also exhibited excellent antioxidant activities in radical scavenging assays and reduced the intracellular level of reactive oxygen species induced by UVB or H2O2 treatment. The antioxidant and antisenescent activities of AEF were greater than those of nonfermented A. koreanum extract. AEF significantly repressed the UVB- or H2O2-induced activities of matrix metalloproteinase (MMP)-1 and -3, overexpression of MMP-1, and nuclear factor κB (NF-κB) activation. This repression of NF-κB activation and MMP-1 overexpression was attenuated by a mitogen-activated protein kinase activator, suggesting that this AEF activity was dependent on this signaling pathway. Taken together, these data indicated that AEF-mediated antioxidant and anti-photoaging activities may produce anti-wrinkle effects on human skin.

Neuroprotective Effect of CeO2@PAA-LXW7 Against H2O2-Induced Cytotoxicity in NGF-Differentiated PC12 Cells.

PubMed

Jia, Jingjing; Zhang, Ting; Chi, Jieshan; Liu, Xiaoma; Sun, Jingjing; Xie, Qizhi; Peng, Sijia; Li, Changyan; Yi, Li

2018-06-07

CeO 2 nanoparticles (nanoceria) have been used in many studies as a powerful free radical scavenger, and LXW7, a small-molecule peptide, can specifically target the integrin αvβ3, whose neuroprotective effects have also been demonstrated. The objective of this study is to observe the neuroprotective effect and potential mechanism of CeO 2 @PAA-LXW7, a new compound that couples CeO 2 @PAA (nanoceria modified with the functional group of polyacrylic acid) with LXW7 via a series of chemical reactions, in H 2 O 2 -induced NGF-differentiated PC12 cells. We examined the effects of LXW7, CeO 2 @PAA, and CeO 2 @PAA-LXW7 on the viability of primary hippocampal neurons and found that there was no significant difference under control conditions, but increased cellular viability was observed in the case of H 2 O 2 -induced injury. We used H 2 O 2 -induced NGF-differentiated PC12 cells as the classical injury model to investigate the neuroprotective effect of CeO 2 @PAA-LXW7. In this study, LXW7, CeO 2 @PAA, and CeO 2 @PAA-LXW7 inhibit H 2 O 2 -induced oxidative stress by reducing the production of reactive oxygen species (ROS) and regulating Bax/Bcl-2, cleaved caspase-3 and mitochondrial cytochrome C (cyto C) in the apoptotic signaling pathways. We found that the levels of phosphorylation of focal adhesion kinase (FAK) and of signal transducer and activator of transcription 3 (STAT3) increased significantly in H 2 O 2 -induced NGF-differentiated PC12 cells, whereas LXW7, CeO 2 @PAA, and CeO 2 @PAA-LXW7 suppressed the increase to different degrees. Among the abovementioned changes, the inhibitory effect of CeO 2 @PAA-LXW7 on H 2 O 2 -induced changes, including the increases in the levels of p-FAK and p-STAT3, is more obvious than that of LXW7 or CeO 2 @PAA alone. In summary, these results suggest that integrin signaling participates in the regulation of apoptosis via the regulation of ROS and of the apoptosis pathway in H 2 O 2 -induced NGF-differentiated PC12 cells. LXW7, CeO

Is [Co4(H2O)2(α-PW9O34)2](10-) a genuine molecular catalyst in photochemical water oxidation? Answers from time-resolved hole scavenging experiments.

PubMed

Natali, Mirco; Berardi, Serena; Sartorel, Andrea; Bonchio, Marcella; Campagna, Sebastiano; Scandola, Franco

2012-09-11

Water oxidation catalysts: evolution of [Co(4)(H(2)O)(2)(α-PW(9)O(34))(2)](10-) to catalytically active species is assessed by laser flash photolysis in sacrificial photocatalytic cycles with Ru(bpy)(3)(2+) as a photosensitizer.

Measurements of the Activity of dissolved H2O in an Andesite Melt

NASA Astrophysics Data System (ADS)

Moore, G. M.; Touran, J. P.; Pu, X.; Kelley, K. A.; Cottrell, E.; Ghiorso, M. S.

2016-12-01

The large effect of dissolved H2O on the physical and chemical nature of silicate melts, and its role in driving volcanism, is well known and underscores the importance of this volatile component. A complete understanding of the chemical behavior of dissolved H2O in silicate melts requires the quantification of its thermodynamic activity as a function of pressure, temperature, and melt composition, particularly at low H2O contents (i.e. at under-saturated conditions). Knowledge of the activity of H2O in silicate melts at H2O-undersaturated conditions will improve our understanding of hydrous phase equilibria, as well as our models of physical melt properties. Measurement of the activity of any silicate melt component, much less that of a volatile component such as H2O, is a difficult experimental task however. By using a modified double capsule design (Matjuschkin et al, 2015) to control oxygen fugacity in piston cylinder experiments, along with high precision X-ray absorption techniques (XANES) to measure iron oxidation state in silicate glasses (Cottrell et al, 2009), we are able to constrain the H2O activity in silicate melts at under-saturated conditions. Preliminary results on an andesite melt with low H2O content (3 wt%) have been shown (Moore et al, 2016) to match predicted H2O activity values calculated using the H2O equation of state of Duan and Zhang (1996) and the H2O solubility model of Ghiorso and Gualda (2015). More recent results on the same andesite melt containing approximately 5 wt% H2O however show a large negative deviation from the predicted values. Reversal experiments involving an oxidized starting material are ongoing, as well as further characterization of the samples to detect the presence of possible contaminants that would induce reduction of the melt beyond that related to the H2O activity (e.g. graphite contamination).

Free radical scavenging potency of quercetin catecholic colonic metabolites: Thermodynamics of 2H+/2e- processes.

PubMed

Amić, Ana; Lučić, Bono; Stepanić, Višnja; Marković, Zoran; Marković, Svetlana; Dimitrić Marković, Jasmina M; Amić, Dragan

2017-03-01

Reaction energetics of the double (2H + /2e - ), i.e., the first 1H + /1e - (catechol→ phenoxyl radical) and the second 1H + /1e - (phenoxyl radical→ quinone) free radical scavenging mechanisms of quercetin and its six colonic catecholic metabolites (caffeic acid, hydrocaffeic acid, homoprotocatechuic acid, protocatechuic acid, 4-methylcatechol, and catechol) were computationally studied using density functional theory, with the aim to estimate the antiradical potency of these molecules. We found that second hydrogen atom transfer (HAT) and second sequential proton loss electron transfer (SPLET) mechanisms are less energy demanding than the first ones indicating 2H + /2e - processes as inherent to catechol moiety. The Gibbs free energy change for reactions of inactivation of selected free radicals indicate that catecholic colonic metabolites constitute an efficient group of more potent scavengers than quercetin itself, able to deactivate various free radicals, under different biological conditions. They could be responsible for the health benefits associated with regular intake of flavonoid-rich diet. Copyright © 2016 Elsevier Ltd. All rights reserved.

Hydrothermal Syntheses and Structures of Three-Dimensional Oxo-fluorovanadium Phosphates: [H 2N(C 2H 4) 2NH 2] 0.5[(VO) 4V(HPO 4) 2(PO 4) 2F 2(H 2O) 4] · 2H 2O and K 2[(VO) 3(PO 4) 2F 2(H 2O)] · H 2O

NASA Astrophysics Data System (ADS)

Bonavia, Grant; Haushalter, R. C.; Zubieta, Jon

1996-11-01

The hydrothermal reactions of FPO3H2with vanadium oxides result in the incorporation of fluoride into V-P-O frameworks as a consequence of metal-mediated hydrolysis of the fluorophosphoric acid to produce F-and PO3-4. By exploiting this convenient source of F-, two 3-dimensional oxo-fluorovanadium phosphate phases were isolated, [H2N(C2H4)2NH2]0.5[(VO)4V(HOP4)2(PO4)2F2(H2O)4) · 2H2O (1 · 2H2O) and K2[(VO)3(PO4)2F2(H2O)] · H2O (2 · H2O). Both anionic frameworks contain (VIVO)-F--phosphate layers, with confacial bioctahedral {(VIVO)2FO6} units as the fundamental motif. In the case of 1, the layers are linked through {VIIIO6} octahedra, while for 2 the interlayer connectivity is provided by edge-sharing {(VIVO)2F2O6} units. Crystal data are 1 · 2H2O, CH10FN0.5O13P2V2.5, monoclinicC2/m,a= 18.425(4) Å,c= 8.954(2) Å, β = 93.69(2)0,V= 1221.1(4) Å3,Z= 4,Dcalc= 2.423 g cm-3; 2 · H2O, H4F2K2O13P2V3, triclinicPoverline1,a= 7.298(1) Å,b= 8.929(2) Å,c = 10.090(2) Å, α = 104.50(2)0, β = 100.39(2)0, δ = 92.13(2)0,V= 623.8(3) Å3,Z= 2,Dcalc= 2.891 g cm-3.

Osmopriming-induced salt tolerance during seed germination of alfalfa most likely mediates through H2O2 signaling and upregulation of heme oxygenase.

PubMed

Amooaghaie, Rayhaneh; Tabatabaie, Fatemeh

2017-07-01

The present study showed that osmopriming or pretreatment with low H 2 O 2 doses (2 mM) for 6 h alleviated salt-reduced seed germination. The NADPH oxidase activity was the main source, and superoxide dismutase (SOD) activity might be a secondary source of H 2 O 2 generation during osmopriming or H 2 O 2 pretreatment. Hematin pretreatment similar to osmopriming improved salt-reduced seed germination that was coincident with the enhancement of heme oxygenase (HO) activity. The semi-quantitative RT-PCR confirmed that osmopriming or H 2 O 2 pretreatment was able to upregulate heme oxygenase HO-1 transcription, while the application of N,N-dimethyl thiourea (DMTU as trap of endogenous H 2 O 2 ) and diphenyleneiodonium (DPI as inhibitor of NADPHox) not only blocked the upregulation of HO but also reversed the osmopriming-induced salt attenuation. The addition of CO-saturated aqueous rescued the inhibitory effect of DMTU and DPI on seed germination and α-amylase activity during osmopriming or H 2 O 2 pretreatment, but H 2 O 2 could not reverse the inhibitory effect of ZnPPIX (as HO inhibitor) or Hb (as CO scavenger) that indicates that the CO acts downstream of H 2 O 2 in priming-driven salt acclimation. The antioxidant enzymes and proline synthesis were upregulated in roots of seedlings grown from primed seeds, and these responses were reversed by adding DMTU, ZnPPIX, and Hb during osmopriming. These findings for the first time suggest that H 2 O 2 signaling and upregulation of heme oxygenase play a crucial role in priming-driven salt tolerance.

Glutaredoxin 2 prevents H(2)O(2)-induced cell apoptosis by protecting complex I activity in the mitochondria.

PubMed

Wu, Hongli; Xing, Kuiyi; Lou, Marjorie F

2010-10-01

Glutaredoxin 2 (Grx2) belongs to the oxidoreductase family and is an isozyme of glutaredoxin 1 (Grx1) present in the mitochondria, however its function is not well understood. The purpose of this study is to evaluate the potential anti-apoptotic function of Grx2 by examining its ability to protect complex I in the mitochondrial electron transport system using human lens epithelial cells as a model. We found that cells treated with 200muM hydrogen peroxide (H(2)O(2)) for 24h exhibited decreased viability and became apoptotic with corresponding Bax up-regulation, Bcl-2 down-regulation, caspase 3 activation and mitochondrial cytochrome c leakage. Grx2 over-expression (OE) could protect cells against H(2)O(2)-induced damage while Grx2 knockdown (KD) showed the opposite effect. Under the same conditions, H(2)O(2) treatment caused 50% inactivation of complex I activity in control cells (vector only), 75% in Grx2 KD cells but only 20% in Grx2 OE cells. Furthermore, the inactivated complex I in the H(2)O(2)-treated cells could be protected mostly by importing the purified nascent Grx2 protein, but not the Grx2 protein mutated at the active site with C70S, or C73S, or with C70S plus C73S. Immunoprecipitation study also revealed that Grx2 co-precipitated with complex I, but not complex II, in the mitochondrial lysate. Thus, the mechanism of Grx2 protection against H(2)O(2)-induced apoptosis is likely associated with its ability to preserve complex I. Published by Elsevier B.V.

Reduction in central H2O2 levels prevents voluntary ethanol intake in mice: a role for the brain catalase-H2O2 system in alcohol binge drinking.

PubMed

Ledesma, Juan Carlos; Baliño, Pablo; Aragon, Carlos M G

2014-01-01

Hydrogen peroxide (H2 O2 ) is the cosubstrate used by the enzyme catalase to form Compound I (the catalase-H2 O2 system), which is the major pathway for the conversion of ethanol (EtOH) into acetaldehyde in the brain. This centrally formed acetaldehyde has been shown to be involved in some of the psychopharmacological effects induced by EtOH in rodents, including voluntary alcohol intake. It has been observed that different levels of this enzyme in the central nervous system (CNS) result in variations in the amount of EtOH consumed. This has been interpreted to mean that the brain catalase-H2 O2 system, by determining EtOH metabolism, mediates alcohol self-administration. To date, however, the role of H2 O2 in voluntary EtOH drinking has not been investigated. In the present study, we explored the consequence of a reduction in cerebral H2 O2 levels in volitional EtOH ingestion. With this end in mind, we injected mice of the C57BL/6J strain intraperitoneally with the H2 O2 scavengers alpha-lipoic acid (LA; 0 to 50 mg/kg) or ebselen (Ebs; 0 to 25 mg/kg) 15 or 60 minutes, respectively, prior to offering them an EtOH (10%) solution following a drinking-in-the-dark procedure. The same procedure was followed to assess the selectivity of these compounds in altering EtOH intake by presenting mice with a (0.1%) solution of saccharin. In addition, we indirectly tested the ability of LA and Ebs to reduce brain H2 O2 availability. The results showed that both LA and Ebs dose-dependently reduced voluntary EtOH intake, without altering saccharin consumption. Moreover, we demonstrated that these treatments decreased the central H2 O2 levels available to catalase. Therefore, we propose that the amount of H2 O2 present in the CNS, by determining brain acetaldehyde formation by the catalase-H2 O2 system, could be a factor that determines an animal's propensity to consume EtOH. Copyright © 2013 by the Research Society on Alcoholism.

[Influence of corynebacteria metabolites on antagonistic activity of H2O2 producing lactobacilli].

PubMed

Bukharin, O V; Sgibnev, A V

2012-01-01

Study combined influence of Corynebacterium genus bacteria metabolites and H2O2 producing lactobacilli on survival rate of Staphylococcus aureus, Escherichia coli and Lactobacillus acidophilus. The ability to inhibit catalase of the test strains used and to reduce bactericidal effect of hydroxyl radical were determined in corynebacteria. H2O2 containing metabolites were obtained by cultivating lactobacilli in mineral medium, the amount of H2O2 was determined by oxidation of TMB by peroxidase. Bactericidal effect of lactobacilli metabolites for test strains treated by corynebacteria metabolites was evaluated by seeding results. Results. Inhibitio by corynebacteria metabolites of S. aureus catalase activity by 30-40% and E. coli catalase activ ity by 40-70% was shown. A reduction of bactericidal effect of hydroxyl radicals by corynebacteria metabolites by 30-35% for S. aureus, 38-42% for E. coli and 70-73% for L. acidophilus was noted. The enchantment of bactericidal effect of lactobacilli after treatment of the test strain by corynebacteria metabolites against S. aureus and E. coli manifested by reduction of the numbe of viable cells by 2-3 lg CFU. For L. acidophilus the bactericidal effect oflactobacilli metabolite in the same conditions reduced, and that led to the increase ofviability by 2-4 lg PFU. A conclusion on the possibility of regulation by associative bacteria the manifestations of antagonistic activity of H2O2 producing dominant microorganisms is made based on the data obtained.

Oxidative degradation of endotoxin by advanced oxidation process (O3/H2O2 & UV/H2O2).

PubMed

Oh, Byung-Taek; Seo, Young-Suk; Sudhakar, Dega; Choe, Ji-Hyun; Lee, Sang-Myeong; Park, Youn-Jong; Cho, Min

2014-08-30

The presence of endotoxin in water environments may pose a serious public health hazard. We investigated the effectiveness of advanced oxidative processes (AOP: O3/H2O2 and UV/H2O2) in the oxidative degradation of endotoxin. In addition, we measured the release of endotoxin from Escherichia coli following typical disinfection methods, such as chlorine, ozone alone and UV, and compared it with the use of AOPs. Finally, we tested the AOP-treated samples in their ability to induce tumor necrosis factor alpha (TNF-α) in mouse peritoneal macrophages. The production of hydroxyl radical in AOPs showed superior ability to degrade endotoxin in buffered solution, as well as water samples from Korean water treatment facilities, with the ozone/H2O2 being more efficient compared to UV/H2O2. In addition, the AOPs proved effective not only in eliminating E. coli in the samples, but also in endotoxin degradation, while the standard disinfection methods lead to the release of endotoxin following the bacteria destruction. Furthermore, in the experiments with macrophages, the AOPs-deactivated endotoxin lead to the smallest induction of TNF-α, which shows the loss of inflammation activity, compared to ozone treatment alone. In conclusion, these results suggest that AOPs offer an effective and mild method for endotoxin degradation in the water systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Borate mineral assemblages in the system Na2OCaOMgOB2O3H2O

USGS Publications Warehouse

Christ, C.L.; Truesdell, A.H.; Erd, Richard C.

1967-01-01

he significant known hydrated borate mineral assemblages (principally of the western United States) in the system Na2OCaOz.sbnd;MgOB2O3H2O are expressible in three ternary composition diagrams. Phase rule interpretation of the diagrams is consistent with observation, if the activity of H2O is generally considered to be determined by the geologic environment. The absence of conflicting tie-lines on a diagram indicates that the several mineral assemblages of the diagram were formed under relatively narrow ranges of temperature and pressure. The known structural as well as empirical formulas for the minerals are listed, and the more recent (since 1960) crystal structure findings are discussed briefly. Schematic Gibbs free energy-composition diagrams based on known solubility-temperature relations in the systems Na2B4O7-H2O and Na2B4O7-NaCl-H2O, are highly useful in the interpretation and prediction of the stability relations in these systems; in particular these diagrams indicate clearly that tincalconite, although geologically important, is everywhere a metastable phase. Crystal-chemical considerations indicate that the same thermodynamic and kinetic behavior observed in the Na2B4O7-H2O system will hold in the Ca2B6O11-H2O system. This conclusion is confirmed by the petrologic evidence. The chemical relations among the mineral assemblages of a ternary diagram are expressed by a schematic "activity-activity" diagram. These activity-activity diagrams permit the tracing-out of the paragenetic sequences as a function of changing cation and H2O activities. ?? 1967.

Porous microspheres of MgO-patched TiO2 for CO2 photoreduction with H2O vapor: temperature-dependent activity and stability.

PubMed

Liu, Lianjun; Zhao, Cunyu; Zhao, Huilei; Pitts, Daniel; Li, Ying

2013-05-07

A novel MgO-patched TiO2 microsphere photocatalyst demonstrated 10 times higher activity toward CO production from CO2 photoreduction with H2O vapor, when the reaction temperature increased from 50 to 150 °C. The catalytic performance of hybrid MgO-TiO2 was much more stable than TiO2, particularly at a higher temperature, likely due to easier desorption of reaction intermediates and the enhanced CO2 adsorption by MgO.

The mechanism for water exchange in [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-), as studied by quantum chemical methods.

PubMed

Vallet, V; Wahlgren, U; Schimmelpfennig, B; Szabó, Z; Grenthe, I

2001-12-05

The mechanisms for the exchange of water between [UO(2)(H(2)O)(5)](2+), [UO(2)(oxalate)(2)(H(2)O)](2)(-)(,) and water solvent along dissociative (D), associative (A) and interchange (I) pathways have been investigated with quantum chemical methods. The choice of exchange mechanism is based on the computed activation energy and the geometry of the identified transition states and intermediates. These quantities were calculated both in the gas phase and with a polarizable continuum model for the solvent. There is a significant and predictable difference between the activation energy of the gas phase and solvent models: the energy barrier for the D-mechanism increases in the solvent as compared to the gas phase, while it decreases for the A- and I-mechanisms. The calculated activation energy, Delta U(++), for the water exchange in [UO(2)(H(2)O)(5)](2+) is 74, 19, and 21 kJ/mol, respectively, for the D-, A-, and I-mechanisms in the solvent, as compared to the experimental value Delta H(++) = 26 +/- 1 kJ/mol. This indicates that the D-mechanism for this system can be ruled out. The energy barrier between the intermediates and the transition states is small, indicating a lifetime for the intermediate approximately 10(-10) s, making it very difficult to distinguish between the A- and I-mechanisms experimentally. There is no direct experimental information on the rate and mechanism of water exchange in [UO(2)(oxalate)(2)(H(2)O)](2-) containing two bidentate oxalate ions. The activation energy and the geometry of transition states and intermediates along the D-, A-, and I-pathways were calculated both in the gas phase and in a water solvent model, using a single-point MP2 calculation with the gas phase geometry. The activation energy, Delta U(++), in the solvent for the D-, A-, and I-mechanisms is 56, 12, and 53 kJ/mol, respectively. This indicates that the water exchange follows an associative reaction mechanism. The geometry of the A- and I-transition states for both [UO

Novel cocrystal of N-phthaloyl-β-alanine with 2,2-bipyridyl: Synthesis, computational and free radical scavenging activity studies

NASA Astrophysics Data System (ADS)

Chahkandi, Mohammad; Bhatti, Moazzam H.; Yunus, Uzma; Rehman, Naima; Nadeem, Muhammad; Tahir, Muhammad Nawaz; Zakria, Muhammad

2018-01-01

In the present work a novel cocrystal adduct of N-phthaloyl-β-alanine and 2,2-bipyridyl as compound 1 with molecular formula C16H13N3O4 was synthesized by slow evaporation process of the ethanoic solution containing these two moieties. In followings, the crystal structure and photophysical properties of 1 was characterized by single X-ray crystal analysis, FTIR, and UV-Vis spectra. The thermal behavior was analyzed by the Thermogravimetric/Differential Thermal Analyzer (TG-DTA). The cocrystal belong to monoclinic crystallographic system with space group P21/n, Z = 4. DPPH radical scavenging activity of the title cocrystal is slightly higher than coformer with lower IC50 value. Finally, using DFT calculations executed at hybrid B3LYP/6-311+G (d, p) level of theory the geometric and electronic structures of the crystalline network of C16H13N3O4 (1), studied. Inter-molecular conventional Osbnd H⋯N as well as the non-conventional Csbnd H⋯O hydrogen bonds (HBs) and Csbnd H···π and Csbnd O···π stacking interactions gathered the monomeric structures of 1 (1-mon) to create the 3D architecture of the network (1-net). The dispersion corrected density functional theory (DFT-D) calculations indicate that Osbnd H⋯N and Csbnd H⋯O HBs, govern the 1-net formation. The calculated UV-Vis spectrum in vacuo has agreement with the experimental one that shows five major bands in the range of 170-271 nm that could assigned to transitions between 2,2-bipyridyl and N-phthaloyl-β-alanine parts of 1 with n → π∗ and π → π* ligand-ligand-charge transfer (LLCT) character. The calculated electronic spectra in solvents (water, acetonitrile, methanol, and n-heptane) comparing with the vacuo one show broad bands with blue shifts.

The discovery of five new H2O megamasers in active galaxies

NASA Technical Reports Server (NTRS)

Braatz, J. A.; Wilson, A. S.; Henkel, C.

1994-01-01

H2O megamasers with (isotropic) luminosities between 60 and 200 solar luminosity (H(sub 0) = 75 km/s/Mpc) have been detected in the Seyfert 2 galaxies Mrk 1, Mrk 1210, and NGC 5506 and in the LINERs NGC 1052 and NGC 2639. No megamasers have been found in Seyfert 1's. The galaxies have redshifts between 1500 and 4800 km/s and are the most distant H2O sources reported to date. NGC 1052 is also the first elliptical galaxy known to contain an H2O maser. The intensity distribution of an H2O five-point map obtained toward NGC 5506 shows that the H2O emission is pointlike compared to the 40 sec telescope beam. The lack of CO emission in NGC 1052 implies a conservative lower limit to the H2O brightness temperature of 1000 K, thus ruling out a thermal origin for the H2O emission. The success of this survey relative to other recent searches makes it evident that H2O megamasers are preferentially found in galaxies with active nuclei.

Electron-Scavenging Chemistry of Benzoquinone on TiO2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henderson, Michael A.; Shen, Mingmin

The chemistry of benzoquinone (BQ) on TiO2(110) was examined using temperature programmed desorption (TPD), electron energy loss spectroscopy (EELS) and Auger electron spectroscopy (AES). BQ adsorbs mostly molecularly on the clean surface, although EELS demonstrates that electrons from surface Ti3+ sites at oxygen vacancy sites (VO) are readily oxidized by the high electron scavenging ability of the molecule. In contrast, when the surface is covered with water, subsequently adsorbed BQ molecules that scavenge surface electrons also abstract H from surface OHbr groups to form hydroquinone (HQ), which desorbs at ~450 K. This work was supported by the US Department ofmore » Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. The research was performed using the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory.« less

Neuroligin-3 protects retinal cells from H2O2-induced cell death via activation of Nrf2 signaling.

PubMed

Li, Xiu-Miao; Huang, Dan; Yu, Qing; Yang, Jian; Yao, Jin

2018-05-25

Intensified oxidative stress can cause severe damage to human retinal pigment epithelium (RPE) cells and retinal ganglion cells (RGCs). The potential effect of neuroligin-3 (NLGN3) against the process is studied here. Our results show that NLGN3 efficiently inhibited hydrogen peroxide (H 2 O 2 )-induced death and apoptosis in human RPE cells and RGCs. H 2 O 2 -induced reactive oxygen species (ROS) production, lipid peroxidation and DNA damage in retinal cells were alleviated by NLGN3. NLGN3 activated nuclear-factor-E2-related factor 2 (Nrf2) signaling, enabling Nrf2 protein stabilization, nuclear translocation and expression of key anti-oxidant enzymes (HO1, NOQ1 and GCLC) in RPE cells and RGCs. Further results demonstrate that NLGN3 activated Akt-mTORC1 signaling in retinal cells. Conversely, Akt-mTORC1 inhibitors (RAD001 and LY294002) reduced NLGN3-induced HO1, NOQ1 and GCLC mRNA expression. Significantly, Nrf2 silencing by targeted shRNAs reversed NLGN3-induced retinal cytoprotection against H 2 O 2 . We conclude that NLGN3 activates Nrf2 signaling to protect human retinal cells from H 2 O 2 . NLGN3 could be further tested as a valuable retinal protection agent. Copyright © 2018 Elsevier Inc. All rights reserved.

New metal-organic frameworks of [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La, Ce) and [Ce2(C2O4)(C6H6O7)2] . 4H2O

NASA Astrophysics Data System (ADS)

Weng, Sheng-Feng; Wang, Yun-Hsin; Lee, Chi-Shen

2012-04-01

Two novel materials, [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La(1a), Ce(1b)) and [Ce2(C2O4)(C6H6O7)2] . 4H2O (2), with a metal-organic framework (MOF) were prepared with hydrothermal reactions and characterized with photoluminescence, magnetic susceptibility, thermogravimetric analysis and X-ray powder diffraction in situ. The crystal structures were determined by single-crystal X-ray diffraction. Compound 1 crystallized in triclinic space group P1¯ (No. 2); compound 2 crystallized in monoclinic space group P21/c (No. 14). The structure of 1 is built from a 1D MOF, composed of deprotonated citric ligands of three kinds. Compound 2 contains a 2D MOF structure consisting of citrate and oxalate ligands; the oxalate ligand arose from the decomposition in situ of citric acid in the presence of CuII ions. Photoluminescence spectra of compounds 1b and 2 revealed transitions between the 5d1 excited state and two levels of the 4f1 ground state (2F5/2 and 2F7/2). Compounds 1b and 2 containing CeIII ion exhibit a paramagnetic property with weak antiferromagnetic interactions between the two adjacent magnetic centers.

Degradation of n-butylparaben and 4- tert-octylphenol in H 2O 2/UV system

NASA Astrophysics Data System (ADS)

BŁędzka, Dorota; Gryglik, Dorota; Olak, Magdalena; Gębicki, Jerzy L.; Miller, Jacek S.

2010-04-01

The degradation of two endocrine disrupting compounds: n-butylparaben (BP) and 4- tert-octylphenol (OP) in the H 2O 2/UV system was studied. The effect of operating variables: initial hydrogen peroxide concentration, initial substrate concentration, pH of the reaction solution and photon fluency rate of radiation at 254 nm on reaction rate was investigated. The influence of hydroxyl radical scavengers, humic acid and nitrate anion on reaction course was also studied. A very weak scavenging effect during BP degradation was observed indicating reactions different from hydroxyl radical oxidation. The second-order rate constants of BP and OP with OH radicals were estimated to be 4.8×10 9 and 4.2×10 9 M -1 s -1, respectively. For BP the rate constant equal to 2.0×10 10 M -1 s -1was also determined using water radiolysis as a source of hydroxyl radicals.

Requirements for functional models of the iron hydrogenase active site: D2/H2O exchange activity in ((mu-SMe)(mu-pdt)[Fe(CO)2(PMe3)]2+)[BF4-].

PubMed

Georgakaki, Irene P; Miller, Matthew L; Darensbourg, Marcetta Y

2003-04-21

Hydrogen uptake in hydrogenase enzymes can be assayed by H/D exchange reactivity in H(2)/D(2)O or H(2)/D(2)/H(2)O mixtures. Diiron(I) complexes that serve as structural models for the active site of iron hydrogenase are not active in such isotope scrambling but serve as precursors to Fe(II)Fe(II) complexes that are functional models of [Fe]H(2)ase. Using the same experimental protocol as used previously for ((mu-H)(mu-pdt)[Fe(CO)(2)(PMe(3))](2)(+)), 1-H(+) (Zhao et al. J. Am. Chem. Soc. 2001, 123, 9710), we now report the results of studies of ((mu-SMe)(mu-pdt)[Fe(CO)(2)(PMe(3))](2)(+)), 1-SMe(+), toward H/D exchange. The 1-SMe(+) complex can take up H(2) and catalyze the H/D exchange reaction in D(2)/H(2)O mixtures under photolytic, CO-loss conditions. Unlike 1-H(+), it does not catalyze H(2)/D(2) scrambling under anhydrous conditions. The molecular structure of 1-SMe(+) involves an elongated Fe.Fe separation, 3.11 A, relative to 2.58 A in 1-H(+). It is proposed that the strong SMe(-) bridging ligand results in catalytic activity localized on a single Fe(II) center, a scenario that is also a prominent possibility for the enzyme active site. The single requirement is an open site on Fe(II) available for binding of D(2) (or H(2)), followed by deprotonation by the external base H(2)O (or D(2)O).

Exploration of H2O-CO2 Solubility in Alkali Basalt at low-H2O

NASA Astrophysics Data System (ADS)

Roggensack, K.; Allison, C. M.; Clarke, A. B.

2017-12-01

A number of recent experimental studies have found conflicting evidence for and against the influence of H2O on CO2 solubility in basalt and alkali-rich mafic magma (e.g. Behrens et al., 2009; Shishkina et al., 2010;2014; Iacono-Marziano et al., 2012). Some of the uncertainty is due to the error with spectroscopic determination (FTIR) of carbon and the challenge of controlling H2O abundance in experiments. It's been widely observed that even experimental capsules without added H2O may produce hydrous glasses containing several wt.% H2O. We conducted fluid-saturated, mixed-fluid (H2O-CO2) experiments to determine the solubility in alkali basalt with particular emphasis on conditions at low-H2O. To limit possible H2O contamination, materials were dried prior to loading and experimental capsules were sealed under vacuum. Experiments were run using a piston-cylinder, in Pt (pre-soaked in Fe) or AuPd capsules and operating at pressures from 400 to 600 MPa. Post-run the capsules were punctured under vacuum and fluids were condensed, separated, and measured by mercury manometry. A comparison between two experiments run at the same temperature and pressure conditions but with different fluid compositions illustrates the correlation between carbonate and H2O solubility. Uncertainties associated with using concentrations calculated from FTIR data can be reduced by directly comparing analyses on wafers of similar thickness. We observe that the experiment with greater H2O absorbance also has a higher carbonate absorbance than the experiment with lower H2O absorbance. Since the experiments were run at the same pressure, the experiment with more water-rich fluid, and higher dissolved H2O, has lower CO2 fugacity, but surprisingly has higher dissolved CO2 content. Overall, the results show two distinct trends. Experiments conducted at low-H2O (0.5 to 0.8 wt.%) show lower dissolved CO2 than those conducted at moderate-H2O (2 to 3 wt.%) at similar CO2 fugacity. These data show that

Radical scavenging and iron-chelating activities of some greens used as traditional dishes in Mediterranean diet.

PubMed

El, Sedef Nehir; Karakaya, Sibel

2004-02-01

This study aimed at evaluating the antioxidative activity of nine different families of greens. Raphanus raphanistrum (wild radish), Anchusa azurea (bugloss), Daucus carota (wild carrot), Sonchus oleraceus (sowthistle), Papaver rhoeas (corn poppy), Malva sylvestris (blue mallow), Foeniculum vulgare (fennel), Cichorium intybus (chicory) and Salicornia europaea (jointed glasswort) are native to the Mediterranean and are commonly consumed as a salad or an ingredient in some recipes. The antioxidative activities, including the radical scavenging effects, inhibition of hydrogen peroxide (H(2)O(2)), and Fe(2+)-chelating activity, were studied. All samples showed antioxidant activity as a radical scavenger in the experiment using the DPPH* radical. The ratio between the slopes of the kinetic model was used to compare antioxidant efficiency of different greens. Greens also possessed antioxidative activity toward H(2)O(2). Especially, greens exhibited a marked scavenging effect on H(2)O(2) at 0.2 g/ml concentration. The Fe(2+) ion-chelating activities of the samples except jointed glasswort were greater than 70%. The antioxidant activity of samples with different methods based on the inhibition of different reactions could not be compared. The current dietary guidelines include recommendations for an increase in the consumption of plant foods. Greens should provide an optimal supply of antioxidant substances in the diet.

Role of H2O2 in hypertension, renin-angiotensin system activation and renal medullary disfunction caused by angiotensin II

PubMed Central

Sousa, T; Oliveira, S; Afonso, J; Morato, M; Patinha, D; Fraga, S; Carvalho, F; Albino-Teixeira, A

2012-01-01

BACKGROUND AND PURPOSE Activation of the intrarenal renin-angiotensin system (RAS) and increased renal medullary hydrogen peroxide (H2O2) contribute to hypertension. We examined whether H2O2 mediated hypertension and intrarenal RAS activation induced by angiotensin II (Ang II). EXPERIMENTAL APPROACH Ang II (200 ng·kg−1·min−1) or saline were infused in Sprague Dawley rats from day 0 to day 14. Polyethylene glycol (PEG)-catalase (10 000 U·kg−1·day−1) was given to Ang II-treated rats, from day 7 to day 14. Systolic blood pressure was measured throughout the study. H2O2, angiotensin AT1 receptor and Nox4 expression and nuclear factor-κB (NF-κB) activation were evaluated in the kidney. Plasma and urinary H2O2 and angiotensinogen were also measured. KEY RESULTS Ang II increased H2O2, AT1 receptor and Nox4 expression and NF-κB activation in the renal medulla, but not in the cortex. Ang II raised plasma and urinary H2O2 levels, increased urinary angiotensinogen but reduced plasma angiotensinogen. PEG-catalase had a short-term antihypertensive effect and transiently suppressed urinary angiotensinogen. PEG-catalase decreased renal medullary expression of AT1 receptors and Nox4 in Ang II-infused rats. Renal medullary NF-κB activation was correlated with local H2O2 levels and urinary angiotensinogen excretion. Loss of antihypertensive efficacy was associated with an eightfold increase of plasma angiotensinogen. CONCLUSIONS AND IMPLICATIONS The renal medulla is a major target for Ang II-induced redox dysfunction. H2O2 appears to be the key mediator enhancing intrarenal RAS activation and decreasing systemic RAS activity. The specific control of renal medullary H2O2 levels may provide future grounds for the treatment of hypertension. PMID:22452317

Estimating Values of H2O-ACTIVITIES in the Mantle Using Amphibole Equilibria

NASA Astrophysics Data System (ADS)

Lamb, W. M.; Hunt, L. E.

2017-12-01

Determining values of H2O activity (aH2O) for mantle rocks will yield a better understanding of those mantle processes that are controlled, in part, by the availability of H2O (e.g., melting and deformation). The H contents of the upper mantle can be estimated from amount of H contained in nominally anhydrous minerals (NAMs). However, for many common NAMs, the relation between aH2O and H content is not well known, and certain NAMs may be prone to retrograde H loss. The activities of H2O and other fluids species (e.g., CO2) may be estimated using mineral equilibria. Equilibria involving amphibole can, for example, be used to estimate values of aH2O and hydrogen fugacity (ƒH2). Spinel equilibria can be applied to estimate values of oxygen fugacity (ƒO2) that, when combined with ƒH2, will provide a second estimate of aH2O. We have characterized mineral chemistries in 11 amphibole-bearing peridotite xenoliths from the southwestern U.S.A. The compositions of co-existing pyroxenes ± garnet yield P-T conditions of ≈ 1.1 GPa, and 880 to 980˚C, and application of dehydration equilibria yields values of aH2O ranging from 0.04 to 0.19. The compositions of coexisting spinel + olivine + opx yield DlogƒO2(FMQ) of -0.2 to +0.9. Values of ƒH2, estimated using amphibole dehydrogenation equilibria (6 to 91 bars) were combined with values of ƒO2 to estimate aH2O in nine samples (≈ 0.02 to 0.12). The difference between these two values of aH2O, estimated using dehydration equilibria versus ƒH2 + ƒO2, is generally < 0.1, suggesting that the amphiboles experienced little or no retrograde H-loss. All samples equilibrated at low values of aH2O, and these values may be used to predict NAM H-contents. For example, according to Gaetani et al. (2014, Cont. Min. Pet., p. 965), the concentration of H in olivine is a function of P, T, the fugacities of H2O and O2, and olivine composition. Their relation yields relatively low predicted H-contents of 10 to 28 wt. ppm for olivine in

New transition metal complexes of 2,4-dihydroxybenzaldehyde benzoylhydrazone Schiff base (H2dhbh): Synthesis, spectroscopic characterization, DNA binding/cleavage and antioxidant activity

NASA Astrophysics Data System (ADS)

Aboafia, Seyada A.; Elsayed, Shadia A.; El-Sayed, Ahmed K. A.; El-Hendawy, Ahmed M.

2018-04-01

New complexes [VO2(Hdhbh)] (1), [VO(phen)(dhbh)].1.5H2O (2), [Zn(Hdhbh)2] (3), [MoO2(dhbh)(D)] (D = H2O (4) or MeOH (5)), [Ru(PPh3)(dhbh)Cl(H2O)] (6), and [Pd(Hdhbh)Cl]·H2O (7) (H2dhbh = Schiff base derived from 2,4-dihydroxybenzaldehyde and benzoylhydrazone) have been isolated and characterized by IR, 1H NMR, Mass, UV-Visible and ESR spectroscopy. They were also investigated by cyclic voltammetry, thermal and magnetic measurements and the structure of complex cis-[MoO2(dhbh)(H2O)] (4) was solved by X-ray crystallography. Analytical data showed that H2dhbh behaves as monobasic/or dibasic tridentate ligand via phenolate O, azomethine N and amide O/or deprotonated amide O atoms. Antioxidant activity of the complexes has been evaluated against DPPH (2,2-diphenyl-1-picrylhydrazyl) radical and it has been found that oxovandium (IV) complex (2) displays the highest radical scavenging potency comparable to ascorbic acid as a standard antioxidant. The DNA binding properties of the ligand and its complexes have been investigated by electronic spectroscopy together with DNA cleavage by gel electrophoresis whose results showed also that vanadium (IV) complex (2) has a significant oxidative cleavage among other complexes.

Synthesis, characterization and tin/copper-nitrogen substitutional effect on photocatalytic activity of honeycomb ordered P2-Na2Ni2TeO6

NASA Astrophysics Data System (ADS)

Kadari, Ramaswamy; Velchuri, Radha; Sreenu, K.; Ravi, Gundeboina; Munirathnam, Nagegownivari R.; Vithal, Muga

2016-11-01

We have successfully prepared visible light active tin/copper-nitrogen co-doped honeycomb ordered P2-Na2Ni2TeO6 photocatalysts by solid state/ion exchange methods. Powder XRD, TG analysis, SEM, surface area, O-N-H analysis, ICP-OES, FT-IR and UV-DRS measurements are employed to characterize all the samples. All the doped compositions adopted hexagonal lattice with space group P63/mcm. The photocatalytic activity of all the samples was studied against the degradation of methyl violet (MV) and methylene blue (MB) under visible light irradiation. The variation of the photocatalytic activity due to the substitution of cation, anion and co-doping in Na2Ni2TeO6 is investigated. Co-doped samples have exhibited higher activity compared to rest of the materials. The role of reactive intermediate species in the photocatalytic degradation of dyes is also studied using appropriate scavengers.

Formation and removal of genotoxic activity during UV/H(2)O(2)-GAC treatment of drinking water.

PubMed

Heringa, M B; Harmsen, D J H; Beerendonk, E F; Reus, A A; Krul, C A M; Metz, D H; Ijpelaar, G F

2011-01-01

The objective of this study was to determine the genotoxic activity of water after UV/H(2)O(2) oxidation and GAC filtration. Pre-treated surface water from three locations was treated with UV/H(2)O(2) with medium pressure (MP) lamps and passed through granulated activated carbon (GAC). Samples taken before and after each treatment step were extracted and concentrated by solid phase extraction (SPE) and analyzed for genotoxicity using the Comet assay with HepG2 cells and the Ames II assay. The Comet assay showed no genotoxic response in any of the samples. In the Ames II, no genotoxic response was obtained with the TAMix (a mix of six strains), but the TA98 strain showed an increase in genotoxic activity after MP-UV/H(2)O(2) for all three locations. GAC post treatment effectively reduced the activities to control levels at two of the three locations and to below the level of the pre-treated water at one site. The results indicate that UV/H(2)O(2) treatment may lead to the formation of genotoxic by-products, which can be removed by subsequent GAC filtration. Copyright © 2010 Elsevier Ltd. All rights reserved.

Papain-templated Cu nanoclusters: assaying and exhibiting dramatic antibacterial activity cooperating with H2O2

NASA Astrophysics Data System (ADS)

Miao, Hong; Zhong, Dan; Zhou, Zinan; Yang, Xiaoming

2015-11-01

Herein, papain-functionalized Cu nanoclusters (CuNCs@Papain) were originally synthesized in aqueous solution together with a quantum yield of 14.3%, and showed obviously red fluorescence at 620 nm. Meanwhile, their corresponding fluorescence mechanism was fully elucidated by fluorescence spectroscopy, HR-TEM, FTIR spectroscopy, and XPS. Subsequently, the as-prepared CuNCs were employed as probes for detecting H2O2. Using CuNCs as probes, H2O2 was determined in the range from 1 μM to 50 μM based on a linear decrease of fluorescence intensity as well as a detection limit of 0.2 μM with a signal-to-noise ratio of 3. More significantly, it has been proved that CuNCs could convert H2O2 to &z.rad;OH, which exhibited dramatic antibacterial activity. Both in vitro and in vivo experiments were performed to validate their antibacterial activity against Gram-positive/negative bacteria and actual wound infection, suggesting their potential for serving as one type of promising antibacterial material.Herein, papain-functionalized Cu nanoclusters (CuNCs@Papain) were originally synthesized in aqueous solution together with a quantum yield of 14.3%, and showed obviously red fluorescence at 620 nm. Meanwhile, their corresponding fluorescence mechanism was fully elucidated by fluorescence spectroscopy, HR-TEM, FTIR spectroscopy, and XPS. Subsequently, the as-prepared CuNCs were employed as probes for detecting H2O2. Using CuNCs as probes, H2O2 was determined in the range from 1 μM to 50 μM based on a linear decrease of fluorescence intensity as well as a detection limit of 0.2 μM with a signal-to-noise ratio of 3. More significantly, it has been proved that CuNCs could convert H2O2 to &z.rad;OH, which exhibited dramatic antibacterial activity. Both in vitro and in vivo experiments were performed to validate their antibacterial activity against Gram-positive/negative bacteria and actual wound infection, suggesting their potential for serving as one type of promising

Cross section data sets for electron collisions with H2, O2, CO, CO2, N2O and H2O

NASA Astrophysics Data System (ADS)

Anzai, K.; Kato, H.; Hoshino, M.; Tanaka, H.; Itikawa, Y.; Campbell, L.; Brunger, M. J.; Buckman, S. J.; Cho, H.; Blanco, F.; Garcia, G.; Limão-Vieira, P.; Ingólfsson, O.

2012-02-01

We review earlier cross section data sets for electron-collisions with H2, O2, CO, CO2, H2O and N2O, updated here by experimental results for their electronic states. Based on our recent measurements of differential cross sections for the electronic states of those molecules, integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis and then assessed against theory (BE f-scaling [Y.-K. Kim, J. Chem. Phys. 126, 064305 (2007)]). As they now represent benchmark electronic state cross sections, those ICSs for the above molecules are added into the original cross section sets taken from the data reviews for H2, O2, CO2 and H2O (the Itikawa group), and for CO and N2O (the Zecca group).

Triosephosphate isomerase tyrosine nitration induced by heme-NaNO2 -H2 O2 or peroxynitrite: Effects of different natural phenolic compounds.

PubMed

Gao, Wanxia; Zhao, Jie; Li, Hailing; Gao, Zhonghong

2017-06-01

Peroxynitrite and heme peroxidases (or heme)-H 2 O 2 -NaNO 2 system are the two common ways to cause protein tyrosine nitration in vitro, but the effects of antioxidants on reducing these two pathways-induced protein nitration and oxidation are controversial. Both nitrating systems can dose-dependently induce triosephosphate isomerase (TIM) nitration, however, heme-H 2 O 2 -NaNO 2 was less destructive to protein secondary structures and led to more nitrated tyrosine residue than 3-morpholinosydnonimine hydrochloride (SIN-1, a peroxynitrite donor). Both of desferrioxamine and catechin could inhibit TIM nitration induced by heme-H 2 O 2 -NaNO 2 and SIN-1 and protein oxidation induced by SIN-1, but promoted heme-H 2 O 2 -NaNO 2 -induced protein oxidation. Moreover, the antagonism of natural phenolic compounds on SIN-1-induced tyrosine nitration was consistent with their radical scavenging ability, but no similar consensus was found in heme-H 2 O 2 -NaNO 2 -induced nitration. Our results indicated that peroxynitrite and heme-H 2 O 2 -NaNO 2 -induced protein nitration was different, and the later one could be a better model for anti-nitration compounds screening. © 2017 Wiley Periodicals, Inc.

Persulfate activation by iron oxide-immobilized MnO2 composite: identification of iron oxide and the optimum pH for degradations.

PubMed

Jo, Young-Hoon; Do, Si-Hyun; Kong, Sung-Ho

2014-01-01

Iron oxide-immobilized manganese oxide (MnO2) composite was prepared and the reactivity of persulfate (PS) with the composite as activator was investigated for degradation of carbon tetrachloride and benzene at various pH levels. Brunauer-Emmett-Teller (BET) surface area of the composite was similar to that of pure MnO2 while the pore volume and diameter of composite was larger than those of MnO2. Scanning electron microscopy couples with energy dispersive spectroscopy (SEM-EDS) showed that Fe and Mn were detected on the surface of the composite, and X-ray diffraction (XRD) analysis indicated the possibilities of the existence of various iron oxides on the composite surface. Furthermore, the analyses of X-ray photoelectron (XPS) spectra revealed that the oxidation state of iron was identified as 1.74. In PS/composite system, the same pH for the highest degradation rates of both carbon tetrachloride and benzene were observed and the value of pH was 9. Scavenger test was suggested that both oxidants (i.e. hydroxyl radical, sulfate radical) and reductant (i.e. superoxide anion) were effectively produced when PS was activated with the iron-immobilized MnO2. Copyright © 2013 Elsevier Ltd. All rights reserved.

Mechanistic analysis of water oxidation catalyst cis-[Ru(bpy) 2(H 2O) 2] 2+: Effect of dimerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erdman, Darren; Pineda-Galvan, Yuliana; Pushkar, Yulia

While the catalytic activity of some Ru-based polypyridine complexes in water oxidation is well established, the relationship between their chemical structure and activity is less known. In this work, the single site Ru complex [Ru(bpy) 2(H 2O) 2] 2+ (bpy = 2,20-bipyridine)—which can exist as either a cis isomer or a trans isomer—is investigated. While a difference in the catalytic activity of these two isomers is well established, with cis-[Ru(bpy) 2(H 2O) 2] 2+ being much more active, no mechanistic explanation of this fact has been presented. The oxygen evolving capability of both isomers at multiple concentrations has been investigated,more » with cis-[Ru(bpy) 2(H 2O) 2] 2+ showing a second-order dependence of O2 evolution activity with increased catalyst concentration. Measurement of the electron paramagnetic resonance (EPR) spectrum of cis-[Ru(bpy) 2(H 2O) 2] 2+, shortly after oxidation with CeIV, showed the presence of a signal matching that of cis,cis-[Ru III(bpy) 2(H 2O)ORu IV(bpy) 2(OH)] 4+, also known as “blue dimer”. The formation of dimers is a concentration-dependent process, which could serve to explain the greater than first order increase in catalytic activity. The trans isomer showed a first-order dependence of O 2 evolution on catalyst concentration. As a result, behavior of [Ru(bpy) 2(H 2O) 2] 2+ isomers is compared with other Ru-based catalysts, in particular [Ru(tpy)(bpy)(H 2O)] 2+ (tpy = 2,20;6,20 0-terpyridine).« less

Mechanistic analysis of water oxidation catalyst cis-[Ru(bpy) 2(H 2O) 2] 2+: Effect of dimerization

DOE PAGES

Erdman, Darren; Pineda-Galvan, Yuliana; Pushkar, Yulia

2017-01-25

While the catalytic activity of some Ru-based polypyridine complexes in water oxidation is well established, the relationship between their chemical structure and activity is less known. In this work, the single site Ru complex [Ru(bpy) 2(H 2O) 2] 2+ (bpy = 2,20-bipyridine)—which can exist as either a cis isomer or a trans isomer—is investigated. While a difference in the catalytic activity of these two isomers is well established, with cis-[Ru(bpy) 2(H 2O) 2] 2+ being much more active, no mechanistic explanation of this fact has been presented. The oxygen evolving capability of both isomers at multiple concentrations has been investigated,more » with cis-[Ru(bpy) 2(H 2O) 2] 2+ showing a second-order dependence of O2 evolution activity with increased catalyst concentration. Measurement of the electron paramagnetic resonance (EPR) spectrum of cis-[Ru(bpy) 2(H 2O) 2] 2+, shortly after oxidation with CeIV, showed the presence of a signal matching that of cis,cis-[Ru III(bpy) 2(H 2O)ORu IV(bpy) 2(OH)] 4+, also known as “blue dimer”. The formation of dimers is a concentration-dependent process, which could serve to explain the greater than first order increase in catalytic activity. The trans isomer showed a first-order dependence of O 2 evolution on catalyst concentration. As a result, behavior of [Ru(bpy) 2(H 2O) 2] 2+ isomers is compared with other Ru-based catalysts, in particular [Ru(tpy)(bpy)(H 2O)] 2+ (tpy = 2,20;6,20 0-terpyridine).« less

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

PubMed

Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

2012-02-20

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

Endothelium-derived hyperpolarizing factor and protein kinase G Iα activation: H2O2 versus S-nitrosothiols.

PubMed

Bautista-Niño, Paula K; van der Stel, Marien; Batenburg, Wendy W; de Vries, René; Roks, Anton J M; Danser, A H Jan

2018-05-15

Protein kinase G (PKG) Iα mediates the cyclic guanosine monophosphate-mediated vasodilatory effects induced by NO. Endothelium-derived hyperpolarizing factors (EDHFs), like H 2 O 2 can activate PKGIα in a cyclic guanosine monophosphate-independent manner, but whether this is true for all EDHFs (e.g., S-nitrosothiols) is unknown. Here, we investigated the contribution of PKGIα to bradykinin-, H 2 O 2 -, L-S-nitrosocysteine-, and light-induced relaxation in porcine coronary arteries, making use of the fact that thioredoxin reductase inhibition with auranofin or 1-chloro-2,4-dinitrobenzene potentiates PKGIα. Thioredoxin reductase inhibition potentiated bradykinin and H 2 O 2 , but not L-S-nitrosocysteine or light. The relaxations by the latter 2 and bradykinin, but not those by H 2 O 2 , were prevented by the soluble guanylyl cyclase (sGC) inhibitor 1H-[1,2,4]oxadiazolo[4,3-a]quinoxalin-1-one. Yet, after S-nitrosothiol depletion with ethacrynic acid, thioredoxin reductase inhibition also potentiated light-induced relaxation, and this was prevented by the Na + -K + ATPase inhibitor ouabain. This indicates that photorelaxation depends on sGC activation by S-nitrosothiols, while only after S-nitrosothiol depletion oxidized PKGIα comes into play, and acts via Na + -K + ATPase. In conclusion, both bradykinin- and light-induced relaxation of porcine coronary arteries depend, at least partially, on oxidized PKGIα, and this does not involve sGC. H 2 O 2 also acts via oxidized PKGIα in an sGC-independent manner. Yet, S-nitrosothiol-induced relaxation is PKGIα-independent. Clearly, PKG activation does not contribute universally to all EDHF responses, and targeting PKGIα may only mimick EDHF under certain conditions. It is therefore unlikely that PKGIα activators will be universal vasodilators. Copyright © 2018 Elsevier B.V. All rights reserved.

Preparation and catalytic activities for H{sub 2}O{sub 2} decomposition of Rh/Au bimetallic nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Haijun, E-mail: zhanghaijun@wust.edu.cn; The State Key Laboratory of Refractory and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081; Deng, Xiangong

2016-07-15

Graphical abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) were prepared by using hydrogen sacrificial reduction method, the activity of Rh80Au20 BNPs were about 3.6 times higher than that of Rh NPs. - Highlights: • Rh/Au bimetallic nanoparticles (BNPs) of 3∼5 nm in diameter were prepared. • Activity for H{sub 2}O{sub 2} decomposition of BNPs is 3.6 times higher than that of Rh NPs. • The high activity of BNPs was caused by the existence of charged Rh atoms. • The apparent activation energy for H{sub 2}O{sub 2} decomposition over the BNPs was calculated. - Abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) weremore » prepared by using hydrogen sacrificial reduction method and characterized by UV–vis, XRD, FT-IR, XPS, TEM, HR-TEM and DF-STEM, the effects of composition on their particle sizes and catalytic activities for H{sub 2}O{sub 2} decomposition were also studied. The as-prepared Rh/Au BNPs possessed a high catalytic activity for the H{sub 2}O{sub 2} decomposition, and the activity of the Rh{sub 80}Au{sub 20} BNPs with average size of 2.7 nm were about 3.6 times higher than that of Rh monometallic nanoparticles (MNPs) even the Rh MNPs possess a smaller particle size of 1.7 nm. In contrast, Au MNPs with size of 2.7 nm show no any activity. Density functional theory (DFT) calculation as well as XPS results showed that charged Rh and Au atoms formed via electronic charge transfer effects could be responsible for the high catalytic activity of the BNPs.« less

A Computational Investigation of the Oxidative Deboronation of BoroGlycine, H2N–CH2–B(OH)2, Using H2O and H2O2

PubMed Central

Larkin, Joseph D.; Markham, George D.; Milkevitch, Matt; Brooks, Bernard R.; Bock, Charles W.

2014-01-01

We report results from a computational investigation of the oxidative deboronation of BoroGlycine, H2N–CH2–B(OH)2, using H2O and H2O2 as the reactive oxygen species (ROS) to yield aminomethanol, H2N–CH2–OH; these results complement our study on the protodeboronation of BoroGlycine to produce methylamine, H2N–CH3 (Larkin et al. J. Phys. Chem. A, 111, 6489–6500, 2007). Second-order Møller-Plesset (MP2) perturbation theory with Dunning-Woon correlation-consistent (cc) basis sets were used for the calculations with comparisons made to results from Density Functional Theory (DFT) at the PBE1PBE/6-311++G(d,p)(cc-pVDZ) levels. The effects of a bulk aqueous environment were also incorporated into the calculations employing PCM and CPCM methodology. Using H2O as the ROS, the reaction H2O + H2N–CH2–B(OH)2 → H2N–CH2–OH + H–B(OH)2 was calculated to be endothermic, the value of ΔH2980 was +12.0 kcal/mol at the MP2(FC)/cc-pVTZ computational level in vacuo and +13.7 kcal/mol in PCM aqueous media; the corresponding value for the activation barrier, ΔH‡, was +94.3 kcal/mol relative to the separated reactants in vacuo and +89.9 kcal/mol in PCM aqueous media. In contrast, the reaction H2O2 + H2N–CH2–B(OH)2 → H2N–CH2–OH + B(OH)3 was calculated to be highly exothermic with a ΔH2980 value of −100.9 kcal/mol at the MP2(FC)/cc-pVTZ computational level in vacuo and −99.6 kcal/mol in CPCM aqueous media; the highest-energy transition state for the multi-step process associated with this reaction involved the rearrangement of H2N–CH2–B(OH)(OOH) to H2N–CH2–O–B(OH)2 with a ΔH‡ value of +23.2 kcal/mol in vacuo relative to the separated reactants. These computational results for BoroGlycine are in accord with the experimental observations for the deboronation of the FDA approved anti-cancer drug Bortezomib (Velcade™, PS-341) where it was found to be the principle deactivation pathway. (Labutti et al. Chem. Res. Toxicol., 19, 539–546

Degradation of nitrobenzene wastewater in an acidic environment by Ti(IV)/H2O2/O3 in a rotating packed bed.

PubMed

Yang, Peizhen; Luo, Shuai; Liu, Youzhi; Jiao, Weizhou

2018-06-23

The rotating packed bed (RPB) as a continuous flow reactor performs very well in degradation of nitrobenzene wastewater. In this study, acidic nitrobenzene wastewater was degraded using ozone (O 3 ) combined with hydrogen peroxide and titanium ions (Ti(IV)/H 2 O 2 /O 3 ) or using only H 2 O 2 /O 3 in a RPB. The degradation efficiency of nitrobenzene by Ti(IV)/H 2 O 2 /O 3 is roughly 16.84% higher than that by H 2 O 2 /O 3 , and it reaches as high as 94.64% in 30 min at a H 2 O 2 /O 3 molar ratio of 0.48. It is also found that the degradation efficiency of nitrobenzene is significantly affected by the high gravity factor, H 2 O 2 /O 3 molar ratio, and Ti(IV) concentration, and it reaches a maximum at a high gravity factor of 40, a Ti(IV) concentration of 0.50 mmol/L, a pH of 4.0, a H 2 O 2 /O 3 molar ratio of 0.48, a liquid flow rate of 120 L/h, and an initial nitrobenzene concentration of 1.22 mmol/L. Both direct ozonation and indirect ozonation are involved in the reaction of O 3 with organic pollutants. The indirect ozonation due to the addition of different amounts of tert-butanol (·OH scavenger) in the system accounts for 84.31% of the degradation efficiency of nitrobenzene, indicating that the nitrobenzene is dominantly oxidized by ·OH generated in the RPB-Ti(IV)/H 2 O 2 /O 3 process. Furthermore, the possible oxidative degradation mechanisms are also proposed to better understand the role of RPB in the removal of pollutants. Graphical abstract ᅟ.

Crystal structures of ZnCl2·2.5H2O, ZnCl2·3H2O and ZnCl2·4.5H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The formation of different complexes in aqueous solutions is an important step in understanding the behavior of zinc chloride in water. The structure of concentrated ZnCl2 solutions is governed by coordination competition of Cl− and H2O around Zn2+. According to the solid–liquid phase diagram, the title compounds were crystallized below room temperature. The structure of ZnCl2·2.5H2O contains Zn2+ both in a tetra­hedral coordination with Cl− and in an octa­hedral environment defined by five water mol­ecules and one Cl− shared with the [ZnCl4]2− unit. Thus, these two different types of Zn2+ cations form isolated units with composition [Zn2Cl4(H2O)5] (penta­aqua-μ-chlorido-tri­chlorido­di­zinc). The trihydrate {hexa­aqua­zinc tetra­chlorido­zinc, [Zn(H2O)6][ZnCl4]}, consists of three different Zn2+ cations, one of which is tetra­hedrally coordinated by four Cl− anions. The two other Zn2+ cations are each located on an inversion centre and are octa­hedrally surrounded by water mol­ecules. The [ZnCl4] tetra­hedra and [Zn(H2O)6] octa­hedra are arranged in alternating rows parallel to [001]. The structure of the 4.5-hydrate {hexa­aqua­zinc tetra­chlorido­zinc trihydrate, [Zn(H2O)6][ZnCl4]·3H2O}, consists of isolated octa­hedral [Zn(H2O)6] and tetra­hedral [ZnCl4] units, as well as additional lattice water mol­ecules. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ZnCl4 tetra­hedra and water mol­ecules as acceptor groups leads to the formation of a three-dimensional network in each of the three structures. PMID:25552980

H2O Paradox and its Implications on H2O in Moon

NASA Astrophysics Data System (ADS)

Zhang, Youxue

2017-04-01

The concentration of H2O in the mantle of a planetary body plays a significant role in the viscosity and partial melting and hence the convection and evolution of the planetary body. Even though the composition of the primitive terrestrial mantle (PTM) is thought to be well known [1-2], the concentration of H2O in PTM remains paradoxial because different methods of estimation give different results [3]: Using H2O/Ce ratio in MORB and OIB and Ce concentration in PTM, the H2O concentration in PTM would be (300÷×1.5) ppm; using mass balance by adding surface water to the mantle [3-4], H2O concentration in PTM would be (900÷×1.3) ppm [2-3]. The inconsistency based on these two seemingly reliable methods is referred to as the H2O paradox [3]. For Moon, H2O contents in the primitive lunar mantle (PLM) estimated from H2O in plagioclase in lunar anorthosite and that from H2O/Ce ratio in melt inclusions are roughly consistent at ˜110 ppm [5-6] even though there is still debate about the volatile depletion trend [7]. One possible solution to the H2O paradox in PTM is to assume that early Earth experienced whole mantle degassing, which lowered the H2O/Ce ratio in the whole mantle but without depleting Ce in the mantle. The second possible solution is that some deep Earth reservoirs with high H2O/Ce ratios have not been sampled by MORB and OIB. Candidates include the transition zone [8] and the D" layer. The third possible solution is that ocean water only partially originated from mantle degassing, but partially from extraterrestrial sources such as comets [9-10]. At present, there is not enough information to determine which scenario is the answer to the H2O paradox. On the other hand, each scenario would have its own implications to H2O in PLM. If the first scenario applies to Moon, because degassed H2O or H2 would have escaped from the lunar surface, the very early lunar mantle could have much higher H2O [11] than that obtained using the H2O/Ce ratio method. The

Nitroxides protect horseradish peroxidase from H2O2-induced inactivation and modulate its catalase-like activity.

PubMed

Samuni, Amram; Maimon, Eric; Goldstein, Sara

2017-08-01

Horseradish peroxidase (HRP) catalyzes H 2 O 2 dismutation while undergoing heme inactivation. The mechanism underlying this process has not been fully elucidated. The effects of nitroxides, which protect metmyoglobin and methemoglobin against H 2 O 2 -induced inactivation, have been investigated. HRP reaction with H 2 O 2 was studied by following H 2 O 2 depletion, O 2 evolution and heme spectral changes. Nitroxide concentration was followed by EPR spectroscopy, and its reactions with the oxidized heme species were studied using stopped-flow. Nitroxide protects HRP against H 2 O 2 -induced inactivation. The rate of H 2 O 2 dismutation in the presence of nitroxide obeys zero-order kinetics and increases as [nitroxide] increases. Nitroxide acts catalytically since its oxidized form is readily reduced to the nitroxide mainly by H 2 O 2 . The nitroxide efficacy follows the order 2,2,6,6-tetramethyl-piperidine-N-oxyl (TPO)>4-OH-TPO>3-carbamoyl proxyl>4-oxo-TPO, which correlates with the order of the rate constants of nitroxide reactions with compounds I, II, and III. Nitroxide catalytically protects HRP against inactivation induced by H 2 O 2 while modulating its catalase-like activity. The protective role of nitroxide at μM concentrations is attributed to its efficient oxidation by P940, which is the precursor of the inactivated form P670. Modeling the dismutation kinetics in the presence of nitroxide adequately fits the experimental data. In the absence of nitroxide the simulation fits the observed kinetics only if it does not include the formation of a Michaelis-Menten complex. Nitroxides catalytically protect heme proteins against inactivation induced by H 2 O 2 revealing an additional role played by nitroxide antioxidants in vivo. Copyright © 2017 Elsevier B.V. All rights reserved.

Crystal and molecular structure of Sr{sub 2}(Edta) . 5H{sub 2}O, Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O, and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O strontium ethylenediaminetetraacetates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polyakova, I. N., E-mail: polyakova@igic.ras.ru; Poznyak, A. L.; Sergienko, V. S.

2009-03-15

Three Sr{sup 2+} compounds with the Edta{sup 4-} and H{sub 2}Edta{sup 2-} ligands-Sr{sub 2}(Edta) . 5H{sub 2}O (I), Sr{sub 2}(H{sub 2}Edta)(HCO{sub 3}){sub 2} . 4H{sub 2}O (II), and Sr{sub 2}(H{sub 2}Edta)Cl{sub 2} . 5H{sub 2}O (III)-are synthesized, and their crystal structures are studied. In I, the Sr(1) atom is coordinated by the hexadentate Edta{sup 4-} ligand following the 2N + 4O pattern and by two O atoms of the neighboring ligands, which affords the formation of zigzag chains. The Sr(2) atom forms bonds with O atoms of five water molecules and attaches itself to a chain via bonds with threemore » O atoms of the Edta{sup 4-} ligands. The Sr(1)-O and Sr(2)-O bond lengths fall in the ranges 2.520(2)-2.656(3) and 2.527(3)-2.683(2) A, respectively. The Sr(1)-N bonds are 2.702(3) and 2.743(3) A long. In II and III, the H{sub 2}Edta{sup 2-} anions have a centrosymmetric structure with the trans configuration of the planar ethylenediamine fragment. The N atoms are blocked by acid protons. In II, the environment of the Sr atom is formed by six O atoms of three H{sub 2}Edta ligands, two O atoms of water molecules, and an O atom of the bicarbonate ion, which is disordered over two positions. In III, the environment of the Sr atom includes six O atoms of four H{sub 2}Edta{sup 2-} ligands and three O atoms of water molecules. The coordination number of the Sr atoms is equal to 8 + 1. In II and III, the main bonds fall in the ranges 2.534(3)-2.732(2) and 2.482(2)-2.746(3) A, whereas the ninth bond is elongated to 2.937(3) and 3.055(3) A, respectively. In II, all the structural elements are linked into wavy layers. The O-H-O interactions contribute to the stabilization of the layer and link neighboring layers. In III, hydrated Sr{sup 2+} cations and H{sub 2}Edta{sup -} anions form a three-dimensional [Sr{sub 2}(H{sub 2}Edta)(H{sub 2}O){sub 3}]{sub n}{sup 2n+} framework. The Cl{sup -} anions are fixed in channels of the framework by hydrogen bonds with four water

Studies of CW lasing action in CO2-CO, N2O-CO, CO2-H2O, and N2O-H2O mixtures pumped by blackbody radiation

NASA Technical Reports Server (NTRS)

Abel, Robert W.; Christiansen, Walter H.; Li, Jian-Guo

1988-01-01

A proof of principle experiment to evaluate the efficacy of CO and H2O in increasing the power output for N2O and CO2 lasing mixtures has been conducted and theoretically analyzed for a blackbody radiation-pumped laser. The results for N2O-CO, CO2-CO, N2O-H2O and CO2-H2O mixtures are presented. Additions of CO to the N2O lasant increased power up to 28 percent for N2O laser mixtures, whereas additions of CO to the CO2 lasant, and the addition of H2O to both the CO2 and N2O lasants, resulted in decreased output power.

Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

PubMed

Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

2012-04-19

The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

Direct Z-scheme TiO2/CdS hierarchical photocatalyst for enhanced photocatalytic H2-production activity

NASA Astrophysics Data System (ADS)

Meng, Aiyun; Zhu, Bicheng; Zhong, Bo; Zhang, Liuyang; Cheng, Bei

2017-11-01

Photocatalytic H2 evolution, which utilizes solar energy via water splitting, is a promising route to deal with concerns about energy and environment. Herein, a direct Z-scheme TiO2/CdS binary hierarchical photocatalyst was fabricated via a successive ionic layer adsorption and reaction (SILAR) technique, and photocatalytic H2 production was measured afterwards. The as-prepared TiO2/CdS hybrid photocatalyst exhibited noticeably promoted photocatalytic H2-production activity of 51.4 μmol h-1. The enhancement of photocatalytic activity was ascribed to the hierarchical structure, as well as the efficient charge separation and migration from TiO2 nanosheets to CdS nanoparticles (NPs) at their tight contact interfaces. Moreover, the direct Z-scheme photocatalytic reaction mechanism was demonstrated to elucidate the improved photocatalytic performance of TiO2/CdS composite photocatalyst. The photoluminescence (PL) analysis of hydroxyl radicals were conducted to provide clues for the direct Z-scheme mechanism. This work provides a facile route for the construction of redox mediator-free Z-scheme photocatalytic system for photocatalytic water splitting.

Quantitative structure-activity relationship for the oxidation of aromatic organic contaminants in water by TAML/H2O2.

PubMed

Su, Hanrui; Yu, Chunyang; Zhou, Yongfeng; Gong, Lidong; Li, Qilin; Alvarez, Pedro J J; Long, Mingce

2018-05-02

Tetra-amido macrocyclic ligand (TAML) activator is a functional analog of peroxidase enzymes, which activates hydrogen peroxide (H 2 O 2 ) to form high valence iron-oxo complexes that selectively degrade persistent aromatic organic contaminants (ACs) in water. Here, we develop quantitative structure-activity relationship (QSAR) models based on measured pseudo first-order kinetic rate coefficients (k obs ) of 29 ACs (e.g., phenols and pharmaceuticals) oxidized by TAML/H 2 O 2 at neutral and basic pH values to gain mechanistic insight on the selectivity and pH dependence of TAML/H 2 O 2 systems. These QSAR models infer that electron donating ability (E HOMO ) is the most important AC characteristic for TAML/H 2 O 2 oxidation, pointing to a rate-limiting single-electron transfer (SET) mechanism. Oxidation rates at pH 7 also depend on AC reactive indices such as f min - and qH + , which respectively represent propensity for electrophilic attack and the most positive net atomic charge on hydrogen atoms. At pH 10, TAML/H 2 O 2 is more reactive towards ACs with a lower hydrogen to carbon atoms ratio (#H:C), suggesting the significance of hydrogen atom abstraction. In addition, lnk obs of 14 monosubstituted phenols is negatively correlated with Hammett constants (σ) and exhibits similar sensitivity to substituent effects as horseradish peroxidase. Although accurately predicting degradation rates of specific ACs in complex wastewater matrices could be difficult, these QSAR models are statistically robust and help predict both relative degradability and reaction mechanism for TAML/H 2 O 2 -based treatment processes. Copyright © 2018 Elsevier Ltd. All rights reserved.

Comparative effect of simulated solar light, UV, UV/H2O2 and photo-Fenton treatment (UV-Vis/H2O2/Fe2+,3+) in the Escherichia coli inactivation in artificial seawater.

PubMed

Rubio, D; Nebot, E; Casanueva, J F; Pulgarin, C

2013-10-15

Innovative disinfection technologies are being studied for seawater, seeking a viable alternative to chlorination. This study proposes the use of H2O2/UV254 and photo-Fenton as disinfection treatment in seawater. The irradiations were carried out using a sunlight simulator (Suntest) and a cylindrical UV reactor. The efficiency of the treatment was compared for Milli-Q water, Leman Lake water and artificial seawater. The presence of bicarbonates and organic matter was investigated in order to evaluate possible effects on the photo-Fenton disinfection treatment. The photo-Fenton treatment, employing 1 mg L(-1) Fe(2+) and 10 mg L(-1) of H2O2, led to the fastest bacterial inactivation kinetics. Using H2O2/UV254 high disinfection rates were obtained similar to those obtained with photo-Fenton under UV254 light. In Milli-Q water, the rate of inactivation for Escherichia coli was higher than in Leman Lake water and seawater due to the lack of inorganic ions affecting negatively bacteria inactivation. The presence of bicarbonate showed scavenging of the OH(•) radicals generated in the treatment of photo-Fenton and H2O2/UV254. Despite the negative effect of inorganic ions, especially HCO3(-), the disinfection treatments with AOPs in lake water and seawater improved significantly the disinfection compared to light alone (simulated sunlight and UV254). In the treatment of photo-Fenton with simulated sunlight, dissolved organic matter had a beneficial effect by increasing the rate of inactivation. This is associated with the formation of Fe(3+)-organo photosensitive complexes leading to the formation of ROS able to inactivate bacteria. This effect was not observed in the photo-Fenton with UV254. Growth of E. coli surviving in seawater was observed 24 and 48 h after treatment with UV light. However, growth of surviving bacteria was not detected after photo-Fenton with UV254 and H2O2/UV254 treatments. This study suggests H2O2/UV254 and photo-Fenton treatments for the

Kinetics and oxidative mechanism for H2O2-enhanced iron-mediated aeration (IMA) treatment of recalcitrant organic compounds in mature landfill leachate.

PubMed

Deng, Yang; Englehardt, James D

2009-09-30

A hydrogen peroxide (H(2)O(2))-enhanced iron (Fe(0))-mediated aeration (IMA) process has been recently demonstrated to effectively remove organic wastes from mature landfill leachate. In this paper, the kinetics and oxidative mechanisms of the enhanced IMA treatment were studied. Bench-scale full factorial tests were conducted in an orbital shaker reactor for treatment of a mature leachate with an initial chemical oxygen demand (COD) of 900-1200 mg/L. At the maximum aeration rate (8.3 mL air/min mL sample), process variables significantly influencing the rates of H(2)O(2) decay and COD removal were pH (3.0-8.0), initial H(2)O(2) doses (0.21-0.84 M), and Fe(0) surface area concentrations (0.06-0.30 m(2)/L). Empirical kinetic models were developed and verified for the degradation of H(2)O(2) and COD. High DO maintained by a high aeration rate slowed the H(2)O(2) self-decomposition, accelerated Fe(0) consumption, and enhanced the COD removal. In hydroxyl radical (OH*) scavenging tests, the rate of removal of glyoxylic acid (target compound) was not inhibited by the addition of para-chlorobenzoic acid (OH* scavenger) at pH 7.0-7.5, ruling out hydroxyl radical as the principal oxidant in neutral-weakly basic solution. These experimental results show that this enhanced IMA technology is a potential alternative for the treatment of high strength recalcitrant organic wastewaters.

Removal of H2O2 and generation of superoxide radical: Role of cytochrome c and NADH

PubMed Central

Velayutham, Murugesan; Hemann, Craig; Zweier, Jay L.

2011-01-01

In cells, mitochondria, endoplasmic reticulum, and peroxisomes are the major sources of reactive oxygen species (ROS) under physiological and pathophysiological conditions. Cytochrome c (cyt c) is known to participate in mitochondrial electron transport and has antioxidant and peroxidase activities. Under oxidative or nitrative stress, the peroxidase activity of Fe3+cyt c is increased. The level of NADH is also increased under pathophysiological conditions such as ischemia and diabetes and a concurrent increase in hydrogen peroxide (H2O2) production occurs. Studies were performed to understand the related mechanisms of radical generation and NADH oxidation by Fe3+cyt c in the presence of H2O2. Electron paramagnetic resonance (EPR) spin trapping studies using 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) were performed with NADH, Fe3+cyt c, and H2O2 in the presence of methyl-β-cyclodextrin. An EPR spectrum corresponding to the superoxide radical adduct of DMPO encapsulated in methyl-β-cyclodextrin was obtained. This EPR signal was quenched by the addition of the superoxide scavenging enzyme Cu,Zn-superoxide dismutase (SOD1). The amount of superoxide radical adduct formed from the oxidation of NADH by the peroxidase activity of Fe3+cyt c increased with NADH and H2O2 concentration. From these results, we propose a mechanism in which the peroxidase activity of Fe3+cyt c oxidizes NADH to NAD•, which in turn donates an electron to O2 resulting in superoxide radical formation. A UV-visible spectroscopic study shows that Fe3+cyt c is reduced in the presence of both NADH and H2O2. Our results suggest that Fe3+cyt c could have a novel role in the deleterious effects of ischemia/reperfusion and diabetes due to increased production of superoxide radical. In addition, Fe3+cyt c may play a key role in the mitochondrial “ROS-induced ROS-release (RIRR)” signaling and in mitochondrial and cellular injury/death. The increased oxidation of NADH and generation of superoxide radical

Influence of the Organic Species and Oxoanion in the Synthesis of two Uranyl Sulfate Hydrates, (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 ­(H 2 O)]·7H 2 O and (H 3 O) 2 [(UO 2 ) 2 (SO 4 ) 3 (H 2 O)]·4H 2 O, and a Uranyl Selenate-Selenite [C 5 H 6 N][(UO 2 )(SeO 4 )(HSeO 3 )

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

2012-08-08

Two uranyl sulfate hydrates, (H3O)2[(UO2)2(SO4)3(H2O)]·7H2O (NDUS) and (H3O)2[(UO2)2(SO4)3(H2O)]·4H2O (NDUS1), and one uranyl selenate-selenite [C5H6N][(UO2)(SeO4)(HSeO3)] (NDUSe), were obtained and their crystal structures solved. NDUS and NDUSe result from reactions in highly acidic media in the presence of L-cystine at 373 K. NDUS crystallized in a closed vial at 278 K after 5 days and NDUSe in an open beaker at 278 K after 2 weeks. NDUS1 was synthesized from aqueous solution at room temperature over the course of a month. NDUS, NDUS1, and NDUSe crystallize in the monoclinic space group P21/n, a = 15.0249(4) Å,b = 9.9320(2) Å, c = 15.6518(4)more » Å, β = 112.778(1)°, V = 2153.52(9) Å3,Z = 4, the tetragonal space group P43212, a = 10.6111(2) Å,c = 31.644(1) Å, V = 3563.0(2) Å3, Z = 8, and in the monoclinic space group P21/n, a = 8.993(3) Å, b = 13.399(5) Å, c = 10.640(4) Å,β = 108.230(4)°, V = 1217.7(8) Å3, Z = 4, respectively.The structural units of NDUS and NDUS1 are two-dimensional uranyl sulfate sheets with a U/S ratio of 2/3. The structural unit of NDUSe is a two-dimensional uranyl selenate-selenite sheets with a U/Se ratio of 1/2. In-situ reaction of the L-cystine ligands gives two distinct products for the different acids used here. Where sulfuric acid is used, only H3O+ cations are located in the interlayer space, where they balance the charge of the sheets, whereas where selenic acid is used, interlayer C5H6N+ cations result from the cyclization of the carboxyl groups of L-cystine, balancing the charge of the sheets.« less

On the role of the termolecular reactions 2O2 + H2 → 2HO2 and 2O2 + H2 → H + HO2 + O2 in formation of the first radicals in hydrogen combustion: ab initio predictions of energy barriers.

PubMed

Monge-Palacios, M; Rafatijo, Homayoon

2017-01-18

We have investigated the role of termolecular reactions in the early chemistry of hydrogen combustion. We performed molecular chemical dynamics simulations using ReaxFF in LAMMPS to identify potential initial reactions for a 1 : 4 mixture of H 2  : O 2 in the NVT ensemble at density 276.3 kg m -3 and ∼3000 K (∼4000 atm) and ∼4000 K (∼5000 atm), and then characterized the saddle points for those reactions using ab initio methods: CCSD(T) = FC/cc-pVTZ//MP2/6-31G, CCSD(T) = FULL/aug-cc-pVTZ//CCSD = FC/cc-pVTZ and CASSCF MP2/6-31G//MP2/6-31G. The main initial reaction is H 2 + O 2 → H + HO 2 , frequently occurring in the presence of a second O 2 as a third body; that is, 2O 2 + H 2 → H + HO 2 + O 2 . The second most frequent reaction is 2O 2 + H 2 → 2HO 2 . We found three saddle points on the triplet PES of these termolecular reactions: one for 2O 2 + H 2 → H + HO 2 + O 2 and two for 2O 2 + H 2 → 2HO 2 . In the latter case, one has a symmetric structure consistent with simultaneous formation of two HO 2 and the other corresponds to a bimolecular reaction between O 2 and H 2 that is "interrupted" by a second O 2 before going to completion. The classical barrier height of the symmetric saddle point for 2O 2 + H 2 → 2HO 2 is 49.8 kcal mol -1 . The barrier to H 2 + O 2 → H + HO 2 is 58.9 kcal mol -1 . The termolecular reaction will be competitive with H 2 + O 2 → H + HO 2 only at sufficiently high pressures.

Copper-promoted circumneutral activation of H2O2 by magnetic CuFe2O4 spinel nanoparticles: Mechanism, stoichiometric efficiency, and pathway of degrading sulfanilamide.

PubMed

Feng, Yong; Liao, Changzhong; Shih, Kaimin

2016-07-01

To evaluate the heterogeneous degradation of sulfanilamide by external energy-free Fenton-like reactions, magnetic CuFe2O4 spinel nanoparticles (NPs) were synthesized and used as catalysts for activation of hydrogen peroxide (H2O2). The physicochemical properties of the CuFe2O4 NPs were characterized with several techniques, including X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and magnetometry. In the catalytic experiments, CuFe2O4 NPs/H2O2 oxidation showed the best degradation performance in the circumneutral conditions that resulted from the presence of Cu(II) on the surface of the CuFe2O4 NPs. The surface area-normalized pseudo-first-order rate constants were calculated as 2.60 × 10(-2) L m(-1) min(-1), 2.58 × 10(-3) L m(-1) min(-1), 1.92 × 10(-3) L m(-1) min(-1), and 7.30 × 10(-4) L m(-1) min(-1) for CuO, CuFe2O4 NPs, Fe3O4, and α-Fe2O3 catalysts, respectively. Thus, solid state Cu(II) was more reactive and efficient than Fe(III) in the circumneutral activation of H2O2; this finding was further supported by the results regarding the stoichiometric efficiency of H2O2. The effects of experimental parameters such as the oxidant dosage and catalyst loading were investigated. The mechanism for H2O2 activation on the spinel surface was explored and could be explained by the solid redox cycles of Fe(II)/Fe(III) and Cu(II)/Cu(I). Based on the products detected, a degradation pathway via the CS bond cleavage is proposed for the degradation of sulfanilamide. The findings of this study suggest that copper can be used as a doping metal to improve the reactivity and expand the effective pH range of iron oxides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetics of CO/CO2 and H2/H2O reactions at Ni-based and ceria-based solid-oxide-cell electrodes.

PubMed

Graves, Christopher; Chatzichristodoulou, Christodoulos; Mogensen, Mogens B

2015-01-01

The solid oxide electrochemical cell (SOC) is an energy conversion technology that can be operated reversibly, to efficiently convert chemical fuels to electricity (fuel cell mode) as well as to store electricity as chemical fuels (electrolysis mode). The SOC fuel-electrode carries out the electrochemical reactions CO2 + 2e(-) ↔ CO + O(2-) and H2O + 2e(-) ↔ H2 + O(2-), for which the electrocatalytic activities of different electrodes differ considerably. The relative activities in CO/CO2 and H2/H2O and the nature of the differences are not well studied, even for the most common fuel-electrode material, a composite of nickel and yttria/scandia stabilized zirconia (Ni-SZ). Ni-SZ is known to be more active for H2/H2O than for CO/CO2 reactions, but the reported relative activity varies widely. Here we compare AC impedance and DC current-overpotential data measured in the two gas environments for several different electrodes comprised of Ni-SZ, Gd-doped CeO2 (CGO), and CGO nanoparticles coating Nb-doped SrTiO3 backbones (CGOn/STN). 2D model and 3D porous electrode geometries are employed to investigate the influence of microstructure, gas diffusion and impurities.Comparing model and porous Ni-SZ electrodes, the ratio of electrode polarization resistance in CO/CO2vs. H2/H2O decreases from 33 to 2. Experiments and modelling suggest that the ratio decreases due to a lower concentration of impurities blocking the three phase boundary and due to the nature of the reaction zone extension into the porous electrode thickness. Besides showing higher activity for H2/H2O reactions than CO/CO2 reactions, the Ni/SZ interface is more active for oxidation than reduction. On the other hand, we find the opposite behaviour in both cases for CGOn/STN model electrodes, reporting for the first time a higher electrocatalytic activity of CGO nanoparticles for CO/CO2 than for H2/H2O reactions in the absence of gas diffusion limitations. We propose that enhanced surface reduction at the

Vibrational spectroscopy of NO + (H2O)n: Evidence for the intracluster reaction NO + (H2O)n --> H3O + (H2O)n - 2 (HONO) at n => 4

NASA Astrophysics Data System (ADS)

Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

1994-05-01

Infrared spectra of mass-selected clusters NO+(H2O)n for n=1 to 5 were recorded from 2700 to 3800 cm-1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

Liquid-phase deposition of TiO2 nanoparticles on core-shell Fe3O4@SiO2 spheres: preparation, characterization, and photocatalytic activity

NASA Astrophysics Data System (ADS)

Ma, Jian-Qi; Guo, Shao-Bo; Guo, Xiao-Hua; Ge, Hong-Guang

2015-07-01

To prevent and avoid magnetic loss caused by magnetite core phase transition involving in high-temperature crystallization of amorphous sol-gel TiO2, core-shell Fe3O4@SiO2@TiO2 composite spheres were synthesized via non-thermal process of TiO2. First, core-shell Fe3O4@SiO2 particles were synthesized through a solvothermal method followed by a sol-gel process. Second, anatase TiO2 nanoparticles (NPs) were directly coated on Fe3O4@SiO2 surface by liquid-phase deposition method, which uses (NH4)2TiF6 as Ti source for TiO2 and H3BO3 as scavenger for F- ions at 50 °C. The morphology, structure, composition, and magnetism of the resulting composites were characterized and their photocatalytic activities were also evaluated. The results demonstrate that TiO2 NPs with an average size of 6-8 nm were uniformly deposited on the Fe3O4@SiO2 surface. Magnetic hysteresis curves indicate that the composite spheres exhibit superparamagnetic characteristics with a magnetic saturation of 32.5 emu/g at room temperature. The magnetic TiO2 composites show high photocatalytic performance and can be recycled five times by magnetic separation without major loss of activity, which meant that they can be used as efficient and conveniently renewable photocatalyst.

Crystal structures of Sr(ClO4)2·3H2O, Sr(ClO4)2·4H2O and Sr(ClO4)2·9H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, strontium perchlorate trihydrate {di-μ-aqua-aquadi-μ-perchlorato-strontium, [Sr(ClO4)2(H2O)3]n}, strontium perchlorate tetra­hydrate {di-μ-aqua-bis­(tri­aqua­diperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona­hydrate {hepta­aqua­diperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]·2H2O}, were crystallized at low temperatures according to the solid–liquid phase diagram. The structures of the tri- and tetra­hydrate consist of Sr2+ cations coordinated by five water mol­ecules and four O atoms of four perchlorate tetra­hedra in a distorted tricapped trigonal–prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol­ecules and thus forming chains parallel to [100]. In the tetra­hydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol­ecules are formed. The structure of the nona­hydrate contains one Sr2+ cation coordinated by seven water mol­ecules and by two O atoms of two perchlorate tetra­hedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol­ecules, which are located on twofold rotation axes. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures. PMID:25552979

Kinetic removal of haloacetonitrile precursors by photo-based advanced oxidation processes (UV/H2O2, UV/O3, and UV/H2O2/O3).

PubMed

Srithep, Sirinthip; Phattarapattamawong, Songkeart

2017-06-01

The objective of the study is to evaluate the performance of conventional treatment process (i.e., coagulation, flocculation, sedimentation and sand filtration) on the removals of haloacetonitrile (HAN) precursors. In addition, the removals of HAN precursors by photo-based advanced oxidation processes (Photo-AOPs) (i.e., UV/H 2 O 2 , UV/O 3 , and UV/H 2 O 2 /O 3 ) are investigated. The conventional treatment process was ineffective to remove HAN precursors. Among Photo-AOPs, the UV/H 2 O 2 /O 3 was the most effective process for removing HAN precursors, followed by UV/H 2 O 2 , and UV/O 3 , respectively. For 20min contact time, the UV/H 2 O 2 /O 3 , UV/H 2 O 2 , and UV/O 3 suppressed the HAN formations by 54, 42, and 27% reduction. Increasing ozone doses from 1 to 5 mgL -1 in UV/O 3 systems slightly improved the removals of HAN precursors. Changes in pH (6-8) were unaffected most of processes (i.e., UV, UV/H 2 O 2 , and UV/H 2 O 2 /O 3 ), except for the UV/O 3 system that its efficiency was low in the weak acid condition. The pseudo first-order kinetic constant for removals of dichloroacetonitrile precursors (k' DCANFP ) by the UV/H 2 O 2 /O 3 , UV/H 2 O 2 and standalone UV systems were 1.4-2.8 orders magnitude higher than the UV/O 3 process. The kinetic degradation of dissolved organic nitrogen (DON) tended to be higher than the k' DCANFP value. This study firstly differentiates the kinetic degradation between DON and HAN precursors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Application of H2O and UV/H2O2 processes for enhancing the biodegradability of reactive black 5 dye.

PubMed

Kalpana, S Divya; Kalyanaraman, Chitra; Gandhi, N Nagendra

2011-07-01

Leather processing is a traditional activity in India during which many organic and inorganic chemicals are added while part of it is absorbed by the leather, the remaining chemicals are discharged along with the effluent. The effluent contains both easily biodegradable and not easily biodegradable synthetic organics like dyes, syntans. Easily biodegradable organics are removed in the existing biological treatment units whereas synthetic organics present in the wastewater are mostly adsorbed over the microbes. As the tannery effluent contains complex chemicals, it is difficult to ascertain the degradation of specific pollutants. To determine the increase in the biodegradability, one of the complex and synthetic organic chemical like dye used in the tanning operation was selected for Advanced Oxidation Process (AOPs) treatment for cleaving complex organics and its subsequent treatment in aerobic process. In the present study, Reactive Black 5 Dye used in the tanning operation was selected for Hydrogen Peroxide (H2O2) and UV/H2O2 pre-treatment for different operating conditions like pH, contact time and different volume of H2O2. A comparison was made between the untreated, Hydrogen Peroxide (H2O2) and UV/H2O2 treated effluent in order to ascertain the influence of AOP on the improvement of biodegradability of effluent. An increase in the BOD5/COD ratio from 0.21 to 0.435 was achieved in the UV/H2O2 pre-treatment process. This pre-treated effluent was further subjected to aerobic process. Biochemical Oxygen Demand (BOD5) and Chemical Oxygen Demand (COD) removal efficiency of the UV/H2O2 pre-treated dye solution in the aerobic process was found to be 86.39% and 77.82% when compared to 52.43% of BOD5 and 51.55% of COD removal efficiency without any pre-treatment. Hence from these results, to increase the biodegradability of Reactive Black 5 dye pre-treatment methods like H2O2 and UV/H2O2 can be used prior to biological treatment process.

Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes.

PubMed

Bokare, Alok D; Choi, Wonyong

2014-06-30

Iron-catalyzed hydrogen peroxide decomposition for in situ generation of hydroxyl radicals (HO(•)) has been extensively developed as advanced oxidation processes (AOPs) for environmental applications. A variety of catalytic iron species constituting metal salts (in Fe(2+) or Fe(3+) form), metal oxides (e.g., Fe2O3, Fe3O4), and zero-valent metal (Fe(0)) have been exploited for chemical (classical Fenton), photochemical (photo-Fenton) and electrochemical (electro-Fenton) degradation pathways. However, the requirement of strict acidic conditions to prevent iron precipitation still remains the bottleneck for iron-based AOPs. In this article, we present a thorough review of alternative non-iron Fenton catalysts and their reactivity towards hydrogen peroxide activation. Elements with multiple redox states (like chromium, cerium, copper, cobalt, manganese and ruthenium) all directly decompose H2O2 into HO(•) through conventional Fenton-like pathways. The in situ formation of H2O2 and decomposition into HO(•) can be also achieved using electron transfer mechanism in zero-valent aluminum/O2 system. Although these Fenton systems (except aluminum) work efficiently even at neutral pH, the H2O2 activation mechanism is very specific to the nature of the catalyst and critically depends on its composition. This review describes in detail the complex mechanisms and emphasizes on practical limitations influencing their environmental applications. Copyright © 2014 Elsevier B.V. All rights reserved.

A novel organic-inorganic hybrid based on a dinuclear copper (II)-oxalate complex, a α-metatungstate cluster [H 2W 12O 40] 6- with catalytic activity in H 2O 2 decomposition

NASA Astrophysics Data System (ADS)

Sun, Ping; Liu, Shuxia; Feng, Dan; Ma, Fengji; Zhang, Wei; Ren, Yuanhang; Cao, Jianfang

2010-04-01

A novel organic-inorganic hybrid compound H 2[Cu 2(bpy) 2(H 2O) 2(μ-ox)] 2[H 2W 12O 40]·9H 2O ( 1) (2,2 '-bipyrine and ox = oxalate) has been successfully synthesized under open-air mild reaction condition and characterized by elemental analysis, IR spectrum, thermal stability analysis, single-crystal X-ray diffraction and magnetic susceptibility measurement. The main structural feature of compound 1 is the presence of α-metatungstate cluster [H 2W 12O 40] 6- as inorganic building blocks, on which the bridged-oxalate dinuclear copper metalorganic units are supported. Magnetic susceptibility studies reveal that the compound 1 shows paramagnetic property with a magnetic moment about the Cu 2+ ion, indicating antiferromagnetic coupling between the neighboring Cu 2+ ions in the structure. The compound 1 also displays a good catalytic activity with the conversion 42.4% for H 2O 2 decomposition.

Degradation and mineralization of Bisphenol A (BPA) in aqueous solution using advanced oxidation processes: UV/H2O2 and UV/S2O8(2-) oxidation systems.

PubMed

Sharma, Jyoti; Mishra, I M; Kumar, Vineet

2015-06-01

This work reports on the removal and mineralization of an endocrine disrupting chemical, Bisphenol A (BPA) at a concentration of 0.22 mM in aqueous solution using inorganic oxidants (hydrogen peroxide, H2O2 and sodium persulfate, Na2S2O8;S2O8(2-)) under UV irradiation at a wavelength of 254 nm and 40 W power (Io = 1.26 × 10(-6) E s(-1)) at its natural pH and a temperature of 29 ± 3 °C. With an optimum persulfate concentration of 1.26 mM, the UV/S2O8(2-) process resulted in ∼95% BPA removal after 240 min of irradiation. The optimum BPA removal was found to be ∼85% with a H2O2 concentration of 11.76 mM. At higher concentrations, either of the oxidants showed an adverse effect because of the quenching of the hydroxyl or sulfate radicals in the BPA solution. The sulfate-based oxidation process could be used over a wider initial pH range of 3-12, but the hydroxyl radical-based oxidation of BPA should be carried out in the acidic pH range only. The water matrix components (bicarbonate, chloride and humic acid) showed higher scavenging effect in hydroxyl radical-based oxidation than that in the sulfate radical-based oxidation of BPA. UV/S2O8(2-) oxidation system utilized less energy (307 kWh/m(3)) EE/O in comparison to UV/H2O2 system (509 kWh/m(3)) under optimum operating conditions. The cost of UV irradiation far outweighed the cost of the oxidants in the process. However, the total cost of treatment of persulfate-based system was much lower than that of H2O2-based oxidation system. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis, characterization, electrochemical investigation and antioxidant activities of a new hybrid cyclohexaphosphate: Cu1.5Li(C2H10N2)P6O18·7H2O

NASA Astrophysics Data System (ADS)

Sleymi, Samira; Lahbib, Karima; Rahmouni, Nihed; Rzaigui, Mohamed; Besbes-Hentati, Salma; Abid, Sonia

2017-09-01

A new organic-inorganic hybrid transition metal phosphate, Cu1.5Li(C2H10N2)P6O18·7H2O, has been prepared and characterized by X-ray diffraction, spectroscopy (infrared, Raman, diffuse reflectance and UV-Vis) and thermal analysis (TG). In addition, its electrochemical behaviors, as well as its antioxidant and antibacterial activities, have been investigated. Its structure is built up by the alternate linkages between copper and phosphate polyhedra, forming puckered layers with intersecting 12-membered rings, in which the ethylenediammonium cations reside. This compound is the first framework structure constructed from cyclohexaphosphates and three distinct copper cations. Cyclic voltammetry study in an acetonitrile solution reveals the facile anodic oxidation of its organic part on a platinum disk and a progressive growing of a thin film, though the repetitive cycling of potential. The title compound was tested for its in vitro antioxidant activities by 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2‧-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), Ferrous chelating ability (FIC) and Ferric Reducing Power (FRP) methods. The antioxidant activity of Cu1.5Li(C2H10N2)P6O18·7H2O was analyzed simultaneously with its antibacterial capacity against Escherichia coli, Salmonella typhimurium, Staphylococus aureus, Enterococcus feacium, Streptococcus agalactiae and Candida albicans. The tested compound showed significant antioxidant activities with low antibacterial properties.

Vibrational energy transfer and relaxation in O2 and H2O.

PubMed

Huestis, David L

2006-06-01

Near-resonant vibrational energy exchange between oxygen and water molecules is an important process in the Earth's atmosphere, combustion chemistry, and the chemical oxygen iodine laser (COIL). The reactions in question are (1) O2(1) + O2(0) --> O2(0) + O2(0); (2) O2(1) + H2O(000) --> O2(0) + H2O(000); (3) O2(1) + H2O(000) <--> O2(0) + H2O(010); (4) H2O(010) + H2O(000) --> H2O(000) + H2O(000); and (5) H2O(010) + O2(0) --> H2O(000) + O2(0). Reanalysis of the data available in the chemical kinetics literature provides reliable values for rate coefficients for reactions 1 and 4 and strong evidence that reactions 2 and 5 are slow in comparison with reaction 3. Analytical solution of the chemical rate equations shows that previous attempts to measure the rate of reaction 3 are unreliable unless the water mole fraction is higher than 1%. Reanalysis of data from the only experiment satisfying this constraint provides a rate coefficient of (5.5 +/- 0.4) x 10(-13) cm3/s at room temperature, between the values favored by the atmospheric and laser modeling communities.

A quantitative study of NF-kappaB activation by H2O2: relevance in inflammation and synergy with TNF-alpha.

PubMed

de Oliveira-Marques, Virgínia; Cyrne, Luísa; Marinho, H Susana; Antunes, Fernando

2007-03-15

Although the germicide role of H(2)O(2) released during inflammation is well established, a hypothetical regulatory function, either promoting or inhibiting inflammation, is still controversial. In particular, after 15 years of highly contradictory results it remains uncertain whether H(2)O(2) by itself activates NF-kappaB or if it stimulates or inhibits the activation of NF-kappaB by proinflammatory mediators. We investigated the role of H(2)O(2) in NF-kappaB activation using, for the first time, a calibrated and controlled method of H(2)O(2) delivery--the steady-state titration--in which cells are exposed to constant, low, and known concentrations of H(2)O(2). This technique contrasts with previously applied techniques, which disrupt cellular redox homeostasis and/or introduce uncertainties in the actual H(2)O(2) concentration to which cells are exposed. In both MCF-7 and HeLa cells, H(2)O(2) at extracellular concentrations up to 25 microM did not induce significantly per se NF-kappaB translocation to the nucleus, but it stimulated the translocation induced by TNF-alpha. For higher H(2)O(2) doses this stimulatory role shifts to an inhibition, which may explain published contradictory results. The stimulatory role was confirmed by the observation that 12.5 microM H(2)O(2), a concentration found during inflammation, increased the expression of several proinflammatory NF-kappaB-dependent genes induced by TNF-alpha (e.g., IL-8, MCP-1, TLR2, and TNF-alpha). The same low H(2)O(2) concentration also induced the anti-inflammatory gene coding for heme oxygenase-1 (HO-1) and IL-6. We propose that H(2)O(2) has a fine-tuning regulatory role, comprising both a proinflammatory control loop that increases pathogen removal and an anti-inflammatory control loop, which avoids an exacerbated harmful inflammatory response.

H2O2 modulates the energetic metabolism of the cloud microbiome

NASA Astrophysics Data System (ADS)

Wirgot, Nolwenn; Vinatier, Virginie; Deguillaume, Laurent; Sancelme, Martine; Delort, Anne-Marie

2017-12-01

Chemical reactions in clouds lead to oxidation processes driven by radicals (mainly HO⚫, NO3⚫, or HO2⚫) or strong oxidants such as H2O2, O3, nitrate, and nitrite. Among those species, hydrogen peroxide plays a central role in the cloud chemistry by driving its oxidant capacity. In cloud droplets, H2O2 is transformed by microorganisms which are metabolically active. Biological activity can therefore impact the cloud oxidant capacity. The present article aims at highlighting the interactions between H2O2 and microorganisms within the cloud system. First, experiments were performed with selected strains studied as a reference isolated from clouds in microcosms designed to mimic the cloud chemical composition, including the presence of light and iron. Biotic and abiotic degradation rates of H2O2 were measured and results showed that biodegradation was the most efficient process together with the photo-Fenton process. H2O2 strongly impacted the microbial energetic state as shown by adenosine triphosphate (ATP) measurements in the presence and absence of H2O2. This ATP depletion was not due to the loss of cell viability. Secondly, correlation studies were performed based on real cloud measurements from 37 cloud samples collected at the PUY station (1465 m a.s.l., France). The results support a strong correlation between ATP and H2O2 concentrations and confirm that H2O2 modulates the energetic metabolism of the cloud microbiome. The modulation of microbial metabolism by H2O2 concentration could thus impact cloud chemistry, in particular the biotransformation rates of carbon compounds, and consequently can perturb the way the cloud system is modifying the global atmospheric chemistry.

Degradation of 5-FU by means of advanced (photo)oxidation processes: UV/H2O2, UV/Fe2+/H2O2 and UV/TiO2--Comparison of transformation products, ready biodegradability and toxicity.

PubMed

Lutterbeck, Carlos Alexandre; Wilde, Marcelo Luís; Baginska, Ewelina; Leder, Christoph; Machado, Ênio Leandro; Kümmerer, Klaus

2015-09-15

The present study investigates the degradation of the antimetabolite 5-fluorouracil (5-FU) by three different advanced photo oxidation processes: UV/H2O2, UV/Fe(2+)/H2O2 and UV/TiO2. Prescreening experiments varying the H2O2 and TiO2 concentrations were performed in order to set the best catalyst concentrations in the UV/H2O2 and UV/TiO2 experiments, whereas the UV/Fe(2+)/H2O2 process was optimized varying the pH, Fe(2+) and H2O2 concentrations by means of the Box-Behnken design (BBD). 5-FU was quickly removed in all the irradiation experiments. The UV/Fe(2+)/H2O2 and UV/TiO2 processes achieved the highest degree of mineralization, whereas the lowest one resulted from the UV/H2O2 treatment. Six transformation products were formed during the advanced (photo)oxidation processes and identified using low and high resolution mass spectrometry. Most of them were formed and further eliminated during the reactions. The parent compound of 5-FU was not biodegraded, whereas the photolytic mixture formed in the UV/H2O2 treatment after 256 min showed a noticeable improvement of the biodegradability in the closed bottle test (CBT) and was nontoxic towards Vibrio fischeri. In silico predictions showed positive alerts for mutagenic and genotoxic effects of 5-FU. In contrast, several of the transformation products (TPs) generated along the processes did not provide indications for mutagenic or genotoxic activity. One exception was TP with m/z 146 with positive alerts in several models of bacterial mutagenicity which could demand further experimental testing. Results demonstrate that advanced treatment can eliminate parent compounds and its toxicity. However, transformation products formed can still be toxic. Therefore toxicity screening after advanced treatment is recommendable. Copyright © 2015 Elsevier B.V. All rights reserved.

Kinetic Studies of Iron Deposition in Horse Spleen Ferritin Using H2O2 and O2 as Oxidants

NASA Technical Reports Server (NTRS)

Lowery, Thomas J., Jr.; Bunker, Jared; Zhang, Bo; Costen, Robert; Watt, Gerald D.

2004-01-01

The reaction of horse spleen ferritin (HoSF) with Fe(2+) at pH 6.5 and 7.5 using O2, H2O2 and 1:1 a mixture of both showed that the iron deposition reaction using H2O2 is approx. 20- to 50-fold faster than the reaction with O2 alone. When H2O2 was added during the iron deposition reaction initiated with O2 as oxidant, Fe(2+) was preferentially oxidized by H2O2, consistent with the above kinetic measurements. Both the O2 and H202 reactions were well defined from 15 to 40 C from which activation parameters were determined. The iron deposition reaction was also studied using O2 as oxidant in the presence and absence of catalase using both stopped-flow and pumped-flow measurements. The presence of catalase decreased the rate of iron deposition by approx. 1.5-fold, and gave slightly smaller absorbance changes than in its absence. From the rate constants for the O2 (0.044 per second) and H2O2 (0.67 per second) iron-deposition reactions at pH 7.5, simulations of steady-state H2O2 concentrations were computed to be 0.45 micromolar. This low value and reported Fe2(+)/O2 values of 2.0-2.5 are consistent with H2O2 rapidly reacting by an alternate but unidentified pathway involving a system component such as the protein shell or the mineral core as previously postulated.

Superoxide radical anion scavenging and dismutation by some Cu2+ and Mn2+ complexes: A pulse radiolysis study

NASA Astrophysics Data System (ADS)

Joshi, Ravi

2017-10-01

Copper (Cu) and manganese (Mn) ions are catalytic centers, in complexed form, in scavenging and dismutation process of superoxide radicals anion (O2.-) by superoxide dismutase enzyme. In the present work, fast reaction kinetics and mechanism of scavenging and dismutation of O2.- by Cu2+, Mn2+ and their complexes formed with some natural ligands have been studied using pulse radiolysis technique. Catechol, gentisic acid, tetrahydroxyquinone, tyrosine, tryptophan, embelin and bilirubin have been used as low molecular weight natural ligands for Cu2+ and Mn2+ to understand superoxide radical scavenging and dismutation reactions. These complexes have been found to be efficient scavengers of O2.- (k 107-109 M-1 s-1). The effects of nature of metal ion and ligand, and stoichiometry of complex on scavenging reaction rate constants are reported. Higher scavenging rate constants have been observed with complexes of: (1) Cu2+ as compared to Mn2+, and (2) at [ligand]/[metal] ratio of one as compared to two. A clear evidence of O2.- dismutation by free metal ions and some of the complexes has been observed. The study suggests that complexes of Cu2+ and Mn2+ with small natural ligands can also act as SOD mimics.

Three-dimensional WS2 nanosheet networks for H2O2 produced for cell signaling

NASA Astrophysics Data System (ADS)

Tang, Jing; Quan, Yingzhou; Zhang, Yueyu; Jiang, Min; Al-Enizi, Abdullah M.; Kong, Biao; An, Tiance; Wang, Wenshuo; Xia, Limin; Gong, Xingao; Zheng, Gengfeng

2016-03-01

Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in living RAW 264.7 macrophage cells and neurons. First-principles calculations further demonstrate that the enhanced sensitivity of probing H2O2 is attributed to the efficient and spontaneous H2O2 adsorption on WS2 nanosheet edge sites. The combined features of 3D WS2 nanosheet networks suggest attractive new opportunities for exploring the physiological roles of reactive oxygen species like H2O2 in living systems.Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in

Dicobalt-μ-oxo polyoxometalate compound, [(α(2)-P2W17O61Co)2O](14-): a potent species for water oxidation, C-H bond activation, and oxygen transfer.

PubMed

Barats-Damatov, Delina; Shimon, Linda J W; Weiner, Lev; Schreiber, Roy E; Jiménez-Lozano, Pablo; Poblet, Josep M; de Graaf, Coen; Neumann, Ronny

2014-02-03

High-valent oxo compounds of transition metals are often implicated as active species in oxygenation of hydrocarbons through carbon-hydrogen bond activation or oxygen transfer and also in water oxidation. Recently, several examples of cobalt-catalyzed water oxidation have been reported, and cobalt(IV) species have been suggested as active intermediates. A reactive species, formally a dicobalt(IV)-μ-oxo polyoxometalate compound [(α2-P2W17O61Co)2O](14-), [(POMCo)2O], has now been isolated and characterized by the oxidation of a monomeric [α2-P2W17O61Co(II)(H2O)](8-), [POMCo(II)H2O], with ozone in water. The crystal structure shows a nearly linear Co-O-Co moiety with a Co-O bond length of ∼1.77 Å. In aqueous solution [(POMCo)2O] was identified by (31)P NMR, Raman, and UV-vis spectroscopy. Reactivity studies showed that [(POMCo)2O]2O] is an active compound for the oxidation of H2O to O2, direct oxygen transfer to water-soluble sulfoxides and phosphines, indirect epoxidation of alkenes via a Mn porphyrin, and the selective oxidation of alcohols by carbon-hydrogen bond activation. The latter appears to occur via a hydrogen atom transfer mechanism. Density functional and CASSCF calculations strongly indicate that the electronic structure of [(POMCo)2O]2O] is best defined as a compound having two cobalt(III) atoms with two oxidized oxygen atoms.

Peroxydisulfate activation by [RuII(tpy)(pic)(H2O)]+. Kinetic, mechanistic and anti-microbial activity studies.

PubMed

Chatterjee, Debabrata; Banerjee, Priyabrata; Bose, Jagadeesh C K; Mukhopadhyay, Sudit

2012-03-07

The oxidation of [Ru(II)(tpy)(pic)H(2)O](+) (tpy = 2,2',6',2''-terpyridine; pic(-) = picolinate) by peroxidisulfate (S(2)O(8)(2-)) as precursor oxidant has been investigated kinetically by UV-VIS, IR and EPR spectroscopy. The overall oxidation of Ru(II)- to Ru(IV)-species takes place in a consecutive manner involving oxidation of [Ru(II)(tpy)(pic)H(2)O](+) to [Ru(III)(tpy)(pic)(OH)](+), and its further oxidation of to the ultimate product [Ru(IV)(tpy)(pic)(O)](+) complex. The time course of the reaction was followed as a function of [S(2)O(8)(2-)], ionic strength (I) and temperature. Kinetic data and activation parameters are interpreted in terms of an outer-sphere electron transfer mechanism. Anti-microbial activity of Ru(II)(tpy)(pic)H(2)O](+) complex by inhibiting the growth of Escherichia coli DH5α in presence of peroxydisulfate has been explored, and the results of the biological studies have been discussed in terms of the [Ru(IV)(tpy)(pic)(O)](+) mediated cleavage of chromosomal DNA of the bacteria.

Full-dimensional, high-level ab initio potential energy surfaces for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2} with application to hydrogen clathrate hydrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Homayoon, Zahra; Conte, Riccardo; Qu, Chen

2015-08-28

New, full-dimensional potential energy surfaces (PESs), obtained using precise least-squares fitting of high-level electronic energy databases, are reported for intrinsic H{sub 2}(H{sub 2}O) two-body and H{sub 2}(H{sub 2}O){sub 2} three-body potentials. The database for H{sub 2}(H{sub 2}O) consists of approximately 44 000 energies at the coupled cluster singles and doubles plus perturbative triples (CCSD(T))-F12a/haQZ (aug-cc-pVQZ for O and cc-pVQZ for H) level of theory, while the database for the three-body interaction consists of more than 36 000 energies at the CCSD(T)-F12a/haTZ (aug-cc-pVTZ for O, cc-pVTZ for H) level of theory. Two precise potentials are based on the invariant-polynomial technique and are comparedmore » to computationally faster ones obtained via “purified” symmetrization. All fits use reduced permutational symmetry appropriate for these non-covalent interactions. These intrinsic potentials are employed together with existing ones for H{sub 2}, H{sub 2}O, and (H{sub 2}O){sub 2}, to obtain full PESs for H{sub 2}(H{sub 2}O) and H{sub 2}(H{sub 2}O){sub 2}. Properties of these full PESs are presented, including a diffusion Monte Carlo calculation of the zero-point energy and wavefunction, and dissociation energy of the H{sub 2}(H{sub 2}O) dimer. These PESs together with an existing one for water clusters are used in a many-body representation of the PES of hydrogen clathrate hydrates, illustrated for H{sub 2}@(H{sub 2}O){sub 20}. An analysis of this hydrate is presented, including the electronic dissociation energy to remove H{sub 2} from the calculated equilibrium structure.« less

Development of an E-H2O2/TiO2 photoelectrocatalytic oxidation system for water and wastewater treatment.

PubMed

Li, X Z; Liu, H S

2005-06-15

In this study, an innovative E-H2O2/TiO2 (E-H2O2 = electrogenerated hydrogen peroxide) photoelectrocatalytic (PEC) oxidation system was successfully developed for water and wastewater treatment. A TiO2/Ti mesh electrode was applied in this photoreactor as the anode to conduct PEC oxidation, and a reticulated vitreous carbon (RVC) electrode was used as the cathode to electrogenerate hydrogen peroxide simultaneously. The TiO2/Ti mesh electrode was prepared with a modified anodic oxidation process in a quadrielectrolyte (H2SO4-H3PO4-H2O2-HF) solution. The crystal structure, surface morphology, and film thickness of the TiO2/Ti mesh electrode were characterized by X-ray diffraction and scanning electron microscopy. The analytical results showed that a honeycomb-type anatase film with a thickness of 5 microm was formed. Photocatalytic oxidation (PC) and PEC oxidation of 2,4,6-trichlorophenol (TCP) in an aqueous solution were performed under various experimental conditions. Experimental results showed that the TiO2/Ti electrode, anodized in the H2SO4-H3PO4-H2O2-HF solution, had higher photocatalytic activity than the TiO2/Ti electrode anodized in the H2SO4 solution. It was found that the maximum applied potential would be around 2.5 V, corresponding to an optimum applied current density of 50 microA cm(-2) under UV-A illumination. The experiments confirmed that the E-H2O2 on the RVC electrode can significantly enhance the PEC oxidation of TCP in aqueous solution. The rate of TCP degradation in such an E-H2O2-assisted TiO2 PEC reaction was 5.0 times that of the TiO2 PC reaction and 2.3 times that of the TiO2 PEC reaction. The variation of pH during the E-H2O2-assisted TiO2 PEC reaction, affected by individual reactions, was also investigated. It was found that pH was well maintained during the TCP degradation in such an E-H2O2/TiO2 reaction system. This is beneficial to TCP degradation in an aqueous solution.

Transcriptome Analysis of H2O2-Treated Wheat Seedlings Reveals a H2O2-Responsive Fatty Acid Desaturase Gene Participating in Powdery Mildew Resistance

PubMed Central

Tang, Lichuan; Zhao, Guangyao; Zhu, Mingzhu; Chu, Jinfang; Sun, Xiaohong; Wei, Bo; Zhang, Xiangqi; Jia, Jizeng; Mao, Long

2011-01-01

Hydrogen peroxide (H2O2) plays important roles in plant biotic and abiotic stress responses. However, the effect of H2O2 stress on the bread wheat transcriptome is still lacking. To investigate the cellular and metabolic responses triggered by H2O2, we performed an mRNA tag analysis of wheat seedlings under 10 mM H2O2 treatment for 6 hour in one powdery mildew (PM) resistant (PmA) and two susceptible (Cha and Han) lines. In total, 6,156, 6,875 and 3,276 transcripts were found to be differentially expressed in PmA, Han and Cha respectively. Among them, 260 genes exhibited consistent expression patterns in all three wheat lines and may represent a subset of basal H2O2 responsive genes that were associated with cell defense, signal transduction, photosynthesis, carbohydrate metabolism, lipid metabolism, redox homeostasis, and transport. Among genes specific to PmA, ‘transport’ activity was significantly enriched in Gene Ontology analysis. MapMan classification showed that, while both up- and down- regulations were observed for auxin, abscisic acid, and brassinolides signaling genes, the jasmonic acid and ethylene signaling pathway genes were all up-regulated, suggesting H2O2-enhanced JA/Et functions in PmA. To further study whether any of these genes were involved in wheat PM response, 19 H2O2-responsive putative defense related genes were assayed in wheat seedlings infected with Blumeria graminis f. sp. tritici (Bgt). Eight of these genes were found to be co-regulated by H2O2 and Bgt, among which a fatty acid desaturase gene TaFAD was then confirmed by virus induced gene silencing (VIGS) to be required for the PM resistance. Together, our data presents the first global picture of the wheat transcriptome under H2O2 stress and uncovers potential links between H2O2 and Bgt responses, hence providing important candidate genes for the PM resistance in wheat. PMID:22174904

Morphology-defined interaction of copper phthalocyanine with O2/H2O

NASA Astrophysics Data System (ADS)

Muckley, Eric S.; Miller, Nicholas; Jacobs, Christopher B.; Gredig, Thomas; Ivanov, Ilia N.

2016-10-01

Copper phthalocyanine (CuPc) is an important hole transport layer for organic photovoltaics (OPVs), but interaction with ambient gas/vapor may lead to changes in its electronic properties and limit OPV device lifetimes. CuPc films of thickness 25 and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. We measured electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. CuPc films deposited at 250°C showed a factor of 5 higher uptake of O2 as detected by a quartz crystal microbalance (QCM), possibly due to the formation of β-CuPc at T>200°C which allows higher O2 mobility between stacked molecules. While weight-based measurements stabilize after ˜10 min of gas exposure, resistance response stabilizes over times >1 h, suggesting that mass change occurs by rapid adsorption at active surface sites whereas resistive response is dominated by slow diffusion of adsorbates into the bulk film. The 25 nm films exhibit higher resistive response than 100 nm films after an hour of O2/H2O exposure due to fast analyte diffusion down to the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold.

Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1).

PubMed

Li, Xiang; Wang, Haopeng; Bowen, Kit H

2010-10-14

The hydrated nucleoside anions, uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1), have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine(-)(H(2)O)(1) and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1

NASA Astrophysics Data System (ADS)

Li, Xiang; Wang, Haopeng; Bowen, Kit H.

2010-10-01

The hydrated nucleoside anions, uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1, have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine-(H2O)1 and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

Complexes in the Photocatalytic Reaction of CO2 and H2O: Theoretical Studies

PubMed Central

Luo, Dongmei; Zhang, Ning; Hong, Sanguo; Wu, Huanwen; Liu, Zhihua

2010-01-01

Complexes (H2O/CO2, e–(H2O/CO2) and h+–(H2O/CO2)) in the reaction system of CO2 photoreduction with H2O were researched by B3LYP and MP2 methods along with natural bond orbital (NBO) analysis. Geometries of these complexes were optimized and frequencies analysis performed. H2O/CO2 captured photo-induced electron and hole produced e–(H2O/CO2) and h+–(H2O/CO2), respectively. The results revealed that CO2 and H2O molecules could be activated by the photo-induced electrons and holes, and each of these complexes possessed two isomers. Due to the effect of photo-induced electrons, the bond length of C=O and H-O were lengthened, while H-O bonds were shortened, influenced by holes. The infrared (IR) adsorption frequencies of these complexes were different from that of CO2 and H2O, which might be attributed to the synergistic effect and which could not be captured experimentally. PMID:21152274

Extraction and free radical scavenging activity of polysaccharide from 'Anji Baicha' (Camellia sinensis (L.) O. Kuntze).

PubMed

Zhang, Zhongshan; Wang, Xiaomei; Li, Jingfen; Wang, Guozhi; Mao, Genxiang

2016-03-01

In this study, the optimization of the extraction conditions of polysaccharide from 'Anji Baicha' (Camellia sinensis (L.) O. Kuntze) (AP) was investigated by response surface methodology (RSM). Three main independent variables (extraction temperature, time, ratio of water to raw material) were taken into consideration. And then the free radical scavenging activities of the sample were investigated including scavenging effects of superoxide and hydroxyl radicals. The RSM analysis showed good correspondence between experimental and predicted values.. The optimal condition to obtain the highest yield of AP was determined as follows: temperature 76.79 °C, time 2.48 h, ratio of water to material 22.53 mL/g. For the free radical scavenging activity, the IC50 values of Vc and AP were 7.78 and 83.25 μg/mL. And for the scavenging effect on hydroxyl radical, that of AP and Vc were 1.80 and 1.69 mg/mL. AP showed excellent antioxidant activity. This exhibited AP had a good potential for antioxidant. The purification and structure needs to be study in further. Copyright © 2015 Elsevier B.V. All rights reserved.

Comparative study of the degradation of real textile effluents by photocatalytic reactions involving UV/TiO2/H2O2 and UV/Fe2+/H2O2 systems.

PubMed

Garcia, J C; Oliveira, J L; Silva, A E C; Oliveira, C C; Nozaki, J; de Souza, N E

2007-08-17

This work investigated the treatability of real textile effluents using several systems involving advanced oxidation processes (AOPs) such as UV/H2O2, UV/TiO2, UV/TiO2/H2O2, and UV/Fe2+/H2O2. The efficiency of each technique was evaluated according to the reduction levels observed in the UV absorbance of the effluents, COD, and organic nitrogen reduction, as well as mineralization as indicated by the formation of ammonium, nitrate, and sulfate ions. The results indicate the association of TiO2 and H2O2 as the most efficient treatment for removing organic pollutants from textile effluents. In spite of their efficiency, Fenton reactions based treatment proved to be slower and exhibited more complicated kinetics than the ones using TiO2, which are pseudo-first-order reactions. Decolorization was fast and effective in all the experiments despite the fact that only H2O2 was used.

Hepatoprotective, antinociceptive and antioxidant activities of cimetidine, ranitidine and famotidine as histamine H2 receptor antagonists.

PubMed

Ahmadi, Amirhossein; Ebrahimzadeh, Mohammad Ali; Ahmad-Ashrafi, Saeb; Karami, Mohammad; Mahdavi, Mohammad Reza; Saravi, Seyed Soheil Saeedi

2011-02-01

The antioxidant, antinociceptive and hepatoprotective effects of H(2) receptor blockers were examined with different experimental models. Antioxidant activities were determined by employing various in vitro assay systems such as 1,1-diphenyl-2-picryl hydrazyl (DPPH) radical-scavenging activity assays, reducing power determination assays, nitric oxide-scavenging activity assays and hydrogen peroxide-scavenging activity assays. Antinociceptive effects were determined using the hot plate test in mice. The hepatoprotective effects of cimetidine, ranitidine and famotidine against hepatotoxicity induced by carbon tetrachloride (CCl(4) ) were determined by measuring the levels of serum enzymes alanine transaminase (ALT), aspartate transaminase (AST) and alkaline phosphatase (ALP) activities in mice. We found that the IC(50) values of cimetidine, ranitidine and famotidine on DPPH radical-scavenging activity were 671±28, 538±21 and 955±43 μg/mL, respectively. Famotidine showed very strong nitric oxide-scavenging activity. All three compounds showed very weak hydrogen peroxide-scavenging activity. Moreover, the compounds did not exhibit any reducing power activity until concentrations of 1.6 mg/mL. All compounds also showed a dose-dependent and marked analgesic activity in mice relative to controls. Pretreatment of mice with cimetidine, ranitidine or famotidine for three consecutive days reduced CCl(4)-induced hepatotoxicity in mice. Treatment with 200 mg/kg ranitidine reduced AST, AST and ALP serum levels, while 200 and 40 mg/kg of cimetidine and famotidine, respectively, reduced AST and ALP serum levels. H(2) blockers exhibited varying levels of antioxidant activities in various assays. Our results indicate that the antioxidant activities of H(2) blockers have an analgesic activity and protective effect on CCl(4)-induced hepatotoxicity in mice. These effects were greater with ranitidine than with the other compounds. © 2010 The Authors Fundamental and Clinical

Modulation of notch signaling pathway to prevent H2O2/menadione-induced SK-N-MC cells death by EUK134.

PubMed

Kamarehei, Maryam; Yazdanparast, Razieh

2014-10-01

The brain in Alzheimer's disease is under increased oxidative stress, and this may have a role in the pathogenesis and neural death in this disorder. It has been verified that numerous signaling pathways involved in neurodegenerative disorders are activated in response to reactive oxygen species (ROS). EUK134, a synthetic salen-manganese antioxidant complex, has been found to possess many interesting pharmacological activities awaiting exploration. The present study is to characterize the role of Notch signaling in apoptotic cell death of SK-N-MC cells. The cells were treated with hydrogen peroxide (H2O2) or menadione to induce oxidative stress. The free-radical scavenging capabilities of EUK134 were studied through the MTT assay, glutathione peroxidase (GPx) enzyme activity assay, and glutathione (GSH) Levels. The extents of lipid peroxidation, protein carbonyl formation, and intracellular ROS levels, as markers of oxidative stress, were also studied. Our results showed that H2O2/menadione reduced GSH levels and GPx activity. However, EUK134 protected cells against ROS-induced cell death by down-regulation of lipid peroxidation and protein carbonyl formation as well as restoration of antioxidant enzymes activity. ROS induced apoptosis and increased NICD and HES1 expression. Inhibition of NICD production proved that Notch signaling is involved in apoptosis through p53 activation. Moreover, H2O2/menadione led to Numb protein down-regulation which upon EUK134 pretreatment, its level increased and subsequently prevented Notch pathway activation. We indicated that EUK134 can be a promising candidate in designing natural-based drugs for ROS-induced neurodegenerative diseases. Collectively, ROS activated Notch signaling in SK-N-MC cells leading to cell apoptosis.

Crystal Structures and Thermal Properties of Two Transition-Metal Compounds {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O and Pb(DNI)2(H2O)4 (DNI = 2,4-Dinitroimidazolate)

PubMed Central

Zhang, Guo-Fang; Cai, Mei-Yu; Jing, Ping; He, Chong; Li, Ping; Zhao, Feng-Qi; Li, Ji-Zhen; Fan, Xue-Zhong; Ng, Seik Weng

2010-01-01

Two transition-metal compounds derived from 2,4-dinitroimidazole, {[Ni(DNI)2(H2O)3][Ni(DNI)2 (H2O)4]}·6H2O, 1, and Pb(DNI)2(H2O)4, 2, were characterized by elemental analysis, FT-IR, TG-DSC and X-ray single-crystal diffraction analysis. Crystal data for 1: monoclinic, space group C2/c, a = 26.826(3), b = 7.7199(10), c = 18.579(2) Å, β = 111.241(2)° and Z = 4; 2: monoclinic, space group C2/c, a = 6.5347(6), b = 17.1727(17), c = 14.1011(14) Å, β = 97.7248(10) and Z = 4. Compound 1 contains two isolated nickel centers in its structure, one being six-coordinate and another five-coordinate. The structure of 2 contains a lead (II) center surrounded by two chelating DNI ligands and four water molecules in distorted square-antiprism geometry. The abundant hydrogen bonds in two compounds link the molecules into three-dimensional network and stabilize the molecules. The TG-DSC analysis reveals that the first step is the loss of water molecules and the final residue is the corresponding metal oxides and carbon. PMID:20526419

Effects of P25 TiO2 Nanoparticles on the Free Radical-Scavenging Ability of Antioxidants upon Their Exposure to Simulated Sunlight.

PubMed

Li, Meng; Chong, Yu; Fu, Peter P; Xia, Qingsu; Croley, Timothy R; Lo, Y Martin; Yin, Jun-Jie

2017-11-15

Although nanosized ingredients, including TiO 2 nanoparticles (NPs), can be found in a wide range of consumer products, little is known about the effects these particles have on other active compounds in product matrices. These NPs can interact with reactive oxygen species (ROS), potentially disrupting or canceling the benefits expected from antioxidants. We used electron spin resonance spectrometry to assess changes in the antioxidant capacities of six dietary antioxidants (ascorbic acid, α-tocopherol, glutathione, cysteine, epicatechin, and epicatechin gallate) during exposure to P25 TiO 2 and/or simulated sunlight. Specifically, we determined the ability of these antioxidants to scavenge 1-diphenyl-2-picryl-hydrazyl radical, superoxide radical, and hydroxyl radical. Exposure to simulated sunlight alone did not lead to noticeable changes in radical-scavenging abilities; however, in combination with P25 TiO 2 NPs, the scavenging abilities of most antioxidants were weakened. We found glutathione to be the most resistant to treatment with sunlight and NPs among these six antioxidants.

VUV photoionization cross sections of HO2, H2O2, and H2CO.

PubMed

Dodson, Leah G; Shen, Linhan; Savee, John D; Eddingsaas, Nathan C; Welz, Oliver; Taatjes, Craig A; Osborn, David L; Sander, Stanley P; Okumura, Mitchio

2015-02-26

The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.

Heterogeneous Ag-TiO2-SiO2 composite materials as novel catalytic systems for selective epoxidation of cyclohexene by H2O2

PubMed Central

Wang, Xin; Xue, Jianyue; Wang, Xinyun; Liu, Xiaoheng

2017-01-01

TiO2-SiO2 composites were synthesized using cetyl trimethyl ammonium bromide (CTAB) as the structure directing template. Self-assembly hexadecyltrimethyl- ammonium bromide TiO2-SiO2/(CTAB) were soaked into silver nitrate (AgNO3) aqueous solution. The Ag-TiO2-SiO2(Ag-TS) composite were prepared via a precipitation of AgBr in soaking process and its decomposition at calcination stage. Structural characterization of the materials was carried out by various techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption and ultraviolet visible spectroscopy (UV-Vis). Characterization results revealed that Ag particles were incorporated into hierarchical TiO2-SiO2 without significantly affecting the structures of the supports. Further heating-treatment at 723 K was more favorable for enhancing the stability of the Ag-TS composite. The cyclohexene oxide was the major product in the epoxidation using H2O2 as the oxidant over the Ag-TS catalysts. Besides, the optimum catalytic activity and stability of Ag-TS catalysts were obtained under operational conditions of calcined at 723 K for 2 h, reaction time of 120 min, reaction temperature of 353 K, catalyst amount of 80 mg, aqueous H2O2 (30 wt.%) as oxidant and chloroform as solvent. High catalytic activity with conversion rate up to 99.2% of cyclohexene oxide could be obtainable in water-bathing. The catalyst was found to be stable and could be reused three times without significant loss of catalytic activity under the optimized reaction conditions. PMID:28493879

Temporal mismatch between induction of superoxide dismutase and ascorbate peroxidase correlates with high H2O2 concentration in seawater from clofibrate-treated red algae Kappaphycus alvarezii.

PubMed

Barros, Marcelo P; Granbom, Malena; Colepicolo, Pio; Pedersén, Marianne

2003-12-01

Algal cells have developed different strategies to cope with the common environmentally promoted generation of H(2)O(2), which include induction of catalase (CAT) and ascorbate peroxidase (APX), massive H(2)O(2) release in seawater, and synthesis of volatile halocarbons by specific peroxidases. The antioxidant adaptability of the economically important carrageenophyte Kappaphycus alvarezii (Doty) Doty (Gigartinales: Rhodophyta) was tested here against exposure to clofibrate (CFB), a known promoter of peroxisomal beta-oxidation in mammals and plants. Possibly as a consequence of CFB-induced H2O2 peroxisomal production, the maximum concentration of H(2)O(2) in the seawater of red algae cultures was found to occur (120+/-17 min) after the addition of CFB, which was followed by a significant decrease in the photosynthetic activity of PSII after 24 h. Interestingly, 4 h after the addition of CFB, the total SOD activity was about 2.5-fold higher than in the control, whereas no significant changes were observed in lipoperoxidation levels (TBARS) or in CAT and APX activities. The two H(2)O(2)-scavenging enzymes were only induced later (after 72 h), whereupon CAT showed a dose-dependent response with increasing concentrations of CFB. A more pronounced increase of TBARS concentration than in the controls was evidenced when a 50 microM Fe(2+/3+) solution (3:2 ratio) was added to CFB-treated cultures, suggesting that the combination of exacerbated H(2)O(2) levels in the seawater-in this work, caused by CFB exposure-and Fenton-reaction catalyst (ferric/ferrous ions), imposes harsh oxidative conditions on algal cultures. The bulk of data suggests that K. alvarezii possesses little ability to promptly induce CAT and APX compared to the immediately responsive antioxidant enzyme SOD and, to avoid harmful accumulation of H(2)O(2), the red alga presumably releases H(2)O(2) into the surrounding medium as an alternative mechanism.

Chlorogenic acid analogues from Gynura nepalensis protect H9c2 cardiomyoblasts against H2O2-induced apoptosis

PubMed Central

Yu, Bang-wei; Li, Jin-long; Guo, Bin-bin; Fan, Hui-min; Zhao, Wei-min; Wang, He-yao

2016-01-01

Aim: Chlorogenic acid has shown protective effect on cardiomyocytes against oxidative stress-induced damage. Herein, we evaluated nine caffeoylquinic acid analogues (1–9) isolated from the leaves of Gynura nepalensis for their protective effect against H2O2-induced H9c2 cardiomyoblast damage and explored the underlying mechanisms. Methods: H9c2 cardiomyoblasts were exposed to H2O2 (0.3 mmol/L) for 3 h, and cell viability was detected with MTT assay. Hoechst 33342 staining was performed to evaluate cell apoptosis. MMPs (mitochondrial membrane potentials) were measured using a JC-1 assay kit, and ROS (reactive oxygen species) generation was measured using CM-H2 DCFDA. The expression levels of relevant proteins were detected using Western blot analysis. Results: Exposure to H2O2 markedly decreased the viability of H9c2 cells and catalase activity, and increased LDH release and intracellular ROS production; accompanied by a loss of MMP and increased apoptotic rate. Among the 9 chlorogenic acid analogues as well as the positive control drug epigallocatechin gallate (EGCG) tested, compound 6 (3,5-dicaffeoylquinic acid ethyl ester) was the most effective in protecting H9c2 cells from H2O2-induced cell death. Pretreatment with compound 6 (1.56–100 μmol/L) dose-dependently alleviated all the H2O2-induced detrimental effects. Moreover, exposure to H2O2 significantly increased the levels of Bax, p53, cleaved caspase-8, and cleaved caspase-9, and decreased the level of Bcl-2, resulting in cell apoptosis. Exposure to H2O2 also significantly increased the phosphorylation of p38, JNK and ERK in the H9c2 cells. Pretreatment with compound 6 (12.5 and 25 μmol/L) dose-dependently inhibited the H2O2-induced increase in the level of cleaved caspase-9 but not of cleaved caspase-8. It also dose-dependently suppressed the H2O2-induced phosphorylation of JNK and ERK but not that of p38. Conclusion: Compound 6 isolated from the leaves of Gynura nepalensis potently protects H9c2

Hydrogen peroxide (H/sub 2/O/sub 2/) stimulates the active transport of 5-hydroxytryptamine (5-HT) into platelets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bosin, T.R.

1986-03-01

Platelets function in a variety of physiological and pathological processes which may be altered by oxidant injury. One such process is the active transport 5-HT, which is an important mechanism in the control of circulating 5-HT levels. Exposure of mouse platelets (10/sup 8//ml) to H/sub 2/O/sub 2/ caused a time-dependent and dose-dependent increase in 5-HT (10/sup -7/M) uptake. The uptake 4 and 10 min following H/sub 2/O/sub 2/ (50 ..mu..M) was 228% and 145% of control values, respectively. Fluoxetine (10/sup -6/M) blocked all 5-HT uptake and catalase (1500 U/ml) blocked the H/sub 2/O/sub 2/-stimulated uptake. Enzymatically produced H/sub 2/O/sub 2/more » (glucose/glucose oxidase) and xanthine (X)/xanthine oxidase (XO) generated oxygen radicals produced quantitatively and qualitatively similar results. The stimulatory response of platelets to X/XO generated oxidants was unaffected by superoxide dismutase (250 U/ml) but, was inhibited using heat-denatured XO, allopurinol (0.5 mM) and catalase; fluoxetine inhibited all 5-HT uptake. Platelets exposed to X/XO in the presence of chelated (EDTA, 100 ..mu..M) or unchelated FeSO/sub 4/, FeNH/sub 4/(SO/sub 4/)/sub 2/ or CuCl (50 ..mu..M) did not have altered 5-HT uptake. These data indicate that brief exposure of platelets to physiological levels of H/sub 2/O/sub 2/ results in marked, reversible stimulation of active 5-HT uptake which may represent a homeostatic defense mechanism when H/sub 2/O/sub 2/ is elevated in the platelet microenvironment.« less

Transfer of a proton between H2 and O2.

PubMed

Kluge, Lars; Gärtner, Sabrina; Brünken, Sandra; Asvany, Oskar; Gerlich, Dieter; Schlemmer, Stephan

2012-11-13

The proton affinities of hydrogen and oxygen are very similar. Therefore, it has been discussed that the proton transfer from the omnipresent H(3)(+) to molecular oxygen in the near thermoneutral reaction H(3)(+) + O(2) <--> O(2)H(+) + H(2) effectively binds the interstellar oxygen in O(2)H(+). In this work, the proton transfer reaction has been investigated in a low-temperature 22-pole ion trap from almost room temperature (280 K) down to the lowest possible temperature limited by freeze out of oxygen gas (about 40 K at a low pressure). The Arrhenius behaviour of the rate coefficient for the forward reaction shows that it is subject to an activation energy of E(A)/k=113 K. Thus, the forward reaction can proceed only in higher temperature molecular clouds. Applying laser-induced reactions to the given reaction (in the backward direction), a preliminary search for spectroscopic signatures of O(2)H(+) in the infrared was unsuccessful, whereas the forward reaction has been successfully used to probe the population of the lowest ortho and para levels of H(3)(+).

Kinetics and Efficiency of H2O2 Activation by Iron-Containing Minerals and Aquifer Materials

PubMed Central

Pham, Anh Le-Tuan; Doyle, Fiona M.; Sedlak, David L.

2014-01-01

To gain insight into factors that control H2O2 persistence and ˙OH yield in H2O2-based in situ chemical oxidation systems, the decomposition of H2O2 and transformation of phenol were investigated in the presence of iron-containing minerals and aquifer materials. Under conditions expected during remediation of soil and groundwater, the stoichiometric efficiency, defined as the amount of phenol transformed per mole of H2O2 decomposed, varied from 0.005 to 0.28%. Among the iron-containing minerals, iron oxides were 2 to 10 times less efficient in transforming phenol than iron-containing clays and synthetic iron-containing catalysts. In both iron-containing mineral and aquifer materials systems, the stoichiometric efficiency was inversely correlated with the rate of H2O2 decomposition. In aquifer materials systems, the stoichiometric efficiency was also inversely correlated with the Mn content, consistent with the fact that the decomposition of H2O2 on manganese oxides does not produce ˙OH. Removal of iron and manganese oxide coatings from the surface of aquifer materials by extraction with citrate-bicarbonate-dithionite slowed the rate of H2O2 decomposition on aquifer materials and increased the stoichiometric efficiency. In addition, the presence of 2 mM of dissolved SiO2 slowed the rate of H2O2 decomposition on aquifer materials by over 80% without affecting the stoichiometric efficiency. PMID:23047055

Kinetics and efficiency of H2O2 activation by iron-containing minerals and aquifer materials.

PubMed

Pham, Anh Le-Tuan; Doyle, Fiona M; Sedlak, David L

2012-12-01

To gain insight into factors that control H(2)O(2) persistence and ·OH yield in H(2)O(2)-based in situ chemical oxidation systems, the decomposition of H(2)O(2) and transformation of phenol were investigated in the presence of iron-containing minerals and aquifer materials. Under conditions expected during remediation of soil and groundwater, the stoichiometric efficiency, defined as the amount of phenol transformed per mole of H(2)O(2) decomposed, varied from 0.005 to 0.28%. Among the iron-containing minerals, iron oxides were 2-10 times less efficient in transforming phenol than iron-containing clays and synthetic iron-containing catalysts. In both iron-containing mineral and aquifer materials systems, the stoichiometric efficiency was inversely correlated with the rate of H(2)O(2) decomposition. In aquifer materials systems, the stoichiometric efficiency was also inversely correlated with the Mn content, consistent with the fact that the decomposition of H(2)O(2) on manganese oxides does not produce ·OH. Removal of iron and manganese oxide coatings from the surface of aquifer materials by extraction with citrate-bicarbonate-dithionite slowed the rate of H(2)O(2) decomposition on aquifer materials and increased the stoichiometric efficiency. In addition, the presence of 2 mM of dissolved SiO(2) slowed the rate of H(2)O(2) decomposition on aquifer materials by over 80% without affecting the stoichiometric efficiency. Copyright © 2012 Elsevier Ltd. All rights reserved.

The reaction of H2O2 with NO2 and NO

NASA Technical Reports Server (NTRS)

Gray, D.; Lissi, E.; Heicklen, J.

1972-01-01

The reactions of NO and NO2 with H2O2 have been examined at 25 C. Reaction mixtures were monitored by continuously bleeding through a pinhole into a monopole mass spectrometer. NO2 was also monitored by its optical absorption in the visible part of the spectrum. Reaction mixtures containing initially 1.5 - 2.5 torr of NO2 and 0.8 - 1.4 torr of H2O2 or 1 - 12 torr of NO and 0.5 - 1.5 torr of H2O2 were studied. The H2O2 - NO reaction was complex. There was an induction period followed by a marked acceleration in reactant removal. The final products of the reaction, NO2, probably H2O, and possibly HONO2 were produced mainly after all the H2O2 was removed. The HONO intermediate was shown to disproportionate to NO2 + NO + H2O in a relatively slow first order reaction. The acceleration in H2O2 removal after the NO - H2O2 reaction is started is caused by NO2 catalysis.

Overlap corrections for emissivity calculations of H2O-CO2-CO-N2 mixtures

NASA Astrophysics Data System (ADS)

Alberti, Michael; Weber, Roman; Mancini, Marco

2018-01-01

Calculations of total gas emissivities of gas mixtures containing several radiatively active species require corrections for band overlapping. In this paper, we generate such overlap correction charts for H2O-CO2-N2, H2O-CO-N2, and CO2-CO-N2 mixtures. These charts are applicable in the 0.1-40 bar total pressure range and in the 500 K-2500 K temperature range. For H2O-CO2-N2 mixtures, differences between our charts and Hottel's graphs as well as models of Leckner and Modak are highlighted and analyzed.

Structurally characterized 1,1,3,3-tetramethylguanidine solvated magnesium aryloxide complexes: [Mg(mu-OEt)(DBP)(H-TMG)]2, [Mg(mu-OBc)(DBP)(H-TMG)]2, [Mg(mu-TMBA)(DBP)(H-TMG)]2, [Mg(mu-DPP)(DBP)(H-TMG)]2, [Mg(BMP)2(H-TMG)2], [Mg(O-2,6-Ph2C6H3)2 (H-TMG)2].

PubMed

Monegan, Jessie D; Bunge, Scott D

2009-04-06

The synthesis and structural characterization of several 1,1,3,3-tetramethylguanidine (H-TMG) solvated magnesium aryloxide complexes are reported. Bu(2)Mg was successfully reacted with H-TMG, HOC(6)H(3)(CMe(3))(2)-2,6 (H-DBP), and either ethanol, a carboxylic acid, or diphenyl phosphate in a 1:1 ratio to yield the corresponding [Mg(mu-L)(DBP)(H-TMG)](2) where L = OCH(2)CH(3) (OEt, 1), O(2)CC(CH(3))(3) (OBc, 2), O(2)C(C(6)H(2)-2,4,6-(CH(3))(3)) (TMBA, 3), or O(2)P(OC(6)H(5))(2) (DPP, 4). Bu(2)Mg was also reacted with two equivalents of H-TMG and HOC(6)H(3)(CMe(3))-2-(CH(3))-6 (BMP) or HO-2,6-Ph(2)C(6)H(3) to yield [Mg(BMP)(2)(H-TMG)(2)] (5) and [Mg(O-2,6-Ph(2)C(6)H(3))(2)(H-TMG)(2)] (6). Compounds 1-6 were characterized by single-crystal X-ray diffraction. Polymerization of l- and rac-lactide with 1 was found to generate polylactide (PLA). A discussion concerning the relevance of compounds 2 - 4 to the structure of Mg-activated phosphatase enzymes is also provided. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, and (1)H, (13)C and (31)P NMR studies.

Degradation of crystal violet by an FeGAC/H2O2 process.

PubMed

Chen, Chiing-Chang; Chen, Wen-Ching; Chiou, Mei-Rung; Chen, Sheng-Wei; Chen, Yao Yin; Fan, Huan-Jung

2011-11-30

Because of the growing concern over highly contaminated crystal violet (CV) wastewater, an FeGAC/H(2)O(2) process was employed in this research to treat CV-contaminated wastewater. The experimental results indicated that the presence of iron oxide-coated granular activated carbon (FeGAC) greatly improved the oxidative ability of H(2)O(2) for the removal of CV. For instance, the removal efficiencies of H(2)O(2), GAC, FeGAC, GAC/H(2)O(2) and FeGAC/H(2)O(2) processes were 10%, 44%, 40%, 43% and 71%, respectively, at test conditions of pH 3 and 7.4mM H(2)O(2). FeGAC/H(2)O(2) combined both the advantages of FeGAC and H(2)O(2). FeGAC had a good CV adsorption ability and could effectively catalyze the hydrogen peroxide oxidation reaction. Factors (including pH, FeGAC dosage and H(2)O(2) dosage) affecting the removal of CV by FeGAC/H(2)O(2) were investigated in this research as well. In addition, the reaction intermediates were separated and identified using HPLC-ESI-MS. The N-demethylation step might be the main reaction pathway for the removal of CV. The reaction mechanisms for the process proposed in this research might be useful for future application of this technology to the removal of triphenylmethane (TPM) dyes. Copyright © 2011 Elsevier B.V. All rights reserved.

Protective effect of Dendrobium officinale polysaccharides on H2O2-induced injury in H9c2 cardiomyocytes.

PubMed

Zhao, Xiaoyan; Dou, Mengmeng; Zhang, Zhihao; Zhang, Duoduo; Huang, Chengzhi

2017-10-01

The preliminary studies have shown that Dendrobium officinale possessed therapeutic effects on hypertension and atherosclerosis. Studies also reported that Dendrobium officinale polysaccharides showed antioxidant capabilities. However, little is known about its effects on myocardial cells under oxidative stress. The present study was designed to study the protective effect of Dendrobium officinale polysaccharides against H 2 O 2 -induced oxidative stress in H9c2 cells. MTT assay was carried out to determine the cell viability of H9c2 cells when pretreated with Dendrobium officinale polysaccharides. Fluorescent microscopy measurements were performed for evaluating the apoptosis in H9c2 cells. Furthermore, effects of Dendrobium officinale polysaccharides on the activities of antioxidative indicators (malondialdehyde, superoxide dismutase), reactive oxygen species (ROS) production and mitochondrial membrane potential (MMP) levels were analyzed. Dendrobium officinale polysaccharides attenuated H 2 O 2 -induced cell death, as determined by the MTT assay. Dendrobium officinale polysaccharides decreased malondialdehyde levels, increased superoxide dismutase activities, and inhibited the generation of intracellular ROS. Moreover, pretreatment with Dendrobium officinale polysaccharides also inhibited apoptosis and increased the MMP levels in H9c2 cells. These results suggested the protective effects of Dendrobium officinale polysaccharides against H 2 O 2 -induced injury in H9c2 cells. The results also indicated the anti-oxidative capability of Dendrobium officinale polysaccharides. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Morphology-controlled synthesis of α-Fe 2O 3 nanostructures with magnetic property and excellent electrocatalytic activity for H 2O 2

NASA Astrophysics Data System (ADS)

Li, Xiyan; Lei, Yongqian; Li, Xiaona; Song, Shuyan; Wang, Cheng; Zhang, Hongjie

2011-12-01

α-Fe 2O 3 nanocrystals (NCs) with different morphologies are successfully synthesized via a facile template-free hydrothermal route. By simply changing the volume ratio of ethanol to water, we obtained three different α-Fe 2O 3 nanostructures of rhombohedra, truncated rhombohedra and hexagonal sheet. The morphologies and structures of the as-obtained products have been confirmed by varieties of characterizations such as X-ray diffraction (XRD), X-ray photoelectron spectrometry (XPS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The influences of the experimental conditions, such as the amount of NaOH and reaction temperature on the morphologies of the as-prepared α-Fe 2O 3 NCs, have been well investigated. Additionally, magnetic investigations show that the as-obtained α-Fe 2O 3 nanostructures show structure-dependent magnetic properties. Furthermore, the electrochemical experiments indicate that the as-prepared α-Fe 2O 3 hexagonal sheets exhibit strong electrocatalytic reduction activity for H 2O 2.

Preparation and enhanced visible-light photocatalytic H2-production activity of CdS-sensitized Pt/TiO2 nanosheets with exposed (001) facets.

PubMed

Qi, Lifang; Yu, Jiaguo; Jaroniec, Mietek

2011-05-21

CdS-sensitized Pt/TiO(2) nanosheets with exposed (001) facets were prepared by hydrothermal treatment of a Ti(OC(4)H(9))(4)-HF-H(2)O mixed solution followed by photochemical reduction deposition of Pt nanoparticles (NPs) on TiO(2) nanosheets (TiO(2) NSs) and chemical bath deposition of CdS NPs on Pt/TiO(2) NSs, successively. The UV and visible-light driven photocatalytic activity of the as-prepared samples was evaluated by photocatalytic H(2) production from lactic acid aqueous solution under UV and visible-light (λ ≥ 420 nm) irradiation. It was shown that no photocatalytic H(2)-production activity was observed on the pure TiO(2) NSs under UV and/or visible-light irradiation. Deposition of CdS NPs on Pt/TiO(2) NSs caused significant enhancement of the UV and visible-light photocatalytic H(2)-production rates. The morphology of TiO(2) particles had also significant influence on the visible-light H(2)-production activity. Among TiO(2) NSs, P25 and the NPs studied, the CdS-sensitized Pt/TiO(2) NSs show the highest photocatalytic activity (13.9% apparent quantum efficiency obtained at 420 nm), exceeding that of CdS-sensitized Pt/P25 by 10.3% and that of Pt/NPs by 1.21%, which can be attributed to the combined effect of several factors including the presence of exposed (001) facets, surface fluorination and high specific surface area. After many replication experiments of the photocatalytic hydrogen production in the presence of lactic acid, the CdS-sensitized Pt/TiO(2) NSs did not show great loss in the photocatalytic activity, confirming that the CdS/Pt/TiO(2) NSs system is stable and not photocorroded. © The Owner Societies 2011

Mixed-ligand Cu II complexes with Me 5dien and heterocyclic acids. Synthesis, antioxidant and anti-inflammatory activity. Crystal structure of [Cu(Me 5dien)(tpaa)(H 2O)](ClO 4)

NASA Astrophysics Data System (ADS)

Christidis, Panayiotis C.; Georgousis, Zacharias D.; Hadjipavlou-Litina, Dimitra; Bolos, Christos A.

2008-01-01

The reaction of sodium salt of 2-thiophenecarboxylic acid (tpca), 2-thiopheneacetic acid (tpaa), 2-furoic acid (fa) and picolinic acid (pica), with [Cu(Me 5dien)(ClO 4) 2] ( 1) (Me 5dien = N, N, N', N″ N″-pentamethyldiethylenetriamine) in a 1:1 molar ratio, afforded new mixed-ligand compounds of the type [Cu(Me 5dien)(tpca)(H 2O)](ClO 4) ( 2), [Cu(Me 5dien)(tpaa)(H 2O)](ClO 4) ( 3), [Cu(Me 5dien)(fa)](BPh 4) ( 4) and [Cu(Me 5dien)(pica)](ClO 4) ( 5). The new mixed-ligand complexes are mononuclear, paramagnetic, conductive compounds with a distorted square pyramidal geometry. The square pyramidal stereochemistry proposed by spectroscopic (IR, UV-vis) data was further confirmed by the X-ray structure analysis of the compound ( 3) in which the Cu atom is coordinated by the three N atoms from the Me 5dien ligand, one O atom from the mono-carboxylate anion, lying on the equatorial square plane, and one O atom from the water molecule, occupying the axial position. The two Cu sbnd O bond distances are 1.955(2) and 2.212(2) Ǻ, respectively. The complexes were tested for antioxidant/anti-inflammatory activity. Complex 4 is the most active against soybean lipoxygenase with IC 50 = 100 μM. The presence of a furoic ring leads to higher lipoxygenase inhibition, whereas the picolinyl-ring supports scavenging activity.

Organic Contaminant Abatement in Reclaimed Water by UV/H2O2 and a Combined Process Consisting of O3/H2O2 Followed by UV/H2O2: Prediction of Abatement Efficiency, Energy Consumption, and Byproduct Formation.

PubMed

Lee, Yunho; Gerrity, Daniel; Lee, Minju; Gamage, Sujanie; Pisarenko, Aleksey; Trenholm, Rebecca A; Canonica, Silvio; Snyder, Shane A; von Gunten, Urs

2016-04-05

UV/H2O2 processes can be applied to improve the quality of effluents from municipal wastewater treatment plants by attenuating trace organic contaminants (micropollutants). This study presents a kinetic model based on UV photolysis parameters, including UV absorption rate and quantum yield, and hydroxyl radical (·OH) oxidation parameters, including second-order rate constants for ·OH reactions and steady-state ·OH concentrations, that can be used to predict micropollutant abatement in wastewater. The UV/H2O2 kinetic model successfully predicted the abatement efficiencies of 16 target micropollutants in bench-scale UV and UV/H2O2 experiments in 10 secondary wastewater effluents. The model was then used to calculate the electric energies required to achieve specific levels of micropollutant abatement in several advanced wastewater treatment scenarios using various combinations of ozone, UV, and H2O2. UV/H2O2 is more energy-intensive than ozonation for abatement of most micropollutants. Nevertheless, UV/H2O2 is not limited by the formation of N-nitrosodimethylamine (NDMA) and bromate whereas ozonation may produce significant concentrations of these oxidation byproducts, as observed in some of the tested wastewater effluents. The combined process of O3/H2O2 followed by UV/H2O2, which may be warranted in some potable reuse applications, can achieve superior micropollutant abatement with reduced energy consumption compared to UV/H2O2 and reduced oxidation byproduct formation (i.e., NDMA and/or bromate) compared to conventional ozonation.

Selective photocatalytic reduction of CO2 by H2O/H2 to CH4 and CH3OH over Cu-promoted In2O3/TiO2 nanocatalyst

NASA Astrophysics Data System (ADS)

Tahir, Muhammad; Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar

2016-12-01

Photocatalytic CO2 reduction by H2O and/or H2 reductant to selective fuels over Cu-promoted In2O3/TiO2 photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N2 adsorption-desorption, UV-vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO2, oxidized as Cu2+ and In3+, promoted efficient separation of photo-generated electron/hole pairs (e-/h+). The results indicate that the reduction rate of CO2 by H2O to CH4 approached to 181 μmol g-1 h-1 using 0.5% Cu-3% In2O3/TiO2 catalyst, a 1.53 fold higher than the production rate over the 3% In2O3/TiO2 and 5 times the amount produced over the pure TiO2. In addition, Cu was found to promote efficient production of CH3OH and yield rate reached to 68 μmol g-1 h-1 over 1% Cu-3% In2O3/TiO2 catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H2 reductant was less favorable for CH4 production, yet a significant amount of CH4 and CH3OH were obtained using a mixture of H2O/H2 reductant. Therefore, Cu-loaded In2O3/TiO2 catalyst has shown to be capable for methanol production, whereas product selectivity was greatly depending on the amount of Cu-loading and the type of reductant. A photocatalytic reaction mechanism was proposed to understand the experimental results over the Cu-loaded In2O3/TiO2 catalyst.

Steady-state studies of the reactions of H2O-CO and CO2-H2 mixtures with liquid iron

NASA Astrophysics Data System (ADS)

Sasaki, Y.; Belton, G. R.

1998-08-01

Studies have been made of the steady-stata composition of liquid iron exposed to high flow rates of H2O-CO mixtures at 1550 °C to 1700 °C and CO2-H2 mixtures at 1600 °C. Values of the steady-state activity of oxygen have been established by measurement of either the carbon concentration or the silicon concentration when the iron was held in a silica crucible. Additions of sulfur or selenium to the iron have been found to result in steady-state oxygen activities, which differ significantly from those expected from water-gas equilibrium. The results are interpreted to show that the ratio of the apparent first-order rate constants for the reactions of H2O and CO2 with liquid iron is about 3 at 1600 °C. It is shown that the dependencies of the rate constants on the activities of sulfur, oxygen, and selenium must, even if complex, be similar for the H2O and CO2 reactions with liquid iron, to a good approximation.

Kinetics of Al + H2O reaction: theoretical study.

PubMed

Sharipov, Alexander; Titova, Nataliya; Starik, Alexander

2011-05-05

Quantum chemical calculations were carried out to study the reaction of Al atom in the ground electronic state with H(2)O molecule. Examination of the potential energy surface revealed that the Al + H(2)O → AlO + H(2) reaction must be treated as a complex process involving two steps: Al + H(2)O → AlOH + H and AlOH + H → AlO + H(2). Activation barriers for these elementary reaction channels were calculated at B3LYP/6-311+G(3df,2p), CBS-QB3, and G3 levels of theory, and appropriate rate constants were estimated by using a canonical variational theory. Theoretical analysis exhibited that the rate constant for the Al + H(2)O → products reaction measured by McClean et al. must be associated with the Al + H(2)O → AlOH + H reaction path only. The process of direct HAlOH formation was found to be negligible at a pressure smaller than 100 atm.

The catalytic effects of H2CO3, CH3COOH, HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

NASA Astrophysics Data System (ADS)

Zhang, Tianlei; Lan, Xinguang; Wang, Rui; Roy, Soumendra; Qiao, Zhangyu; Lu, Yousong; Wang, Zhuqing

2018-07-01

The addition reaction of CH2OO + H2O → CH2(OH)OOH without and with X (X = H2CO3, CH3COOH and HCOOH) and H2O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH2OO + H2O → CH2(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH2OO...H2O is favourable one. Water-assisted CH2OO + H2O → CH2(OH)OOH can occur by H2O moiety of (H2O)2 or the whole (H2O)2 forming cyclic structure with CH2OO, where the latter form is more favourable. Because the concentration of H2CO3 is unknown, the influence of CH3COOH, HCOOH and H2O were calculated within 0-30 km altitude of the Earth's atmosphere. The results calculated within 0-5 km altitude show that H2O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%-77.26% and 0.04%-1.76%. Within 5-30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%-98.28%. However, compared with the reaction of CH2OO + HCOOH, the rate of CH2OO...H2O + HCOOH is much slower.

Enhanced photo-degradation of paracetamol on n-platinum-loaded TiO2: The effect of ultrasound and OH/hole scavengers.

PubMed

Ziylan-Yavaş, Asu; Ince, Nilsun H

2016-11-01

Elimination/mineralization of paracetamol (PCT) was investigated by catalytic oxidation under ultrasound, UV and both. The catalyst was synthesized by immobilization of nPt on TiO2 to benefit from the ability of Pt to facilitate charge transfer processes and to separate e(-)/h(+) pairs. It was found that increasing the Pt-loading enhanced the rate of sonochemical reactions, but retarded that of photolytic reactions, due to reduced UV absorption on the surface. Simultaneous application of sonolysis and photolysis was synergistic due to disaggregation of the particles and homogenization of the active species over the catalyst surface. The decay of PCT was highly dependent on the availability of OH, as the reactions were nearly terminated in the presence of a strong OH scavenger-2-propanol. However, a remarkable rate enhancement was observed in the presence of a suitable dose of I(-), which scavenges both OH and hvb(+). The result was explained by the production of excess radicals upon sonolysis of iodide solutions, and the reactivity of PCT with them. Finally, carbon mineralization was significantly hindered in the presence of both scavengers due to increased competition for OH and inefficient formation of hydroquinone arising from reduced availability of hvb(+). Copyright © 2016 Elsevier Ltd. All rights reserved.

Improved hydrogen storage properties of MgH2 catalyzed with TiO2

NASA Astrophysics Data System (ADS)

Jangir, Mukesh; Meena, Priyanka; Jain, I. P.

2018-05-01

In order to improve the hydrogenation properties of the MgH2, various concentration of rutile Titanium Oxide (TiO2) (X wt%= 5, 10, 15 wt %) is added to MgH2 by ball milling and the catalytic effect of TiO2 on hydriding/dehydriding properties of MgH2 has been investigated. Result shows that the TiO2 significantly reduced onset temperature of desorption. Onset temperature as low as 190 °C were observed for the MgH2-15 wt% TiO2 sample which is 60 °C and 160 °C lower than the as-milled and as-received MgH2. Fromm the Kissinger plot the activation energy of 15 wt% TiO2 added sample is calculated to be -75.48 KJ/mol. These results indicate that the hydrogenation properties of MgH2-TiO2 have been improved compared to the as-milled and as-received MgH2. Furthermore, XRD and XPS were performed to characterize the structural evolution upon milling and dehydrogenation.

FLYING-WATER Renewables-H2-H2O TERRAFORMING: PERMANENT Drought(s)-Elimination FOREVER!!!

NASA Astrophysics Data System (ADS)

Ertl, G.; Alefeld, G.; Youdelis, W.; Radd, H.; Oertle, G.; Siegel, Edward

2011-03-01

"H2O H2O everywhere; ne'er a drop to drink"[Coleridge(1798)]; now: "H2 H2 everywhere; STILL ne'er a drop to drink": ONLY H2 (or methane CH4) can be FLYING-WATER(F-W) chemical-rain-in-pipelines Hindenberg-effect (H2-UP;H2O-DOWN): {O/H2O}=[16]/[18] 90 % ; O already in air uphill; NO H2O pumping need! In global-warming driven H2O-starved glacial-melting world, rescue is possible ONLY by Siegel [{3rd Intl. Conf. Alt.-Energy }(1980)-vol.5/p.459!!!] Renewables-H2-H2O purposely flexible versatile agile customizable scaleable retrofitable integrated operating-system. Rosenfeld[Science 315,1396(3/9/2007)]-Biello [Sci.Am.(3/9/2007)] crucial geomorph-ology which ONLY maximal-buoyancy H2 can exploit, to again make "Mountains into Fountains", ``upthrust rocks trapping the clouds to precipitate their rain/snow/H2O'': "terraforming"(and ocean-rebasificaton!!!) Siegel proprietary magnetic-hydrogen-valve (MHV) permits H2 flow in already in-ground dense BCC/ferritic-steels pipelines-network (NO new infrastructure) counters Tromp[Science 300,1740(2003)] dire warning of global-pandemics (cancers/ blindness/famine) Hydrogen-economy CATASTROPHIC H2 ozone-layer destruction sobering cavat to dangerous H2-automotion-economy panacea hype!!!

Pellino-1 Protects Periodontal Ligament Stem Cells Against H2O2-Induced Apoptosis via Activation of NF-κB Signaling.

PubMed

Tian, Jiangang; Gu, Liufang; Adams, Andrew; Wang, Xueliang; Huang, Ruizhe

2018-06-02

To determine the protective effects of Pellino-1 against H 2 O 2 -induced apoptosis in periodontal ligament stem cells (PDLSC). We demonstrated that H 2 O 2 decreases PDLSC viability by 40 and 50% with the concentrations of 400 and 500 μM, respectively, with an observed downregulation of Pellino-1 mRNA and protein; we further concluded that overexpression of Pellino-1 significantly lowers 8-hydroxy-2'-deoxyguanosine levels by 10% and upregulates superoxide dismutase 1, glutathione peroxidase levels, and catalase mRNA levels by 200, 40, and 250%, respectively. More importantly, we found that overexpression of Pellino-1 inhibited H 2 O 2 -induced cellular apoptosis through the activation of the NF-κB signaling pathway. Pellino-1 may be critically important for cell survival in the presence of oxidative elements; activation of the NF-κB signaling cascade was required for the overexpression of Pellino-1 to protect the cells from H 2 O 2 -induced apoptosis.

Self-encapsulation of [MII(phen)2(H2O)2]2+ (M=Co, Zn) in one-dimensional nanochannels of [MII(H2O)6(BTC)2]4- (M=Co, Cu, Mn): a high HQ/CAT ratio catalyst for hydroxylation of phenols.

PubMed

Bi, Jianhong; Kong, Lingtao; Huang, Zixiang; Liu, Jinhuai

2008-06-02

Four novel three-dimensional (3D) microporous supramolecular compounds containing nanosized channels, namely, [Co(phen)2(H2O)2]2[Co(H2O)6].2BTC.21.5H2O (1), [Co(phen)2(H2O)2]2[Cu(H2O)6].2BTC.21.5H2O (2), [Co(phen)2(H2O)2]2[Mn(H2O)6].2BTC.18H2O (3), and [Zn(phen)2(H2O)2]2[Mn(H2O)6].2BTC.22.5H2O (4), were synthesized from 1,3,5-benzenetricarboxylate (BTC), 1,10-phenanthroline (phen), and the transition-metal salt(s) by self-assembly. Single-crystal X-ray structural analysis showed that the resulting 3D microporous supramolecular frameworks consist of a two-dimensional (2D) hydrogen-bonded host framework of [MII(H2O)6(BTC)2]4- (M=Co for 1, Cu for 2, Mn for 3, 4) with rectangular-shaped cavities containing [MII(phen)2(H2O)2]2+ (M=Co for 1-3, Zn for 4) guests. The guest complex is encapsulated in the 2D hydrogen-bonded host framework by hydrogen bonding and aromatic pi-pi stacking interactions, forming the 3D hydrogen-bonded framework. The catalytic activities of 1, 2, 3, and 4 were studied using hydroxylation of phenols with 30% aqueous H2O2 as a test reaction. The compounds displayed a good phenol conversion ratio and excellent channel selectivity in the hydroxylation reaction, with a maximum hydroquinone (HQ)/catechol (CAT) ratio of 3.9.

Theoretical studies of UO(2)(OH)(H(2)O)(n) (+), UO(2)(OH)(2)(H(2)O)(n), NpO(2)(OH)(H(2)O)(n), and PuO(2)(OH)(H(2)O)(n) (+) (n

PubMed

Cao, Zhiji; Balasubramanian, K

2009-10-28

Extensive ab initio calculations have been carried out to study equilibrium structures, vibrational frequencies, and the nature of chemical bonds of hydrated UO(2)(OH)(+), UO(2)(OH)(2), NpO(2)(OH), and PuO(2)(OH)(+) complexes that contain up to 21 water molecules both in first and second hydration spheres in both aqueous solution and the gas phase. The structures have been further optimized by considering long-range solvent effects through a polarizable continuum dielectric model. The hydrolysis reaction Gibbs free energy of UO(2)(H(2)O)(5) (2+) is computed to be 8.11 kcal/mol at the MP2 level in good agreement with experiments. Our results reveal that it is necessary to include water molecules bound to the complex in the first hydration sphere for proper treatment of the hydrated complex and the dielectric cavity although water molecules in the second hydration sphere do not change the coordination complex. Structural reoptimization of the complex in a dielectric cavity seems inevitable to seek subtle structural variations in the solvent and to correlate with the observed spectra and thermodynamic properties in the aqueous environment. Our computations reveal dramatically different equilibrium structures in the gas phase and solution and also confirm the observed facile exchanges between the complex and bulk solvent. Complete active space multiconfiguration self-consistent field followed by multireference singles+doubles CI (MRSDCI) computations on smaller complexes confirm predominantly single-configurational nature of these species and the validity of B3LYP and MP2 techniques for these complexes in their ground states.

Total phenolic contents and free-radical scavenging activities of grape (Vitis vinifera L.) and grape products.

PubMed