Intermediates and Transition States in Reactions of Allylic and Homoallylic Systems. II. Factors Affecting the Distribution of Products from Allylic Carbonium Ions

1961 ◽  
Vol 83 (4) ◽  
pp. 895-900
Author(s):  
Richard A. Sneen ◽  
Arnold M. Rosenberg
RSC Advances ◽  
2017 ◽  
Vol 7 (37) ◽  
pp. 22757-22770 ◽  
Author(s):  
Hooshang Atabaki ◽  
Davood Nori-Shargh ◽  
Mohamad Momen-Heravi

The variations of Δ[(HCGAE(X3–C4weakening) – HCGAE(X3–C4strengthening)] parameters correlate well with the variations of the retro-ene decomposition reactions barrier heights going from compound1to compound3.


2018 ◽  
Vol 475 (16) ◽  
pp. 2611-2620 ◽  
Author(s):  
Jagadish P. Hazra ◽  
Nisha Arora ◽  
Amin Sagar ◽  
Shwetha Srinivasan ◽  
Abhishek Chaudhuri ◽  
...  

Mechanical cues often influence the factors affecting the transition states of catalytic reactions and alter the activation pathway. However, tracking the real-time dynamics of such activation pathways is limited. Using single-molecule trapping of reaction intermediates, we developed a method that enabled us to perform one reaction at one site and simultaneously study the real-time dynamics of the catalytic pathway. Using this, we showed single-molecule calligraphy at nanometer resolution and deciphered the mechanism of the sortase A enzymatic reaction that, counter-intuitively, accelerates bacterial adhesion under shear tension. Our method captured a force-induced dissociation of the enzyme–substrate bond that accelerates the forward reaction 100×, proposing a new mechano-activated catalytic pathway. In corroboration, our molecular dynamics simulations in the presence of force identified a force-induced conformational switch in the enzyme that accelerates proton transfer between CYS184 (acceptor) and HIS120 (donor) catalytic dyads by reducing the inter-residue distances. Overall, the present study opens up the possibility of studying the influence of factors affecting transition states in real time and paves the way for the rational design of enzymes with enhanced efficiency.


Author(s):  
F. A. Heckman ◽  
E. Redman ◽  
J.E. Connolly

In our initial publication on this subject1) we reported results demonstrating that contrast is the most important factor in producing the high image quality required for reliable image analysis. We also listed the factors which enhance contrast in order of the experimentally determined magnitude of their effect. The two most powerful factors affecting image contrast attainable with sheet film are beam intensity and KV. At that time we had only qualitative evidence for the ranking of enhancing factors. Later we carried out the densitometric measurements which led to the results outlined below.Meaningful evaluations of the cause-effect relationships among the considerable number of variables in preparing EM negatives depend on doing things in a systematic way, varying only one parameter at a time. Unless otherwise noted, we adhered to the following procedure evolved during our comprehensive study:Philips EM-300; 30μ objective aperature; magnification 7000- 12000X, exposure time 1 second, anti-contamination device operating.


Author(s):  
Christine M. Dannels ◽  
Christopher Viney

Processing polymers from the liquid crystalline state offers several advantages compared to processing from conventional fluids. These include: better axial strength and stiffness in fibers, better planar orientation in films, lower viscosity during processing, low solidification shrinkage of injection moldings (thermotropic processing), and low thermal expansion coefficients. However, the compressive strength of the solid is disappointing. Previous efforts to improve this property have focussed on synthesizing stiffer molecules. The effect of microstructural scale has been overlooked, even though its relevance to the mechanical and physical properties of more traditional materials is well established. By analogy with the behavior of metals and ceramics, one would expect a fine microstructure (i..e. a high density of orientational defects) to be desirable.Also, because much microstructural detail in liquid crystalline polymers occurs on a scale close to the wavelength of light, light is scattered on passing through these materials.


1990 ◽  
Vol 54 (11) ◽  
pp. 638-643 ◽  
Author(s):  
PC Damiano ◽  
ER Brown ◽  
JD Johnson ◽  
JP Scheetz

1976 ◽  
Vol 7 (4) ◽  
pp. 207-219 ◽  
Author(s):  
Constance P. DesRoches

A statistical review provides analysis of four years of speech therapy services of a suburban school system which can be used for comparison with other school system programs. Included are data on the percentages of the school population enrolled in therapy, the categories of disabilities and the number of children in each category, the sex and grade-level distribution of those in therapy, and shifts in case-load selection. Factors affecting changes in case-load profiles are identified and discussed.


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