scholarly journals Synthesis and polarographic studies of beta-substituted phenylcystine derivatives

1970 ◽  
Vol 48 (13) ◽  
pp. 2000-2005 ◽  
Author(s):  
R. J. Thibert ◽  
C. Patel
Keyword(s):  
Sodium Acetate ◽  
Supporting Electrolyte ◽  
Anhydrous Methanol ◽  
Ethyl Esters ◽  
Polarographic Method ◽  
Substituent Constant ◽  
Wave Potential ◽  
Polar Substituent ◽  
Half Wave ◽  
The Relationship

The synthesis of N-benzoyl-threo-β-p-substituted phenylcystine ethyl esters via azlactone intermediates is reported. A polarographic method for their determination using 0.1 M sodium acetate in anhydrous methanol as the supporting electrolyte was investigated. The relationship between the half-wave potential and the Taft polar substituent constant, σ*, was studied.

Polarography of some coordination compounds of platinum. I. Hexammineplatinum (IV) and Tris(ethylenediamine)platinum(IV) ions

1955 ◽  
Vol 8 (2) ◽  
pp. 158 ◽  
Author(s):  
JR Hall ◽  
RA Plowman
Keyword(s):  
Potassium Chloride ◽  
Supporting Electrolyte ◽  
Platinum Metal ◽  
Potassium Nitrate ◽  
Diffusion Current ◽  
Polarographic Reduction ◽  
Wave Potential ◽  
Half Wave Potential ◽  
Half Wave ◽  
Continuous Discharge

The polarographic reduction of tris(ethylenediamine)platinum(IV) and the hexammineplatinum(IV) ions has been studied in potassium chloride, potassium nitrate, and potassium nitrate plus ammonia solutions. Both ions were reduced irreversibly producing similarly shaped waves, showing well-defined diffusion current regions corresponding to two-electron reductions of the complexes. A linear relationship existed between diffusion current and concentration within the range examined. In aqueous potassium chloride and potassium nitrate media, the waves contained slight inflexions at positions corresponding to one-electron additions. The phenomenon suggested the transient presence of platinum(III) ions, and indicated that the half-wave potential of the reduction of the complexes to the trivalent state was very close to the half-wave potential of the reduction from platinum(IV) to platinum(II). The values were so close together as to indicate the improbability of isolating the trivalent complexes. Gelatin enhanced the inflexion in the wave but shifted the wave in a more negative direction. An increased concentration of supporting electrolyte also shifted the wave to a more negative position. In all cases a continuous discharge began at about -1.3 V (v. S.C.E.). This discharge was so far removed from that of the potassium ions of the supporting electrolyte that it was attributed to the discharge of hydrogen. Since the initial reduction of the platinum complexes corresponded to a two-electron change, it can be represented by reduction to a tetrammine ion. It is postulated that at higher applied potentials (namely, -1.3 V v. S.C.E.) the reduction proceeded further, producing platinum metal. This platinum metal would be in an active state, insoluble in mercury, and being on the surface, would lower the overvoltage of hydrogen leading to its discharge at a more positive potential than on a pure mercury surface. This view was supported by the fact that gas bubbles were observed at the dropping electrode when a voltage greater than -1.3 V was applied to the electrode for some time. When ammonia was added to the supporting electrolyte, a wave, without an inflexion, and corresponding to an irreversible two-electron reduction, was obtained at more negative potentials. The bivalent tetrammineplatinum(II) and bis(ethylenediamine)platinum(II) ions also gave polarograms showing the continuous discharge of hydrogen.

scholarly journals Synthesis of DHA/EPA Ethyl Esters via Lipase-Catalyzed Acidolysis Using Novozym® 435: A Kinetic Study

Catalysts ◽  
2020 ◽  
Vol 10 (5) ◽  
pp. 565 ◽  
Author(s):  
Chia-Hung Kuo ◽  
Chun-Yung Huang ◽  
Chien-Liang Lee ◽  
Wen-Cheng Kuo ◽  
Shu-Ling Hsieh ◽  
...  
Keyword(s):  
Ethyl Ester ◽  
Ethyl Esters ◽  
Raw Material ◽  
Maximum Reaction Rate ◽  
Mechanism Model ◽  
Maximum Reaction ◽  
Substrate Ratio ◽  
Free Fatty Acid Form ◽  
The Relationship ◽  
Predictive Relationship

DHA/EPA ethyl ester is mainly used in the treatment of arteriosclerosis and hyperlipidemia. In this study, DHA+EPA ethyl ester was synthesized via lipase-catalyzed acidolysis of ethyl acetate (EA) with DHA+EPA concentrate in n-hexane using Novozym® 435. The DHA+EPA concentrate (in free fatty acid form), contained 54.4% DHA and 16.8% EPA, was used as raw material. A central composite design combined with response surface methodology (RSM) was used to evaluate the relationship between substrate concentrations and initial rate of DHA+EPA ethyl ester production. The results indicated that the reaction followed the ordered mechanism and as such, the ordered mechanism model was used to estimate the maximum reaction rate (Vmax) and kinetic constants. The ordered mechanism model was also combined with the batch reaction equation to simulate and predict the conversion of DHA+EPA ethyl ester in lipase-catalyzed acidolysis. The integral equation showed a good predictive relationship between the simulated and experimental results. 88–94% conversion yields were obtained from 100–400 mM DHA+EPA concentrate at a constant enzyme activity of 200 U, substrate ratio of 1:1 (DHA+EPA: EA), and reaction time of 300 min.

Polarography of nickel in concentrated chloride media

1966 ◽  
Vol 19 (8) ◽  
pp. 1343 ◽  
Author(s):  
TM Florence
Keyword(s):  
Ionic Strength ◽  
Graphite Electrode ◽  
Supporting Electrolyte ◽  
Anhydrous Methanol ◽  
Pyrolytic Graphite ◽  
Hydration Number ◽  
Mercury Electrode ◽  
Specific Adsorption ◽  
Dropping Mercury Electrode ◽  
Pyrolytic Graphite Electrode

In concentrated chloride media, nickel is reduced at far more positive potentials than in dilute solutions. The positive shift in half-wave potential increases as the ionic strength is raised, and is also greater when the cation of the supporting electrolyte has a high hydration number. Evidence is presented to show that the reduction in overpotential is due to the formation of a nickel chloride complex, [Ni(H2O)5Cl]+, which has a stoicheiometric stability constant of 0.094 � 0.009 at an ionic strength of 10.0. Spectrophotometric results show that this nickel species is not formed in low ionic strength solutions. In anhydrous methanol saturated with lithium chloride, nickel is present as the tetrachloro complex, [NiCl,]2-, which has similar polarographic behaviour to the monochloro complex. Current-potential curves recorded at a rotated pyrolytic graphite electrode enabled the behaviour of nickel to be studied in the absence of specific adsorption of the chloride ion. Nickel is reduced at more positive potentials at a dropping mercury electrode than at the pyrolytic graphite electrode, and the results indicate that this difference is due to specific adsorption of chloride on the mercury electrode.

Half-wave potential-ph diagram for the parabenzoquinone system in n,n-dimethylformamide

1969 ◽  
Vol 2 (3) ◽  
pp. 123-132 ◽  
Author(s):  
J. Badoz-lambling ◽  
G. Demange-guerin
Keyword(s):  
Wave Potential ◽  
Half Wave Potential ◽  
Half Wave

scholarly journals Modified Carbon Nanotubes: Surface Properties and Activity in Oxygen Reduction Reaction

Catalysts ◽  
2021 ◽  
Vol 11 (11) ◽  
pp. 1354
Author(s):  
Vera Bogdanovskaya ◽  
Inna Vernigor ◽  
Marina Radina ◽  
Vladimir Sobolev ◽  
Vladimir Andreev ◽  
...  
Keyword(s):  
Carbon Nanotubes ◽  
Zeta Potential ◽  
Oxygen Reduction Reaction ◽  
Oxygen Reduction ◽  
Surface Area ◽  
Surface Properties ◽  
Reduction Reaction ◽  
Wave Potential ◽  
Half Wave Potential ◽  
Half Wave

In order to develop highly efficient and stable catalysts for oxygen reduction reaction (ORR) that do not contain precious metals, it is necessary to modify carbon nanotubes (CNT) and define the effect of the modification on their activity in the ORR. In this work, the modification of CNTs included functionalization by treatment in NaOH or HNO3 (soft and hard conditions, respectively) and subsequent doping with nitrogen (melamine was used as a precursor). The main parameters that determine the efficiency of modified CNT in ORR are composition and surface area (XPS, BET), hydrophilic–hydrophobic surface properties (method of standard contact porosimetry (MSP)) and zeta potential (dynamic light scattering method). The activity of CNT in ORR was assessed following half-wave potential, current density within kinetic potential range and the electrochemically active surface area (SEAS). The obtained results show that the modification of CNT with oxygen-containing groups leads to an increase in hydrophilicity and, consequently, SEAS, as well as the total (overall) current. Subsequent doping with nitrogen ensures further increase in SEAS, higher zeta potential and specific activity in ORR, reflected in the shift of the half-wave potential by 150 mV for CNTNaOH-N and 110 mV for CNTHNO3-N relative to CNTNaOH and CNTHNO3, respectively. Moreover, the introduction of N into the structure of CNTHNO3 increases their corrosion stability.

Substituent effects on polarographic reduction of some photographic color intermediates

1976 ◽  
Vol 54 (8) ◽  
pp. 1205-1210 ◽  
Author(s):  
Ahmad S. Shawali ◽  
Bahgat E. El-Anadouli
Keyword(s):  
Dissociation Constants ◽  
Substituent Effects ◽  
Protonated Form ◽  
Acid Dissociation ◽  
Polarographic Reduction ◽  
Substituent Constant ◽  
Acid Dissociation Constants ◽  
Controlled Potential Electrolysis ◽  
Half Wave ◽  
Controlled Potential

Polarographic reduction of two series of benzoylacetanilides has been investigated in 40% (by volume) ethanolic Britton–Robinson buffers. One series (A) contains substituents on the anilide moiety, and the second (B) has substituents on both the anilide and benzoyl moieties. Polarographic controlled-potential electrolysis data indicate that the electroactive species in both series is the protonated form (ArCOCH2CONHAr′)H+. The reduction half-wave potentials of anilides of series A were found to be independent of the nature of the substituent, whereas those of series B show a good linear relationship when plotted vs. the σ substituent constant of the substituent on the benzoyl moiety (ρ = 0.284, r = 0.995). Values of the acid dissociation constants of the keto (K1) and enol (K2) tautomers of the anilides of series A were calculated; unlike their E1/2 values, the pK1 data show a linear correlation with the Hammett substituent constant, σ. The pK2 values show, however, little variation with σ.

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