Development of photocatalytic paint based on TiO2 and photopolymer resin for the degradation of organic pollutants in water.

While the use of TiO2 nanoparticles in the form of slurry/suspension requires energy-intensive separation processes, its immobilization in solid support may open new opportunities in the area of sustainable water treatment technologies. In this study, a novel method for the development of photocatalytic paint based on TiO2 nanoparticles and acrylate-based photopolymer resin is reported. The paint (TiO2@polymer) was applied on substrates such as plastic petri dish and glass jar, which was polymerized/solidified by ultraviolet light irradiation. The painted petri dish and glass jar were used for the photocatalytic degradation of model organic pollutants viz. methyl orange (MO), methylene blue (MB), and indole in deionized water, simulated fresh drinking water, and tap water matrices. The photocatalytic degradation studies were performed under sunlight and UV-B light were used for. The sunlight-assisted photocatalytic degradation of MO and MB was found to be faster and more efficient than the UV-B light-assisted ones. Under UV-B light irradiation, it took 120 min to degrade about 80% of 6 ppm MB solution, whereas under sunlight irradiation it took 60 min to degrade about 90% of the same MB solution. The photocatalytic paint generated hydroxyl radical (·OH) under the UV-B and sunlight irradiation, which was studied by the terephthalic acid fluorescence tests. Further, the potential release of TiO2 during the exposure to UV irradiation was studied by single particle ICP-MS analysis.

Nanoscale nickel metal organic framework decorated over graphene oxide and carbon nanotubes for water remediation.

In this report, highly crystalline and well-dispersed nano-sized nickel metal organic framework (MOFs) was decorated over graphene oxide (GO) and carbon nanotubes (CNTs) platforms to form hybrid nanocomposites. These as-synthesized hybrid nanocomposites were synthesized through a one-pot green solvothermal method. The prepared nanocomposites were characterized by SEM, TEM, EDS, XRD, FT-IR, Raman and TGA techniques. XRD analysis revealed the crystalline structure of the hybrid nanocomposites. Morphological and elemental studies also verified successful decoration of nickel-benzene dicarboxylate (Ni-BDC) MOFs over GO and CNT platforms. Chemical analysis collected through IR, and thermal analysis collected through TGA technique, illustrated the presence of all the components in the hybrid nanomaterials. Methylene blue (MB) was used as a model organic pollutant to analyze the adsorption capacity of the prepared nanocomposites. According to the findings, a strong interaction exists between the MB molecule and the developed adsorbents at which due to the synergistic effect, the hybrid nanocomposites show several times higher adsorption capacity compared to that of parent materials. This improvement can be due to several reasons: high surface area of the MOFs in the composites resulting from the smaller size of MOFs, presence of the pores formed between the MOFs and the platforms and different morphological characteristic of Ni-BDC MOFs in hybrid nanocomposites, compared to bare Ni-BDC MOFs. Furthermore, the isotherm and kinetic studies revealed that the adsorption of MB onto the newly prepared adsorbents could best be explained by the Langmuir and Pseudo-second order kinetic models. A regeneration study demonstrated the highly stable nature of the hybrid nanocomposites.

Sustainable synthesis and remarkable adsorption capacity of MOF/graphene oxide and MOF/CNT based hybrid nanocomposites for the removal of Bisphenol A from water.

A series of novel absorbents based on Cu-BDC MOFs decorated over graphene oxide (GrO) and carbon nanotubes (CNTs) hybrid nanocomposites, namely Cu-BDC@GrO and Cu-BDC@CNT, are synthesized via a facile and one-pot green solvothermal method for water remediation. The nanocomposites were characterized by XRD, TEM, SEM, EDS, Raman, FTIR, TGA, XPS, Zetasizer and ICP-OES instruments. XRD results confirmed the high crystalline structure of the synthesized hybrid nanocomposites. Morphological analysis by SEM and TEM verified the successful decoration of nano-sized Cu-BDC MOFs over GrO and CNT platforms; whereas, EDS and XPS analysis confirmed the presence of all components in the hybrid nanocomposites. Bisphenol A was used in this study as a model organic pollutant that is sometimes present in the industrial wastewater to test the adsorption capacity of the prepared hybrid nanomaterials toward their removal from water. The hybrid nanomaterials showed remarkable adsorption capacity of 182.2 and 164.1 mg/g toward the removal of BPA, which was several times higher than that of 60.2 mg/g for Cu-BDC MOF itself. The Langmuir, Freundlich, Temkin and D-R isotherm models were applied to analyze the experimental data and the results revealed that the Freundlich model describes the experimental data best. A kinetic study was carried out and it showed that the prepared nanomaterials could remove maximum amount of BPA from water in 30 min. The pseudo-first order, pseudo-second order and intra-particle diffusion models were applied to evaluate the kinetic data and the results suggested that the kinetics data could be well fitted to the pseudo-second order kinetic model. Additionally, the BAP adsorption process onto the hybrid nanocomposites was spontaneous and exothermic. The π-π interactions between the BPA and hybrid nanomaterials played a vital role during the BPA adsorption process. The higher adsorption capacity and water stability makes them a good candidate for water remediation applications.

Adsorption of methylene blue and tetracycline onto biomass-based material prepared by sulfuric acid reflux.

The adsorptive removal of environmental pollutants is an effective method for the treatment of contaminated water. Thus, the preparation of adsorbents from low-cost, readily available, and renewable resources has garnered immense attention in recent years. In this study, a facile one-step method for the preparation of a high-capacity adsorbent is demonstrated by refluxing pine cones in concentrated sulfuric acid. With sulfuric acid reflux, the pine cones undergone carbonization as well as functionalization with sulfonic acid groups. The adsorbent demonstrated high adsorption capacity for two emerging organic pollutants, methylene blue (MB) and tetracycline (TC). Different variables such as pH, temperature, contact time, and initial concentration of the pollutants were analyzed and showed that the adsorption capacity for MB increased in a basic pH and vice versa for TC. Also, the elevated temperature favored the adsorption for both MB and TC. The maximum adsorption capacity was found to be 1666.66, and 357.14 mg g-1 for MB and TC, respectively. In comparison to the pristine pine cone, the sulfuric acid treated pine cone demonstrated an extraordinary improvement in the adsorption capacity. The adsorption of MB and TC was performed from the tap water matrix and similar adsorption capacities were found. A packed glass column was also prepared to demonstrate the adsorption of MB from tap water under flow conditions.

A standardized extract of the fruit of Hovenia dulcis alleviated alcohol-induced hangover in healthy subjects with heterozygous ALDH2: A randomized, controlled, crossover trial.

ETHNOPHARMACOLOGICAL RELEVANCE: Hovenia dulcis, known as the oriental raisin tree, is mainly found in East Asia. It has long been used as traditional folk remedies for alcohol intoxication. AIM OF THE STUDY: To examine the anti-hangover effect of Hovenia dulcis Thunb. fruit extract (HDE) in a randomized controlled crossover trial. MATERIALS AND METHODS: Twenty-six eligible male adults with heterozygous ALDH2 (23.7±0.3 years old) consumed 360mL of Korean Soju (50g alcohol) together with HDE (2460mg) or matched placebo with subsequent crossover. The blood samples were taken at baseline and 1, 4, and 12h post-treatment. RESULTS: Blood alcohol, acetaldehyde, and total hangover scores were highest at 1h post-treatment with no difference between groups, but declines in hangover symptom scores were significant in the HDE group compared to the placebo group. Significant differences between groups were also observed on interleukin (IL)-6, IL-10, IL-10/IL-6 ratio, and aspartate aminotransferase levels, but not on endotoxins. Pearson correlation analysis revealed a positive correlation between total hangover symptom scores and IL-6 and IL-10 level. Further analyses by CYP2E1 polymorphism at rs10776687, rs2031920, rs3813867, and rs4838767 alleles showed a reversed association, suggesting that CYP2E1 polymorphism might be an effect modifier. CONCLUSIONS: The results suggest that a favorable effect of HDE on alcohol hangovers might be associated with enhancing homeostatic regulation of inflammatory response. The magnitude of impact might be different in the presence of CYP2E1 polymorphism.

Differential expression of uterine calcium transporter 1 and plasma membrane Ca2+ ATPase 1b during rat estrous cycle.

Calcium-related proteins include the calcium transporters 1 and 2 (CaT1 and CaT2), plasma membrane Ca2+-ATPase 1b (PMCA1b), and calbindin-D9k and -D28k. The expression of CaT1 and PMCA1b and their potential roles in the uterine tissue remain to be clarified. Thus, in the present study, the expression patterns of CaT1 and PMCA1b were examined to predict their roles in rat uterus during the estrous cycle. Both CaT1 and PMCA1b mRNAs were detected in rat uterus. Uterine CaT1 mRNA was highly expressed at diestrus compared with proestrus, whereas PMCA1b expression was not altered during the estrus cycle. To evaluate the sex steroids involved in uterine CaT1 mRNA regulation, 17beta-estradiol (E2) and/or progesterone (P4) were injected into immature rats. Treatment with P4 or E2 plus P4 resulted in an increase in CaT1 mRNA, but a synergetic effect of E2 plus P4 was not detected. Uterine CaT1 mRNA was induced by P4 in a time- and dose-dependent manner, with maximal transcript detected 12 h after the final P4 injection. Treatment with RU486, a progesterone receptor (PR) antagonist, completely blocked P4-induced CaT1 mRNA, indicating that P4 regulates CaT1 mRNA expression via a PR-mediated pathway. In addition, CaT1 mRNA was expressed in uterine endometrium and glandular endometrium at diestrus in P4-treated rats. Together, these results suggest that CaT1 is regulated by P4 at diestrus via a PR-dependent pathway.

Estrogen receptor alpha pathway is involved in the regulation of Calbindin-D9k in the uterus of immature rats.

It has been demonstrated in our previous studies that Calbindin-D9k (CaBP-9k) is a potent biomarker for screening estrogen-like chemicals in the rat model. Although treatments with 17beta-estradiol (E2) and endocrine disrupting compounds resulted in the up-regulation of uterine CaBP-9k, the mechanism of CaBP-9k induction by these compounds through two subtypes of estrogen receptors (ERalpha and ERbeta) is unclear. Thus, in the present study, immature rats were treated with propyl pyrazole triol (PPT, an ERalpha-selective ligand), diarylpropionitrile (DPN, an ERbeta-selective ligand), E2, or dimethyl sulfoxide (DMSO, a vehicle control) for three days in order to clarify which subtype of ER is involved in the uterine CaBP-9k induction. Following injection with these ER ligands, uterine CaBP-9k expression was analyzed by Northern blot and immunoblot assays. Uterine CaBP-9k expression is mainly mediated by PPT in a dose- and time-dependent manner in immature rats, whereas no significant alteration of the uterine CaBP-9k gene was observed after DPN treatment. In addition, an estrogenicity of PPT in inducing CaBP-9k expression was completely blocked by the anti-estrogen ICI 182,780, implying that uterine CaBP-9k is solely induced by ERalpha. A single treatment with PPT rapidly increased the protein levels of ERalpha and PR, an E2-mediated gene, in these tissues. Taken together, these results indicate that uterine CaBP-9k is induced by E2 and endocrine disrupting chemicals via the ERalpha pathway, but not ERbeta, in the uterus of immature rats.

Effect of genistein as a selective estrogen receptor beta agonist on the expression of Calbindin-D9k in the uterus of immature rats.

Genistein, a phytoestrogen possessing a high affinity for estrogen receptor beta (ERbeta), is of increasing interest because of its possible influence on the physiology of mammalian reproductive tracts. Although estrogen has been demonstrated to regulate Calbindin-D9k (CaBP-9k) in the rat uterus as with other calcium binding proteins, the role of ERbeta on the modulation of CaBP-9k remains to be elucidated. To elucidate the effect of genistein as a selective ERbeta agonist on uterine expression of CaBP-9k mRNA and protein, immature female rats were injected with genistein daily for three consecutive days in a dose-dependent (0.4, 4, and 40 mg/kg/day) and time-dependent (40 mg/kg/day; 3, 6, 12, 24, 48, and 72 h) manner. Then, the expression of CaBP-9k mRNA and protein was analyzed by Northern hybridization and Western blot, respectively, in the absence or presence of ICI 182,780 (ICI), an estrogen antagonist. In addition, the protein levels of ERalpha and ERbeta and mRNA level of progesterone receptor (PR) were further measured following genistein treatment to elucidate which of ERs is involved in CaBP-9k modulation. In a dose-dependent experiment, the highest dose of genistein (40 mg/kg/day) for 3 days significantly induced uterine CaBP-9k protein as 17beta-estradiol (E2) did. In addition, its maximal mRNA expression was observed at 3 and 6 h, and it returned to control level at 24 h in a time-dependent experiment. In parallel with its mRNA level, the protein level of CaBP-9k was significantly induced by genistein at 3 h and sustained up to 48 h. The pretreatment with ICI, followed by genistein or E2, completely blocked genistein- and E2-induced CaBP-9k protein in the uterus of immature rats. Interestingly, genistein was demonstrated to induce ERalpha protein, but not ERbeta and PR mRNA, an E2-responsive gene, in this tissue. These results imply that genistein, an ERbeta ligand, may regulate CaBP-9k gene through ERalpha pathway. Taken together, the present study demonstrated that genistein enhanced CaBP-9k gene via ERalpha in the uterus of immature rats, suggesting that ERalpha may be a key mediator in uterine CaBP-9k gene induction in immature rats.