Temperature and pressure dependences of thermal cis-to-trans isomerization of azobenzenes which evidence an inversion mechanism

1981 ◽  
Vol 103 (17) ◽  
pp. 5161-5165 ◽  
Author(s):  
Tsutomu Asano ◽  
Toshio Okada ◽  
Seiji Shinkai ◽  
Kazuyoshi Shigematsu ◽  
Yumiko Kusano ◽  
...  
Keyword(s):  
Trans Isomerization ◽  
Temperature And Pressure ◽  
Inversion Mechanism

Die Lösungsmittelabhängigkeit der thermischen cis-trans-Isomerisierung von N-Benzylidenanilinen mit Donator/Akzeptor-Substituenten.

1976 ◽  
Vol 31 (7) ◽  
pp. 953-959 ◽  
Author(s):  
U. Berns ◽  
G. Heinrich ◽  
H. Gusten
Keyword(s):  
Ground State ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Solvent Polarity ◽  
Linear Functions ◽  
Aryl Group ◽  
Trans Isomerization ◽  
Solvatochromic Shifts ◽  
Z Value ◽  
Inversion Mechanism

Thermal cis →-trans isomerization of eight N-benzylideneanilines with donor and/or acceptor substituents in the para, para'-positions was studied in different solvents by observing the rapid relaxation to the thermodynamic stable trans isomer following flash photolysis. With the push-pull effect of the substituents in the direction of the N-aryl group the rate constant at 25°C is by three powers of 10 faster compared to the N–benzylideneaniline with opposite arrangement of substituents. The rate constants are independent of the nature of the substituents in the para-position of the benzylidene group. The rate constants of N-(4-nitrobenzylidene)-p-anisidine are linear functions of the solvent polarity scale based on solvatochromic shifts (Kosowers Z-value or Dimroths ET-value). With increasing push-pull effect of the substituents in the direction of the N-aryl group the rate constants do no longer depend on the polarity of the solvent. The observed solvent effects on the rates and the activation energies for thermal cis→ trans isomerization suggest that the transition state of the reaction is less polar than the ground state of the sterically hindered cis-N-benzylideneaniline, thus favouring an inversion mechanism to become operative with respect to the N-benzylideneanilines.

Heat-Etching with a Bullivant Type II Simple Freeze-Cleave Device

1970 ◽  
Vol 28 ◽  
pp. 106-107 ◽  
Author(s):  
Ronald S. Weinstein ◽  
N. Scott McNutt
Keyword(s):  
New Zealand ◽  
General Hospital ◽  
Massachusetts General Hospital ◽  
Type I ◽  
Type Ii ◽  
Collaborative Effort ◽  
Temperature And Pressure ◽  
The University

The Type I simple cold block device was described by Bullivant and Ames in 1966 and represented the product of the first successful effort to simplify the equipment required to do sophisticated freeze-cleave techniques. Bullivant, Weinstein and Someda described the Type II device which is a modification of the Type I device and was developed as a collaborative effort at the Massachusetts General Hospital and the University of Auckland, New Zealand. The modifications reduced specimen contamination and provided controlled specimen warming for heat-etching of fracture faces. We have now tested the Mass. General Hospital version of the Type II device (called the “Type II-MGH device”) on a wide variety of biological specimens and have established temperature and pressure curves for routine heat-etching with the device.

ESEM - A multipurpose surface Electron Microscope

1986 ◽  
Vol 44 ◽  
pp. 632-633 ◽  
Author(s):  
G.D. Danilatos
Keyword(s):  
Electron Microscope ◽  
Room Temperature ◽  
Environmental Scanning ◽  
Gas Composition ◽  
Saturated Water Vapor ◽  
Surface Electron ◽  
Current State ◽  
Saturated Water ◽  
New Type ◽  
Temperature And Pressure

Over recent years a new type of electron microscope - the environmental scanning electron microscope (ESEM) - has been developed for the examination of specimen surfaces in the presence of gases. A detailed series of reports on the system has appeared elsewhere. A review summary of the current state and potential of the system is presented here.The gas composition, temperature and pressure can be varied in the specimen chamber of the ESEM. With air, the pressure can be up to one atmosphere (about 1000 mbar). Environments with fully saturated water vapor only at room temperature (20-30 mbar) can be easily maintained whilst liquid water or other solutions, together with uncoated specimens, can be imaged routinely during various applications.

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