Search results for: erbium ions

Authors: Raghvendra Singh Yadav, Ivo Kuřitka, Jarmila Vilcakova, Pavel Urbánek, Michal Machovsky, Milan Masař, Martin Holek

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Herein, we reported the influence of La³⁺ substitution on structural, magnetic and dielectric properties of CoFe₂O₄ nanoparticles synthesized by starch-assisted sol-gel combustion method. X-ray diffraction pattern confirmed the formation of cubic spinel structure of La³⁺ ions doped CoFe₂O₄ nanoparticles. Raman and Fourier Transform Infrared spectroscopy study also confirmed cubic spinel structure of La³⁺ substituted CoFe₂O₄ nanoparticles. The field emission scanning electron microscopy study revealed that La³⁺ substituted CoFe2O4 nanoparticles were in the range of 10-40 nm. The magnetic properties of La³⁺ substituted CoFe₂O₄ nanoparticles were investigated by using vibrating sample magnetometer. The variation in saturation magnetization, coercivity and remanent magnetization with La³⁺ concentration in CoFe2O4 nanoparticles was observed. The variation of real and imaginary part of dielectric constant, tan δ, and AC conductivity were studied with change of concentration of La³⁺ ions in CoFe₂O₄ nanoparticles. The variation in optical properties was studied via UV-Vis absorption spectroscopy. Acknowledgment: This work was supported by the Ministry of Education, Youth and Sports of the Czech Republic – Program NPU I (LO1504).

Keywords: starch, sol-gel combustion method, nanoparticles, magnetic properties, dielectric properties

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Authors: Nour El Houda Bensiradj, Nafila Zouaghi, Taha Bensiradj

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The pollution of water resources is characterized by the presence of microorganisms, chemicals, or industrial waste. Generally, this waste generates effluents containing large quantities of heavy metals, making the water unsuitable for consumption and causing the death of aquatic life and associated biodiversity. Currently, it is very important to assess the impact of heavy metals in water pollution as well as the processes for treating and reducing them. Among the methods of water treatment and disinfection, we mention the complexation of metal ions using ligands which serve to precipitate and subsequently eliminate these ions. In this context, we are interested in the study of complexes containing heavy metals such as zinc, nickel, and cadmium, which are present in several industrial discharges and are discharged into water sources. We will use the ligands of triethanolamine (TEA) and nitrilotriacetic acid (NTA). The theoretical study is based on molecular modeling, using the density functional theory (DFT) implemented in the Gaussian 09 program. The geometric and energetic properties of the above complexes will be calculated. Spectral properties such as infrared, as well as reactivity descriptors, and thermodynamic properties such as enthalpy and free enthalpy will also be determined.

Keywords: heavy metals, NTA, TEA, DFT, IR, reactivity descriptors

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Authors: Allam Srinivasa Rao, Ch. Annapurna Devi, G. Vijaya Prakash

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A new-fangled series of white light emitting 1 mol% of Dy3+ ions doped Single-Alklai and Mixed-Alkai fluoro tungstunate tellurite glasses have been prepared using melt quenching technique and their spectroscopic behaviour was investigated by studying XRD, optical absorption, photoluminescence and lifetime measurements. The bonding parameter studies reveal the ionic nature of the Dy-O bond in the present glasses. From the absorption spectra, the Judd–Ofelt (J-O) intensity parameters have been determined which are used to explore the nature of bonding and symmetry orientation of the Dy–ligand field environment. The evaluated J-O parameters (Ω_4>Ω_2>Ω_6) for all the glasses are following the same trend. The photoluminescence spectra of all the glasses exhibit two intensified peaks in blue and Yellow regions corresponding to the transitions 4F9/2→6H15/2 (483 nm) and 4F9/2→6H13/2 (575 nm) respectively. From the photoluminescence spectra, it is observed that the luminescence intensity is maximum for Dy3+ ion doped potassium combination of fluoro tungstunate tellurite glass (TeWK: 1Dy). The J-O intensity parameters have been used to determine the various radiative properties for the different emission transitions from the 4F9/2 fluorescent level. The highest emission cross-section and branching ratio values observed for the 4F9/2→6H15/2 and 4F9/2→6H13/2 transitions suggest the possible laser action in the visible region from these glasses. By using the experimental lifetimes (τ_exp) measured from the decay spectral features and radiative lifetimes (τ_R), the quantum efficiencies (η) for all the glasses have been evaluated. Among all the glasses, the potassium combined fluoro tungstunate tellurite (TeWK:1Dy) glass has the highest quantum efficiency (94.6%). The CIE colour chromaticity coordinates (x, y), (u, v), colour correlated temperature (CCT) and Y/B ratio were also estimated from the photoluminescence spectra for different compositions of glasses. The (x, y) and (u, v) chromaticity colour coordinates fall within the white light region and the white light can be tuned by varying the composition of the glass. From all these studies, we are suggesting that the 1 mol% of Dy3+ ions doped TeWK glass is more suitable for lasing and White-LED applications.

Keywords: dysprosium, Judd-Ofelt parameters, photo luminescence, tellurite glasses

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Authors: Ningombam Linthoingambi Devi, Amrendra Kumar

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The long term sampling at one of the most populated city in Indo-Gangetic region shows higher mass concentration of atmospheric aerosol (PM₂.₅) during spring season (144.70µg/m³), summer season (91.96 µg/m³), the autumn season (266.48µg/m³) and winter season (367.09 µg/m³) respectively. The concentration of PM₂.₅ in Patna across the year shows much higher than the limit fixed by the national ambient air quality level fixed by central pollution control board India (CPCB, India) and World Health Organization (WHO). Different water-soluble cation (Na⁺, K⁺, Ca²⁺, NH₄⁺ , and Mg²⁺) and anion (Cl⁻, NO₃⁻ , and SO₄²⁻) species were detected in PM₂.₅. Results show the significantly higher loaded of water-soluble ions during winter and spring seasons. The acidity of the atmosphere was revealed and calculated using selected major cations (K⁺, Ca²⁺ , and NH₄⁺) and anions (SO₄²⁻, and NO₃⁻). A regression correlation was analyzed to check the significant linkage between the acidity and alkalinity ions. During the winter season (r² = 0.79) and spring season (r² = 0.64) shows good significant correlation between the cations and anions. The ratio of NO₃⁻/SO₄²⁻ indicates the sources of secondary pollutants were mainly influenced by industrial and vehicular emission however SO₄²⁻ mostly emitted from industries during the winter season.

Keywords: aerosols, inorganic species, source apportionment, Indo-Gangetic region

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Authors: Dilip Saikia, Suparna Bhattacharjee, Nirab Adhikary

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In this piece of work, we have presented the synthesis and characterization of CdTe/ZnS core/shell (CS) quantum dots (QD). CS QDs are used as a fluorescence probe to design a simple cost-effective and ultrasensitive sensor for the detection of toxic Hg(II) in an aqueous medium. Mercaptosuccinic acid (MSA) has been used as a capping agent for the synthesis CdTe/ZnS CS QD. Photoluminescence quenching mechanism has been used in the detection experiment of Hg(II). The designed sensing technique shows a remarkably low detection limit of about 1 picomolar (pM). Here, the CS QDs are synthesized by a simple one-pot aqueous method. The synthesized CS QDs are characterized by using advanced diagnostics tools such as UV-vis, Photoluminescence, XRD, FTIR, TEM and Zeta potential analysis. The interaction between CS QDs and the Hg(II) ions results in the quenching of photoluminescence (PL) intensity of QDs, via the mechanism of excited state electron transfer. The proposed mechanism is explained using cyclic voltammetry and zeta potential analysis. The designed sensor is found to be highly selective towards Hg (II) ions. The analysis of the real samples such as drinking water and tap water has been carried out and the CS QDs show remarkably good results. Using this simple sensing method we have designed a prototype low-cost electronic device for the detection of Hg(II) in an aqueous medium. The findings of the experimental results of the designed sensor is crosschecked by using AAS analysis.

Keywords: photoluminescence, quantum dots, quenching, sensor

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Authors: Olawuyi Sikiru Owolabi

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A research was carried out to assess the biochemical effects of crude oil contaminated cat fish on selected rat kidney function tests. Thirty-six (36) albino rats (rattus novergicus) were grouped into six (6) of (6) in each group. The rats in group one served as control and they were placed on feed formulated with catfish cultured in borehole water while those ones from group 2 to group 6 were placed on feed formulated with catfish exposed to various concentrations of crude oil (0.1%,0.25%,0.5%,0.75% and 1% respectively).The results obtained showed that there was a significant increase in serum concentration of creatinine, Urea, sodium and potassium ions in the kidney of experimental rats when compared with the control. This may be interpreted to mean possible adverse effects on the kidney. Several studies have been done especially on the biological effects of crude oil in fish. These include Direct Lethal Toxicity, Sub-Lethal disruption of physiological and behavioral activities, interference with feeding and reproduction, direct coating or tainting of fish, effect of entry of hydrocarbons into the food web as well as alteration of biological habitat. The present study attempts to assess the effects of crude oil contaminated diet on rat kidney by carrying out some kidney function tests like determination of serum sodium and potassium ions by flame photometry method, determination of serum urea and determination of serum creatinine.

Keywords: crude oil, serum urea, creatinine, wistar rats

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Authors: Mitsunobu Iwasaki, Akifumi Iseda

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Yttrium aluminum garnet doped with cerium (Ⅲ) ions (Y3Al5O12:Ce3+, YAG:Ce3+) has attracted a great attention because it can efficiently convert the blue light into a very broad yellow emission band, which produces white light emitting diodes and is applied for panel displays. To improve the brightness and resolution of the display, a considerable attention has been directed to develop fine phosphor particles. We have prepared YAG:Ce3+ nanophosphors by environmental-friendly wet process. The peak maximum of absorption spectra of surface plasmon of Ag nanopaticles are close to that of the excitation spectra (460 nm) of YAG:Ce3+. It can be expected that Ag nanoparticles supported onto the surface of YAG:Ce3+ (Ag-YAG:Ce3+) enhance the absorption of Ce3+ ions. In this study, we have prepared Ag-YAG:Ce3+ nanophosphors and investigated their photoluminescent properties. YCl3･6H2O and AlCl3･6H2O with a molar ratio of Y:Al=3:5 were dissolved in ethanol (100 ml), and CeCl3•7H2O (0.3 mol%) was further added to the above solution. Then, NaOH (4.6×10-2 mol) dissolved in ethanol (50 ml) was added dropwise to the mixture under reflux over 2 hours, and the solution was further refluxed for 1 hour. After cooling to room temperature, precipitates in the reaction mixture were heated at 673 K for 1 hour. After the calcination, the particles were immersed in AgNO3 solution for 1 hour, followed by sintering at 1123 K for 1 hour. YAG:Ce3+ were confirmed to be nanocrystals with a crystallite size of 50-80 nm in diameter. Ag nanoparticles supported onto YAG:Ce3+ were single nanometers in diameter. The excitation and emission spectra were 454 nm and 539 nm at a maximum wavelength, respectively. The emission intensity was maximum for Ag-YAG:Ce3+ immersed into 0.5 mM AgCl (Ag-YAG:Ce (0.5 mM)). The absorption maximum (461 nm) was increased for Ag-YAG:Ce3+ in comparison with that for YAG:Ce3+, indicating that the absorption was enhanced by the addition of Ag. The external and internal quantum efficiencies became 11.2 % and 36.9 % for Ag-YAG:Ce (0.5 mM), respectively. The emission intensity and absorption maximum of Ag-YAG:Ce (0.5 mM)×n (n=1, 2, 3) were increased with an increase of the number of supporting times (n), respectively. The external and internal quantum efficiencies were increased for the increase of n, respectively. The external quantum efficiency of Ag-YAG:Ce (0.5 mM) (n=3) became twice as large as that of YAG:Ce. In conclusion, Ag nanoparticles supported onto YAG:Ce3+ increased absorption and quantum efficiency. Therefore, the support of Ag nanoparticles enhanced the photoluminescent properties of YAG:Ce3+.

Keywords: plasmon, quantum efficiency, silver nanoparticles, yttrium aluminum garnet

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Authors: Merouani Djilali Redha, F. Abdelmalek, A. A. Addou

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Advanced oxidation processes (AOPs) utilizing Homogenous photocatalysis (Fenton and photo-Fenton reactions), and Heterogeneous photocatalyse (TiO2 and ZnO) were investigated for the degradation of commercial azo dye ‘Orange G’ wastewater. Fenton and photo-Fenton experimental conditions were: Hydrogen peroxide concentration (10-2 M), Ferrous ions concentration (5.10-4 M), pH (2.8 – 3), UV lamp power (6 watt). Adding more ferrous ions enhanced the oxidation rate for the H2O2/Fe2+ and UV/H2O2/Fe2+ processes. The optimum catalyst loading was found 2.0 g.L-1 in our case for both catalysts TiO2 and ZnO. A comparative study of the photocatalytic degradation showed that these two catalysts have a comparable reactivity; it follows a pseudo-first-order kinetics. The degradation trends followed the order: UV365/Fenton > UV365/TiO2 > Solar Fenton > Solar TiO2 > Fenton ~UV365/ZnO. Among AOPs, processes using Fenton type reagent are relatively cheap and easy to operate and maintain. Moreover, UV365/Fenton process has been shown as effective in the treatment of OG dye. Dye was degraded following second-order kinetics. The rate constants was 0,041 .10+6 L.M-1.min-1. The degradation was followed by spectrophotometric method, chemical oxygen demand (COD) measures and high performance liquid chromatography analyses (HPLC). Some aromatic and aliphatic degradation compounds were identified. Degradation of Orange G by UV Fenton mechanism was also proposed.

Keywords: AOPs, homogeneous catalysis, heterogeneous catalysis, acid orange 10, hydroxyl radical

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Authors: L. Khalfa, M. Bagane, M. L. Cervera, S. Najjar

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The aim of this work is to present a low cost adsorbent for removing toxic heavy metals from aqueous solutions. Therefore, we are interested to investigate the efficiency of natural clay minerals collected from south Tunisia and their modified form using sulfuric acid in the removal of toxic metal ions: Zn(II) and Pb(II) from synthetic waste water solutions. The obtained results indicate that metal uptake is pH-dependent and maximum removal was detected to occur at pH 6. Adsorption equilibrium is very rapid and it was achieved after 90 min for both metal ions studied. The kinetics results show that the pseudo-second-order model describes the adsorption and the intraparticle diffusion models are the limiting step. The treatment of natural clay with sulfuric acid creates more active sites and increases the surface area, so it showed an increase of the adsorbed quantities of lead and zinc in single and binary systems. The competitive adsorption study showed that the uptake of lead was inhibited in the presence of 10 mg/L of zinc. An antagonistic binary adsorption mechanism was observed. These results revealed that clay is an effective natural material for removing lead and zinc in single and binary systems from aqueous solution.

Keywords: heavy metal, activated clay, kinetic study, competitive adsorption, modeling

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Authors: Abdul Ghaffar Memon, Xiao Hong Zhou, Yunpeng Xing, Ruoyu Wang, Miao He

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Due to deleterious environmental and health effects of the Hg²⁺ ions, various online, detection methods apart from the traditional analytical tools have been developed by researchers. Biosensors especially, label, label-free, colorimetric and optical sensors have advanced with sensitive detection. However, there remains a gap of ultrasensitive quantification as noise interact significantly especially in the AuNP based label-free colorimetry. This study reported an amplification strategy using Exo-III enzyme for target recycling of Hg²⁺ ions in a T-rich hairpin loop metallobase label-free colorimetric nanosensor with an improved sensitivity using unmodified gold nanoparticles (uGNPs) as an indicator. The two T-rich metallobase hairpin loop structures as 5’- CTT TCA TAC ATA GAA AAT GTA TGT TTG -3 (HgS1), and 5’- GGC TTT GAG CGC TAA GAA A TA GCG CTC TTT G -3’ (HgS2) were tested in the study. The thermodynamic properties of HgS1 and HgS2 were calculated using online tools (http://biophysics.idtdna.com/cgi-bin/meltCalculator.cgi). The lab scale synthesized uGNPs were utilized in the analysis. The DNA sequence had T-rich bases on both tails end, which in the presence of Hg²⁺ forms a T-Hg²⁺-T mismatch, promoting the formation of dsDNA. Later, the Exo-III incubation enable the enzyme to cleave stepwise mononucleotides from the 3’ end until the structure become single-stranded. These ssDNA fragments then adsorb on the surface of AuNPs in their presence and protect AuNPs from the induced salt aggregation. The visible change in color from blue (aggregation stage in the absence of Hg²⁺) and pink (dispersion state in the presence of Hg²⁺ and adsorption of ssDNA fragments) can be observed and analyzed through UV spectrometry. An ultrasensitive quantitative nanosensor employing Exo-III assisted target recycling of mercury ions through label-free colorimetry with nanomolar detection using uGNPs have been achieved and is further under the optimization to achieve picomolar range by avoiding the influence of the environmental matrix. The proposed strategy will supplement in the direction of uGNP based ultrasensitive, rapid, onsite, label-free colorimetric detection.

Keywords: colorimetric, Exo-III, gold nanoparticles, Hg²⁺ detection, label-free, signal amplification

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Authors: Lalita, Niladri Sarkar, Subhasis Ghosh

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Since the discovery of high temperature superconductivity (HTSC) in cuprates, several aspects of this phenomena have fascinated physics community. The most debated one is the linear temperature dependence of normal state resistivity over wide range of temperature in violation of with Fermi liquid theory. The linear-in-T resistivity (LITR) is the indication of strongly correlated metallic, known as “strange metal”, attributed to non Fermi liquid theory (NFL). The proximity of superconductivity to LITR suggests that there may be underlying common origin. The LITR has been shown to be due to unknown dissipative phenomena, restricted by quantum mechanics and commonly known as ‘‘Planckian dissipation” , the term first coined by Zaanen and the associated inelastic scattering time τ and given by 1/τ=αkBT/ℏ, where ℏ, kB and α are reduced Planck’s constant, Boltzmann constant and a dimensionless constant of order of unity, respectively. Since the first report, experimental support for α ~ 1 is appearing in literature. There are several striking issues which remain to be resolved if we desire to find out or at least get a clue towards microscopic origin of maximal dissipation in cuprates. (i) Universality of α ~ 1, recently some doubts have been raised in some cases. (ii) So far, Planckian dissipation has been demonstrated in overdoped Cuprates, but if the proximity to quantum criticality is important, then Planckian dissipation should be observed in optimally doped and marginally underdoped cuprates. The link between Planckian dissipation and quantum criticality still remains an open problem. (iii) Validity of Planckian dissipation in all cuprates is an important issue. Here, we report reversible change in the superconducting behavior of high temperature superconductor Bi2Sr2Ca2Cu3O10+δ (Bi-2223) under dynamic doping induced by photo-excitation. Two doped Bi-223 samples, which are x = 0.16 (optimal-doped), x = 0.145 (marginal-doped) have been used for this investigation. It is realized that steady state photo-excitation converts magnetic Cu2+ ions to nonmagnetic Cu1+ ions which reduces superconducting transition temperature (Tc) by killing superfluid density. In Bi-2223, one would expect the maximum of suppression of Tc should be at charge transfer gap. We have observed suppression of Tc starts at 2eV, which is the charge transfer gap in Bi-2223. We attribute this transition due to Cu-3d9(Cu2+) to Cu-3d10(Cu+), known as d9 − d10 L transition, photoexcitation makes some Cu ions in CuO2 planes as spinless non-magnetic potential perturbation as Zn2+ does in CuO2 plane in case Zn-doped cuprates. The resistivity varies linearly with temperature with or without photo-excitation. Tc can be varied by almost by 40K be photoexcitation. Superconductivity can be destroyed completely by introducing ≈ 2% of Cu1+ ions for this range of doping. With this controlled variation of Tc and resistivity, detailed investigation has been carried out to reveal Planckian dissipation underdoped to optimally doped Bi-2223. The most important aspect of this investigation is that we could vary Tc dynamically and reversibly, so that LITR and associated Planckian dissipation can be studied over wide ranges of Tc without changing the doping chemically.

Keywords: linear resistivity, HTSC, Planckian dissipation, strange metal

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Authors: Mohammad Hassan Ramezan zadeh 1 , Majid Seifi 2 , Hoda Hekmat ara 2 1Biomedical Engineering Department, Near East University, Nicosia, Cyprus 2Physics Department, Guilan University , P.O. Box 41335-1914, Rasht, Iran.

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Magnetic nano particles of ferric chloride were synthesised using a co-precipitation technique. For the optimal results, ferric chloride at room temperature was added to different surfactant with different ratio of metal ions/surfactant. The samples were characterised using transmission electron microscopy, X-ray diffraction and Fourier transform infrared spectrum to show the presence of nanoparticles, structure and morphology. Magnetic measurements were also carried out on samples using a Vibrating Sample Magnetometer. To show the effect of surfactant on size distribution and crystalline structure of produced nanoparticles, surfactants with various charge such as anionic cetyl trimethyl ammonium bromide (CTAB), cationic sodium dodecyl sulphate (SDS) and neutral TritonX-100 was employed. By changing the surfactant and ratio of metal ions/surfactant the size and crystalline structure of these nanoparticles were controlled. We also show that using anionic stabilizer leads to smallest size and narrowest size distribution and the most crystalline (polycrystalline) structure. In developing our production technique, many parameters were varied. Efforts at reproducing good yields indicated which of the experimental parameters were the most critical and how carefully they had to be controlled. The conditions reported here were the best that we encountered but the range of possible parameter choice is so large that these probably only represent a local optimum. The samples for our chemical process were prepared by adding 0.675 gr ferric chloride (FeCl3, 6H2O) to three different surfactant in water solution. The solution was sonicated for about 30 min until a transparent solution was achieved. Then 0.5 gr sodium hydroxide (NaOH) as a reduction agent was poured to the reaction drop by drop which resulted to participate reddish brown Fe2O3 nanoparticles. After washing with ethanol the obtained powder was calcinated in 600°C for 2h. Here, the sample 1 contained CTAB as a surfactant with ratio of metal ions/surfactant 1/2, sample 2 with CTAB and ratio 1/1, sample 3 with SDS and ratio 1/2, sample 4 SDS 1/1, sample 5 is triton-X-100 with 1/2 and sample 6 triton-X-100 with 1/1.

Keywords: iron oxide nanoparticles, stabilizer, co-precipitation, surfactant

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Authors: Tesfay Gebremicheal Reda, K. Samatha, Paul Douglas Sanasi, D. Parajuli

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Nanoparticle technology is fast progressing and is being employed in innumerable medical applications. At this time, the public's health is seriously threatened by the rise of bacterial strains resistant to several medications. Metal nanoparticles are a potential alternate approach for tackling this global concern, and this is the main focus of this study. The citrate precursor sol-gel synthesis method was used to synthesize the Niₓ Co₁₋ₓ Fe₂ O₄, (where x = 0.0:0.2:1.0) nanoparticle. XRD identified the development of the cubic crystal structure to have a preferential orientation along (311), and the average particle size was found to be 29-38 nm. The average crystallizes assessed with ImageJ software and origin 22 of the SEM are nearly identical to the XRD results. In the created NCF NPs, the FT-IR spectroscopy reveals structural examinations and the redistribution of cations between octahedral (505-428 cm⁻¹) and tetrahedral (653-603 cm⁻¹) locales. As the Co²⁺ cation is substituted with Ni²⁺, the coercive fields HC decrease from 2384 Oe to 241.93 Oe. Band gap energy rises as Ni concentration increases, which may be attributed to the fact that the ionic radii of Ni²⁺ ions are smaller than that of Co²⁺ ions, which results in a strong electrostatic interaction. On the contrary, except at x = 0.4, the dielectric constant decreases as the nickel concentration increases. According to the findings of this research work, nanoparticles are composed of Ni₀.₄ Co₀.₆ Fe₂ O₄ have demonstrated a promising value against S. aureus and E. coli, and it suggests a proposed model for their potential use as a source of antibacterial agent.

Keywords: antimicrobial, band gap, citrate precursor, dielectric, nanoparticle

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Authors: Muhammad Ajmal, Muhammad Siddiq, Nurettin Sahiner

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We prepared poly(methacrylic acid-co-acrylonitrile) (p(MAc-co-AN)) microgels by inverse suspension polymerization, and converted the nitrile groups into amidoxime groups to obtain more hydrophilic amidoximated poly(methacrylic acid-co-acrylonitile) (amid-p(MAc-co-AN)) microgels. Amid-microgels were used as microreactors for in situ synthesis of copper and cobalt nanoparticles. Cu (II) and Co (II) ions were loaded into microgels from their aqueous metal salt solutions and then converted to corresponding metal nanoparticle (MNP) by treating the loaded metal ions with sodium borohydride (NaBH4). The characterization of the prepared microgels and microgel metal nanoparticle composites was carried out by SEM, TEM and TG analysis. The amounts of metal nanoparticles within microgels were estimated by AAS measurements by dissolving the MNP entrapped within microgels by concentrated HCl acid treatment. Catalytic performances of the prepared amid-p(MAc-co-AN)-M (M: Cu, Co) microgel composites were investigated by using them as catalyst for the degradation of cationic and anionic organic dyes such as eosin Y (EY), methylene blue (MB) and methyl Orange (MO), and for the reduction of nitro aromatic pollutants like 2-nitrophenol (2-NP) and 4-nitrophenol (4-NP) to their corresponding amino phenols. Here, we also report for the first time, the simultaneous degradation/reduction of MB, EY, and 4-NP by amid-p(MAc-co-AN)-Cu microgel composites. Different parameters affecting the reduction rates such as metal types, amount of catalysts, temperature and the amount of reducing agent were investigated.

Keywords: microgels, nanoparticles, catalyst, pollutants

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Authors: Gehan El-Sayed Sharaf El-Deen

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In this study, super paramagnetic iron-oxide nano- materials (SPMIN) were investigated for removal of toxic heavy metals from aqueous solution. The magnetic nanoparticles of 12 nm were synthesized using a co-precipitation method and characterized by transmission electron microscopy (TEM), transform infrared spectroscopy (FTIR), x-ray diffraction (XRD) and vibrating sample magnetometer (VSM). Batch experiments carried out to investigate the influence of different parameters such as contact time, initial concentration of metal ions, the dosage of SPMIN, desorption,pH value of solutions. The adsorption process was found to be highly pH dependent, which made the nanoparticles selectively adsorb these three metals from wastewater. Maximum sorption for all the studies cations obtained at the first half hour and reached equilibrium at one hour. The adsorption data of heavy metals studied were well fitted with the Langmuir isotherm and the equilibrium data show the percent removal of Ni2+, Zn2+ and Cd2+ were 96.5%, 80% and 75%, respectively. Desorption studies in acidic medium indicate that Zn2+, Ni2+ and Cd2+ were removed by 89%, 2% and 18% from the first cycle. Regeneration studies indicated that SPMIN nanoparticles undergoing successive adsorption–desorption processes for Zn2+ ions retained original metal removal capacity. The results revealed that the most prominent advantage of the prepared SPMIN adsorbent consisted in their separation convenience compared to the other adsorbents and SPMIN has high efficiency for removal the investigated metals from aqueous solution.

Keywords: heavy metals, magnetic nanoparticles, removal efficiency, Batch technique

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Authors: M. G. Mostafa, S. M. Helal Uddin, A. B. M. H. Haque, M. R. Hasan

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The study was carried out to understand the hydro-geochemistry and ground water quality in Rajshahi City of Bangladesh. 240 groundwater (shallow and deep tubewell) samples were collected during the year 2009-2010 covering pre-monsoon, monsoon and post-monsoon seasons and analyzed for various physico-chemical parameters including major ions. The results reveal that the groundwater was slightly acidic to neutral in nature, total hardness observed in all samples fall under hard to very hard category. The concentration of calcium, iron, manganese, arsenic and lead ions were found far above the permissible limit in most of the shallow tubewells water samples. The analysis results show that the mean concentrations of cations and anions were observed in the order: Ca > Mg > Na > K > Fe > Mn > Pb > Zn > Cu > As (total) > Cd and HCO3-> Cl-> SO42-> NO3-, respectively. The concentrations of TH, TDS, HCO3-, NO3-, Ca, Fe, Zn, Cu, Pb, and As (total) were found to be higher during post-monsoon compare to pre-monsoon, whilst K, Mg, Cd, and Cl were found higher during pre-monsoon and monsoon. Ca-HCO3 was identified as the major hydro chemical facie using piper trilinear diagram. Higher concentration of toxic metals including Fe, Mn, As and Pb were found indicating various health hazards. The results also illustrate that the rock water interaction was the major geochemical process controlling the chemistry of groundwater in the study area.

Keywords: physio-chemical parameters, groundwater, geochemistry, Rajshahi city

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Authors: Teerapon Pirom, Ura Pancharoen

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Amoxicillin is an antibiotic which is widely used to treat various infections in both human beings and animals. However, when amoxicillin is released into the environment, it is a major problem. Amoxicillin causes bacterial resistance to these drugs and failure of treatment with antibiotics. Liquid membrane is of great interest as a promising method for the separation and recovery of the target ions from aqueous solutions due to the use of carriers for the transport mechanism, resulting in highly selectivity and rapid transportation of the desired metal ions. The simultaneous processes of extraction and stripping in a single unit operation of liquid membrane system are very interesting. Therefore, it is practical to apply liquid membrane, particularly the HFSLM for industrial applications as HFSLM is proved to be a separation process with lower capital and operating costs, low energy and extractant with long life time, high selectivity and high fluxes compared with solid membranes. It is a simple design amenable to scaling up for industrial applications. The extraction and recovery for (Amoxicillin) through the hollow fiber supported liquid membrane (HFSLM) using aliquat336 as a carrier were explored with the experimental data. The important variables affecting on transport of amoxicillin viz. extractant concentration and operating time were investigated. The highest AMOX- extraction percentages of 85.35 and Amoxicillin stripping of 80.04 were achieved with the best condition at 6 mmol/L [aliquat336] and operating time 100 min. The extraction reaction order (n) and the extraction reaction rate constant (kf) were found to be 1.00 and 0.0344 min-1, respectively.

Keywords: aliquat336, amoxicillin, HFSLM, kinetic

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Authors: Lela Pintarić, Iva Rezić, Ana Vrsalović Presečki

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Considering an enormous increase of the use of metal nanoparticles with the exactly defined characteristics, the main goal of this research was to found the optimal and environmental friendly method of their synthesis. The synthesis of the inorganic core-shell nanoparticles was optimized as a model. The core-shell nanoparticles are composed of the enzyme core belted with the metal ions, oxides or salts as a shell. In this research, enzyme urease was the core catalyst and the shell nanoparticle was made of silver. Silver nanoparticles are widespread utilized and some of their common uses are: as an addition to disinfectants to ensure an aseptic environment for the patients, as a surface coating for neurosurgical shunts and venous catheters, as an addition to implants, in production of socks for diabetics and athletic clothing where they improve antibacterial characteristics, etc. Characteristics of synthesized nanoparticles directly depend on of their size, so the special care during this optimization was given to the determination of the size of the synthesized nanoparticles. For the purpose of the above mentioned optimization, sixteen experiments were generated by the Design of Experiments (DoE) method and conducted under various temperatures, with different initial concentration of the silver nitrate and constant concentration of the urease of two separate manufacturers. Synthesized nanoparticles were analyzed by the Nanoparticle Tracking Analysis (NTA) method on Malvern NanoSight NS300. Results showed that the initial concentration of the silver ions does not affect the concentration of the synthesized silver nanoparticles neither their size distribution. On the other hand, temperature of the experiments has affected both of the mentioned values.

Keywords: core-shell nanoparticles, optimization, silver, urease

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Authors: Mahmoud A. Rabah, Said El Sheikh

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This work shows the preparation of chromium nanoparticles from tannery waste solution on glassy carbon by chemical method compared to electrokinetic process. The waste solution contains free and soluble fats, calcium, iron, magnesium and high sodium in addition to the chromium ions. Filtration helps removal of insoluble matters. Diethyl ether successfully extracted soluble fats. The method started by removing calcium as insoluble oxalate salts at hot conditions in a faint acidic medium. The filtrate contains iron, magnesium, chromium ions and sodium chloride in excess. Chromium was separated selectively as insoluble hydroxide sol-gel at pH 6.5, filtered and washed with distilled water. Part of the gel reacted with sulfuric acid to produce chromium sulfate solution having 15-25 g/L concentration. Electrokinetic deposition of chromium nanoparticles on a carbon cathode was carried out using platinum anode under different galvanostatic conditions. The chemical method involved impregnating the carbon specimens with chromium hydroxide gel followed by reduction using hydrazine hydrate or by thermal reduction using hydrogen gas at 1250°C. Chromium grain size was characterized by TEM, FT-IR and SEM. Properties of the Cr grains were correlated to the conditions of the preparation process. Electrodeposition was found to control chromium particles to be more identical in size and shape as compared to the chemical method.

Keywords: chromium, electrodeposition, nanoparticles, tannery waste solution

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Authors: Saleh O. Allehabi, V. A. Dzubaa, V. V. Flambaum, Jiguang Li, A. V. Afanasjev, S. E. Agbemava

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Recently developed versions of the configuration method for open shells, configuration interaction with perturbation theory (CIPT), and configuration interaction with many-body perturbation theory (CI+MBPT) techniques are used to study the electronic structure of Er, Fm, and No atoms. Excitation energies of odd states connected to the even ground state by electric dipole transitions, the corresponding transition rates, isotope shift, hyperfine structure, ionization potentials, and static scalar polarizabilities are calculated. The way of extracting parameters of nuclear charge distribution beyond nuclear root mean square (RMS) radius, e.g., a parameter of quadrupole deformation β, is demonstrated. In nuclei with spin > 1/2, parameter β is extracted from the quadrupole hyperfine structure. With zero nuclear spin or spin 1/2, it is impossible since quadrupole zero, so a different method was developed. The measurements of at least two atomic transitions are needed to disentangle the contributions of the changes in deformation and nuclear RMS radius into field isotopic shift. This is important for testing nuclear theory and for searching for the hypothetical island of stability. Fm and No are heavy elements approaching the superheavy region, for which the experimental data are very poor, only seven lines for the Fm element and one line for the No element. Since Er and Fm have similar electronic structures, calculations for Er serve as a guide to the accuracy of the calculations. Twenty-eight new levels of Fm atom are reported.

Keywords: atomic spectra, electronic transitions, isotope effect, electron correlation calculations for atoms

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Authors: Kane Esien, Eadaoin McCourt, Peter Nockemann, Soveig Felton

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Magnetic ionic liquids (MILs) are a class of ionic liquid incorporating one or more magnetic atoms into the anion or cation of the ionic liquid, endowing the ionic liquid with magnetic properties alongside the existing properties of ionic liquids. MILs have applications in e.g. fluid-fluid separations, electrochemistry, and polymer chemistry. In this study three different types of Bis-Lanthanoates, that exist in different phases, have been synthesised and characterised (Ln = lanthanide): 1) imidazolium lanthanide acetate – [C4Mim]2[Ln2(OAc)8] – forms a crystalline solid at room temperature, 2) phosphonium lanthanide acetate – [P666 14]2[Ln2(OAc)8] – is in a solid glassy state, and 3) phosphonium lanthanide octanoate – [P666 14]2[Ln2(Oct)8] – is an ionic liquid. X-ray diffraction of the crystalline solid imidazolium lanthanide acetate – [C4Mim]2[Ln2(OAc)8] confirm that the Ln(III) ions form dimers, bridged by carboxyl groups, but cannot yield information about samples phosphonium lanthanide acetate – [P666 14]2[Ln2(OAc)8] (glass) and phosphonium lanthanide octanoate – [P666 14]2[Ln2(Oct)8] (ionic liquid) since these lack long-range order. SQUID magnetometry studies show that all three samples have effective magnetic moments consistent with non-interacting Ln(III) ions at room temperature but deviate from this behavior in the same way below 50 K. Through modeling the magnetic response, we are able to show that we have formed magnetic dimers, in all compounds, that are weakly antiferromagnetically interacting

Keywords: dimeric ionic liquids, interactions, SQUID, structure

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Authors: Ariesny Vera, Rodrigo Montecinos

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The rare-earth elements (REEs) or rare-earth metals (REMs), correspond to seventeen chemical elements composed by the fifteen lanthanoids, as well as scandium and yttrium. Lanthanoids corresponds to lanthanum and the f-block elements, from cerium to lutetium. Scandium and yttrium are considered rare-earth elements because they have ionic radii similar to the lighter f-block elements. These elements were called rare earths because they are simply more difficult to extract and separate individually than the most metals and, generally, they do not accumulate in minerals, they are rarely found in easily mined ores and are often unfavorably distributed in common ores/minerals. REEs show unique chemical and physical properties, in comparison to the other metals in the periodic table. Nowadays, these physicochemical properties are utilized in a wide range of synthetic, catalytic, electronic, medicinal, and military applications. Because of their applications, the global demand for rare earth metals is becoming progressively more important in the transition to a self-sustaining society and greener economy. However, due to the difficult separation between lanthanoid ions, the high cost and pollution of these processes, the scientists search the development of a method that combines selectivity and quantitative separation of lanthanoids from the leaching liquor, while being more economical and environmentally friendly processes. This motivation has favored the design and development of more efficient and environmentally friendly cation extractors with the incorporation of compounds as ionic liquids, membrane inclusion polymers (PIM) and supramolecular systems. Supramolecular chemistry focuses on the development of host-guest systems, in which a host molecule can recognize and bind a certain guest molecule or ion. Normally, the formation of a host-guest complex involves non-covalent interactions Additionally, host-guest interactions can be influenced among others effects by the structural nature of host and guests. The different macrocyclic hosts for lanthanoid species that have been studied are crown ethers, cyclodextrins, cucurbituryls, calixarenes and pillararenes.Among all the factors that can influence and affect lanthanoid (III) coordination, perhaps the most basic of them is the systematic control using macrocyclic substituents that promote a selective coordination. In this sense, macrocycles pillar[n]arenes (P[n]As) present a relatively easy functionalization and they have more π-rich cavity than other host molecules. This gives to P[n]As a negative electrostatic potential in the cavity which would be responsible for the selectivity of these compounds towards cations. Furthermore, the cavity size, the linker, and the functional groups of the polar headgroups could be modified in order to control the association of lanthanoid cations. In this sense, different P[n]As systems, specifically derivatives of the pentamer P[5]A functionalized with amide, amine, phosphate and sulfate derivatives, have been designed in terms of experimental synthesis and molecular dynamics, and the interaction between these P[5]As and some lanthanoid ions such as La³+, Eu³+ and Lu³+ has been studied by physicochemical characterization by 1H-NMR, ITC and fluorescence in the case of Eu³+ systems. The molecular dynamics study of these systems was developed in hexane as solvent, also taking into account the lanthanoid ions mentioned above, and the respective comparison studies between the different ions.

Keywords: lanthanoids, macrocycles, pillar[n]arenes, rare-earth metal extraction, supramolecular chemistry, supramolecular complexes.

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Authors: Andreea Cârâc, Elena Morosan, Ana Corina Ionita, Rica Bosencu, Geta Carac

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Lanthanum carbonate exhibits a considerable ability to bind phosphate and the substitution of Ca2+ ions by divalent or trivalent lanthanide metal ions attracted attention during the past few years. Although Lanthanum carbonate has not been approved by the FDA for treatment of hyperphosphatemia, we prospectively evaluated the efficacy of the combination of Calcium hydroxyapatite and Lanthanum carbonate for the treatment of hyperphosphatemia on mice. Calcium hydroxyapatite commonly referred as CHAp is a bioceramic material and is one of the most important implantable materials due to its biocompatibility and osteoconductivity. We prepared calcium hydroxyapatite and lanthanum carbonate. CHAp was prepared by co-precipitation method using Ca(OH)2, H3PO4, NH4OH with calcination at 1200ºC. Lanthanum carbonate was prepared by chemical method using NaHCO3 and LaCl3 at low pH environment , ph below 4.0 The confirmation of both substances structures was made using XRD characterization, FTIR spectra and SEM /EDX analysis. The study group included 20 subjects-mice divided into four groups according to the administered substance: lanthanum carbonate (group A), lanthanum carbonate + CHAp (group B), CHAp (group C) and salt water (group D). The results indicate a phosphate decrease when subjects (mice) were treated with CHAp and lanthanum carbonate (0.5 % CMC), in a single dose of 1500 mg/kg. Serum phosphate concentration decreased [from 4.5 ± 0.8 mg/dL) to 4.05 ± 0.2 mg/dL), P < 0.01] in group A and to 3.6 ± 0.2 mg/dL] only after the 24 hours of combination therapy. The combination of CHAp and lanthanum carbonate is a suitable regimen for hyperphosphatemia treatment subjects because it avoids both the hypercalcemia of CaCO3 and the adverse effects of CHAp. The ability of CHAp to decrease the serum phosphate concentration is 1/3 that of lanthanum carbonate.

Keywords: calcium hydroxyapatite, hyperphosphatemia, lanthanum carbonate, phosphate, structures

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Authors: S. Shanthi

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Catalyzed oxidation processes show extraordinary guarantee for application in numerous wastewater treatment ranges. Advanced oxidation processes are emerging innovation that might be utilized for particular objectives in wastewater treatment. This research work provides a solution for removal a refractory organic compound 2,4-dichlorophenoxyaceticacid a common water pollutant. All studies were done in batch mode in a constantly stirred reactor. Alternative ozonation processes catalysed by transition metals or granular activated carbon have been investigated for degradation of organics. Catalytic ozonation under study are homogeneous catalytic ozonation, which is based on ozone activation by transition metal ions present in aqueous solution, and secondly as heterogeneous catalytic ozonation in the presence of Granular Activated Carbon (GAC). The present studies reveal that heterogeneous catalytic ozonation using GAC favour the ozonation of 2,4-dichlorophenoxyaceticacid by increasing the rate of ozonation and a much higher degradation of substrates were obtained in a given time. Be that it may, Fe2+and Fe3+ ions decreased the rate of degradation of 2,4-dichlorophenoxyaceticacid indicating that it acts as a negative catalyst. In case of heterogeneous catalytic ozonation using GAC catalyst it was found that during the initial 5 minutes of contact solution concentration decreased significantly as the pollutants were adsorbed initially. Thereafter the substrate started getting oxidized and ozonation became a dominates the treatment process. The exhausted GAC was found to be regenerated in situ. The percentage reduction of the substrate was maximum achieved in minimum possible time when GAC catalyst is employed.

Keywords: ozonation, homogeneous catalysis, heterogeneous catalysis, granular activated carbon

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Authors: V. Viswanathan, Md. Irshad Ahmad, Prashant K. Singh, Nayeem Ahmad, Pradeep Sharma, Sujata Sharma, Tej P Singh

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Lactoperoxidase (LPO) is a heme containing mammalian enzyme which uses hydrogen peroxide (H2O2) to catalyze the conversion of substrates into oxidized products. LPO is found in body fluids and tissues such as milk, saliva, tears, mucosa and other body secretions. The previous structural studies have shown that LPO converts substrates, thiocyanate (SCN‾) and iodide (I‾) ions into oxidized products, hypothiocyanite (OSCN‾) and hypoiodite (IO‾) ions, respectively. We report here a new structure of the complex of LPO with an oxidized product, nitrite (NO2‾). This product was generated from NO using the two step reaction of LPO by adding hydrogen peroxide (H2O2) in the solution of LPO in 0.1M phosphate buffer at pH 6.8 as the first step. In the second step, NO gas was added to the above mixture. This was crystallized using 20% (w/v) PEG-3350 and 0.2M ammonium iodide at pH 6.8. The structure determination showed the presence of NO2‾ ion in the distal heme cavity of the substrate binding site of LPO. The structure also showed that the propionate group, which is linked to pyrrole ring D of the heme moiety, was disordered. Similarly, the side chain of Asp108, which is covalently linked to heme moiety, was also split into two components. As a result of these changes, the conformation of the side chain of Arg255 was altered, allowing it to form new interactions with the disordered carboxylic group of propionate moiety. These structural changes are indicative of an intermediate state in the catalytic reaction pathway of LPO.

Keywords: lactoperoxidase, structure, nitric oxide, nitrite ion, intermediate, complex

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Authors: Ghazala Anjum, Farooq Hussain Bhat, Ravi Kumar

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Multiferroic materials are vital for new application and memory devices, not only because of the presence of multiple types of domains but also as a result of cross correlation between coexisting forms of magnetic and electrical orders. In spite of wide studies done on multiferroic bulk ceramic materials their realization in thin film form is yet limited due to some crucial problems. During the last few years, special attention has been devoted to synthesis of thin films like of BiFeO₃. As they allow direct integration of the material into the device technology. Therefore owing to the process of exploration of new multiferroic thin films, preparation, and characterization of La₀.₈Bi₀.₂Fe₀.₇Mn₀.₃O₃ (LBFMO3) thin film on LaAlO₃ (LAO) substrate with LaNiO₃ (LNO) being the buffer layer has been done. The fact that all the electrical and magnetic properties are closely related to the electronic structure makes it inevitable to study the electronic structure of system under study. Without the knowledge of this, one may never be sure about the mechanism responsible for different properties exhibited by the thin film. Literature review reveals that studies on change in atomic and the hybridization state in multiferroic samples are still insufficient except few. The technique of x-ray absorption (XAS) has made great strides towards the goal of providing such information. It turns out to be a unique signature to a given material. In this milieu, it is time honoured to have the electronic structure study of the elements present in the LBFMO₃ multiferroic thin film on LAO substrate with buffer layer of LNO synthesized by RF sputtering technique. We report the electronic structure studies of well characterized LBFMO3 multiferroic thin film on LAO substrate with LNO as buffer layer using near-edge X-ray absorption fine structure (NEXAFS). Present exploration has been performed to find out the valence state and crystal field symmetry of ions present in the system. NEXAFS data of O K- edge spectra reveals a slight shift in peak position along with growth in intensities of low energy feature. Studies of Mn L₃,₂- edge spectra indicates the presence of Mn³⁺/Mn⁴⁺ network apart from very small contribution from Mn²⁺ ions in the system that substantiates the magnetic properties exhibited by the thin film. Fe L₃,₂- edge spectra along with spectra of reference compound reveals that Fe ions are present in +3 state. Electronic structure and valence state are found to be in accordance with the magnetic properties exhibited by LBFMO/LNO/LAO thin film.

Keywords: magnetic, multiferroic, NEXAFS, x-ray absorption fine structure, XMCD, x-ray magnetic circular dichroism

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Authors: Amina Ramadni, Safia Taleb, André Dératani

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The present study presents, firstly, to characterize the physicochemical quality of brackish groundwater of the Terminal Complex (TC) from the region of Eloued-souf and to investigate the presence of fluoride, and secondly, to study the comparison of adsorbing power of three materials, such as (activated alumina AA, sodium clay SC and hydroxyapatite HAP) against the groundwater in the region of Eloued-souf. To do this, a sampling campaign over 16 wells and consumer taps was undertaken. The results show that the groundwater can be characterized by very high fluoride content and excessive mineralization that require in some cases, specific treatment before supply. The study of adsorption revealed removal efficiencies fluoride by three adsorbents, maximum adsorption is achieved after 45 minutes at 90%, 83.4% and 73.95%, and with an adsorbed fluoride content of 0.22 mg/L, 0.318 mg/L and 0.52 mg/L for AA, HAP and SC, respectively. The acidity of the medium significantly affects the removal fluoride. Results deducted from the adsorption isotherms also showed that the retention follows the Langmuir model. The adsorption tests by adsorbent materials show that the physicochemical characteristics of brackish water are changed after treatment. The adsorption mechanism is an exchange between the OH^- ions and fluoride ions. Three materials are proving to be effective adsorbents for fluoride removal that could be developed into a viable technology to help reduce the salinity of the Saharan hyper-fluorinated waters. Finally, a comparison between the results obtained from the different adsorbents allowed us to conclude that the defluoridation by AA is the process of choice for many waters of the region of Eloued-souf, because it was shown to be a very interesting and promising technique.

Keywords: fluoride removal, hydrochemical characterization of groundwater, natural materials, nanofiltration

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Authors: Peter Thissen

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In this work, we report about the influence of the chemical potential of water on the carbonation reaction of wollastonite (CaSiO3) as model surface of cement and concrete. Total energy calculations based on density functional theory (DFT) combined with kinetic barrier predictions based on nudge elastic band (NEB) method show that the exposure of the water-free wollastonite surface to CO2 results in a barrier-less carbonation. CO2 reacts with the surface oxygen and forms carbonate (CO32-) complexes together with a major reconstruction of the surface. The reaction comes to a standstill after one carbonate monolayer has been formed. In case one water monolayer is covering the wollastonite surface, the carbonation is no more barrier-less, yet ending in a localized monolayer. Covered with multilayers of water, the thermodynamic ground state of the wollastonite completely changes due to a metal-proton exchange reaction (MPER, also called early stage hydration) and Ca2+ ions are partially removed from solid phase into the H2O/wollastonite interface. Mobile Ca2+ react again with CO2 and form carbonate complexes, ending in a delocalized layer. By means of high resolution time-of-flight secondary-ion mass-spectroscopy images (ToF-SIMS), we confirm that hydration can lead to a partially delocalization of Ca2+ ions on wollastonite surfaces. Finally, we evaluate the impact of our model surface results by means of Low Energy Ion Scattering (LEIS) spectroscopy combined with careful discussion about the competing reactions of carbonation vs. hydration.

Keywords: Calcium-silicate, carbonation, hydration, metal-proton exchange reaction

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Authors: T. Ul Rehman, S. Agnello, F. M. Gelardi, M. M. Calvino, G. Lazzara, G. Buscarino, M. Cannas

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Metal-Organic Frameworks (MOFs) have emerged as promising candidates for detecting metal ions owing to their large surface area, customizable porosity, and diverse functionalities. In recent years, there has been a surge in research focused on MOFs with luminescent properties. These frameworks are constructed through coordinated bonding between metal ions and multi-dentate ligands, resulting in inherent fluorescent structures. Their luminescent behavior is influenced by factors like structural composition, surface morphology, pore volume, and interactions with target analytes, particularly metal ions. MOFs exhibit various sensing mechanisms, including photo-induced electron transfer (PET) and charge transfer processes such as ligand-to-metal (LMCT) and metal-to-ligand (MLCT) transitions. Among these, MIL-53(Al) stands out due to its flexibility, stability, and specific affinity towards certain metal ions, making it a promising platform for selective metal ion sensing. This study investigates the structural, thermal, and luminescent properties of MIL-53(Al) metal-organic framework (MOF) upon Fe3+ cation exchange. Two separate sets of samples were prepared to activate the MOF powder at different temperatures. The first set of samples, referred to as MIL-53(Al), activated (120°C), was prepared by activating the raw powder in a glass tube at 120°C for 12 hours and then sealing it. The second set of samples, referred to as MIL-53(Al), activated (300°C), was prepared by activating the MIL-53(Al) powder in a glass tube at 300°C for 70 hours. Additionally, 25 mg of MIL-53(Al) powder was dispersed in 5 mL of Fe3+ solution at various concentrations (0.1-100 mM) for the cation exchange experiment. The suspension was centrifuged for five minutes at 10,000 rpm to extract MIL-53(Al) powder. After three rounds of washing with ultrapure water, MIL-53(Al) powder was heated at 120°C for 12 hours. For PXRD and TGA analyses, a sample of the obtained MIL-53(Al) was used. We also activated the cation-exchanged samples for time-resolved photoluminescence (TRPL) measurements at two distinct temperatures (120 and 300°C) for comparative analysis. Powder X-ray diffraction patterns reveal amorphization in samples with higher Fe3+ concentrations, attributed to alterations in coordination environments and ion exchange dynamics. Thermal decomposition analysis shows reduced weight loss in Fe3+-exchanged MOFs, indicating enhanced stability due to stronger metal-ligand bonds and altered decomposition pathways. Raman spectroscopy demonstrates intensity decrease, shape disruption, and frequency shifts, indicative of structural perturbations induced by cation exchange. Photoluminescence spectra exhibit ligand-based emission (π-π* or n-π*) and ligand-to-metal charge transfer (LMCT), influenced by activation temperature and Fe3+ incorporation. Quenching of luminescence intensity and shorter lifetimes upon Fe3+ exchange result from structural distortions and Fe3+ binding to organic linkers. In a nutshell, this research underscores the complex interplay between composition, structure, and properties in MOFs, offering insights into their potential for diverse applications in catalysis, gas storage, and luminescent devices.

Keywords: Fe³⁺ cation exchange, luminescent metal-organic frameworks (LMOFs), MIL-53(Al), solid-state analysis

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Authors: Phillip Ahn, Bryan Kim

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Copper is perhaps the most prevalent heavy metal used in the manufacturing industries, from food additives to metal-mechanic factories. Common methodologies to remove copper are expensive and produce undesired by-products. A good decontaminating candidate should be environment-friendly, inexpensive, and capable of eliminating low concentrations of the metal. This work suggests chemically modified spent tea leaves of chamomile, peppermint and green tea in their thiolated, sulfonated and carboxylated forms as candidates for the removal of copper from solutions. Batch experiments were conducted to maximize the adsorption of copper (II) ions. Effects such as acidity, salinity, adsorbent dose, metal concentration, and presence of surfactant were explored. Experimental data show that maximum adsorption is reached at neutral pH. The results indicate that Cu(II) can be removed up to 53%, 22% and 19% with the thiolated, carboxylated and sulfonated adsorbents, respectively. Maximum adsorption of copper on TPM (53%) is achieved with 150 mg and decreases with the presence of salts and surfactants. Conversely, sulfonated and carboxylated adsorbents show better adsorption in the presence of surfactants. Time-dependent experiments show that adsorption is reached in less than 25 min for TCM and 5 min for SCM. Instrumental analyses determined the presence of active functional groups, thermal resistance, and scanning electron microscopy, indicating that both adsorbents are promising materials for the selective recovery and treatment of metal ions from wastewaters. Finally, columns were prepared with these adsorbents to explore their application in scaled-up processes, with very positive results. A long-term goal involves the recycling of the exhausted adsorbent and/or their use in the preparation of biofuels due to changes in materials’ structures.

Keywords: heavy metal removal, adsorption, wastewaters, water remediation

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