RESUMEN

Raw mango peel (RMP) was first saponified to yield saponified mango peel (SMP), which was then loaded with Zr(IV) ions to form a biosorbent for As(III) scavenging.The biosorption behaviors and mechanisms of As(III) scavenging using RMP and Zr(IV)-loaded saponified mango peel (Zr(IV)-SMP) were investigated batchwise. The As(III) scavenging efficiency of RMP increased from 20.13 % to 87.32 % after Zr(IV) loading. Optimum contact time of 6 h has been investigated for As(III) scavenging by Zr(IV)-SMP, and the data on kinetics is well fitted to the pseudo-second-order (PSO) model. Similarly, isotherm data of Zr(IV)-SMP fitted well to the Langmuir isotherm model with the maximum As(III) scavenging potential of 45.52 mg/g. Chloride (Cl-) and nitrate (NO3 -) have negligible influence on As(III) scavenging, but sulphate (SO4 2-) interferes significantly. The exhausted Zr(IV)-SMP could be easily regenerated by treating with 2MNaOH. A mechanistic study indicates that As(III) scavenging is primarily contributed to electrostatic interaction and ligand exchange, which is confirmed from both instrumental and chemical characterizations techniques. Tubewell underground water polluted with a trace amount of arsenic (98.63 µg/L) could be successfully lowered down to the WHO standard (10 µg/L) by applying a small amount of Zr(IV)-SMP. Therefore, the Zr(IV)-SMP investigated in this work can be a low-cost, environmentally benign, and promising alternative for scavenging trace levels of arsenic from contaminated water.

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The occurrence of arsenic in the surroundings raises apprehension because its detrimental impacts on both human health and the ecology. Since adsorption is an effective, affordable method that can be adjusted to specific environmental circumstances, it is a sustainable solution for the removal of arsenic from the aquatic environment. Utilizing biomass that has been chemically activated may be a viable way to increase the adsorption capacity of the material, reduce arsenic pollution, and protect the environment and human health. In the proposed research, Fe(III) loaded saponified Punica granatum peel (Fe(III)-SPGP) has been synthesized to remove arsenic from aqueous solutions. FTIR and SEM analysis were utilized to carry out the characterization of the biosorbents. Batch experiments were carried out by altering several factors including pH and contact time, in addition to initial concentration and desorption. The most effective pH for As(III) adsorption using Fe(III)-SPGP was discovered to be 9.0. After determining that a pseudo-second-order kinetic model was the one that provided the greatest fit for the results of the experiment, the model developed by Langmuir was applied. It was discovered that the maximum adsorption of As(III) that could be adsorbed by Fe(III)-SPGP was 63.29 mg/g. The spent biosorbent may easily be reused again in subsequent applications. Based on these findings, Fe(III)-SPGP shows promise as a cheap effective sorbent for excising contaminants of As(III).

RESUMEN

We studied the sequestration of hexavalent chromium Cr(VI) from an aqueous solution using chemically modified pomegranate peel (CPP) as an efficient bio-adsorbent. The synthesized material was characterized by X-ray diffraction spectroscopy (XRD), Fourier-transform infrared spectroscopy (FTIR), energy dispersive spectroscopy (EDS), and scanning electron microscopy (SEM). The impacts of parameters like solution pH, Cr(VI) concentration, contact time, and adsorbent dosage were investigated. Experimental results of the isotherm studies and adsorption kinetics were found agreeing to the Langmuir isotherm model and pseudo-second-order kinetics, respectively. The CPP showed appreciable Cr(VI) remediation capacity with a maximal loading capacity of 82.99 mg/g at pH 2.0, which was obtained in 180 min at room temperature. Thermodynamic studies revealed the biosorption process as spontaneous, feasible, and thermodynamically favorable. The spent adsorbent was eventually regenerated and reused, and the safe disposal of Cr(VI) was ensured. The study revealed that the CPP can be effectively employed as an affordable sorbent for the excision of Cr(VI) from water.

RESUMEN

Pomelo, Citrus maxima, peel was chemically modified with lime water and then loaded with Fe(III) to develop anion exchange sites for effective sequestration of As(V) from water. Biosorbent characterizations were done by using FTIR, SEM, XRD, EDX, and Boehm's titration. The batch biosorption studies were carried out at various pHs using modified and non-modified biosorbents and optimum biosorption of As(V) occurred at acidic pH (3.0-5.0) for both the biosorbents. A kinetic study showed a fast biosorption rate and obtained results fitted well with the pseudo-second-order (PSO) model. When isotherm data were modeled using the Langmuir and Freundlich isotherm models, the Langmuir isotherm model fit the data better and produced maximal As(V) biosorption capacities of 0.72 ± 03, 0.86 ± 06, and 0.95 ± 05 mmol/g at temperatures 293± 1K, 298± 1K and 303± 1K, respectively. Desorptionof As(V) was effective using 0.1 M NaOH in batch mode. Negative values of ΔG° for all temperatures with positive ΔH° confirmed the spontaneous and endothermic nature of As(V) biosorption. The existence of co-existing chloride (Cl-), nitrate (NO3 -), sodium (Na+), and calcium (Ca2+) showed insignificant interference whereas a high concentration of sulphate (SO4 2-) and phosphate (PO4 3-) significantly lowered As(V) biosorption percentage. Arsenic concentrations in actual arsenic polluted groundwater could be reduced to the WHO drinking water standard (10 µg/L) by using only 1 g/L of investigated Fe(III)-SPP. The dynamic biosorption of As(V) in a fixed bed system showed that Fe(III)-SPP was effective also in continuous mode and different design parameters for fixed bed system were determined using Thomas, Adams-Bohart, BDST, and Yoon-Nelson models. Therefore, from all of these results it is suggested that Fe(III)-SPP investigated in this study can be a potential, low cost and environmentally benign biosorbent material for an effective removal of trace amounts of arsenic from polluted water.

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In this work, the excision of hexavalent chromium (Cr(VI)) was studied from an aqueous solution using the chemically modified arecanut leaf sheath (CALS) as a novel bio-adsorbent. The as-prepared adsorbent was characterized by using instrumental methods including Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The effect of several factors, including solution pH, contact time, and sorbent dosages were examined to identify the optimum condition for the sorption ability. The optimal pH of Cr(VI) biosorption was 2.0, and equilibrium was reached in 150 min. Adsorption was shown to be pseudo-second-order in kinetic investigations, and the Langmuir isotherm with maximal adsorption efficiency was determined as 109.89 mg/g. The spent biosorbent can be easily regenerated and reused. For the biosorption of oxyanions of chromium, both electrostatic attraction and ligand exchange mechanism play critical roles. From the results, the CALS appears to be a potential low-cost effective sorbent to remove Cr (VI) from water.

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Porin A from Mycobacterium smegmatis (MspA) is a highly stable, octameric channel protein, which acts as the main transporter of electrolytes across the cell membrane. MspA features a narrow, negatively charged constriction zone, allowing stable binding of various analytes thereby blocking the channel. Investigation of channel blocking of mycobacterial porins is of significance in developing alternate treatment methods for tuberculosis. The concept that ruthenium(II)quaterpyridinium complexes have the capability to act as efficient channel blockers for MspA and related porins, emerged after very high binding constants were measured by high-performance liquid chromatography and steady-state luminescence studies. Consequently, the interactions between the ruthenium(II) complex RuC2 molecules and MspA, leading to RuC2@MspA assemblies, have been studied utilizing time-resolved absorption/emission, atomic force microscopy, dynamic light scattering, ζ potential measurements, and isothermal titration calorimetry. The results obtained provide evidence for the formation of clusters/large aggregates of RuC2 and MspA. The results are of interest with respect to utilizing prospective channel blockers in porins. The combination of results from conceptually different techniques shed some light onto the chemical nature of MspA-channel blocker interactions thus contributing to the development of a paradigm for channel blocking.

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Two photochromic spirodihydroindolizine/betaine systems for tethering to peptides and proteins via a maleimide function have been prepared. The absorption spectra of the betaines are in the red region of the visible spectrum and in the near-IR spectral domain, which are suitable energies of light for future in vivo applications. The half-times of cyclization have been determined for both DHI/betaine systems. The findings are consistent with a thermal barrier of varying size between the transoid and cisoid conformers of the betaines.

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The work presented here aims at utilizing poly-N-isopropyl-acrylamide/acrylic acid copolymers to create nanostructured layers on mica surfaces by a simple spin-casting procedure. The average composition of the copolymers determined by elemental analysis correlates excellently with the feed composition indicating that the radical polymerization process is statistical. The resulting surfaces were characterized by Atomic Force Microscopy (magnetic AC-mode) at the copolymer/air interface. Postpolymerization modification of the acrylic acid functions with perfluoro-octyl-iodide decreased the tendency towards spontaneous formation of nanopores. Crosslinking of individual polymer chains permitted the generation of ultraflat layers, which hosted the mycobacterial channel protein MspA, without compromising its channel function. The comparison of copolymers of very similar chemical composition that have been prepared by living radical polymerization and classic radical polymerization indicated that differences in polydispersity played only a minor role when poly-N-isopropyl-acrylamide/acrylic acid copolymers were spincast, but a major role when copolymers featuring the strongly hydrophobic perfluoro-octyl-labels were used. The mean pore diameters were 23.8+/-4.4 nm for P[(NIPAM)(95.5)-co-(AA)(4.5)] (PDI (polydispersity index)=1.55) and 21.8+/-4.2 nm for P[(NIPAM)(95.3)-co-(AA)(4.7)] (PDI=1.25). The depth of the nanopores was approx. 4 nm. When depositing P[(NIPAM)(95)-co-(AA)(2.8)-AAC(8)F(17 2.2)] (PDI=1.29) on Mica, the resulting mean pore diameter was 35.8+/-7.1 nm, with a depth of only 2 nm.

RESUMEN

We have revisited the photochromic spiro-dihydroindolizine/betaine (DHI/B) system applying state-of-the-art density functional theory (DFT) calculations in combination with stationary and time-resolved absorption measurements. DHI/B-systems are becoming increasingly important as potential molecular machines, molecular switches, and photoswitchable electron-acceptors. The knowledge of the exact mechanisms of ring opening and closure, as well as of the geometries of DHI and betaine can provide critical information that will enable the design of better molecular machines and optical switches. The first surprising result concerns the electronic structure of the betaines, which is quite different than commonly assumed. The photochemical ring opening of DHI's to betaines is a conrotatory 1,5 electrocyclic reaction, whereas the thermal ring-closing occurs in the disrotatory mode. According to our results, the electrocyclic back reaction of the betaines to the DHI is NOT rate determining, as previously thought, but instead the kinetics are dictated by the cis-trans-isomerization of the betaine.

RESUMEN

A considerably arduous test of a novel class of composite materials consisting of [Ru(bpy)3]2+ and TiO2 codoped zeolites Y is presented here. The [Ru(bpy)3]2+ and TiO2 codoped zeolites Y served as photocatalysts in the oxidation of the model compounds 2,4-dimethylaniline (2,4-xylidine) by H2O2 in an acidic aqueous medium. Zeolite-embedded TiO2 (nano)particles play an important role in the degradation mechanism. The first step in this complex mechanism is the photoelectron transfer from photoexcited [Ru(bpy)3]2+*, located inside the supercage of zeolite Y, to a neighboring TiO2 nanoparticle. During this electron transfer process, electron injection into the conduction band of TiO2 is achieved. The second decisive step is the reaction of this electron with H2O2, which was previously chemisorbed at the surface-region of the TiO2 nanoparticles. In this reaction, a TiO2 bound hydroxyl radical (TiO2-HO.) is created. This highly reactive intermediate initiates then the oxidation of 2,4-xylidine, which enters the zeolites framework in its protonated form (Hxyl+). The formation of 2,4-dimethylphenol as first detectable reaction product indicated that this oxidation proceeds via an electron transfer mechanism. Furthermore, [Ru(bpy)3]3+, which was created in the initiating photoelectron transfer reaction between [Ru(bpy)3]2+* and TiO2, also takes place in the oxidation of Hxyl+. [Ru(bpy)3]2+ is recycled in that reaction, which also belongs to the group of electron transfer reactions. In addition to the primary steps of this particular Advanced Oxidation Process (AOP), the dependence of the efficiency of the 2,4-xylidine degradation as a function of the [Ru(bpy)3]2+ and TiO2 loadings of the zeolite Y framework is also reported here. The quenching of [Ru(bpy)3]2+* by H2O2 as well as the photocatalytic activity of the [Ru(bpy)3]2+ and TiO2 codoped zeolite Y catalysts both follow a distinct percolation behavior in dependence of their TiO2 content.

RESUMEN

Steady-state and time-resolved studies have been performed on four compounds of the pterin family (pterin, 6-carboxypterin, 6-formylpterin and folic acid) in aqueous solution, using the single photon counting technique. The fluorescence characteristics (spectra, quantum yields, lifetimes) of these compounds and their dependence on the pH have been investigated. Most pterins can exist in two acid-base forms over the pH range between 3 and 13. Emission spectra and excitation spectra were obtained for both forms of each compound studied. Fluorescence quantum yields (phi(F)) in acidic and basic media were measured. The phi(F) of folic acid (< 0.005 in both media) is very low compared to those of pterin (0.27 in basic media and 0.33 in acidic media), 6-carboxypterin (0.18 in basic media and 0.28 in acidic media) and 6-formylpterin (0.07 in basic media and 0.12 in acidic media). The variation in integrated fluorescence intensity and fluorescence lifetimes (tau(F)) was analysed as a function of pH. Dynamic quenching by OH- was observed and the corresponding bimolecular rate constants for quenching of fluorescence (k(q)) were calculated. The reported values for k(q) (M(-1) s(-1)) are 3.6 x 10(9), 1.9 x 10(9) and 1.1 x 10(10) M(-1) s(-1) for pterin, 6-carboxypterin and 6-formylpterin, respectively.

Asunto(s)

RESUMEN

Toxic asbestos fibers are known to be carriers of carcinogenic polyaromatic hydrocarbons (PAH) when ingested by human lungs. To clarify the asbestos-PAH interactions, the adsorption properties of four different asbestos, namely amosite, anthofillite, crocidolite, and chrysotile (termed AMOS, ANTHO, CROX, and CHRYS, respectively), toward pyrene (py) were investigated by electron paramagnetic resonance (EPR) and fluorescence spectroscopy, both steady state and time resolved. Pyrene was labeled with a nitroxide TEMPO radical (py-T) for the EPR study. EPR provided information on the adsorption ability of the surface toward py-T and on the interactions between py-T and surface sites, mainly cooperative in nature. Pyrene molecules organize on AMOS samples in a packed layer; the radical works as a separator and prevents the attaching of the py-T molecules at the surface, but the N-O groups of the few adsorbed molecules directly interact with the surface. The interacting sites at the ANTHO surface are quite far from each other; therefore py-T instead of py may form a monolayer at the asbestos surface. The surface of CROX strongly adsorbs both excimers of py and monomers of py-T, orienting the nitroxide groups toward the polar sites at the surface. The surface of CHRYS is the most adsorbing toward py and py-T, but the nitroxide group does not directly interact with the surface. By increasing concentration, py-T saturates the CROX and the CHRYS surface interacting sites, and then forms a disordered liquid-like multilayer. The close average distance calculated for py-T adsorbed at the CROX surface (12 Å) suggests that the py-T molecules intercalate in an "up-and-down" conformation. The chemical composition of the different asbestos and their different structural properties affect the distribution of the polar sites at the external surface, modifying the adsorption properties. This study confirms the synergetic effect between the toxicity of the asbestos fibers and the adsorption of polyaromatic hydro carbons at their surface, which mainly depends on the surface properties of the asbestos. Copyright 2001 Academic Press.