Macromolecular Chiral Amplification through a Random Coil to One-Handed Helix Transformation Induced by Metal Ion Coordination in an Aqueous Solution

2020 ◽  
Vol 53 (14) ◽  
pp. 6002-6017
Author(s):  
Huajun Huang ◽  
Huimin Duan ◽  
Lijie Yin ◽  
Dongming Qi ◽  
Jiadan Xue ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Random Coil ◽  
Chiral Amplification

Kinetics and mechanism of the reaction of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione

1990 ◽  
Vol 55 (8) ◽  
pp. 1984-1990 ◽  
Author(s):  
José M. Hernando ◽  
Olimpio Montero ◽  
Carlos Blanco
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Activation Parameters ◽  
Enol Form ◽  
Kinetics And Mechanism ◽  
Kinetic Constants ◽  
Steric Factors ◽  
Kinetics Of ◽  
Mechanism Of The Reaction

The kinetics of the reactions of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione to form the corresponding monocomplexes have been studied spectrophotometrically in the range 5 °C to 16 °C at I 25 mol l-1 in aqueous solution. In the proposed mechanism for the two complexes, the enol form reacts with the metal ion by parallel acid-independent and inverse-acid paths. The kinetic constants for both pathways have been calculated at five temperatures. Activation parameters have also been calculated. The results are consistent with an associative activation for Fe(H2O)63+ and dissociative activation for Fe(H2O)5(OH)2+. The differences in the results for the complexes of heptanediones studied are interpreted in terms of steric factors.

scholarly journals H2O coordination in macropa complexes of f elements (Ac, La, Lu): feasibility of the 11th coordination site

2021 ◽  
Author(s):  
Attila Kovács ◽  
Zoltán Varga
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Density Functional ◽  
Molecular Level ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Coordination Site ◽  
Additional Ligand ◽  
Ligand Coordination ◽  
Bonding Properties

AbstractThe feasibility of an additional ligand coordination at the 11th coordination site of actinium, lanthanum, and lutetium ions in 10-fold coordinated macropa complexes has been studied by means of density functional theory calculations. The study covered the two main macropa conformers, Δ(δλδ)(δλδ) and Δ(λδλ)(λδλ), favoured by larger (Ac3+, La3+) and smaller (Lu3+) ions, respectively. At the molecular level, the coordination of H2O is the most favourable to the largest Ac3+ while only slightly less to La3+. Protonation of the picoline arms enhances the coordination by shifting the metal ion closer to the open site of the ligand. The choice of macropa conformer has only a slight influence on the strength and bonding properties of the H2O coordination. Aqueous solution environment decreases considerably the energy gain of H2O coordination at the 11th coordination site.

Determination of the complexation properties of a crosslinked poly(acrylic acid) gel with copper(II), nickel(II), and lead(II) in dilute aqueous solution

2001 ◽  
Vol 79 (4) ◽  
pp. 370-376 ◽  
Author(s):  
Catherine Morlay ◽  
Yolande Mouginot ◽  
Monique Cromer ◽  
Olivier Vittori
Keyword(s):  
Aqueous Solution ◽  
Ionic Strength ◽  
Acrylic Acid ◽  
Metal Ion ◽  
Conditional Stability ◽  
Binding Properties ◽  
Complex Species ◽  
Complexing Capacity ◽  
Dilute Aqueous Solution ◽  
Poly Acrylic Acid

The possible removal of copper(II), nickel(II), or lead(II) by an insoluble crosslinked poly(acrylic acid) was investigated in dilute aqueous solution. The binding properties of the polymer were examined at pH = 6.0 or 4.0 with an ionic strength of the medium µ = 0.1 or 1.0 M (NaNO3) using differential pulse polarography as an investigation means. The highest complexing capacity of the polyacid was obtained with lead(II) at pH = 6.0 with µ = 0.1 M, 4.8 mmol Pb(II)/g polymer. The conditional stability constants of the complex species formed were determined using the method proposed by Ruzic assuming that only the 1:1 complex species was formed; for lead(II) at pH = 6.0 and µ = 0.1 M, log K' = 5.3 ± 0.2. It appeared that the binding properties of the polymer increased, depending on the metal ion, in the following order: Ni(II) < Cu(II) < Pb(II). The complexing capacity and log K' values decreased with the pH or with an increase of the ionic strength. These results were in agreement with the conclusions of our previous studies of the hydrosoluble linear analogues. Finally, with the insoluble polymer, the log K' values were comparable to those previously obtained with the linear analogue whereas the complexing capacity values expressed in mmol g-1 were slightly lower.Key words: insoluble crosslinked poly(acrylic acid), copper(II), nickel(II), and lead(II) complexation.

scholarly journals Donor Atom Preference of Organoruthenium and Organorhodium Cations on the Interaction with Novel Ambidentate (N,N) and (O,O) Chelating Ligands in Aqueous Solution

Molecules ◽  
2021 ◽  
Vol 26 (12) ◽  
pp. 3586
Author(s):  
Sándor Nagy ◽  
András Ozsváth ◽  
Attila Cs. Bényei ◽  
Etelka Farkas ◽  
Péter Buglyó
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Platinum Group Metal ◽  
Molecular Structures ◽  
Chelating Ligands ◽  
Metal Ion Binding ◽  
Biologically Relevant ◽  
X Ray Crystallography ◽  
Ligand Ratio ◽  
Ph Range

Two novel, pyridinone-based chelating ligands containing separated (O,O) and (Namino,Nhet) chelating sets (Namino = secondary amine; Nhet = pyrrole N for H(L3) (1-(3-(((1H-pyrrole-2-yl)methyl)amino)propyl)-3-hydroxy-2-methylpyridin-4(1H)-one) or pyridine N for H(L5) (3-hydroxy-2-methyl-1-(3-((pyridin-2-ylmethyl)amino)propyl)pyridin-4(1H)-one)) were synthesized via reduction of the appropriate imines. Their proton dissociation processes were explored, and the molecular structures of two synthons were assessed by X-ray crystallography. These ambidentate chelating ligands are intended to develop Co(III)/PGM (PGM = platinum group metal) heterobimetallic multitargeted complexes with anticancer potential. To explore their metal ion binding ability, the interaction with Pd(II), [(η6-p-cym)Ru]2+ and [(η5-Cp*)Rh]2+ (p-cym = 1-methyl-4-isopropylbenzene, Cp* = pentamethyl-cyclopentadienyl anion) cations was studied in aqueous solution with the combined use of pH-potentiometry, NMR and HR ESI-MS. In general, organorhodium was found to form more labile complexes over ruthenium, while complexation of the (N,N) chelating set was slower than the processes of the pyridinone unit with (O,O) coordination. Formation of the organoruthenium complexes starts at lower pH (higher thermodynamic stabilities of the corresponding complexes) than for [(η5-Cp*)Rh]2+ but, due to the higher affinity of [η6-p-cym)Ru]2+ towards hydrolysis, the complexed ligands are capable of competing with hydroxide ion in a lesser extent than for the rhodium systems. As a result, under biologically relevant conditions, the rhodium binding effectivity of the ligands becomes comparable or even slightly higher than their effectivity towards ruthenium. Our results indicate that H(L3) is a less efficient (N,N) chelator for these metal ions than H(L5). Similarly, due to the relative effectivity of the (O,O) and (N,N) chelates at a 1:1 metal-ion-to-ligand ratio, H(L5) coordinates in a (N,N) manner to both cations in the whole pH range studied while, for H(L3), the complexation starts with (O,O) coordination. At a 2:1 metal-ion-to-ligand ratio, H(L3) cannot hinder the intensive hydrolysis of the second metal ion, although a small amount of 2:1 complex with [(η5-Cp*)Rh]2+ can also be detected.

Metal ion – biomolecule interactions. X. Synthesis, spectroscopic and magnetic resonance investigations of methylmercury(II) complexes of the sulfur modified nucleosides 6- mercaptopurine riboside and 2-amino-6-mercaptopurine riboside

1986 ◽  
Vol 64 (3) ◽  
pp. 442-448 ◽  
Author(s):  
E. Buncel ◽  
R. Kumar ◽  
A. R. Norris
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Chemotherapeutic Agents ◽  
Modified Nucleosides ◽  
Coupling Constants ◽  
Heterocyclic Ligands ◽  
Methylmercury Poisoning ◽  
Insight Into ◽  
C Nmr ◽  
Ligand Bond

A number of methylmercurated complexes of 6-mercaptopurine riboside and 2-amino-6-mercaptopurine riboside (6-MNucH2) containing S-bound CH3Hg(II) in neutral and cationic complexes (as in [CH3Hg(6-MNucH)] and [CH3Hg(6-MNucH2)]NO3), S- and N-bound CH3Hg(II) (as in [(CH3Hg)2(6-MNucH)]NO3), and S-, N-, C-bound CH3Hg(II) (as in [(CH3Hg)3(6-MNuc)]NO3) have been prepared in aqueous solution at appropriate pH and mole ratios of the constituents. The complexes were characterized by means of 1H and 13C nmr and ir spectroscopy and elemental analysis. Formation of C-bound methylmercurated species extends our previous results obtained with xanthosine, inosine, and imidazole derivatives, and substantiates our proposal that activation through electrophilic coordination at N(7) is a requirement for C(8)—H abstraction. 2J(1H–199Hg) coupling constants, measured in (CD3)2SO for a number of CH3Hg(II) complexes of N-, S-, and C-donor heterocyclic ligands, including the 6-mercaptopurine riboside of the present study, correlate well with the 1J(13C–199Hg) coupling constants, according to 1J = 8.4602J − 155.6. The significance of this correlation in terms of the strength of the Hg–ligand bond is considered. The results could provide insight into the apparent selectivity of binding of CH3Hg(II) by bio-ligands, as well as in the design of chemotherapeutic agents for the treatment of methylmercury poisoning.

Photodegradation of New Methylene Blue N in Aqueous Solution Using Zinc Oxide and Titanium Dioxide as Catalyst

2012 ◽  
Author(s):  
Rusmidah Ali ◽  
Boon Siew Ooi
Keyword(s):  
Aqueous Solution ◽  
Methylene Blue ◽  
Zinc Oxide ◽  
Titanium Dioxide ◽  
Optimum Condition ◽  
Metal Ion ◽  
Optimum Ratio ◽  
Photodegradation Rate ◽  
Uv Visible ◽  
Uv Lamp

Dalam kajian ini, ZnO dan TiO2 digunakan sebagai fotomangkin dalam pendegradasian pewarna New Methylene Blue N (NMBN). Kadar fotodegradasi diukur menggunakan alat spektrofotometer UV-Vis. Dalam kajian ini, New Methylene Blue N menunjukkan nilai serapan pada λ = 590 nm dan λ = 286 nm. Lampu UV (λ = 354 nm) digunakan dalam proses fotodegradasi. Dalam proses degradasi menggunakan ZnO menunjukkan 81.42% NMBN terdegradasi pada λ = 590 nm dan 77.75% pada λ = 286 nm. Sebaliknya, degradasi menggunakan TiO2 adalah 25.68% pada λ = 590 nm dan 26.37% pada λ = 286 nm. Peratus degradasi New Methylene Blue N ialah 88.89% dan 68.94% pada masing-masing λ = 590 nm dan λ = 286 nm apabila ditambahkan dengan H2O2. Campuran ZnO dan TiO2 dalam nisbah 85: 15 (0.085 g; 0.015 g) merupakan campuran fotomangkin yang paling optimum iaitu dengan peratus degradasi NMBN sebanyak 96.97% dan 93.61% pada λ = 590 nm dan λ = 286 nm. Penambahan ion logam Cu2+ memberikan peratus degradasi tertinggi berbanding ion logam lain iaitu 83.83% pada λ = 590 nm. Penambahan ion logam Pb2+ memberikan peratus degradasi tertinggi pada λ = 286 nm iaitu 81.25% pewarna terdegradasi. Keadaan optimum dicapai pada pH 5.90, dengan peratus degradasi tertinggi iaitu 92.84% dan 89.30% pada masing-masing λ = 590 nm dan λ = 286 nm. Kata kunci: New Methylene Blue N; fotodegradasi; larutan; ZnO; TiO2 In this study, ZnO and TiO2 are used as photocatalyst to degrade the dye, New Methylene Blue N (NMBN). The photodegradation rate was measured using UV-Visible spectrophotometer. In this study, New Methylene Blue N showed absorption values at λ = 590 nm and λ = 286 nm. UV lamp (λ = 354 nm) is used in the photodegradation process. Results showed that ZnO is a better photocatalyst compared to TiO2. The degradation by ZnO showed that 81% of NMBN was degraded at λ = 590 nm and 77.75% at λ = 286 nm. In contratst, the degradation using TiO2 was 25.68% at λ = 590 nm and 26.37% at λ = 286 nm. The percent degradation of New Methylene Blue N is 88.89% and 68.94% at λ = 590 nm and λ = 286 nm respectively when H2O2 was added. A mixture of ZnO and TiO2 in the ratio of 85: 15 (0.085 g: 0.015 g) is the most optimum ratio for the mixed photocatalyst where the degradation percentage of NMBN are 96.97% and 93.61% at λ = 590 nm and λ = 286 nm. The addition of Cu2+ metal ion gave the highest percentage of degradation (83.83% at λ = 590 nm) compared to other metal ions. The addition of Pb2+ gave the highest percentage of degradation at λ = 286 nm with 81.25% degradation of the dye. The optimum condition was achieved at pH 5.90, which gave the highest percentage degradation, 92.84% and 89.30% at λ = 590 nm and λ = 286 nm respectively. Key words: New Methylene Blue N; photodegradation; aqueous; ZnO; TiO2

scholarly journals Ricinus CommunisPericarp Activated Carbon Used as an Adsorbent for the Removal of Ni(II) From Aqueous Solution

2008 ◽  
Vol 5 (4) ◽  
pp. 761-769 ◽  
Author(s):  
S. Madhavakrishnan ◽  
K. Manickavasagam ◽  
K. Rasappan ◽  
P. S. Syed Shabudeen ◽  
R. Venkatesh ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Particle Size ◽  
Activated Carbon ◽  
Contact Time ◽  
Metal Ion ◽  
Ricinus Communis ◽  
Ion Concentration ◽  
Batch Mode ◽  
Adsorption Data ◽  
Initial Ph

Activated carbon prepared from Ricinus communis Pericarp was used to remove Ni(II) from aqueous solution by adsorption. Batch mode adsorption experiments are carried out by varying contact time, metal-ion concentration, carbon concentration and pH to assess kinetic and equilibrium parameters. The adsorption data were modeled by using both Langmuir and Freundlich classical adsorption isotherms. The adsorption capacity (Qo) calculated from the Langmuir isotherm was 31.15 mg/g of activated carbon at initial pH of 5.0±0.2 for the particle size 125-250 µm.

scholarly journals A Study on the Photocatalytic Reduction of Some Metal Ions in Aqueous Solution Using UV- Titanium Dioxide System

2019 ◽  
pp. 1-7
Author(s):  
I. O. Ekwere ◽  
M. Horsfall ◽  
J. O. E. Otaigbe
Keyword(s):  
Aqueous Solution ◽  
Titanium Dioxide ◽  
Metal Ions ◽  
Metal Ion ◽  
Uv Light ◽  
Kinetic Studies ◽  
Photocatalytic Reduction ◽  
Alkaline Ph ◽  
Removal Of Metal ◽  
Removal Of Metal Ions

The photocatalytic reduction of Cu (II), Pb (II), Cd (II) and Cr (VI) ions in aqueous solution has been investigated. The photocatalyst utilized was nano titanium dioxide, composed of 80% anatase and 20% rutile; the UV light source was a 15 W UV bulb with a wavelength of 254 nm. The results obtained indicated a reduction efficiency order as follows; Cr6+ > Cu2+ > Pb2+ > Cd2+. It was observed that these results correlate with the respective reduction potentials of the metal ions. The effect of pH on the photocatalytic reduction of the metal ions was also carried out and results obtained indicated that with the exception of Cr (VI) ions, higher percentage removal of metal ions from their aqueous solution was recorded at alkaline pH than at acidic pH. This was attributed to an extensive formation of precipitate by the metal ions at alkaline pH. Kinetic studies revealed that the removal of metal ions from their solutions largely followed the pseudo- first-order kinetics. Therefore, the results of this study will be useful in metal ion removal from industrial waste water using photocatalytic process.

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