scholarly journals Intermediates in monensin biosynthesis: A late step in biosynthesis of the polyether ionophore monensin is crucial for the integrity of cation binding

2014 ◽  
Vol 10 ◽  
pp. 361-368 ◽  
Author(s):  
Wolfgang Hüttel ◽  
Jonathan B Spencer ◽  
Peter F Leadlay
Keyword(s):  
Cation Binding ◽  
Sodium Ion ◽  
Cyclic Ethers ◽  
P450 Monooxygenase ◽  
Methyl Transferase ◽  
X Ray ◽  
Ring Expansions ◽  
Streptomyces Cinnamonensis ◽  
Late Step ◽  
Ionophore Monensin

Polyether antibiotics such as monensin are biosynthesised via a cascade of directed ring expansions operating on a putative polyepoxide precursor. The resulting structures containing fused cyclic ethers and a lipophilic backbone can form strong ionophoric complexes with certain metal cations. In this work, we demonstrate for monensin biosynthesis that, as well as ether formation, a late-stage hydroxylation step is crucial for the correct formation of the sodium monensin complex. We have investigated the last two steps in monensin biosynthesis, namely hydroxylation catalysed by the P450 monooxygenase MonD andO-methylation catalysed by the methyl-transferase MonE. The corresponding genes were deleted in-frame in a monensin-overproducing strain ofStreptomyces cinnamonensis. The mutants produced the expected monensin derivatives in excellent yields (ΔmonD: 1.13 g L−1dehydroxymonensin; ΔmonE: 0.50 g L−1demethylmonensin; and double mutant ΔmonDΔmonE: 0.34 g L−1dehydroxydemethylmonensin). Single crystals were obtained from purified fractions of dehydroxymonensin and demethylmonensin. X-ray structure analysis revealed that the conformation of sodium dimethylmonensin is very similar to that of sodium monensin. In contrast, the coordination of the sodium ion is significantly different in the sodium dehydroxymonensin complex. This shows that the final constitution of the sodium monensin complex requires this tailoring step as well as polyether formation.

Defect-Mediated Conductivity Enhancements in Na3-xPn1-xWxS4 (Pn = P, Sb) using Aliovalent Substitutions

2019 ◽  
Author(s):  
Till Fuchs ◽  
Sean Culver ◽  
Paul Till ◽  
Wolfgang Zeier
Keyword(s):  
Ionic Conductivity ◽  
Vacancy Concentration ◽  
Sodium Ion ◽  
High Ionic Conductivity ◽  
Ionic Conductors ◽  
X Ray Diffraction ◽  
X Ray ◽  
Solid State Batteries ◽  
Ion Conducting ◽  
Very High

<p>The sodium-ion conducting family of Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, with <i>Pn</i> = P, Sb, have gained interest for the use in solid-state batteries due to their high ionic conductivity. However, significant improvements to the conductivity have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, the solid solutions with WS<sub>4</sub><sup>2-</sup> introduction are explored. The influence of the substitution with WS<sub>4</sub><sup>2-</sup> for PS<sub>4</sub><sup>3-</sup> and SbS<sub>4</sub><sup>3-</sup>, respectively, is monitored using a combination of X-ray diffraction, Raman and impedance spectroscopy. With increasing vacancy concentration improvements resulting in a very high ionic conductivity of 13 ± 3 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>P<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> and 41 ± 8 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>Sb<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.</p>

Defect-Mediated Conductivity Enhancements in Na3-xPn1-xWxS4 (Pn = P, Sb) using Aliovalent Substitutions

2019 ◽  
Author(s):  
Till Fuchs ◽  
Sean Culver ◽  
Paul Till ◽  
Wolfgang Zeier
Keyword(s):  
Ionic Conductivity ◽  
Vacancy Concentration ◽  
Sodium Ion ◽  
High Ionic Conductivity ◽  
Ionic Conductors ◽  
X Ray Diffraction ◽  
X Ray ◽  
Solid State Batteries ◽  
Ion Conducting ◽  
Very High

<p>The sodium-ion conducting family of Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, with <i>Pn</i> = P, Sb, have gained interest for the use in solid-state batteries due to their high ionic conductivity. However, significant improvements to the conductivity have been hampered by the lack of aliovalent dopants that can introduce vacancies into the structure. Inspired by the need for vacancy introduction into Na<sub>3</sub><i>Pn</i>S<sub>4</sub>, the solid solutions with WS<sub>4</sub><sup>2-</sup> introduction are explored. The influence of the substitution with WS<sub>4</sub><sup>2-</sup> for PS<sub>4</sub><sup>3-</sup> and SbS<sub>4</sub><sup>3-</sup>, respectively, is monitored using a combination of X-ray diffraction, Raman and impedance spectroscopy. With increasing vacancy concentration improvements resulting in a very high ionic conductivity of 13 ± 3 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>P<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> and 41 ± 8 mS·cm<sup>-1</sup> for Na<sub>2.9</sub>Sb<sub>0.9</sub>W<sub>0.1</sub>S<sub>4</sub> can be observed. This work acts as a stepping-stone towards further engineering of ionic conductors using vacancy-injection via aliovalent substituents.</p>

scholarly journals X-ray crystallography reveals molecular recognition mechanism for sugar binding in a melibiose transporter MelB

2021 ◽  
Vol 4 (1) ◽  
Author(s):  
Lan Guan ◽  
Parameswaran Hariharan
Keyword(s):  
Molecular Recognition ◽  
Binding Pocket ◽  
Cation Binding ◽  
Recognition Mechanism ◽  
X Ray ◽  
X Ray Crystallography ◽  
Sugar Binding ◽  
Sugar Specificity ◽  
Major Facilitator ◽  
Mfs Transporters

AbstractMajor facilitator superfamily_2 transporters are widely found from bacteria to mammals. The melibiose transporter MelB, which catalyzes melibiose symport with either Na+, Li+, or H+, is a prototype of the Na+-coupled MFS transporters, but its sugar recognition mechanism has been a long-unsolved puzzle. Two high-resolution X-ray crystal structures of a Salmonella typhimurium MelB mutant with a bound ligand, either nitrophenyl-α-d-galactoside or dodecyl-β-d-melibioside, were refined to a resolution of 3.05 or 3.15 Å, respectively. In the substrate-binding site, the interaction of both galactosyl moieties on the two ligands with MelBSt are virturally same, so the sugar specificity determinant pocket can be recognized, and hence the molecular recognition mechanism for sugar binding in MelB has been deciphered. The conserved cation-binding pocket is also proposed, which directly connects to the sugar specificity pocket. These key structural findings have laid a solid foundation for our understanding of the cooperative binding and symport mechanisms in Na+-coupled MFS transporters, including eukaryotic transporters such as MFSD2A.

The Effect of Enzymatic Depolymerization of Arterial Mucopolysaccharides on Sodium Ion Content and Vessel Reactivity

1971 ◽  
Vol 40 (4) ◽  
pp. 293-303 ◽  
Author(s):  
G. S. Harris ◽  
W. A. Palmer
Keyword(s):  
Cation Binding ◽  
Sodium Ion ◽  
Sodium Ions ◽  
High Concentration ◽  
Ion Content ◽  
Binding Properties ◽  
Arterial Walls ◽  
Testicular Hyaluronidase ◽  
Enzymatic Depolymerization

1. The presence of mucopolysaccharides within arterial walls may be associated with the high concentration of sodium ions within this tissue. These polyanions are sensitive to enzymatic depolymerization which results in a loss of the cation binding properties of the molecule. 2. In this study testicular hyaluronidase perfused through isolated arterial segments resulted in a decrease in reactivity of the artery to 65% that of control arteries. Associated with this finding was a 33% decrease in the sodium ion content of the stimulated hyaluronidase-treated artery. When a variety of other sympathetically innervated tissues were treated with hyaluronidase there was no decrease in reactivity or sodium ion content.

Understanding the Structural Phase Transitions in Na 3 V 2 (PO 4 ) 3 Symmetrical Sodium‐Ion Batteries Using Synchrotron‐Based X‐Ray Techniques

Small Methods ◽  
2021 ◽  
pp. 2100888
Author(s):  
Ranjith Thangavel ◽  
Daseul Han ◽  
Brindha Moorthy ◽  
Bala Krishnan Ganesan ◽  
Megala Moorthy ◽  
...  
Keyword(s):  
Phase Transitions ◽  
Structural Phase ◽  
Sodium Ion ◽  
Sodium Ion Batteries ◽  
Structural Phase Transitions ◽  
X Ray

Characteristic evaluation of pencil-drawn carbon electrode by potassium and sodium ion selectivity measurement and energy-dispersive X-ray spectroscopy

2020 ◽  
Vol 59 (4) ◽  
pp. 047001
Author(s):  
Ryotaro Kawahara ◽  
Masao Kamahori ◽  
Naoya Murase ◽  
Tomotaka Goto ◽  
Takashi Minemoto ◽  
...  
Keyword(s):  
Ion Selectivity ◽  
Sodium Ion ◽  
Energy Dispersive ◽  
Carbon Electrode ◽  
X Ray

scholarly journals Hydrothermal Activation of Porous Nitrogen-Doped Carbon Materials for Electrochemical Capacitors and Sodium-Ion Batteries

Nanomaterials ◽  
2020 ◽  
Vol 10 (11) ◽  
pp. 2163 ◽  
Author(s):  
Yuliya V. Fedoseeva ◽  
Egor V. Lobiak ◽  
Elena V. Shlyakhova ◽  
Konstantin A. Kovalenko ◽  
Viktoriia R. Kuznetsova ◽  
...  
Keyword(s):  
Photoelectron Spectroscopy ◽  
Carbon Nanomaterials ◽  
Carbon Materials ◽  
Sodium Ion ◽  
Carbon Surface ◽  
Energy Storage And Conversion ◽  
Sodium Ion Batteries ◽  
X Ray ◽  
Nitrogen Doped ◽  
Nitrogen Doped Carbon

Highly porous nitrogen-doped carbon nanomaterials have distinct advantages in energy storage and conversion technologies. In the present work, hydrothermal treatments in water or ammonia solution were used for modification of mesoporous nitrogen-doped graphitic carbon, synthesized by deposition of acetonitrile vapors on the pyrolysis products of calcium tartrate. Morphology, composition, and textural characteristics of the original and activated materials were studied by transmission electron microscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, infrared spectroscopy, and nitrogen gas adsorption method. Both treatments resulted in a slight increase in specific surface area and volume of micropores and small mesopores due to the etching of carbon surface. Compared to the solely aqueous medium, activation with ammonia led to stronger destruction of the graphitic shells, the formation of larger micropores (1.4 nm vs. 0.6 nm), a higher concentration of carbonyl groups, and the addition of nitrogen-containing groups. The tests of nitrogen-doped carbon materials as electrodes in 1M H2SO4 electrolyte and sodium-ion batteries showed improvement of electrochemical performance after hydrothermal treatments especially when ammonia was used. The activation method developed in this work is hopeful to open up a new route of designing porous nitrogen-doped carbon materials for electrochemical applications.

Studies of molecular structure parameters of 20-piperidin-2-yl-5α-pregnan-3β,20-diol and its N-methyl derivative: two inhibitors of Δ24(25) sterol methyl transferase and Δ24(24′) sterol methyl reductase of Trypanosoma cruzi

2001 ◽  
Vol 57 (5) ◽  
pp. 714-721 ◽  
Author(s):  
Reinaldo Atencio ◽  
Gonzalo Visbal ◽  
Sara Pekerar ◽  
Jham Papale ◽  
Julio A. Urbina
Keyword(s):  
Trypanosoma Cruzi ◽  
Structural Parameters ◽  
Spectroscopic Characterization ◽  
Structural Parameter ◽  
Torsion Angles ◽  
Methyl Transferase ◽  
X Ray ◽  
The Family ◽  
Fused Ring ◽  
The Mean

Molecular structural parameters of two potential drugs against Trypanosoma cruzi epimastigotes, 20-piperidin-2-yl-5α-pregnan-3β,20-diol (1) and 20-N-methylpiperidin-2-yl-5α-pregnan-3β, 20-diol (2) were studied using a combination of a stereoselective synthetic route, spectroscopic characterization and single-crystal X-ray analysis. Both compounds were synthesized with an R configuration at C20. This chirality is a consequence of the stereoselectivity observed during the formation of the intermediate 20-pyridin-2-yl-5α-pregnan-3β,20R-diol (4). NMR data indicated that the six-membered aza ring of (2) is conformationally more restrained, in CDCl3 solution, than (1). X-ray studies showed that maximum deviations among structural molecular parameters of (1) and (2) correspond to torsion angles along the C20—C22 bonds, leading to a different relative orientation of the N atom; a critical structural parameter for the binding properties of aza-sterols to Δ24(25) sterol methyl transferase. Cremer–Pople parameters of the five-membered rings of (1) and (2) lie in the observed range for a family of tetracyclic fused ring systems retrieved from the CSD. The φ2 parameter of (1) lies just on the mean of the family, while φ2 of (2) deviates significantly towards the lower limit.

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