Redox-Switched Bonding of Protons to Ferrocenophanes, Ferrocene Cryptands, and Simple Ferrocene Amines. Correlation of X-ray Structural Data and Cyclic Voltammetry Derived Redox Potentials

1994 ◽  
Vol 33 (18) ◽  
pp. 4098-4104 ◽  
Author(s):  
Herbert Plenio ◽  
Jianjun Yang ◽  
Ralph Diodone ◽  
Juergen Heinze
Keyword(s):  
Cyclic Voltammetry ◽  
Structural Data ◽  
Redox Potentials ◽  
X Ray

Syntheses, theoretical studies, and crystal structures of [Ni(II)SSRRL](PF6)2 and [Ni(II)SRSRL](Cl)(PF6) that contains anagostic interactions

2020 ◽  
pp. 1-10
Author(s):  
Peyton C. Bainbridge ◽  
Rudy L. Luck ◽  
Nick K. Newberry
Keyword(s):  
Theoretical Calculations ◽  
Structural Data ◽  
Theoretical Studies ◽  
Redox Potentials ◽  
X Ray ◽  
H Nmr ◽  
Irreversible Oxidation ◽  
Square Planar ◽  
Reduced Products ◽  
Reversible Reduction

The syntheses of two square planar nickel complexes containing the condensation and subsequently reduced products obtained by reacting [Ni(en)3](BF4)2 and acetone are reported. The complexes 5,5,7,12,12,14-hexamethyl-1(S),4(S),8(R),11(R)-tetraazacyclotetradecane-nickel(II)[PF6]2 and 5,5,7,12,12,14-hexamethyl-1(S),4(R),8(S),11(R)-tetraazacyclotetradecane-nickel(II)[Cl][PF6] labelled as [Ni(II)SSRRL](PF6)2 and [Ni(II)SRSRL](Cl)(PF6), respectively, were found to have slightly different solubilities that allowed for their purification. The complexes were characterized by FTIR, 1H NMR, and UV–vis spectra. Redox potentials, determined by cyclic voltammetry, established that [Ni(II)SSRRL](PF6)2 exhibits a reversible oxidation (E1/2(ox) = 0.85 V) and reduction (E1/2(red) = −1.59 V), whereas [Ni(II)SRSRL](Cl)(PF6) displays an irreversible oxidation (Epa(ox) = 1.37 V) and reversible reduction (E1/2(red) = −1.62 V) relative to the ferrocene couple at 0.0 V. Single crystal X-ray determinations established that one of the compounds, [Ni(II)SSRRL](PF6)2, contained two [Formula: see text] anions, whereas the other compound, [Ni(II)SRSRL](Cl)(PF6), contained one Cl− and one [Formula: see text] anion. In the solid state, compound [Ni(II)SSRRL](PF6)2 was held together by H-bonds between H atoms on the Ni containing dication and F atoms in the [Formula: see text] anion. Compound [Ni(II)SRSRL](Cl)(PF6) crystallized in the form of dimers held together by interactions between H atoms attached to N atoms on adjacent cations binding to two Cl− anions in the middle with these dimers held together by further H-bonding to interstitial [Formula: see text] anions. Complex [Ni(II)SRSRL](Cl)(PF6) was found to contain anagostic interactions on the bases of NMR (downfield shift in C–H protons) and structural data (2.3 < d(H-Ni) < 2.9 Å), as well as theoretical calculations.

Tubulin structure at intermediate resolution

1995 ◽  
Vol 53 ◽  
pp. 852-853
Author(s):  
K. H. Downing ◽  
S. G. Wolf ◽  
E. Nogales
Keyword(s):  
High Resolution ◽  
Structural Data ◽  
Therapeutic Drug ◽  
Zinc Ions ◽  
Two Dimensional ◽  
X Ray Diffraction ◽  
X Ray ◽  
Negative Stain ◽  
Functional Mechanisms ◽  
Tubulin Structure

Microtubules are involved in a host of critical cell activities, many of which involve transport of organelles through the cell. Different sets of microtubules appear to form during the cell cycle for different functions. Knowledge of the structure of tubulin will be necessary in order to understand the various functional mechanisms of microtubule assemble, disassembly, and interaction with other molecules, but tubulin has so far resisted crystallization for x-ray diffraction studies. Fortuitously, in the presence of zinc ions, tubulin also forms two-dimensional, crystalline sheets that are ideally suited for study by electron microscopy. We have refined procedures for forming the sheets and preparing them for EM, and have been able to obtain high-resolution structural data that sheds light on the formation and stabilization of microtubules, and even the interaction with a therapeutic drug.Tubulin sheets had been extensively studied in negative stain, demonstrating that the same protofilament structure was formed in the sheets and microtubules. For high resolution studies, we have found that the sheets embedded in either glucose or tannin diffract to around 3 Å.

Hydrophobic Ferrocene Derivatives as Potential Standards in Electrochemistry

1997 ◽  
Vol 62 (2) ◽  
pp. 185-198 ◽  
Author(s):  
Jaroslav Podlaha ◽  
Petr Štěpnička ◽  
Róbert Gyepes ◽  
Vladimír Mareček ◽  
Alexander Lhotský ◽  
...  
Keyword(s):  
Surface Tension ◽  
Cyclic Voltammetry ◽  
Redox Potential ◽  
Diffusion Coefficients ◽  
Carbon Electrodes ◽  
X Ray Diffraction ◽  
Ferrocene Derivatives ◽  
X Ray ◽  
Special Cases ◽  
As Solubility

Ferrocene (FcH) derivatives monosubstituted by palmitoyl (1), hexadecyl (2), 1-adamantoyl (3) or 1-adamantylmethyl (4) groups were sythesized and characterized by NMR, mass and 57Fe Mossbauer spectroscopy. The structure of 1-adamantoylferrocene was determined by single-crystal X-ray diffraction. Cyclic voltammetry on gold and glass-like carbon electrodes demonstrated that the compounds can serve as electrochemical standards for special cases since their ferrocene/ferricinium redox potential remains stable and reversible, while the properties such as solubility, diffusion coefficients and surface tension are strongly solvent-dependent.

scholarly journals Surfactant-free synthesis of carbon-supported silver (Ag/C) nanobars as an efficient electrocatalyst for alcohol tolerance and oxidation of sodium borohydride in alkaline medium

2021 ◽  
Vol 3 (6) ◽  
Author(s):  
Santanu Dey ◽  
Pradipta Chakraborty ◽  
Dhiraj Kumar Rana ◽  
Subhamay Pramanik ◽  
Soumen Basu
Keyword(s):  
Cyclic Voltammetry ◽  
Ethylene Glycol ◽  
Alkaline Medium ◽  
Sodium Borohydride ◽  
Metallic Silver ◽  
Alcohol Tolerance ◽  
Current Ratio ◽  
X Ray ◽  
Scan Rate ◽  
Borohydride Oxidation

AbstractWe have synthesized carbon-supported silver (Ag/C) nanobars by a simple surfactant-free hydrothermal method using glucose as the reducing reagent as well as the source of carbon in Ag/C nanobars. Physicochemical characterization of the materials was performed by X-ray Diffraction (XRD), field emission scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The XRD pattern confirmed the presence of a pure metallic silver phase. No carbon phase was detected, which indicates that the carbon exists mainly in the amorphous form. The electrocatalytic activity of Ag/C in different electrolyte solutions such as 0.5 M NaOH, 0.5 M NaOH + 1 M ethanol (EtOH), 0.5 M NaOH + 1 M ethylene glycol (EG), and 0.5 M NaOH + 0.01 M NaBH4 (sodium borohydride) was studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and chronoamperometry (CA) study. Alcohol tolerance of the catalysts was also established in the presence of ethanol and ethylene glycol. The forward-to-backward current ratio from cyclic voltammetry (CV) study of Ag/C-20 (20 h) in 0.5 M NaOH + 1 M ethanol solution at 100 mV s−1 scan rate is 4.13 times higher compared to that of Ag/C-5 (5 h). Hence, Ag/C-20 is a better candidate for the tolerance of ethanol. In the presence of ethylene glycol (1 M) in 0.5 M NaOH solution, it is obtained that the forward-to-backward current ratio at the same scan rate for Ag/C-20 is lower than that in the presence of ethanol. The durability of the catalyst was studied by chronoamperometry measurement. We studied the electrochemical kinetics of Ag/C catalysts for borohydride oxidation in an alkaline medium. The basic electrochemical results for borohydride oxidation show that Ag/C has very well strength and activity for direct borohydride oxidation in an alkaline medium. The reaction of borohydride oxidation with the contemporaneous BH4−. hydrolysis was noticed at the oxidized silver surface. Among all the synthesized Ag/C catalysts, Ag/C-20 exhibited the best electrocatalytic performance for borohydride oxidation in an alkaline medium. The activation energy and the number of exchange electrons at Ag/C-20 electrode surface for borohydride electro-oxidation were estimated as 57.2 kJ mol−1 and 2.27, respectively.

Compressibility of β-As4S4: an in situ high-pressure single-crystal X-ray study

2012 ◽  
Vol 76 (4) ◽  
pp. 963-973 ◽  
Author(s):  
G. O. Lepore ◽  
T. Boffa Ballaran ◽  
F. Nestola ◽  
L. Bindi ◽  
D. Pasqual ◽  
...  
Keyword(s):  
Pressure Range ◽  
Substantial Reduction ◽  
Structural Data ◽  
Unit Cell ◽  
Van Der Waals Interactions ◽  
X Ray Diffraction ◽  
Unit Cell Parameters ◽  
X Ray ◽  
Cell Parameters ◽  
Intermolecular Distances

AbstractAmbient temperature X-ray diffraction data were collected at different pressures from two crystals of β-As4S4, which were made by heating realgar under vacuum at 295ºC for 24 h. These data were used to calculate the unit-cell parameters at pressures up to 6.86 GPa. Above 2.86 GPa, it was only possible to make an approximate measurement of the unit-cell parameters. As expected for a crystal structure that contains molecular units held together by weak van der Waals interactions, β-As4S4 has an exceptionally high compressibility. The compressibility data were fitted to a third-order Birch–Murnaghan equation of state with a resulting volume V0 = 808.2(2) Å3, bulk modulus K0 = 10.9(2) GPa and K' = 8.9(3). These values are extremely close to those reported for the low-temperature polymorph of As4S4, realgar, which contains the same As4S4 cage-molecule. Structural analysis showed that the unit-cell contraction is due mainly to the reduction in intermolecular distances, which causes a substantial reduction in the unit-cell volume (∼21% at 6.86 GPa). The cage-like As4S4 molecules are only slightly affected. No phase transitions occur in the pressure range investigated.Micro-Raman spectra, collected across the entire pressure range, show that the peaks associated with As–As stretching have the greatest pressure dependence; the S–As–S bending frequency and the As–S stretching have a much weaker dependence or no variation at all as the pressure increases; this is in excellent agreement with the structural data.

Steric Parameters of Conformationally Flexible Ligands from X-ray Structural Data. 1. P(OR)3Ligands in Equivalent Ligand Environments

2000 ◽  
Vol 19 (25) ◽  
pp. 5273-5280 ◽  
Author(s):  
Jeremy M. Smith ◽  
Neil J. Coville ◽  
Leanne M. Cook ◽  
Jan C. A. Boeyens
Keyword(s):  
Structural Data ◽  
X Ray ◽  
Equivalent Ligand ◽  
Flexible Ligands

scholarly journals Purification, crystallization and preliminary X-ray diffraction analysis of a hydroxycinnamoyl-CoA shikimate/quinate hydroxycinnamoyltransferase (HCT) fromCoffea canephorainvolved in chlorogenic acid biosynthesis

2012 ◽  
Vol 68 (7) ◽  
pp. 824-828 ◽  
Author(s):  
Laura A. Lallemand ◽  
James G. McCarthy ◽  
Sean McSweeney ◽  
Andrew A. McCarthy
Keyword(s):  
Structural Data ◽  
Coffea Canephora ◽  
Molecular Replacement ◽  
X Ray Diffraction ◽  
X Ray ◽  
Cell Parameters ◽  
Key Enzyme ◽  
Substrate Specifities ◽  
Drop Technique ◽  
Better Than

Chlorogenic acids (CGAs) are a group of soluble phenolic compounds that are produced by a variety of plants, includingCoffea canephora(robusta coffee). The last step in CGA biosynthesis is generally catalysed by a specific hydroxycinnamoyl-CoA quinate hydroxycinnamoyltransferase (HQT), but it can also be catalysed by the more widely distributed hydroxycinnamoyl-CoA shikimate/quinate hydroxycinnamoyltransferase (HCT). Here, the cloning and overexpression of HCT fromC. canephorainEscherichia colias well as its purification and crystallization are presented. Crystals were obtained by the sitting-drop technique at 293 K and X-ray diffraction data were collected on the microfocus beamline ID23-2 at the ESRF. The HCT crystals diffracted to better than 3.0 Å resolution, belonged to space groupP42212 with unit-cell parametersa=b= 116.1,c= 158.9 Å and contained two molecules in the asymmetric unit. The structure was solved by molecular replacement and is currently under refinement. Such structural data are needed to decipher the molecular basis of the substrate specifities of this key enzyme, which belongs to the large plant acyl-CoA-dependent BAHD acyltransferase superfamily.

The influence of the host–guest interaction on the oxidation of natural flavonoid dyes

2011 ◽  
Vol 76 (12) ◽  
pp. 1651-1667 ◽  
Author(s):  
Šárka Ramešová ◽  
Romana Sokolová ◽  
Ilaria Degano ◽  
Magdaléna Hromadová ◽  
Miroslav Gál ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Inclusion Complex ◽  
Fluorescence Intensity ◽  
Oxidation Product ◽  
Aqueous Media ◽  
Electrochemical Methods ◽  
Redox Potentials ◽  
Decomposition Products ◽  
Degradation Processes ◽  
Bioorganic Compounds

The influence of the molecular cavity protection on degradation processes of bioorganic compounds quercetin and luteolin used as the original dyes in old tapestries was studied. The degradation processes were studied by electrochemical methods in aqueous media. The products of the exhaustive electrolysis were separated and identified by GC-MS analysis. Cyclic voltammetry characteristics indicate that the inclusion complex is formed. The inclusion affects the redox potentials of both oxidation waves related to the different dissociation forms of the flavonoid molecule. It was shown that decomposition products formed by the oxidation of quercetin are stabilized in the cavity of β-cyclodextrin, including the main oxidation product 2(3′,4′-dihydroxybenzoyl)-2,4,6-trihydroxybenzofuran-3(2H)-one. The formation of the 1:1 inclusion complex of luteolin with β-cyclodextrin is supported by the enhancement of fluorescence intensity. In the case of quercetin, a decrease of fluorescence intensity occurs when 1:1 inclusion complex with β-cyclodextrin is formed.

Electrochemical aromatization of dihydroazines. Effect of chalcogenophosphoryl (CGP) substituents on anodic oxidation of 9-CGP-9,10-dihydroacridines

Synthesis ◽  
2021 ◽  
Author(s):  
Alexander Schepochkin ◽  
Oleg N. Chupakhin ◽  
Nadezhda Demina ◽  
Maxim Averkov ◽  
Tatyana Shimanovskaya ◽  
...  
Keyword(s):  
Cyclic Voltammetry ◽  
Structural Analysis ◽  
Quantum Chemical Calculations ◽  
Anodic Oxidation ◽  
Quantum Chemical ◽  
X Ray

The effect of chalcogenophosphoryl fragments on the anodic oxidation of 9-chalcogenophosphoryl-9,10-dihydroacridines was studied in detail. The data of X-ray structural analysis, quantum chemical calculations and cyclic voltammetry obtained for these compounds provide an explanation of the observed features. The direct electrochemical phosphorylation of acridine was first carried out successfully.

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