Thermal Decomposition Studies of Layered Metal Hydroxynitrates (Metal: Cu, Zn, Cu/Co, and Zn/Co)

Layered metal hydroxynitrates and mixed metal hydroxynitrates (copper/cobalt hydroxynitrates and zinc/cobalt hydroxynitrates at different mole ratios) were synthesized by hydrolysis of urea and metal nitrates at 140°C. Layered metal hydroxyl nitrates derive their structure from brucite mineral and generally crystallize in hexagonal and monoclinic phases. Isothermal decomposition studies of Cu2(OH)3(NO3), Co2(OH)3(NO3), Cu1.5Co0.5(OH)3(NO3), Cu1.34Co0.66(OH)3(NO3), Zn5(OH)8(NO3)2(H2O)2, Zn3.75Co1.25(OH)8(NO3)2(H2O)2, and Zn3.35Co1.65(OH)8(NO3)2(H2O)2 samples were carried out at different intervals of temperature and the structural transformations during the process were monitored using powder X-ray diffractograms. Biphasic mixture of metal hydroxynitrate/metal oxide is observed in case of cobalt/zinc based layered hydroxynitrates, while copper hydroxynitrate or copper/cobalt metal hydroxynitrate decomposes in a single step. The decomposition temperatures of layered metal hydroxynitrates and mixed layered metal hydroxides depend on the method of preparation, their composition and the nature of metal ion, and their coordination.

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Dinuclear Lanthanide(III) Complexes from the Use of Methyl 2-Pyridyl Ketoxime: Synthetic, Structural, and Physical Studies

Molecules ◽

10.3390/molecules26061622 ◽

2021 ◽

Vol 26 (6) ◽

pp. 1622

Author(s):

Christina D. Polyzou ◽

Helen Nikolaou ◽

Catherine P. Raptopoulou ◽

Konstantis F. Konidaris ◽

Vlasoula Bekiari ◽

...

Keyword(s):

Metal Ion ◽

Structural Characteristics ◽

Exchange Interactions ◽

X Ray ◽

X Ray Crystallography ◽

Elemental Analyses ◽

3D Architecture ◽

Inorganic Ligands ◽

Hydrolysis Of ◽

The Eu

The first use of methyl 2-pyridyl ketoxime (mepaoH) in homometallic lanthanide(III) [Ln(III)] chemistry is described. The 1:2 reactions of Ln(NO3)3·nH2O (Ln = Nd, Eu, Gd, Tb, Dy; n = 5, 6) and mepaoH in MeCN have provided access to complexes [Ln2(O2CMe)4(NO3)2(mepaoH)2] (Ln = Nd, 1; Ln = Eu, 2; Ln = Gd, 3; Ln = Tb, 4; Ln = Dy, 5); the acetato ligands derive from the LnIII—mediated hydrolysis of MeCN. The 1:1 and 1:2 reactions between Dy(O2CMe)3·4H2O and mepaoH in MeOH/MeCN led to the all-acetato complex [Dy2(O2CMe)6(mepaoH)2] (6). Treatment of 6 with one equivalent of HNO3 gave 5. The structures of 1, 5, and 6 were solved by single-crystal X-ray crystallography. Elemental analyses and IR spectroscopy provide strong evidence that 2–4 display similar structural characteristics with 1 and 5. The structures of 1–5 consist of dinuclear molecules in which the two LnIII centers are bridged by two bidentate bridging (η1:η1:μ2) and two chelating-bridging (η1:η2:μ2) acetate groups. The LnIII atoms are each chelated by a N,N’-bidentate mepaoH ligand and a near-symmetrical bidentate nitrato group. The molecular structure of 6 is similar to that of 5, the main difference being the presence of two chelating acetato groups in the former instead of the two chelating nitrato groups in the latter. The geometry of the 9-coordinate LnIII centers in 1, 5 and 6 can be best described as a muffin-type (MFF-9). The 3D lattices of the isomorphous 1 and 5 are built through H-bonding, π⋯π stacking and C-H⋯π interactions, while the 3D architecture of 6 is stabilized by H bonds. The IR spectra of the complexes are discussed in terms of the coordination modes of the organic and inorganic ligands involved. The Eu(III) complex 2 displays a red, metal-ion centered emission in the solid state; the TbIII atom in solid 4 emits light in the same region with the ligand. Magnetic susceptibility studies in the 2.0–300 K range reveal weak antiferromagnetic intramolecular GdIII…GdIII exchange interactions in 3; the J value is −0.09(1) cm−1 based on the spin Hamiltonian Ĥ = −J(ŜGd1·ŜGd2).

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A Single-Step Synthesis of Rutile TiO2 Dendrite Crystal with Sonication

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.356-360.399 ◽

2011 ◽

Vol 356-360 ◽

pp. 399-402 ◽

Cited By ~ 1

Author(s):

Xi Kui Wang ◽

Wei Lin Guo ◽

Chen Wang

Keyword(s):

Electron Microscopy ◽

Thermal Analysis ◽

Single Step ◽

Sonochemical Method ◽

X Ray Diffraction ◽

X Ray ◽

Transmission Electron ◽

Crystallite Sizes ◽

Crystalline Forms ◽

Hydrolysis Of

A single-step sonochemical method to directly prepare rutile nanocrystal TiO2 has been developed. TiO2 nanaoparticles were synthesized by the hydrolysis of TiCl4 in the presence of water and ethanol under ultrasonic irradiationat 70 °C for 3 h. The crystalline forms and crystallite sizes of the produts were characterized by X-ray diffraction, transmission electron microscopy and thermogravimetry-differential thermal analysis. The TEM images showed the morphology of as-prapared TiO2 was pinnate in shape and the average sizes were ca. 4/12 nm (W/L). The columnar particles were linked together each other at the certain principle, forming the shape like dendrite crystal. The formation mechanism of the dendrite crystal nanocrystalline TiO2 was also discussed.

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Applications of Coordination Chemistry in Biological Systems

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314086239 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C1376-C1376

Author(s):

Gurpreet Kaur ◽

Richard Hartshorn

Keyword(s):

Metal Ions ◽

Metal Binding ◽

Binding Sites ◽

Metal Ion ◽

Hydrolytic Enzymes ◽

Dinuclear Complexes ◽

X Ray Diffraction ◽

X Ray ◽

Nitrophenyl Phosphate ◽

Hydrolysis Of

A novel 2,2′:6′,2″-terpyridine–picolylamine-based bridging ligand has been synthesized and fully characterized using a variety of analysis techniques including single crystal X-ray diffraction. As shown in figure (a), the ligand has both tridentate and bidentate metal binding sites available to coordinate with various metal ions. By varying the size of anions both dinuclear complexes and supramolecular assemblies have been produced. Addition of metal salts containing small anions like halides result in formation of Cu2L and Zn2L dinuclear complexes, figure (b), where one metal ion binds at each of the binding sites of the ligand. The metal ions in these complexes mimic active site of the hydrolytic enzymes and promote phosphatediester hydrolysis of model DNA/RNA compounds. Nearly ten times increase in the rate of hydrolysis of bis(p-nitrophenyl)phosphate (BNPP) is observed in comparison to the parent terpyridine and picolylamine complexes under physiological conditions. Larger anions like PF6-, ClO4-, SO42- , NO3- result in formation of Zn4L4 type squares via. head-to-head and tail-to-tail, HH-TT, (H=tridentate site, T=bidentate site) coordination of the ligand. The octahedrally bound Zn(II) ion between two tridentate sites can be replaced with Fe(II) to prepare Fe2Zn2L4 squares. A flat molecule of terephthalic acid was also deliberately encapsulated in the middle of the Fe2Zn2L4 square as shown in figure (c). The head-to-tail, HT, coordination of the ligand in case of Ni(II) results in formation of decanickel wheels, like [Ni10L10Cl4(H2O)6](Cl)15Br·~140H2O shown in figure (d). Due to the large structure of the molecule X-ray crystallographic studies rather have been quite challenging.

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Identification of acid-insoluble filter-plugging compounds and optimal acid-washing procedures for tubular backpulse pressure filters

TAPPI Journal ◽

10.32964/tj10.1.17 ◽

2011 ◽

Vol 10 (1) ◽

pp. 17-23

Author(s):

KEVIN TAYLOR ◽

RICH ADDERLY ◽

GAVIN BAXTER

Keyword(s):

Calcium Sulfate ◽

Membrane Filter ◽

Sulfamic Acid ◽

Xrd Analysis ◽

Metal Sulfides ◽

X Ray Diffraction ◽

X Ray ◽

Gypsum Formation ◽

Acid Washing ◽

Hydrolysis Of

Over time, performance of tubular backpulse pressure filters in kraft mills deteriorates, even with regular acid washing. Unscheduled filter replacement due to filter plugging results in significant costs and may result in mill downtime. We identified acid-insoluble filter-plugging materials by scanning electron microscope/energy-dispersion X-ray spectroscopy (SEM/EDS) and X-ray diffraction (XRD) analysis in both polypropylene and Gore-Tex™ membrane filter socks. The major filter-plugging components were calcium sulfate (gypsum), calcium phosphate (hydroxylapatite), aluminosilicate clays, metal sulfides, and carbon. We carried out detailed sample analysis of both the standard acid-washing procedure and a modified procedure. Filter plugging by gypsum and metal sulfides appeared to occur because of the acid-washing procedure. Gypsum formation on the filter resulted from significant hydrolysis of sulfamic acid solution at temperatures greater than 130°F. Modification of the acid-washing procedure greatly reduced the amount of gypsum and addition of a surfactant to the acid reduced wash time and mobilized some of the carbon from the filter. With surfactant, acid washing was 95% complete after 40 min.

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Investigation of the products of carbothermal reduction of yttrium oxide by the hydrolysis method

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19840936 ◽

1984 ◽

Vol 49 (4) ◽

pp. 936-943 ◽

Cited By ~ 4

Author(s):

Bohumil Hájek ◽

Pavel Karen ◽

Vlastimil Brožek

Keyword(s):

Yttrium Oxide ◽

Carbothermal Reduction ◽

Stoichiometric Ratio ◽

X Ray Diffraction ◽

X Ray ◽

Hydrolysis Method ◽

Sample Decomposition ◽

Products Of Reaction ◽

Hydrolysis Of ◽

Lower Carbon

For the investigation of the products of reaction of yttrium oxide with carbon mixed in various proportions, the chemical and X-ray diffraction methods of analysis were combined with the gas chromatographic analysis of the mixture of hydrocarbons and hydrogen formed on the sample decomposition with water. The carboreduction of Y2O3 was examined at relatively low temperatures, convenient for obtaining the reaction intermediates in higher yields. At 1 600 °C and pressures of 10-3 Pa the reduction of a mixture of Y2O3 with carbon in a stoichiometric ratio of 1 : 7 yields YC2 in equilibrium with 20% of Y2OC phase. At lower carbon contents (down to the Y2O3 : C ratio of 1 : 2) tha fraction of the Y2OC phase increases up to approximately 30%. In addition to Y2O3, the reaction mixture contains also Y2C, Y2OC and a phase giving propyne on hydrolysis. The presence of traces of C3 hydrocarbons and small amounts of methane in the product of hydrolysis of the carbide sample prepared by the carbothermal reduction of the oxide can be explained in terms of the occurrence of the Y15C19 phase, probably substituted in part by oxygen, and of the Y2OC phase. The results are compared with those obtained previously for the Sc2O3 + C system.

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ChemInform Abstract: KINETICS OF THE METAL ION CATALYZED ESTER HYDROLYSIS OF O-ACETYL DI-2-PYRIDYL KETOXIME

Chemischer Informationsdienst ◽

10.1002/chin.198551084 ◽

1985 ◽

Vol 16 (51) ◽

Author(s):

J. SUH ◽

M. P. SUH ◽

J. D. LEE

Keyword(s):

Metal Ion ◽

Ester Hydrolysis ◽

Kinetics Of ◽

Hydrolysis Of

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Pyrene Carboxylate Ligand Based Coordination Polymers for Microwave-Assisted Solvent-Free Cyanosilylation of Aldehydes

Molecules ◽

10.3390/molecules26041101 ◽

2021 ◽

Vol 26 (4) ◽

pp. 1101

Author(s):

Anirban Karmakar ◽

Anup Paul ◽

Elia Pantanetti Sabatini ◽

M. Fátima C. Guedes da Silva ◽

Armando J. L. Pombeiro

Keyword(s):

Coordination Polymer ◽

Single Crystal ◽

Coordination Polymers ◽

Metal Ion ◽

Solvent Free ◽

Lewis Acidity ◽

Carboxylate Ligand ◽

X Ray Diffraction ◽

X Ray ◽

Microwave Assisted

The new coordination polymers (CPs) [Zn(μ-1κO1:1κO2-L)(H2O)2]n·n(H2O) (1) and [Cd(μ4-1κO1O2:2κN:3,4κO3-L)(H2O)]n·n(H2O) (2) are reported, being prepared by the solvothermal reactions of 5-{(pyren-4-ylmethyl)amino}isophthalic acid (H2L) with Zn(NO3)2.6H2O or Cd(NO3)2.4H2O, respectively. They were synthesized in a basic ethanolic medium or a DMF:H2O mixture, respectively. These compounds were characterized by single-crystal X-ray diffraction, FTIR spectroscopy, thermogravimetric and elemental analysis. The single-crystal X-ray diffraction analysis revealed that compound 1 is a one dimensional linear coordination polymer, whereas 2 presents a two dimensional network. In both compounds, the coordinating ligand (L2−) is twisted due to the rotation of the pyrene ring around the CH2-NH bond. In compound 1, the Zn(II) metal ion has a tetrahedral geometry, whereas, in 2, the dinuclear [Cd2(COO)2] moiety acts as a secondary building unit and the Cd(II) ion possesses a distorted octahedral geometry. Recently, several CPs have been explored for the cyanosilylation reaction under conventional conditions, but microwave-assisted cyanosilylation of aldehydes catalyzed by CPs has not yet been well studied. Thus, we have tested the solvent-free microwave-assisted cyanosilylation reactions of different aldehydes, with trimethylsilyl cyanide, using our synthesized compounds, which behave as highly active heterogeneous catalysts. The coordination polymer 1 is more effective than 2, conceivably due to the higher Lewis acidity of the Zn(II) than the Cd(II) center and to a higher accessibility of the metal centers in the former framework. We have also checked the heterogeneity and recyclability of these coordination polymers, showing that they remain active at least after four recyclings.

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Snapshots of a Non-Canonical RdRP in Action

Viruses ◽

10.3390/v13071260 ◽

2021 ◽

Vol 13 (7) ◽

pp. 1260

Author(s):

Diego S. Ferrero ◽

Michela Falqui ◽

Nuria Verdaguer

Keyword(s):

Metal Ion ◽

Rna Viruses ◽

Ion Binding ◽

Genome Replication ◽

Metal Ion Binding ◽

Insect Virus ◽

X Ray ◽

Template Strand ◽

Nucleotide Incorporation ◽

Elongation Process

RNA viruses typically encode their own RNA-dependent RNA polymerase (RdRP) to ensure genome replication and transcription. The closed “right hand” architecture of RdRPs encircles seven conserved structural motifs (A to G) that regulate the polymerization activity. The four palm motifs, arranged in the sequential order A to D, are common to all known template dependent polynucleotide polymerases, with motifs A and C containing the catalytic aspartic acid residues. Exceptions to this design have been reported in members of the Permutotetraviridae and Birnaviridae families of positive single stranded (+ss) and double-stranded (ds) RNA viruses, respectively. In these enzymes, motif C is located upstream of motif A, displaying a permuted C–A–B–D connectivity. Here we study the details of the replication elongation process in the non-canonical RdRP of the Thosea asigna virus (TaV), an insect virus from the Permutatetraviridae family. We report the X-ray structures of three replicative complexes of the TaV polymerase obtained with an RNA template-primer in the absence and in the presence of incoming rNTPs. The structures captured different replication events and allowed to define the critical interactions involved in: (i) the positioning of the acceptor base of the template strand, (ii) the positioning of the 3’-OH group of the primer nucleotide during RNA replication and (iii) the recognition and positioning of the incoming nucleotide. Structural comparisons unveiled a closure of the active site on the RNA template-primer binding, before rNTP entry. This conformational rearrangement that also includes the repositioning of the motif A aspartate for the catalytic reaction to take place is maintained on rNTP and metal ion binding and after nucleotide incorporation, before translocation.

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Multidimensional Ln-Aminophthalate Photoluminescent Coordination Polymers

Materials ◽

10.3390/ma14071786 ◽

2021 ◽

Vol 14 (7) ◽

pp. 1786

Author(s):

Carla Queirós ◽

Chen Sun ◽

Ana M. G. Silva ◽

Baltazar de Castro ◽

Juan Cabanillas-Gonzalez ◽

...

Keyword(s):

Water Content ◽

Coordination Polymers ◽

Metal Ion ◽

Low Cost ◽

Microwave Assisted Synthesis ◽

X Ray Diffraction ◽

X Ray ◽

Wide Range ◽

Ft Ir ◽

Ft Ir Spectroscopy

The development of straightforward reproducible methods for the preparation of new photoluminescent coordination polymers (CPs) is an important goal in luminescence and chemical sensing fields. Isophthalic acid derivatives have been reported for a wide range of applications, and in addition to their relatively low cost, have encouraged its use in the preparation of novel lanthanide-based coordination polymers (LnCPs). Considering that the photoluminescent properties of these CPs are highly dependent on the existence of water molecules in the crystal structure, our research efforts are now focused on the preparation of CP with the lowest water content possible, while considering a green chemistry approach. One- and two-dimensional (1D and 2D) LnCPs were prepared from 5-aminoisophthalic acid and Sm3+/Tb3+ using hydrothermal and/or microwave-assisted synthesis. The unprecedented LnCPs were characterized by single-crystal X-ray diffraction (SCRXD), powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM), and their photoluminescence (PL) properties were studied in the solid state, at room temperature, using the CPs as powders and encapsulated in poly(methyl methacrylate (PMMA) films, envisaging the potential preparation of devices for sensing. The materials revealed interesting PL properties that depend on the dimensionality, metal ion, co-ligand used and water content.

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