Chemical constituents from wetland soil fungus Penicillium oxalicum GY1.

A new azo compound, penoxalin (1), a new isochroman carboxylic acid, penisochroman B (3), two new natural products, penisochroman A (2) and 2,6-dihydroxy-4-[(2R)-2-hydroxyheptyl] benzoic acid (4), together with four known compounds (5-8) were isolated from wetland soil fungus Penicillium oxalicum GY1. All structures were elucidated by extensive NMR spectroscopic evidences together with mass spectrometry. The absolute configuration of penoxalin (1) was determined by calculated ECD spectrum, while the absolute configuration of new natural product penisochroman A (2) was established for the first time by single crystal X-ray diffraction. In addition, all compounds were evaluated for their cytotoxic activity in vitro. 2, 6-Dihydroxy-4-[(2R)-2-hydroxyheptyl] benzoic acid (4) displayed significant cytotoxicity against human esophageal carcinoma cells OE19 with an IC50 value of 5.50 µM.

Nitrogen-Doped Carbon Dots from Averrhoa carambola Fruit Extract as a Fluorescent Probe for Methyl Orange.

In this study, a simple and green hydrothermal treatment was performed to prepare nitrogen-doped carbon dots (NCDs) from Averrhoa carambola (AC) fruit extract as a carbon precursor and L-arginine (Arg) as a nitrogen dopant. The AC-NCDs were characterized by UV light, fluorescence spectroscopy, transmission electron microscopy, FTIR spectroscopy, Raman spectroscopy, UV-vis spectroscopy, and zeta potential analyzer. The AC-NCDs were spherical and the average diameter was estimated to be 6.67 nm. The AC-NCDs exhibited the maximum emission intensity at 446 nm with 360 nm excitation wavelength. The fluorescence quenching behavior of AC-NCDs after interacting with methyl orange (MO) dye was studied. The interaction of AC-NCDs and MO was achieved within 3 min and the fluorescence quenching was maintained to a fixed value even after 30 min. The linearity was obtained in the range of 1 to 25 µM MO with a 0.30 µM detection limit. Furthermore, the pH values affected the quenching behavior of the AC-NCDs/MO system where the interaction mechanisms were driven by the electrostatic interaction, π-π interaction, inner filter effect, and energy transfer. The pH 5 maintained higher quenching efficiency while other pH values slightly decreased the quenching efficiency. Incoming applications, the AC-NCDs can be used in various important fields, especially for environmental protection.

Magnetic xanthate modified chitosan as an emerging adsorbent for cationic azo dyes removal: Kinetic, thermodynamic and isothermal studies.

In the present study, a novel xanthate modified magnetic chitosan, with Al2O3/Fe3O4 core-shell particle as magnetic core, was synthesized, characterized and used as an efficient adsorbent for the removal of cationic azo dye models. The adsorption study demonstrated that the xanthate modification of magnetic chitosan significantly improves its adsorption activity toward methylene blue and safranin O. The optimized adsorbent dosage was obtained 0.8 mg g-1 and the process was found to be optimal in the wide pH range of 4-11. The kinetic data were evaluated well utilizing the pseudo-second-order model and it was shown that the adsorption kinetics was controlled by film diffusion and intra-particle diffusion, simultaneously. Also, the equilibrium data were fitted by Langmuir (R2 > 0.95) and very well correlated with Sips isotherm (R2 > 0.990) model. The maximum adsorption capacities were obtained 197.8 and 169.8 mg g-1 toward the methylene blue and Safranin O at 35 °C respectively. The thermodynamic analysis confirmed the endothermic, spontaneous and irreversible adsorption process.

Large-scale converting waste coffee grounds into functional carbon materials as high-efficient adsorbent for organic dyes.

Functional carbon materials have been fabricated through simple and effective catalytic carbonization with waste coffee grounds (CGs) as carbon precursor and FeCl3 as catalyst. The effect of FeCl3 loading and carbonization temperature on carbon yield was investigated. The morphology and structure of as-synthesized carbons was characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and nitrogen isothermal adsorption/desorption measurement, respectively. Furthermore, the carbon materials showed high efficiency for the removal of methylene blue (MB, 653.6 mg g-1), methyl orange (MO, 465.8 mg g-1) and rhodamine B (RB, 366.1 mg g-1). More importantly, the carbon was magnetic, so it can be easily separated by a magnet and reused multiple times. This work not only exploited a low-cost and large-scale preparation method to synthesize functional carbon materials from bioresources, but also provided an eco-friendly and effective adsorbent in water purification applications.

Synthesis of a bio-based polyurethane/chitosan composite foam using ricinoleic acid for the adsorption of Food Red 17 dye.

A novel bio-based polyurethane/chitosan foam (PU/chitosan) was synthesized using a polyol derived from castor oil and applied to remove Food Red 17 dye (FR17) from aqueous solutions. PU/chitosan foam presented better characteristics and adsorption potential than polyurethane foam (PU). PU/chitosan foam showed a semi-crystalline structure, with several functional groups, high porosity and good mechanical properties. These characteristics are adequate for adsorptive separations. Using identical adsorption conditions, PU/chitosan was able to remove >98% of FR17 dye from the solution, while, PU removed only 40%. The adsorption of FR17 on PU/chitosan composite foam was favored at pH 2. Pseudo-second order model was the most adequate to represent the kinetic data. The equilibrium data followed the Sips model, with a maximum adsorption capacity of 267.24 mg g-1. The adsorption process was spontaneous, favorable and endothermic. The results showed that polyurethane foams are capable to support chitosan, generating an adsorbent with better mechanical characteristics and high potential to remove anionic dyes from aqueous media.

Synthesis and characterization of Zr(IV) doped immobilized cross-linked chitosan/perlite composite for acid orange II adsorption.

To enhance the adsorption capacity of chitosan for acid orange II (AOII) adsorption, a novel adsorbent, zirconium(IV) doped immobilized cross-linked chitosan/perlite (Zr(IV)-CS-PT) composite was synthesized and characterized. Batch studies were conducted to analyze the effect of different parameters on AOII adsorption, such as Zr (IV) loading amount, pH, adsorbent dosage and temperature. Also, kinetic data revealed that AOII adsorption was well described by pseudo-second order kinetic model. Langmuir adsorption isotherm model was best described the isotherm data and maximum adsorption capacity was found 476.2 mg/g at natural pH. The thermodynamic data showed that the AOII adsorption occurred spontaneously and endothermic nature. Desorption and recycle experiments showed that after six cycle the adsorption efficiency was decreased from 95.6% to 90.1%, which shows the Zr(IV)-CS-PT is a reusable, cost-effective and high adsorption capacity adsorbent.

Study of the effect of an acid treatment of a natural Moroccan bentonite on its physicochemical and adsorption properties.

In this study, a natural bentonite taken from a deposit in the Northeast of Morocco has been purified (PB) and treated with various HCl molarities (xHPB) in order to obtain an HCl/Bentonite weight ratio equal to 0.2, 0.4 and 0.6. The obtained physicochemical characterization results indicated that the PB sample is composed mainly of the montmorillonite phase. The impact of acid treatment was investigated by identifying changes in the chemical composition, cation exchange capacity, infrared absorption bands, crystalline structure, morphology of the particles and specific surface area. The adsorption behavior of methylene blue (MB) and methyl orange (MO) in aqueous solution onto PB and xHPB samples was investigated by varying the initial concentration of dyes, the contact time and the temperature. The obtained results showed that the experimental data best fit the Langmuir model and the pseudo-second-order kinetic model. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) studies carried out after MB and MO adsorption onto PB samples indicated that MB cations were intercalated, in the form of monomers and dimers, with a large amount of monomers, slightly tilted against the plane of the clay surface. While MO molecules adsorb, with a near perpendicular alignment, with their SO3- group and O- atoms facing the mineral surface plane.

Ultrasound-assisted removal of Acid Red 17 using nanosized Fe3O4-loaded coffee waste hydrochar.

The Fe3O4-loaded coffee waste hydrochar (Fe3O4-CHC) was synthesized using a simple precipitation method. The as-prepared adsorbent was characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and Fourier transform infrared spectroscopy (FT-IR). The EDX analysis indicated the presence of Fe in the structure of Fe3O4-CHC. The specific surface area of hydrochar increased from 17.2 to 34.7m2/g after loading of Fe3O4 nanoparticles onto it. The prepared Fe3O4-CHC was used for removal of Acid Red 17 (AR17) through ultrasound-assisted process. The decolorization efficiency decreased from 100 to 74% with the increase in initial dye concentration and from 100 to 91 and 85% in the presence of NaCl and Na2SO4, respectively. The synthesized Fe3O4-CHC exhibited good stability in the repeated adsorption-desorption cycles. The high correlation coefficient (R2=0.997) obtained from Langmuir model indicated that physical and monolayer adsorption of dye molecules occurred on the Fe3O4-CHC surface. Furthermore, the by-products generated through the degradation of AR17 was identified by gas chromatography-mass spectrometry analysis.

Cross-linked beads of activated oil palm ash zeolite/chitosan composite as a bio-adsorbent for the removal of methylene blue and acid blue 29 dyes.

Cross-linked beads of activated oil palm ash zeolite/chitosan (Z-AC/C) composite were prepared through the hydrothermal treatment of NaOH activated oil palm ash followed by beading with chitosan. The effects of initial dye concentration (50-400mg/L), temperature (30°C-50°C) and pH (3-13) on batch adsorption of methylene blue (MB) and acid blue 29 (AB29) were studied. Adsorption of both dyes was better described by Pseudo-second-order kinetics and Freundlich isotherm model. The maximum adsorption capacities of Z-AC/C were 151.51, 169.49, and 199.20mg/g for MB and 212.76, 238.09, and 270.27mg/g for AB29 at 30°C, 40°C, and 50°C, respectively.

Adsorption Assisted Photocatalytic Removal of Methyl Orange by MgAl2O4-Sb2S3 Composite Material.

BACKGROUND: The current article is about the water treatment in which colored water contaminated by methyl orange has been used for adsorption assisted photocatalysis. Coupling of photocatalysis with the traditional water treatment processes has been in practice since last couple of years for the improvement of degradation efficiencies, for example, photocatalysis coupled with ultrafilteration, adsorption, flocculation, biological methods, photolysis, membrane distillation, etc. Among all these coupling approaches, adsorption assisted photocatalysis being a very simple and highly efficient approach is suffering from few drawbacks on the account of high cost, low stability and surface area of the adsorbent support. The present study is a contribution towards improvement in this coupling approach. A low cost, highly stable spinel magnesium aluminate (MgAl2O4) material synthesized at nanoscale is used for composite formation with antimony sulphide (Sb2S3) material having high absorption coefficient in the visible light of solar spectrum. A review of recent patents shows that the field of photoctalysis is dominated by the traditional TiO2 catalyst. The modification of TiO2 by either composite formation or by doping is the main focus. METHODS: Coprecipitation method is used for the synthesis of spinel in which the desired precursors in the respective molar ratios were mixed and annealing of the resulting precipitates was carried out at 800oC for 8 h. Sb2S3 was synthesized by the hydrothermal method in which the required molar solution of precursors was mixed with urea solution and the whole mixture was maintained at 105oC for 6 hrs in a Teflon lined autoclave. The resulting suspension was then annealed at 37oC for 3 hours. The composite of Sb2S3 and MgAl2O4 has been synthesized by mixing both the materials in 1:1 and heat treated in an oven at a temperature of 200oC. RESULTS: Peaks in X-ray diffraction pattern correspond to both the Sb2S3 and spinel phase. All the peaks corresponding to the Sb2S3 and spinel phase were found to be shifted to higher d-spacing values. This indicates the expansion of unit cells of the Sb2S3 and MgAl2O4 phases. Thermal studies show that only 3% weight loss is observed at a temperature of 200-1000oC which may be due to the loss of surface water from the sample. Surface area, pore volume and pore size obtained from N2 adsorption were 143m2/g, 0.21cc/g and 23.26Å, respectively. The removal efficiency of 0.1g catalyst for methyl orange solution of 5mg/L concentration after reaction in dark conditions for the time of one hour was calculated to be 24% owing to the adsorption. The visible light degradation efficiency of the 0.1g catalyst for 1, 5, 19, 25 and 50 mg/L concentrations of MO solutions were 97, 93, 75, 72 and 62% respectively. The dosage of the catalyst was found to have a direct relationship with the degradation efficiency. Lower pH was found suitable for the degradation owing to better interaction of catalyst surface and the adsorbed dye. Percent degradation increased with the increase in the time and temperature of reaction. The degradation kinetics followed pseudo first order rate equation; the calculated value of rate constant was 0.0102 min-1. CONCLUSION: The mechanism involves the excitation of electrons in the valence band of Sb2S3 to the conduction band by the absorption of visible and UV light. The electrons and holes participate in the surface reactions resulting in the formation of superoxide and hydroxyl radicals which degrade the targeted polluted. Lower concentration of MO solutions, acidic pH, higher catalyst dosage and greater reaction times were found suitable for the degradation efficiency.

The mechanism for degrading Orange II based on adsorption and reduction by ion-based nanoparticles synthesized by grape leaf extract.

Biomolecules taken from plant extracts have often been used in the single-step synthesis of iron-based nanoparticles (Fe NPs) due to their low cost, environmental safety and sustainable properties. However, the composition of Fe NPs and the degradation mechanism of organic contaminants by them are limited because these are linked to the reactivity of Fe NPs. In this study, Fe NPs synthesized by grape leaf extract served to remove Orange II. Batch experiments showed that more than 92% of Orange II was removed by Fe NPs at high temperature based on adsorption and reduction and confirmed by kinetic studies. To understand the role of Fe NPs in the removal process of azo dye, surface analysis via X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) were employed, showing that the Fe NPs were composed of biomolecules, hydrous iron oxides and Fe(0), thus providing evidence for the adsorption of Orange II onto hydrous iron oxides and its reduction by Fe(0). Degraded products such as 2-naphthol were identified using LC-MS analysis. A degradation mechanism based on asymmetrical azo bond cleavage for the removal of Orange II was proposed.

Multi-response optimization using Taguchi design and principle component analysis for removing binary mixture of alizarin red and alizarin yellow from aqueous solution by nano γ-alumina.

The nanostructure of γ-alumina was used as an effective adsorbent for simultaneous removing of a mixture of alizarin red and alizarin yellow from aqueous solutions. The Taguchi design and principle component analysis were applied to explore effective parameters for achieving a higher adsorption capacity and removal percentage of the binary mixture containing alizarin red and alizarin yellow. Seven factors including temperature, contact time, initial pH value, the shaker rate, the sorbent dose, and initial concentrations of alizarin red and alizarin yellow in three levels were considered through the Taguchi technique. A L27 orthogonal array was used to determine the signal-to-noise ratio. Then, the removal percentage (R%) and adsorption capacity (q) of the above-mentioned dyes were transformed into an accurate S/N ratio. The Taguchi method indicates that the solution pH has the most contribution in controlling the removal percentage of alizarin red and alizarin yellow. Under optimal condition, the maximum removal percentages of 99% and 78.5%, and the capacity uptake of 54.4 and 39.0mg g(-1) were obtained for both alizarin red and alizarin yellow, respectively. Isotherm modeling and kinetic investigations showed that Langmuir, modified Langmuir, and pseudo-second-order models describe both the adsorption equilibrium and kinetic behavior well. The Fourier transform infrared analysis also firmly confirmed the involving active sites of nano γ-alumina in the adsorption process.

Removal of Chemazol Reactive Red 195 from aqueous solution by dehydrated beet pulp carbon.

An agricultural low-cost by-product, dehydrated beet pulp carbon (DBPC) was used as an adsorbent for removal of Chemazol Reactive Red 195 (CRR 195) from aqueous solution. The surface area of DBPC was measured as 9.5m(2)g(-1) by using BET method. The results indicated that adsorption was strongly pH-dependent and optimum pH was determined as 1.0. The maximum dye adsorption capacity was obtained as 58.0 mg g(-1)at the temperature of 50°C at this pH value. The Freundlich and Langmuir adsorption models were used for the mathematical description of the adsorption equilibrium and it was reported that, experimental data fitted very well to Freundlich model. Mass transfer and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate-controlling steps. It was found that both external mass transfer and intra-particle diffusion played an important role in the adsorption mechanisms of dye and adsorption kinetics followed the pseudo-first-order type kinetic model. The thermodynamic parameters such as, Gibbs free energy changes (ΔG°), standard enthalpy change (ΔH°) and standard entropy change (ΔS°) had been determined. The results show that adsorption of CRR 195 on DBPC is endothermic and spontaneous in nature.

[Studies on chemical constituents in fruit of Gardenia jasminoides].

OBJECTIVE: To study the chemical constituents in Gardenia jasminoides. METHOD: The constituents were isolated by column chromatography on silica gel and ODS, and identified by NMR, MS spectroscopic methods. RESULT: Nine compounds, imperatorin (1), isoimperatorin (2), crocetin (3), 5-hydroxy-7, 3', 4', 5'-tetrainethoxyflavone (4), 2-methyl-3, 5-dihydroxychromone (5), sudan III (6), geniposide (7), crocin (8), crocin-3 (9) were isolated and identified. CONCLUSION: Compounds 1-6 were isolated from this plant for the first time.

Micellar electrokinetic chromatography method for the determination of several natural red dyestuff and lake pigments used in art work.

The identification of organic colorants used in artistic paintings is an important information source for reconstructing the working techniques found in a particular work and for defining a programme for the restoration and conservation of the painting. In this work, sodium dodecyl sulfate (SDS) was used as a surfactant in micellar electrokinetic chromatography (MEKC) for separating a broad range of red organic pigments, based on their colouring matters: madder (colouring matters: alizarin, quinizarin and purpurin), cochineal (colouring matter: carminic acid), red sandalwood (colouring matter: santalin), brazilwood (colouring matter: brazilin), lac dye (colouring matter: laccaic acid) and dragon's blood (colouring matter: dracorhodin). The running electrolyte used was 20 mM borax (pH 9), containing 20 mM SDS and 10% acetonitrile as organic modifier. Separation was carried out by applying a +20 kV voltage at the injection end, 25 degrees C and 214 nm/254 nm as detection wavelengths. All colorants were separated within less than 13 min with a good baseline resolution. The method was applied to the analysis of paint samples obtained from the Diocesan Museum of Holy Art of Bilbao.