Aromatic N-oxides. VI. Anhydro base intermediate and the rate-controlling step in the reaction of 4-alkylpyridine N-oxide with acid anhydrides

1970 ◽  
Vol 35 (8) ◽  
pp. 2792-2796 ◽  
Author(s):  
Vincent J. Traynelis ◽  
Sister Ann. Immaculata Gallagher
Keyword(s):  
Anhydro Base ◽  
Acid Anhydrides ◽  
Rate Controlling Step

Novel epoxy/anhydride alternatives for biological electron microscopy: Physical and performance characteristis of embed 812 and LX 112 in combination with NSA/NMA/DMAE

1989 ◽  
Vol 47 ◽  
pp. 1000-1001
Author(s):  
Joe A. Mascorro ◽  
Gerald S. Kirby
Keyword(s):  
Electron Microscopy ◽  
Flow Rate ◽  
Succinic Anhydride ◽  
Volume Flow Rate ◽  
Mass Density ◽  
Uranyl Acetate ◽  
Volume Flow ◽  
Base Resin ◽  
And Performance ◽  
Acid Anhydrides

Embedding media based upon an epoxy resin of choice and the acid anhydrides dodecenyl succinic anhydride (DDSA), nadic methyl anhydride (NMA), and catalyzed by the tertiary amine 2,4,6-Tri(dimethylaminomethyl) phenol (DMP-30) are widely used in biological electron microscopy. These media possess a viscosity character that can impair tissue infiltration, particularly if original Epon 812 is utilized as the base resin. Other resins that are considerably less viscous than Epon 812 now are available as replacements. Likewise, nonenyl succinic anhydride (NSA) and dimethylaminoethanol (DMAE) are more fluid than their counterparts DDSA and DMP- 30 commonly used in earlier formulations. This work utilizes novel epoxy and anhydride combinations in order to produce embedding media with desirable flow rate and viscosity parameters that, in turn, would allow the medium to optimally infiltrate tissues. Specifically, embeding media based on EmBed 812 or LX 112 with NSA (in place of DDSA) and DMAE (replacing DMP-30), with NMA remaining constant, are formulated and offered as alternatives for routine biological work.Individual epoxy resins (Table I) or complete embedding media (Tables II-III) were tested for flow rate and viscosity. The novel media were further examined for their ability to infilftrate tissues, polymerize, sectioning and staining character, as well as strength and stability to the electron beam and column vacuum. For physical comparisons, a volume (9 ml) of either resin or media was aspirated into a capillary viscocimeter oriented vertically. The material was then allowed to flow out freely under the influence of gravity and the flow time necessary for the volume to exit was recored (Col B,C; Tables). In addition, the volume flow rate (ml flowing/second; Col D, Tables) was measured. Viscosity (n) could then be determined by using the Hagen-Poiseville relation for laminar flow, n = c.p/Q, where c = a geometric constant from an instrument calibration with water, p = mass density, and Q = volume flow rate. Mass weight and density of the materials were determined as well (Col F,G; Tables). Infiltration schedules utilized were short (1/2 hr 1:1, 3 hrs full resin), intermediate (1/2 hr 1:1, 6 hrs full resin) , or long (1/2 hr 1:1, 6 hrs full resin) in total time. Polymerization schedules ranging from 15 hrs (overnight) through 24, 36, or 48 hrs were tested. Sections demonstrating gold interference colors were collected on unsupported 200- 300 mesh grids and stained sequentially with uranyl acetate and lead citrate.

Oxidation of hydrogen peroxide at the dropping mercury electrode

1984 ◽  
Vol 49 (10) ◽  
pp. 2320-2331 ◽  
Author(s):  
Miroslav Březina ◽  
Martin Wedell
Keyword(s):  
Hydrogen Peroxide ◽  
Superoxide Anion ◽  
Ph Value ◽  
Mercury Electrode ◽  
Electrode Process ◽  
Electrochemical Processes ◽  
Dropping Mercury Electrode ◽  
Oxidation Of Hydrogen ◽  
Decreasing Ph ◽  
Rate Controlling Step

Reduction of oxygen and oxidation of hydrogen peroxide at the dropping mercury electrode are electrochemical processes strongly influenced both by the pH value and the anions in solution. With decreasing pH, both processes become irreversible, especially in the presence of anions with a negative φ2 potential of the diffusion part of the double layer. In the case of irreversible oxygen reduction, the concept that the rate-controlling step of the electrode process is the acceptance of the first electron with the formation of the superoxide anion, O2-, was substantiated. Oxidation of hydrogen peroxide becomes irreversible at a lower pH value than the reduction of oxygen. The slowest, i.e. rate-controlling step of the electrode process in borate buffers at pH 9-10 is the transfer of the second electron, i.e. oxidation of superoxide to oxygen.

Topography of the Free Energy Landscape on the Claisen-Schmidt Condensation: Solvent and Temperature Effect in the Rate-Controlling Step

2021 ◽  
Author(s):  
Nayara Dantas Coutinho ◽  
Hugo Gontijo Machado ◽  
Valter Henrique Carvalho-Silva ◽  
Wender A. Silva
Keyword(s):  
Free Energy ◽  
Temperature Effect ◽  
Strong Influence ◽  
Aldol Condensation ◽  
Energy Landscape ◽  
Bond Formation ◽  
Free Energy Landscape ◽  
Rate Controlling Step ◽  
Formation Step

Recent studies have assigned hydroxide elimination and C=C bond formation step in base-promoted aldol condensation the role of having a strong influence in the overall rate reaction, in contrast to...

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