Positivity/negativity effect

The 3-, 4-, 5- and 6-positions in the pyridazine nucleus are electron deficient due to the negative mesomeric effect of the nitrogen atoms. Therefore, electrophilic substitution in pyridazines is difficult even in the presence of one or two electron-donating groups. The first reported example is nitration of 4-amino-3,6-dimethoxypyridazine to yield the corresponding 5-nitro derivative. Nitration of 3-methoxy-5-methylpyridazine gives the 6-nitro-,... 

The 260 nm band of chiral thiiranes is optically active and a Cotton effect is observed R) (+)-methylthiirane shows a negative Cotton effect at ca. 250 nm followed by a positive effect below 200 nm. An MO analysis indicates that charge transfer contributions are most important in determining the optical activity of the transition (81JCS(F2)503). The... 

The n t effect of the presence of other elements is conveniently assessed by comparing the intensity of the analytical line in their presence with the intensity calculated from Equation 7-1. The net effect may be to increase the intensity over that calculated (positive), or to decrease it (negative). Individual effects may result from the following causes (1) Presence of an element with absorption coefficient smaller than that of E positive absorption effect). (2) The reverse of this situation negative absorption effect). (3) Presence of an element a characteristic line... 

Fig. 7—2. Spectral data to illustrate absorption and enhancement effects for three transition elements. (To avoid crowding, only part of the cobalt absorption curve is shown.) See Table 7-1. Case B. Substitution of A1 for Fe decreases absorption of incident beam and has little effect on analytical line. Net positive absorption effect. Case C. Substitution of Pb for Fe decreases absorption of primary beam but greatly increases absorption of analytical line. Net negative absorption effect. Case D. Note wavelength relationship indicated in figure. Enhancement impossible. Case E. Note wavelength relationship in figure. Enhancement occurs.

Hi-receptors in the adrenal medulla stimulates the release of the two catecholamines noradrenaline and adrenaline as well as enkephalins. In the heart, histamine produces negative inotropic effects via Hr receptor stimulation, but these are normally masked by the positive effects of H2-receptor stimulation on heart rate and force of contraction. Histamine Hi-receptors are widely distributed in human brain and highest densities are found in neocortex, hippocampus, nucleus accumbens, thalamus and posterior hypothalamus where they predominantly excite neuronal activity. Histamine Hrreceptor stimulation can also activate peripheral sensory nerve endings leading to itching and a surrounding vasodilatation ( flare ) due to an axonal reflex and the consequent release of peptide neurotransmitters from collateral nerve endings. 

A complex phenomena that promotes the use of fat for energy (a positive effect) and permits fat stores to accumulate in the body, causing buffalo hump and moon- or round-shaped face (a negative effect). 

Wanzlick showed that the stability of carbenes is increased by a special substitution pattern of the disubstituted carbon atom [12-16]. Substituents in the vicinal position, which provide n-donor/a-acceptor character (Scheme 2, X), stabilize the lone pair by filling the p-orbital of the carbene carbon. The negative inductive effect reduces the electrophilicity and therefore also the reactivity of the singlet carbene. 

Figure 6.12. Example of rules Gl, G2 and G3 Effect of pCo (=Pd) and of Na coverage and corresponding UWr and AO values on the rate of CO oxidation on Pt films deposited on P"-A1203 at fixed Po2=6 kPa71 Note that dr/dO(= dr/edUWR) always traces dr/dpco for negative, positive and zero (volcano peak) values. In the right figure the raw data (left) have been fitted to a polynomial expression.71 Reprinted with permission from Academic Press.

Air injection This measure has a positive effect on the silanization efficiency without negatively influencing the properties of the material. The combination of air injection with working in an open mixer adds the positive effects of the two measures. 

Figure22-10. Regulation of long-chain fatty acid oxidation in the liver. (FFA, free fatty acids VLDL, very low density lipoprotein.) Positive ( ) and negative ( ) regulatory effects are represented by broken arrows and substrate flow by solid arrows.

Figure 25-8. Control of adipose tissue lipolysis. (TSH, thyroid-stimulating hormone FFA, free fatty acids.) Note the cascade sequence of reactions affording amplification at each step. The lipolytic stimulus is "switched off" by removal of the stimulating hormone the action of lipase phosphatase the inhibition of the lipase and adenylyl cyclase by high concentrations of FFA the inhibition of adenylyl cyclase by adenosine and the removal of cAMP by the action of phosphodiesterase. ACTFI,TSFI, and glucagon may not activate adenylyl cyclase in vivo, since the concentration of each hormone required in vitro is much higher than is found in the circulation. Positive ( ) and negative ( ) regulatory effects are represented by broken lines and substrate flow by solid lines.

In a system, when 0 = 180°, the distance between spins A and C (tac) will be a maximum and the nOe between A and C a mimimum. When 9 decreases from 180°, r c decreases and the direct nOe between A and C increases. As a result of the consequently more effective A-C relaxation, the B-C relaxation process becomes relatively less important, and the indirect negative A-C contribution is correspondingly decreased. When 0 = 78°, r c = 1.26, so there will be no net nOe between A and C, even though the A and C spins are very close to each other. This is because the direct (positive) and indirect (negative) nOe effects are equal and opposite. 

When the potential of the magnesium electrode is made more positive, the rate of Mg+ ion formation increases, and with it that of reaction (16.5). Therefore, the rate of hydrogen evolution increases instead of falling off, with increasing anodic polarization of the magnesium (see Section 13.7). This phenomenon has become known as the negative difference effect. 

OCP of magnesium is 0.6 to 1.1 V more positive than the thermodynamic value. The negative difference effect that is seen in anodic magnesium dissolution (see Section 16.2) can, in part, be attributed to partial mechanical disintegration of the passivating layer during magnesium dissolution. 

The behavior of aluminum in neutral and weakly alkaline solutions resembles the behavior of magnesium, but the negative difference effect is much less pronounced at aluminum. The steady-state potential of aluminum is approximately 1V more positive than the thermodynamic value. Yet unlike magnesium, aluminum will not passivate in strongly alkaline solutions, but undergoes fast dissolution to soluble aluminates. 

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