Addition Of Metal Ions Research Articles

Synthesis of multicolor silver nanostructures for colorimetric sensing of metal ions (Cr3+, Hg2+ and K+) in industrial water and urine samples with different spectral characteristics

In this work, we have synthesized four different color (yellow, orange, green, and blue (multicolor)) silver nanostructures (AgNSs) by chemical reduction method where silver nitrate, sodium borohydride and hydrogen peroxide were used as reagents. The as-synthesized multicolor AgNSs were successfully functionalized with bovine serum albumin (BSA) and applied as a colorimetric sensor for the assaying of metal cations (Cr3+, Hg2+, and K+). The addition of metal ions (Cr3+, Hg2+, and K+) into BSA functionalized AgNSs (BSA-AgNSs) causes the aggregation of BSA-AgNSs, and are accompanied by visual color changes with red or blue shift in the surface plasmon resonance (SPR) band of BSA-AgNSs. The BSA-AgNSs show different SPR characteristic for each metal ions (Cr3+, Hg2+, and K+) with exhibiting different spectral shift and color change. The yellow color BSA-AgNSs (Y-BSA-AgNSs) act as a probe for sensing Cr3+, orange color BSA-AgNSs (O-BSA-AgNSs) act as probe for Hg2+ ion assay, green color BSA-AgNSs (G-BSA-AgNSs) act as a probe for the assaying of both K+ and Hg2+, and blue color BSA-AgNSs (B-BSA-AgNSs) act as a sensor for colorimetric detection of K+ ion. The detection limits were found to be 0.26 μM for Cr3+ (Y-BSA-AgNSs), 0.14 μM for Hg2+ (O-BSA-AgNSs), 0.05 μM for K+ (G-BSA-AgNSs), 0.17 μM for Hg2+ (G-BSA-AgNSs), and 0.08 μM for K+ (B-BSA-AgNSs), respectively. Furthermore, multicolor BSA-AgNSs were also applied for assaying of Cr3+, and Hg2+ in industrial water samples and K+ in urine sample.

Ligand-Directed Metalation of a Gold Pyrazolate Cluster.

Solid "[AuL]" (HL = 3-[pyrid-2-yl]-5-tertbutyl-1H-pyrazole) can be crystallized as cyclic [Au3(μ-L)3] and [Au4(μ-L)4] clusters from different solvents. The crystalline tetramer contains a square Au4 core with an HT:TH:TH:HT arrangement of ligand substituents, which preorganizes the cluster to chelate to additional metal ions via its pendant pyridyl groups. The addition of 0.5 equiv of AgBF4 to [AuL] yields [Ag2Au4(μ3-L)4][BF4]2, where two edges of the Au4 square are spanned by Ag+ ions via metallophilic Ag···Au contacts. Treatment of [AuL] with [Cu(NCMe)4]PF6 affords the metalloligand helicate [Cu2Au2(μ-L)4][PF6]2, via oxidation of the copper and partial fragmentation of the cluster.

Immobilization of Subtilisin Carlsberg and its use for transesterification of N-acetyl-L-phenylalanine ethyl ester in organic medium.

In this study, inorganic-based carrier perlite (PER) and cyclodextrin-modified perlite (PER-CD) were used for Subtilisin Carlsberg (SC) immobilization. For enzyme immobilization, the supports aminated with 3-aminotriethoxysilane were first activated with glutaraldehyde (GA) and genipin (GE), and then, the immobilized enzymes (PER-SC and PER-CD-SC) were obtained. The reaction medium for SC immobilization consisted of 500mg carrier and 5ml (1mg/ml) enzyme solution. The immobilization conditions were pH 8.0, 25°C, and 2h incubation time. Free and immobilized SC were used for transesterification of N-acetyl-L-phenylalanine ethyl ester (APEE) with 1-propanol in tetrahydrofuran (THF). The transesterification activity of the enzyme and the yield of the transesterification reaction were determined by gas chromatography (GC). 50mg of immobilized or 2.5mg of free SC was added to the reaction medium, which was prepared as 1mmol APEE and 10mmol alcohol in 10mL of THF. The conditions for the transesterification reaction were 60°C and 24h of incubation. The structure and surface morphology of the prepared carriers were characterized using scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Casein substrate was used in the optimization study. The optimum temperature and pH for SC activity were found to be 50°C and pH 8.0, respectively, for free and immobilized SC. The thermal stability of immobilized SC was found to be greater than that of free SC. At the end of 4h of exposure to high temperature, the immobilized enzyme maintained its activity at approximately 50%, while the free enzyme was maintained at approximately 20%. However, modification with cyclodextrin did not alter the thermal stability. The transesterification yield was found to be approximately 55% for the free enzyme, while it was found to be approximately 68% and 77% for PER-SC and PER-CD-SC, respectively. The effect of metal ions and salts on transesterification yield was examined. The results showed that the addition of metal ions decreased the percentage of transesterification by approximately 10% compared to the control group, whereas the addition of salt significantly decreased the percentage of transesterification by 60-80% compared to the control group.

Metal additives for boosting hydrogen production in anaerobic fermentation: Focus on the change of gene expression and cost analysis

Dark fermentation has emerged as a promising strategy for sustainable hydrogen production. However, the low hydrogen yield produced by anaerobic microbes continues to be a challenge. Although metal ion additives have been proposed to enhance hydrogen production, their entire impacts and underlying mechanisms are poorly understood. The present study aimed to examine the effects of Fe2+, Ni2+, Mg2+, and Mo6+ on dark fermentative hydrogen production, as well as their influences on microbial community analysis and gene expression in a batch system. The experiments were conducted under anaerobic conditions at 37 °C, utilizing 100 mM glucose as a substrate and an initial pH of 6.8. The results showed that Mo6+ at 0.015 mg-Mo6+/L significantly enhanced the hydrogen yield (2.21-fold increment) by upregulating nitrogenase gene expression (2.19-fold increment). Fe2+ at 50 mg-Fe2+/L was the second most effective metal ion, with a 1.81-fold increase in hydrogen yield and upregulation of ferredoxin (1.83-fold increment) and pyruvate formate-lyase gene (3.36-fold increment) expression. Mg2+ at 70 mg-Mg2+/L and Ni2+ at 25 mg-Ni2+/L also increased hydrogen yield by 1.51-fold and 1.31-fold, respectively, with upregulation of glyceraldehyde-3-phosphate dehydrogenase (1.02-fold and 1.81-fold increments, respectively) and ATP synthase (1.46-fold and 1.10-fold increments, respectively) expressions for both metal additives, pyruvate formate-lyase (2.77-fold increment) and pyruvate kinase (1.44-fold increment) gene expression for Mg2+. Regarding the mixed metal approach, it was observed that although certain combinations of mixed metals, such as Mg2++Mo6+, resulted in an enhancement of hydrogen yield by a factor of 1.37-fold, the increment was found to be lower than that of an individual metal. Therefore, the results of this study suggest that using a single metal would be more effective. Economic potential calculations further revealed that Mo6+ exhibited the highest economic feasibility, with the lowest expense of 2.02x10−5 $-metal/m3-H2, accounting for 0.002% of the average total production cost. This was followed by Mg2+, Fe2+, and Ni2+. Overall, our findings provide mechanistic insights into the use of metal ion additives for clean hydrogen production and offer a foundation for optimising their economic feasibility in large-scale hydrogen production.

Recent Progress in Electrolyte Additives for Highly Reversible Zinc Anodes in Aqueous Zinc Batteries

Aqueous zinc batteries (AZBs) are one of the most promising large-scale energy storage devices by virtue of their high specific capacity, high degree of safety, non-toxicity, and significant economic benefits. However, Zn anodes in aqueous electrolyte suffer from zinc dendrites and side reactions, which lead to a low coulombic efficiency and short life cycle of the cell. Since electrolytes play a key role in the Zn plating/stripping process, versatile strategies have been developed for designing an electrolyte to handle these issues. Among these strategies, electrolyte additives are considered to be promising for practical application because of the advantages of low cost and simplicity. Moreover, the resulting electrolyte can maximally preserve the merits of the aqueous electrolyte. The availability and effectiveness of additives have been demonstrated by tens of research works. Up to now, it has been essential and timely to systematically overview the progress of electrolyte additives in mild acidic/neutral electrolytes. These additives are classified as metal ion additives, surfactant additives, SEI film-forming additives, and complexing additives, according to their functions and mechanisms. For each category of additives, their functional mechanisms, as well as the latest developments, are comprehensively elaborated. Finally, some perspectives into the future development of additives for advanced AZBs are presented.

Prion Protein Octarepeat Domain Forms Transient β-Sheet Structures upon Residue-Specific Binding to Cu(II) and Zn(II) Ions.

Misfolding of the cellular prion protein (PrPC) is associated with the development of fatal neurodegenerative diseases called transmissible spongiform encephalopathies (TSEs). Metal ions appear to play a crucial role in PrPC misfolding. PrPC is a combined Cu(II) and Zn(II) metal-binding protein, where the main metal-binding site is located in the octarepeat (OR) region. Thus, the biological function of PrPC may involve the transport of divalent metal ions across membranes or buffering concentrations of divalent metal ions in the synaptic cleft. Recent studies have shown that an excess of Cu(II) ions can result in PrPC instability, oligomerization, and/or neuroinflammation. Here, we have used biophysical methods to characterize Cu(II) and Zn(II) binding to the isolated OR region of PrPC. Circular dichroism (CD) spectroscopy data suggest that the OR domain binds up to four Cu(II) ions or two Zn(II) ions. Binding of the first metal ion results in a structural transition from the polyproline II helix to the β-turn structure, while the binding of additional metal ions induces the formation of β-sheet structures. Fluorescence spectroscopy data indicate that the OR region can bind both Cu(II) and Zn(II) ions at neutral pH, but under acidic conditions, it binds only Cu(II) ions. Molecular dynamics simulations suggest that binding of either metal ion to the OR region results in the formation of β-hairpin structures. As the formation of β-sheet structures can be a first step toward amyloid formation, we propose that high concentrations of either Cu(II) or Zn(II) ions may have a pro-amyloid effect in TSE diseases.

Space-Confined Metal Ion Strategy for Carbon Materials Derived from Cobalt Benzimidazole Frameworks with High Desalination Performance in Simulated Seawater.

Various metal ions with different valence states (Mg2+ , Al3+ , Ca2+ , Ti4+ , Mn2+ , Fe3+ , Ni2+ , Zn2+ , Pb2+ , Ba2+ , Ce4+ ) are successfully confined in quasi-microcube shaped cobalt benzimidazole frameworks using a space-confined synthesis strategy. More importantly, a series of derived carbon materials that confine metal ions are obtained by high-temperature pyrolysis. Interestingly, the derived carbon materials exhibited electric double-layer and pseudocapacitance properties because of the presence of metal ions with various valence states. Moreover, the presence of additional metal ions within carbon materials may create new phases, which can accelerate Na+ insertion/extraction and thus increase electrochemical adsorption. Density functional theory results showed that carbon materials in which Ti ions are confined exhibit enhanced insertion/extraction of Na+ resulting from the presence of the characteristic anatase crystalline phases of TiO2 . The Ti-containing materials have an impressive desalination capacity (62.8mgg-1 ) in capacitive deionization (CDI) applications with high cycling stability. This work provides a facile synthetic strategy for the confinement of metal ions in metal-organic frameworks and thus supports the further development of derived carbon materials for seawater desalination by CDI.

Electrostatic Interactions in the Formation of DNA Complexes with Cis- and Trans-Isomers of Azobenzene-Containing Surfactants in Solutions with Di- and Trivalent Metal Ions.

The effect of the presence of divalent and trivalent metal ions in solutions upon DNA packaging induced by the photosensitive azobenzene-containing surfactant is considered. It has been shown that the addition of divalent and trivalent metal ions does not affect the DNA-surfactant interaction for both the cis- and the trans-isomers of the surfactant. At the same time, the ionic strength of the solution, which is provided by a certain concentration of the salt, has a huge impact. It affects the association of surfactant molecules with each other and their binding to DNA. It has been shown by computer simulation that cobalt hexamine is attracted to the N7 atom of guanine in the major groove of DNA and does not penetrate into grooves near the AT base pairs.

Catalytic hydrogenation of levulinic acid to γ-valerolactone over lignin-metal coordinated carbon nanospheres in water

The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) has attracted much attention, as GVL can be used as biofuel, green solvent, and platform chemical. Inspired by Stöber method, various lignin-metal coordinated colloidal nanospheres (LCS) from lignin and cetyltrimethylammonium bromide (CTAB) were synthesized in which the metal ions (Co2+) replace formaldehyde as the crosslinker. The characterization of the catalyst revealed that alkali lignin was first self-assembled with CTAB through electrostatic attraction to form a lignin polymer, the subsequent addition of metal ions (Co2+) promoted the aggregation of lignin polymers and generated the LCS. Increasing calcination temperature for LCS resulted in the Co2+ being reduced to metallic Co. The lignin-metal coordinated colloidal nanospheres calcined at 500 °C possess both CoO and metallic Co active sites, which effectively accelerated the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) than simplex metallic Co active sites. A 99.8 % yield of GVL with 100 % LA conversion was obtained after 60 min reaction time at 200 °C and 2 MPa H2.

A glucose tolerant β-glucosidase from a newly isolated Neofusicoccum parvum strain F7: production, purification, and characterization

Cellulase-producing microorganisms produce low titres of β-glucosidases with low tolerance to glucose. This study aimed to improve production, purify, and characterize a β-glucosidase from a newly isolated Neofusicoccum parvum strain F7. β-Glucosidase production was significantly enhanced by a sequential statistical modelling approach from 1.5-fold in Plackett–Burman design to 2.5 U/ml in the Box–Behnken design compared to the preliminary one variable at a time experiments (1.6 U/ml). The optimal conditions for enzyme production by BBD were 12 days of fermentation at 20 °C, 175 rpm, 0.5% glycerol and 1.5% casein in pH 6.0 buffer. Three β-glucosidase isoforms referred to as Bgl1, Bgl2, Bgl3 were purified and characterized from the optimized crude extract displaying IC50 values of 2.6, 22.6 and 319.5 mM for glucose, respectively. Bgl3 with a molecular mass of approximately 65 kDa demonstrated the highest tolerance to glucose among the isoforms. The optimum activity and stability for Bgl3 was observed at pH 4.0 in 50 mM sodium acetate buffer with 80% β-glucosidase residual activity retained for three hours. This isoform also retained 60% residual activity at 65 °C for one hour which was then reduced to 40% which remained stable for another 90 min. The β-glucosidase activity of Bgl3 was not enhanced after the addition of metal ions in assay buffers. The Km and vmax for 4-nitrophenyl-β-d-glucopyranoside were 1.18 mM and 28.08 µmol/min, respectively indicating high affinity for the substrate. The ability to withstand the presence of glucose in conjunction with its thermophilic nature indicates promise for this enzyme in industrial application.

Triazole‐bearing oligo(ethylene glycol)‐strapped zinc porphyrins as dual mode ion‐binding receptors

AbstractA series of triazole‐bearing oligo(ethylene glycol)‐strapped zinc porphyrins (PZn4EG and PZn5EG) have been prepared as artificial ion‐binding receptors. Both PZn4EG and PZn5EG exhibit UV/Vis absorption changes in a solvent‐dependent manner upon titration with halides and alkali metal ions. In tetrahydrofuran, both PZn4EG and PZn5EG exhibit spectral shifts upon the addition of halide ions through axial coordination, whereas the absorption does not change upon the addition of alkali metal ions. On the other hand, in 10% MeCN/CHCl3, the UV/Vis absorption spectra of both PZn4EG and PZn5EG do not change upon the addition of an excess amount of halide ions; however, PZn4EG and PZn5EG show selective alkali metal ion‐binding properties in this solvent. PZn4EG and PZn5EG display dramatic color changes and spectral shifts upon the addition of Li+ and K+, respectively. Because of the dramatic color changes that occurred upon binding, the determination of alkali metal ions would be possible.

Cation trivalent tune of crystalline structure and magnetic properties in coprecipitated cobalt ferrite nanoparticles

CoFe2O4, CoBi0.1Fe1.9O4, CoLa0.1Fe1.9O4, and CoAl0.1Fe1.9O4 nanoparticles were successfully synthesized by the coprecipitation method. After annealing at 700 °C for 5 h, the x-ray Diffractometer results confirm that a single phase of cobalt ferrite-based nanoparticles is obtained, which is suitable for ICDD 22-1086. The addition of Bi3+, La3+ and Al3+ ions to the cobalt ferrite nanoparticles modified the crystallite size and lattice constant. Trivalent metal cation substitution tunes the crystallite size which has also been confirmed by measuring the grains with Scanning Electron Microscope images. In the Far Transform Infra-Red curve, the addition of metal ions (Bi3+, La3+, and Al3+) to cobalt ferrite nanoparticles resulted in absorption peaks at the tetrahedral and octahedral sites without any additional absorption peaks. The VSM results showed that saturation magnetization decreased drastically in the presence of trivalent non-magnetic cations, which confirms the replacement of Fe3+ by trivalent non-magnetic cations. The kOe order of the coercive field was obtained in this experiment. The largest coercive field of the cobalt ferrite nanoparticles was obtained with the addition of La3+ ions, i.e. 3.67 kOe suggest to support both Jahn-Teller effect and strain-induced magnetism.

Precise analysis of thyroxine enantiomers in pharmaceutical formulation by mobility difference based on cyclodextrin

Identification and determination of chiral pharmaceutical residues is still a challenging analytical puzzle. In this work, a simple, rapid, and effective method for chiral D/L-tetraiodothyronine (T4) separation and quantitative was developed based on host–guest recognition using ion mobility spectrometry-mass spectrometry (IMS-MS). The D/L-T4 enantiomers were mobility separated by their diastereomeric complexes through mixing with cyclodextrin (CD) and metal ions. D/L-T4 was first separated by complexing with host molecule (α-, β-, γ-CD), observing weak peak-to-peak resolution (Rp-p) by the formed binary complex [CD + D/L-T4-H]+, and the Rp-p decreased with the CD size increasing. However, the separation effect of D/L-T4 was much improved with the addition of divalent metal ions (G2+) by the formed ternary complex [CD + D/L-T4 + G]2+. In comparison, α-CD related complexes can possess the best separation effect for D/L-T4 in most cases. Considering the high selectivity, non-toxic, and chemically stable of β-CD, [β-CD + D/L-T4 + Ca]2+ was selected for D/L-T4 analysis (RP-P = 0.764). Whereafter, chemical theoretical conformations for [β-CD + D/L-T4 + H]+ and [β-CD + D/L-T4 + Ca]2+ were optimized, discovering similar micro-interaction modes between [β-CD + D-T4 + H]+ and [β-CD + L-T4 + H]+; while with the addition of Ca2+, significantly different interaction modes were observed between [β-CD + D-T4 + Ca]2+ and [β-CD + L-T4 + Ca]2+. And theoretical collision cross section (CCS) trends for the complexes were consistent with that of the experimental results. Additionally, calibration curves were linear within 1.00 to 104 ng mL−1 with coefficient (R2 > 0.99), gaining the limit of detection (LODs) calculation of 0.11 ng mL−1, and the detection range between D-T4 and L-T4 of 45.6:1 to 1:59.8. Finally, the method was applied for D/L-T4 detection in Levothyroxine tablets, the detection content has good consistency on drug labeling. Because the proposed method exhibited good analytical performance in terms of speed, selectivity, sensitivity, and reproducibility of the measurements, that can be a promising strategy for effective D/L-T4 detection in pharmaceutical industries or other practical samples.

Moist‐Electric Generator with Efficient Output and Scalable Integration Based on Carbonized Polymer Dot and Liquid Metal Active Electrode

AbstractMoisture‐enabled electricity generation (MEG) is highly promising in next‐generation energy conversion. However, the practical applications of existing MEG devices are limited due to their low current and voltage outputs, strong dependence on high moisture, and inflexible nature. Herein, an efficient MEG integrated with flexible, all‐weather, and scalable fabrication characteristics based on the rational combination of carbonized polymer dots (CPDs) and liquid metal (LM) active electrodes is developed for the first time. Remarkably, the fabricated MEG device can produce a stable voltage output of 800 mV and a record high current density of 1640 µA cm−2. Even at a low air humidity of 15%, the MEG device can provide a high voltage output of 0.65 V and a considerable current density of 12 µA cm−2. The prompted diffusion of hydrogen ions in CPDs and the additional metal ions ionized from the LM electrode contribute synergistically to the high electricity generation. Additionally, the device can be easily integrated on various flexible substrates and generate an ultrahigh voltage of 210 V to power commercial electronics, showing great potential in large‐scale fabrication and application.

Taking Charge: Metal Ions Accelerate Amyloid Aggregation in Sequence Variants of α-Synuclein.

Αlpha-synuclein (αS) is an intrinsically disordered protein which exhibits a high degree of conformational heterogeneity. In vivo, αS experiences various environments which cause adaptation of its structural ensemble. Divalent metal ions are prominent in synaptic terminals where αS is located and are thought to bind to the αS C-terminal region. Herein, we used native nanoelectrospray ionization ion mobility-mass spectrometry to investigate changes in the charge state distribution and collision cross sections of wild-type N-terminally acetylated (NTA) αS, along with a deletion variant (ΔΔNTA) which inhibits amyloid formation and a C-terminal truncated variant (119NTA) which increases the rate of amyloid formation. We also examine the effect of the addition of divalent metal ions, Ca2+, Mn2+, and Zn2+, and correlate the conformational properties of the αS monomer with the ability to aggregate into amyloid, measured using Thioflavin T fluorescence and negative stain transmission electron microscopy. We find a correlation between the population of species with a low collision cross section and accelerated amyloid assembly kinetics, with the presence of metal ions resulting in protein compaction and causing ΔΔ to regain its ability to form an amyloid. The results portray how the αS conformational ensemble is governed by specific intramolecular interactions that influence its amyloidogenic behavior.

Effect of Metal Ions on the Interaction of Condensed Tannins with Protein

A quantitative analysis of the precipitate effects of metal ions (Al3+, Fe2+, Cu2+, Zn2+) by bovine serum albumin (BSA) on two condensed tannins (CT) from sorghum and plum was presented in this study. The results showed that adding metal ions enhanced the precipitation of proteins by CT, depending on the type and concentration of the metal ions used in the reaction system. The presence of metal ions and precipitation results on the CT-protein complex showed that Al3+ and Fe2+ had a higher binding ability with CT and a weaker influence on the precipitation of the CT-protein complex than Cu2+ and Zn2+. However, when the initial reaction solution contained excessive amounts of BSA, the extra addition of metal ions had no significant effect on the amount of BSA precipitation. Reversely, adding Cu2+ or Zn2+ into the reaction solution increased the amount of precipitated BSA when the amount of CT was excessive. In addition, the amounts of CT from plum, rather than sorghum, generated more protein precipitate in the presence of Cu2+ or Zn2+, which may be due to the different binding modes between the metal ion and the CT-BSA complex. This study also proposed a model of the interaction between the metal ion and the CT-protein precipitate.

Cu(II)-Triggered Ion Channel Properties of a 2,2'-Bipyridine-Modified Amphotericin B.

The development of stimuli-responsive synthetic channels that open and close in response to physical and chemical changes in the surrounding environment has attracted attention because of their potential bioapplications such as sensing, drug release, antibiotics, and molecular manipulation tools to control membrane transport in cells. Metal coordination is ideal as a stimulus for stimuli-responsive channels because it allows for reversible gating behavior through the addition and removal of metal ions and fine-tuning of channel structure through coordination geometry defined by the type of the metal ion and ligand. We have previously reported on transition metal-ion dependent ion permeability control of Amphotericin B (AmB) modified with a metal coordination site, 2,2'-bipyridine ligand (bpy-AmB). AmB is one of the polyene macrolide antibiotics, and it is known that the interaction between AmB and ergosterol molecules is required for AmB channel formation. In contrast, the Cu2+ coordination to the bpy moiety of bpy-AmB induces formation of Ca2+ ion-permeable channels in the ergosterol-free POPC membrane. However, the details of bpy-AmB properties such as channel stability, ion selectivity, pore size, and the effect of ergosterol on channel formation remain unclear. Here, we investigate bpy-AmB channels triggered by transition metal coordination in POPC or ergosterol-containing POPC liposomes using an HPTS assay, electrophysiological measurements, and time-resolved UV-vis spectral measurements. These analyses reveal that bpy-AmB channels triggered by Cu2+ ions are more stable and have larger pore sizes than the original AmB channels and enable efficient permeation of various cations. We believe that our channel design will lead to the construction of metal coordination-triggered synthetic ion channels.

Cagelike Octacopper Methylsilsesquioxanes: Self-Assembly in the Focus of Alkaline Metal Ion Influence-Synthesis, Structure, and Catalytic Activity.

A family of unusual octacopper cage methylsilsesquioxanes 1-4 were prepared and characterized. Features of their cagelike (prismatic) structure were established using X-ray diffraction studies. Effects of distortion of prismatic cages 1-4 due to variation of (i) additional alkaline metal ions (K, Rb, or Cs), (ii) combination of solvating ligands, and (iii) nature of encapsulating species were found. Opportunities for the design of supramolecular 1D extended structures were found. These opportunities are based on (i) formate linkers between copper centers (in the case of Cu8K2-based compound 2) or (ii) crown ether-like contacts between cesium ions and siloxane cycles (in the case of Cu8Cs2-based compound 4). Cu8Cs2-complex 4 was evaluated in the catalysis of alkanes and alcohols. Complex 4 exhibits high catalytic activity. The yield of cyclohexane oxidation products is 35%. The presence of nitric acid is necessary as a co-catalyst. The oxidation of alcohols with the participation of complex 4 as a catalyst and tert-butyl hydroperoxide as an oxidizer also proceeds in high yields of up to 98%.

CONVERSION OF NIGERIAN OILSAND TO LIGHT CRUDE IN THE PRESENCE OF ENHANCED FLUID CATALYTIC CRACKING (FCC) CATALYST.

Conversion of heavy oil to light crude in the presence of a catalyst better known as catalytic upgrading of heavy and extra-heavy oil is been explored worldwide as one important in-situ upgrading technology among others. In this study, an equilibrated Fluid Catalytic Cracking (FCC) catalyst was sourced from a refinery, enhanced by the addition of transition metal ions, characterized using X-Ray Diffractometer (XRD), X-Ray Flourencence (XRF) and Fourier Transform - Infrared (FT-IR) techniques and tested in upgrading heavy crude oil. The enhanced FCC (Fluid Catalytic Cracking) commercial catalyst, hydrogen and glycerol were added into bitumen (32000cSt measured at 40oC) in a high-pressure batch reactor at 350oC for reaction time of two hours, pressure of 10bar and catalyst to bitumen ratio of 0.02. Viscosity reduction after thermal upgrade were 83 and 98% at room temperature and at 40oC respectively while the reduction after catalyst upgrade were 87.9 and 98.9% correspondingly under the same conditions. It was found that there was improved API gravity from 11.6 to 26.0 in thermal reaction and 30.5 in catalytic reaction. Other physiochemical properties of the bitumen investigated also improved significantly towards the production of lighter oil. The structural compositions of the bitumen before and after the reaction at 350oC were investigated using Fourier Transform - Infrared (FT-IR) and Gas Chromatograph – Mass Spectrometer (GC-MS). The result shows that the heavy molecular compounds like resins and asphaltene were broken down to lighter compounds. Keywords: Bitumen, Oilsand, Fluid Catalytic Cracking, Catalyst, Heavy oil, Upgrade.

Oxidation of ciprofloxacin by the synergistic effect of DBD plasma and persulfate: reactive species and influencing factors analysis

A synergistic system of water falling film dielectric barrier discharge (DBD) plasma and persulfate (PS) was set up and used for oxidizing ciprofloxacin (CIP) in water. Results of reactive species formation in the DBD-only system as well as the DBD–PS system verified the PS activation in the DBD system. Influencing factors on CIP degradation and the degradation process were also been studied. The obtained results showed that the presence of PS could greatly improve the degradation and mineralization of CIP and that the degradation efficiency could reach 97.73% after only 40 min treatment with 4 mM PS addition. The increase of PS concentration, the lower CIP concentration, the acidic solution pH and the addition of metal ions (Fe2+ and Cu2+) enhanced the CIP degradation, while the existence of Cl− and HC had a negative effect. The experiments related to scavenger addition confirmed the contribution of the main reactive species to the CIP oxidation. Three probable degradation pathways were proposed by analyzing the inorganic ions and organic byproducts formed during the CIP degradation. The toxicity evaluation results of the CIP and its intermediates confirmed the effectiveness of the DBD–PS synergistic system.