Kinetic stability study

Table 1 Microcalorimetric kinetic stability studies of degradation of BPO in the presence of excipients in water at 313 K...

Notari RE. On the merits of a complete kinetic stability study. Drug Stabil 1996 1 1-2. 

In order to study the influence of substituents on the spectral behaviour and on the thermal and kinetic stability of silanones, two new organic silanones, dimethylsilicate [144a] and silabenzophenone [144b], have been examined. These were obtained in the vacuum pyrolysis of the corresponding epoxides [145a] and [145b] (Khabashesku et al., 1988c). 

Studies have shown that carbene reactivity toward a wide variety of substrates is dramatically affected by the nature and multiplicity of the electronic state. - Similarly, the structure, electronic state, thermochemical stability, and reaction kinetics of both singlet and triplet carbenes can be significantly affected by the R-substituents. If R provides steric hindrance, the carbene center can be shielded to slow down inter-molecular reactions (kinetic stabilization). Additionally, bulky and/or geometrically... 

Fig. 6. Schematic representation of the relation between thermodynamic and kinetic stability in the studied equilibria.

The nanoemulsion mean droplet sizes were much smaller than those obtained in other systems using polar oil mixtures (above 500 nm) [18]. The findings verify that the low-energy emulsification methods are valid not only for aliphatic [9,10,13, 75, 76, 79-81] and semipolar oils [82-84], as reported in most studies devoted to low-energy emulsification, but also for polar solvent-preformed polymer mixtures. These nanoemulsions show good kinetic stability at 25 °C over a period of at least 24 h,... 

Summary Two strategies can be used to study highly reactive species. One is kinetic stabilization by bulky groups. The other is the direct observation of the parent species under extreme conditions (matrix isolation techniques). The latter method has the advantage that the observed spectra can be correlated with the results of quantum chemical calculations. 

We have used such cells (J 4) to generate and measure the kinetic stability over a wide temperature range of a wide variety of unstable species. The easiest experiments - and the first performed - were simply the photolysis of a metal carbonyl in liquid xenon doped with dissolved N2 and hence replacement of CO by N2. The V(N-N) IR bands are little weaker than v(C-O) bands and hence detection and characterization are straightforward, particularly when use is made of previous matrix studies. Species examined include Cr (CO) (N )x x = Ni(CO)3(N ) ( 16). ... 

From the discussion presented of reactions in solids, it should be apparent that it is not practical in most cases to determine the concentration of some species during a kinetic study. In fact, it may be necessary to perform the analysis in a continuous way as the sample reacts with no separation necessary or even possible. Experimental methods that allow measurement of the progress of the reaction, especially as the temperature is increased, are particularly valuable. Two such techniques are thermo-gravimetric analysis (TGA) and differential scanning calorimetry (DSC). These techniques have become widely used to characterize solids, determine thermal stability, study phase changes, and so forth. Because they are so versatile in studies on solids, these techniques will be described briefly. 

The kinetically-stabilized complexes of the cage ligands normally yield redox reagents free of the exchange problems often associated with simple complexes. Indeed, the redox chemistry of the complexes shows a number of unusual features for example, saturated cages of the type mentioned in Chapter 3 are able to stabilize rare (monomeric) octahedral Rh(n) species (d7 electronic configuration) (Harrowfield etal., 1983). In a further study, radiolytical or electrochemical reduction of the Pt(iv) complexes of particular cages has been demonstrated to yield transient complexes of platinum in the unusual 3+ oxidation state (Boucher et al., 1983). 

Optically active selenoxides are known to be unstable toward racemization. An optically active selenoxide having a steroidal frame was obtained for the first time by Jones and co-workers in 1970.7 Enantiomeric selenoxides were prepared by Davis et al. in 1983,8 and an enantiomerically pure selenoxide was isolated for the first time by us in 1989.9 Many optically active selenoxides, which are kinetically stabilized by bulky substituents, were synthesized over the last two decades, and their stereochemistry and stability toward racemization were studied.3,5,10 Recently, some optically active selenoxides, which were thermodynamically stabilized by the intramolecular coordination of a Lewis base to the selenium atom, have been isolated. Optically active selenoxides 1 and 2 were obtained by optical resolution on chiral columns, and their stereochemistry and stability toward racemization under various conditions were clarified (Scheme 1).11,12... 

C-NMR spectroscopic studies on a-substituted tris(ethynyl)methyl cations 49 prepared from alcohols 50 (equation 18) provided evidence for the participation of resonance structures with allenyl cationic character38. The parent tris(ethenyl)methyl cation (49, R = H) cannot be generated under stable carbocation conditions (SbFs/FSOsH) presumably due to the highly reactive unsubstituted termini of the three ethynyl groups and the resulting low kinetic stability. The chemical shift data (Table 1) give evidence that in all cases Ca and CY are deshielded more than Cg (relative to their precursor alcohols). 

The use of visible and UV spectrometry for quantitative analysis by comparing the absorbance of standards and samples at a selected wavelength is one of the most widespread of all analytical techniques. It is also one of the most sensitive. The analysis of mixtures of two or more components is facilitated by the additivity of absorbances. This has been discussed earlier (p. 356). Other applications include measurement of the absorption of complexes as a function of solution conditions or time to establish their composition, and to determine thermodynamic and kinetic stability for analytical purposes or for more fundamental studies. 

A thermal stability study was first carried out to determine the following information (1) the solidification temperature as a function of the concentration of the sulfonate (2) the enthalpy of decomposition by DTA (3) the autocatalytic nature of the decomposition by Dewar flask (4) kinetic data for decomposition by Dewar flask (5) the time to maximum rate by ARC, and (6) the heat generation as a function of temperature, also by ARC. In addition, the enthalpy of dilution was determined for various potential water leak rates. These data were useful in defining emergency response times. 

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