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1.
1,3-Oxazines have a wide variety of biological activities. Naphthoquinone scaffolds also exhibit several biological responses such as antithrombotic, apoptosis and lipoxygenase inhibitors. There is, therefore, a need to develop efficient green methodologies for hybridizing the two scaffolds in a single entity. Herein, we report a novel protocol for the synthesis of 3-aryl-3,4-dihydro-2H-naphtho[2,3-e][1,3]oxazine-5,10-diones by one-pot three-component condensation of 2-hydroxy-1,4-naphthoquinone, aromatic amines and formaldehyde in glycerol at 50 °C. After separation of products, the glycerol–water layer was extracted using ethyl acetate and the dried glycerol layer was successfully reused several times. The products were obtained in 85–95 % yields in 5–10 min. This environmentally benign protocol holds advantages of high yields, operational simplicity and easy workup over our earlier report.  相似文献   

2.
Synthesis and characterization of Cu(II), Ni(II), and Zn(II) Schiff bases complexes resulted from the condensation of salicylaldehyde derivatives with o-amino phenol were discussed using elemental analysis (carbon, hydrogen, and nitrogen), molar conductance, magnetic measurements, mass spectra, and electronic spectra. The essential bands of infrared, 1HNMR, and UV-Vis spectra as well as thermogravimetric analysis corresponding to the active groups within the three ligands and their complexes were interpreted. The dehydration and decomposition processes of the [Cu(H2L1)(H2O)](OAc)2, [Ni(H2L1)(H2O)]SO4 · H2O, [Zn(H2L1)(H2O)]SO4 · H2O, [Cu(H2L2)(H2O)](OAc)2, [Ni(H2L2)(H2O)]SO4 · H2O, [Zn(H2L2)(H2O)]SO4 · 2H2O, [Cu(H2L3)(H2O)](OAc)2 · H2O, [Ni(H2L3)(H2O)]SO4 · 2H2O, [Zn(H2L3)(H2O)]SO4 complexes were studied thermodynamically using the integral method applying the Coats–Redfern and Horowitz–Metzger equations and the thermodynamic parameters were calculated. It was found from the elemental analysis and the thermal studies, that the ligand behaves as tridentate ligand forming chelates with 1 : 1 (metal : ligand) stoichiometrically. The molar conductance measurements of the complexes in dimethyl sulfoxide solvent indicate that the complexes have an electrolytic nature. The biological activities of the three ligands in comparison with metal(II) complexes were studied against different Gram positive and Gram negative bacteria.  相似文献   

3.
Pyranopyridine derivatives are an important class of heterocyclic compounds due to their biological activities such as antitumor and antibacterial. However, conventional procedures for their synthesis produce large amounts of toxic by-products. Therefore, there is a need to develop simple, efficient and environmentally benign procedures. Here, a one-pot multicomponent protocol is designed for the synthesis of pyrano[2,3-b]pyridone derivatives by reaction of equimolar amounts of 6-hydroxy-1,4-dimethyl-1,2-dihydropyridines, aryl aldehydes and malononitrile, using both microwave heating and solar thermal energy in aqueous EtOH (50%) in the presence of a catalytic amount of K2CO3. The products were obtained in 84–90% yields in 10–20 min by microwave heating, and in 90–96% yields in 2–3 h using solar energy.  相似文献   

4.
Due to the slow rate of incorporation of inert-metal ions into free-base porphyrins compared to other transition metals, several methods have been proposed to accelerate the rate of metalation. However, these methods have disadvantages such as low yields, difficulties of purification of final products, and environmental effects. To avoid those disadvantages, we reacted Pt(II) and Pd(II) salts with H2(TPP), H2(TMPyP)4+, and their β-pyrrole derivatives, H2(Br8TPP) and H2(Br8TMPyP)4+, in 1-butyl-3-methylimidazolium bromide ([bmim]+Br) under microwave irradiation. The combination of microwave heating and ionic liquids provides efficient thermal energy transfer among the porphyrins and metal salts. In addition, ionic liquids stabilize charged species as well as their intermediates, due to their high dipole moment and high boiling point. This not only shortens the reaction time but also gives high yields of products at relatively low temperatures, of about 100°C compared to conventional synthesis methods: 150°C for DMF, 190°C for DMSO. Here, we demonstrate that Pt(II)/Pt(II) metalloporphyrins are synthesized at high rates, e.g. 6–30 min for 100% metalation, with high yields of 79–93% in [bmim]+Br by microwave activation.  相似文献   

5.
为探讨咪唑类离子液体氯化1-辛基-3-甲基咪唑([C_8mim][C1])对洋葱的遗传毒性,用浓度分别为2.5、5、10和20mmol·L~(-1)的[C_8mim][C1]处理洋葱内表皮细胞和洋葱根尖8 h,用浓度为10 mmol·L~(-1)的[C_8mim][C1]处理洋葱内表皮细胞和洋葱根尖4 h、8 h、12 h和24 h,研究[C_8mim][C1]对洋葱内表皮细胞核的影响和对洋葱根尖有丝分裂指数和染色体畸变的影响。结果显示,与对照组相比,随着[C_8mim][Cl]处理浓度和时间的增加,洋葱内表皮细胞核偏移率明显升高,根尖细胞有丝分裂指数显著降低,染色体畸变现象明显,畸变率升高。研究表明,当浓度达到2.5 mmol·L~(-1)时,[C_8mim][Cl]对洋葱具有遗传毒性。  相似文献   

6.
Ten 2-(substituted benzylidene)-7-(4-chlorophenyl)-5-(furan-2-yl)-2H-thiazolo[3,2-a]pyrimidin-3(7H)-one derivatives were synthesized and evaluated. A series of heterocyclic, 2-(substituted benzylidene)-7-(4-chlorophenyl)-5-(furan-2-yl)-2H-thiazolo[3,2-a]pyrimidin-3(7H)-one were synthesized by reaction of 7-(4-chloro phenyl)-5-(furan-2-yl)-2H-thiazolo[3,2-a]pyrimidin-3(7H)-one with appropriately substituted aldehydes in the presence of anhydrous sodium acetate and glacial acetic acid. The antinociceptive activity was evaluated by tail-flick technique, anti-inflammatory activity was evaluated by carrageenan-induced paw edema test and their ulcerogenicity index was determined. The para-substituted methyl, hydroxy, fluoro, chloro, bromo, and nitro derivatives showed significant antinociceptive and anti-inflammatory activities. The detailed synthesis, spectroscopic data, and pharmacological screening of the synthesized compounds were reported.  相似文献   

7.
The interactions of 10 different chromium(III) complexes with isolated calf thymus DNA have been analysed by studying the electronic and fluoresence spectra of intercalated ethidiumbromide. Triply charged cationic complexes including: [Cr(urea)6]Cl3.3H2O, [Cr(1,10‐phenanthroline)3](ClO4)3.2H2O, [Cr(2,2'‐bipyridyl)3] (ClO4)3.2H2O, [Cr(ethylendiamine)3]Cl3.3.5H2O and [Cr(NH3)6](NO3)3 displaced the dye from DNA. Similar effects were observed in experiments using the non‐intercalating dye bisbenzimidazole ("Hoechst 33258"). However, singly charged cationic, anionic and uncharged chromium(III) complexes such as: cis‐[Cr(1,10‐phenanthroline)2Cl2]Cl.2H2O, cis‐[Cr(2,2'‐bipyridyl)2Cl2]Cl.2H2O, [Cr(glutathione)2]Na2, [Cr(cysteine)2]Na.2H2O and [Cr(glycine)3] were unable to displace both ethidiumbromide and bisbenzimidazole from DNA. There was no evidence for the formation of co‐ordinate bonds between chromium(III) and DNA for any of the above complexes. The charge and type of ligand are important in controlling the interaction of chromium(III) with isolated DNA in vitro. Our findings indicate that the outer sphere interaction of a chromium(III) complex with DNA is weak and unlikely to be the mechanism by which chromate causes DNA impairments in vivo and in vitro.  相似文献   

8.
The reversible capture of CO2 from fossil-fueled industries and the absorption of CO2 for natural-gas-sweetening purposes are industrial issues closely related to very important environmental, economical, and technological concerns. Biological amino acids can be used for task-specific ionic liquids for reversible CO2 capture. Several groups have reported efficient and reversible CO2 capture by such ionic liquids under rigorously dry conditions. However, we have observed that CO2 capture by amino acid ionic liquids is hugely impacted by the presence of water. In addition, the amino acid anions appear to play only a transitory role in the CO2 capture in the first minutes of exposure to a wet CO2 stream. Here, we studied the interaction of two ionic liquids—tetramethylammonium glycinate ([N1111][Gly]) and tetraethylammonium prolinate ([N2222][Pro])—with CO2 under wet conditions, by 13C-NMR. Results show that CO2 is initially captured in a carbamate form by the amine-functionalized anions of these salts. This capture mode is unambiguously confirmed by a single-crystal X-ray study of the CO2-ionic liquid complex. However, in solution, as additional CO2 is added, the carbamate releases the covalently bound CO2, and the CO2 remaining in solution shifts in form to an equilibrium mixture of carbonate and bicarbonate. Indeed, when the amount of CO2 present in the system exceeds about one-half mole per mole of ionic liquid present, the ionic liquid–carbamate complex is detected in only trace amounts, and the neutralized amino acids are readily identifiable by NMR.  相似文献   

9.
为探讨咪唑类离子液体氯化1-辛基-3-甲基咪唑([C8mim][Cl])对酵母细胞的增殖生长和细胞膜通透性的影响,以不同浓度的[C8mim][Cl]处理酵母细胞,研究离子液体对酵母细胞增殖和菌落形成的影响,通过测定酵母细胞外液蛋白质和核酸的含量,判断膜通透性的大小和[C8mim][Cl]对细胞膜性结构的损伤。结果显示,0.1 mmol·L-1的[C8mim][Cl]延长了酵母细胞到达对数生长期的时间,在6~9 h之间对酵母细胞的增殖存在明显的抑制作用。1 mmol·L-1的[C8mim][Cl]使酵母细胞增殖不能到达对数生长期,对酵母细胞的增殖一直具有较强的抑制作用。随着离子液体浓度的增加,小菌落的数量增多。当平板内[C8mim][Cl]浓度达到10 mmol·L-1时,完全抑制了菌落的形成。[C8mim][Cl]处理酵母细胞后,细胞外液中OD280、OD260的值显著升高。研究表明,细胞膜等膜性结构通透性的增加是离子液体[C8mim][Cl]抑制酵母细胞增殖生长的原因之一。  相似文献   

10.
Post-treatment impacts of a novel combined hydrogen peroxide (H2O2) oxidation and WOx/ZrO2 catalysis used for the removal of 1,4-dioxane and chlorinated volatile organic compound (CVOC) contaminants were investigated in soil and groundwater microbial community. This treatment train removed ~90% 1,4-dioxane regardless of initial concentrations of 1,4-dioxane and CVOCs. The Illumina Miseq platform and bioinformatics were used to study the changes to microbial community structure. This approach determined that dynamic shifts of microbiomes were associated with conditions specific to treatments as well as 1,4-dioxane and CVOCs mixtures. The biodiversity was observed to decrease only after oxidation under conditions that included high levels of 1,4-dioxane and CVOCs, but increased when 1,4-dioxane was present without CVOCs. WOx/ZrO2 catalysis reduced biodiversity across all conditions. Taxonomic classification demonstrated oxidative tolerance for members of the genera Massilia and Rhodococcus, while catalyst tolerance was observed for members of the genera Sphingomonas and Devosia. Linear discriminant analysis effect size was a useful statistical tool to highlight representative microbes, while the multidimensional analysis elucidated the separation of microbiomes under the low 1,4-dioxane-only condition from all other conditions containing CVOCs, as well as the differences of microbial population among original, post-oxidation, and post-catalysis states. The results of this study enhance our understanding of microbial community responses to a promising chemical treatment train, and the metagenomic analysis will help practitioners predict the microbial community status during the post-treatment period, which may have consequences for long-term management strategies that include additional biodegradation treatment or natural attenuation.
  相似文献   

11.
A simple and efficient ionic liquid-based ligandless microextraction method has been developed for preconcentration of cadmium ions (Cd2+) as a step prior to its determination by flame atomic absorption spectrometry (FAAS) with a micro-sample introduction system. In this approach, the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6] and ethanol were used as extractant and dispersive solvents to preconcentrate the Cd2+ in different waters, acid digested scalp hair, and nail samples. Some analytical parameters influencing the extraction efficiency of Cd2+ and its subsequent determination, including pH, IL volume, dispersant solvent volume, sample volume, temperature, incubation time, and matrix effect, were optimized. Under optimal conditions, the limit of detection (LOD), limit of quantification (LOQ), and enhancement factor (EF) were 0.4 μg L?1, 1.3 μg L?1, and 50, respectively. The relative standard deviation (RSD) of 100 μgL?1 Cd2+ was 4.3% (n = 6). The validity of the proposed method was checked by determining Cd2+ in certified reference material (TM-25.3 fortified water) and standard addition; the results showed sufficient recovery (>98%) of Cd2+ within the certified value. The method was applied for preconcentration and determination of cadmium in waters and biological samples.  相似文献   

12.
Effects of selected ionic liquids on the efficiency of CPO oxidation of methyl-parathion were studied. In general, the activity of CPO decreases with the increased concentration of ionic liquid. For ionic liquids with the same cation, those with PF6 ? exhibit strongest inhibition toward CPO, while those with either BF4 ? or metSO4 ? show relatively lesser inhibition. It was further demonstrated that even for buffer solutions containing up to 30% concentration of ionic liquids such as EAN, BMIMmetSO4, and EtPyTFA, CPO still can retain high activity (70–100% compared to that in citrate buffer) for oxidation of methyl-parathion. Photothermal enhancement factors of 3.5 times and corresponding improvements of sensitivity in the determination of organophosphates by the FIA-TLS method are predicted in 30% ionic liquids.  相似文献   

13.
Copper recovery is the core of waste printed circuit boards (WPCBs) treatment. In this study, we proposed a feasible and efficient way to recover copper from WPCBs concentrated metal scraps by direct electrolysis and factors that affect copper recovery rate and purity, mainly CuSO4·5H2O concentration, NaCl concentration, H2SO4 concentration and current density, were discussed in detail. The results indicated that copper recovery rate increased first with the increase of CuSO4·5H2O, NaCl, H2SO4 and current density and then decreased with further increasing these conditions. NaCl, H2SO4 and current density also showed a similar impact on copper purity, which also increased first and then decreased. Copper purity increased with the increase of CuSO4·5H2O. When the concentration of CuSO4·5H2O, NaCl and H2SO4 was respectively 90, 40 and 118 g/L and current density was 80 mA/cm2, copper recovery rate and purity was up to 97.32% and 99.86%, respectively. Thus, electrolysis proposes a feasible and prospective approach for waste printed circuit boards recycle, even for e-waste, though more researches are needed for industrial application.
  相似文献   

14.
The thiazole ring system is one of the most important heterocycles in nature, as it represents an important structural motif of many biological compounds, including vitamin B1 (Thiamin), carboxylase and penicillin. There is, therefore, an urgent need to design rapid, efficient and environmentally benign protocols for the synthesis of thiazoles. Herein, we have developed a one-pot protocol for the synthesis of 4-aryl-2-aminothiazoles from the reaction of aromatic ketones, NBS (N-Bromosuccinimide) and thioureas under microwave irradiation at 80–85 °C in PEG (polyethylene glycol)-400 and water as a green reaction medium. The products were obtained in 84–89% yields in 28–32 min. The method has several advantages such as use of green solvent, easy work-up, excellent yield and avoiding use of lachrymatric α-haloketones.  相似文献   

15.
N2O is a powerful greenhouse gas and plays an important role in destructing the ozone layer. This present work investigated the effects of Pd doping on N2O formation over Pt/BaO/Al2O3 catalyst. Three types of catalysts, Pt/BaO/Al2O3, Pt/Pd mechanical mixing catalyst (Pt/BaO/Al2O3 + Pd/Al2O3) and Pt-Pd co-impregnation catalyst (Pt-Pd/BaO/Al2O3) were prepared by incipient wetness impregnation method. These catalysts were first evaluated in NSR activity tests using H2/CO as reductants and then carefully characterized by BET, CO chemisorption, CO-DRIFTs and H2-TPR techniques. In addition, temperature programmed reactions of NO with H2/CO were conducted to obtain further information about N2O formation mechanism. Compared with Pt/BaO/Al2O3, (Pt/BaO/ Al2O3 + Pd/Al2O3) produced less N2O and more NH3 during NO x storage and reduction process, while an opposite trend was found over (Pt-Pd/BaO/Al2O3 + Al2O3). Temperature programmed reactions of NO with H2/CO results showed that Pd/Al2O3 component in (Pt/BaO/Al2O3 + Pd/Al2O3) played an important role in NO reduction to NH3, and the formed NH3 could reduce NO x to N2 leading to a decrease in N2O formation. Most of N2O formed over (Pt-Pd/BaO/Al2O3 + Al2O3) was originated from Pd/BaO/Al2O3 component. H2-TPR results indicated Pd-Ba interaction resulted in more difficultto- reduce PdOx species over Pd/BaO/Al2O3, which inhibits the NO dissociation and thus drives the selectivity to N2O in NO reduction.
  相似文献   

16.
An efficient method for prediction in the capture of SO2 from flue gas by imidazolium ionic liquids was reported, where the concentration of SO2 is 2000 ppm. On the basis of quantitative calculations through a combination of Langmuir simulation, theoretical calculation and quantum chemical method, SO2 absorption and desorption performance from flue gas by twelve kinds of imidazolium ionic liquids with different anions were designed and predicted. Then, among them, five kinds of imidazolium ionic liquids were chosen and prepared to investigate their behavior of SO2 absorption capacity, desorption residue, and available absorption capacity. The results indicated that the experimental values were in good agreement with the predicted values. Thus, an ideal ionic liquid [Emim][Tetz] was obtained through the predictive method for the capture of SO2 of 2000 ppm, which showed high available absorption capacity of 0.24 g SO2 per g ionic liquid and excellent reversibility.  相似文献   

17.
Surface O3 production has a highly nonlinear relationship with its precursors. The spatial and temporal heterogeneity of O3-NO x -VOC-sensitivity regimes complicates the control-decision making. In this paper, the indicator method was used to establish the relationship between O3 sensitivity and assessment indicators. Six popular ratios indicating ozone-precursor sensitivity, HCHO/NO y , H2O2/ HNO3, O3/NO y , O3/NO z , O3/HNO3, and H2O2/NO z , were evaluated based on the distribution of NOx- and VOC-sensitive regimes. WRF-Chem was used to study a serious ozone episode in fall over the Pearl River Delta (PRD). It was found that the south-west of the PRD is characterized by a VOCsensitive regime, while its north-east is NO x -sensitive, with a sharp transition area between the two regimes. All indicators produced good representations of the elevated ozone hours in the episode on 6 November 2009, with H2O2/HNO3 being the best indicator. The threshold sensitivity levels for HCHO/NOy, H2O2/HNO3, O3/NO y , O3/NO z , O3/HNO3, and H2O2/NO z were estimated to be 0.41, 0.55, 10.2, 14.0, 19.1, and 0.38, respectively. Threshold intervals for the indicators H2O2/HNO3, O3/NO y , O3/NO z , O3/HNO3, and H2O2/NO z were able to identify more than 95% of VOC- and NO x -sensitive grids. The ozone episode on 16 November 16 2008 was used to independently verify the results, and it was found that only H2O2/HNO3 and H2O2/NO z were able to differentiate the ozone sensitivity regime well. Hence, these two ratios are suggested as the most appropriate indicators for identifying fall ozone sensitivity in the PRD. Since the species used for indicators have seasonal variation, the utility of those indicators for other seasons should be investigated in the future work.
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18.
We report for the first time the direct conversion of raw grape berry biomass to hydroxymethylfurfural (HMF) using ionic liquid solvents with metal chloride catalysts. Exploiting raw plant biomass as a biorefinery feedstock is innovative for sustainable chemical industry. The use of the raw biomass to synthesize compounds can indeed lead to less energy consumption and less CO2 emissions. Using raw plant biomass skips pretreatment steps that are required to produce biomaterials such as carbohydrates or cellulosic biomass. Here, grape berry biomass was used as a raw chemical feedstock for the production of hydroxymethylfurfural, a key platform intermediate for syntheses of future renewable biofuels. We examined 3 ionic liquid solvents, 3 reaction temperatures, 5 chloride catalysts, and 5 concentrations of HCl. We found an increasing HMF yields depending on reaction conditions. 1-octyl-3-methylimidazolium chloride was most effective for HMF synthesis. Addition of HCl or metal chlorides alone showed little improvement. The highest HMF yield of about 100 mg HMF per mL of grape biomass extract was obtained using 0.3 M HCl, [OMIM]Cl, and CrCl2 at 100°C for 3 h. Our study provides a model system of sustainable production of valuable compounds from raw plant biomass.  相似文献   

19.
The effects of cadmium (3CdSO4·8H2O), zinc (ZnSO4·7H2O) and lead [Pb (NO3)2] on mortality, and cadmium, zinc and mercury (HgCl2) on osmoregulation, have been recorded for marine and estuarine species of isopods (Crustacea). The marine species studied were Idotea baltica, I. neglecta, I. emarginata and Eurydice pulchra, which were adapted to 100, 80, 60 and 40% sea water (SW) (100% SW э 34‰ S). The estuarine species used were Jaera albifrons sensu stricto and J. nordmanni, which were adapted to 100, 50, 10 and 1% SW. Both groups of isopods have low mortalities in 100% SW with 10 and 20 ppm of cadmium, zinc and lead, but a decrease in salinity caused an increase in the toxicities of these metals and reduced the LT50 values (time, in hours, to 50% mortality). Mortalities at 10°C were generally higher than those recorded at 5°C. Cadmium had no significant effect on the osmoregulation of I. baltica and I. emarginata in 100 and 80% SW at 5°C, but this metal significantly lowered the blood osmotic concentration of I. neglecta in 80% SW. Zinc did not alter the haemolymph osmotic concentration of I. neglecta in 100 and 80% SW, but significantly lowered the blood osmotic concentration of I. baltica in 100% SW. Cadmium, zinc and mercury also significantly altered the osmoregulatory ability of J. albifrons in dilute saline.  相似文献   

20.
Degradation of azo dyes in water by Electro-Fenton process   总被引:19,自引:0,他引:19  
The degradation of the azo dyes azobenzene, p-methyl red and methyl orange in aqueous solution at room temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potential-controlled electrolysis conditions, using a Pt anode and a carbon felt cathode. The electrochemical production of Fenton's reagent (H2O2, Fe2+) allows a controlled in situ generation of hydroxyl radicals (·OH) by simultaneous reduction of dioxygen and ferrous ions on the carbon felt electrode. In turn, hydroxyl radicals react with azo dyes, thus leading to their mineralization into CO2 and H2O. The chemical composition of the azo dyes and their degradation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol. Degradation of the initial azo dyes was assessed by the measurement of the chemical oxygen demand (COD). Kinetic analysis of these data showed a pseudo-first order degradation reaction for all azo dyes. A pathway of degradation of azo dyes is proposed. Specifically, the degradation of dyes and intermediates proceeds by oxidation of azo bonds and aromatic ring by hydroxyl radicals. The results display the efficiency of the Electro-Fenton process to degrade organic matter. Electronic Publication  相似文献   

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