Carbon sites

Figure 4-3. Absolute values of the INDO/SCI-calculalcd electron wavcfunctions v/(a, jt, = 34) calculated for the eleven-ring PPV oligomer as a function of carbon site (hole fixed on site 34) for the excited stales corresponding to (a) die first absorption peak (3.0 cV) (b) the second absorption peak (3.8 eV) (c) the third absorption peak (5.6 eV) (d) lire fourth absorption peak (6.3 eV) and (e) lire fifth absorption peak (7.0 cV). The energies given between parentheses refer to the theoretical values.

The most important types of these methods are the isomerizing rearrangements. According to whether the reaction occurs at the sulfone site or at the carbon site on the one hand, or at both sites on the other, one should distinguish between unifold and twofold transformations (Schemes 2 and 3). 

One way in which to probe the structural surroundings of a protein is to monitor the pH behavior of specific carbon sites of the C probes. pH-titration studies, of given resonances, had previously been used for probing of the protein structure, because they are known to provide information concerning electrostatic (salt-bridging) interactions in the protein, neighboring group-ionizations, and local environments. ... 

Bifunctional spacer molecules of different sizes have been used to construct nanoparticle networks formed via self-assembly of arrays of metal colloid particles prepared via reductive stabilization [88,309,310]. A combination of physical methods such as TEM, XAS, ASAXS, metastable impact electron spectroscopy (MIES), and ultraviolet photoelectron spectroscopy (UPS) has revealed that the particles are interlinked through rigid spacer molecules with proton-active functional groups to bind at the active aluminium-carbon sites in the metal-organic protecting shells [88]. 

The main danger factor is the polyhaiogenation on one carbon site only. The substitution (1) or elimination (2) reaction can then lead to an intermediate carbene (or to a transition state that has this character). Its reactivity and instability will create accidents. 

Naturally, very long T,c values are expected for solids as viewed from the expected correlation time at the low temperature side of the T c minimum (0.1-0.2 s) as shown in Figure 1. Indeed, their values turns out to be the order of 10-30 s for carbon sites in the absence of internal fluctuations as in polysaccharides such as (1 — 3)-p-D-glucan and (1 —> 3)-p-D-xylan,46 8 fibrous proteins such as collagen49 and silk fibroin,50 free and metal-complexed ionophores,51 or in some instances up to 1000 s as in crystalline polyethylene.52... 

With few exceptions (125 or 126), marine isocyano-related, cyclic compounds generally have their nitrogenous functions attached to secondary or tertiary carbon sites. Without exception, cationic centers which are allylic, secondary, or tertiary are reasonable transient intermediates. Marine thiocyanates, of which few (11, 36, 81 and 82) are known, may accomodate the bent -S-C=N moiety. The resultant quartemary carbon of thiocyanate 36 (R S-C = N), though less favorable than that of the absent isothiocyanate... 

CF refers to a free carbon site on the surface, C(02) refers to... 

The use of an anionic reagent for addition at carbonyl carbon rather than a fully esterified form of a trivalent phosphorus acid obviates a troublesome aspect of the Abramov reaction. Specifically no dealkylation step is required. Mechanistic investigations257 258 indicate that the reaction proceeds much as a simple "aldol"-type reaction in which the anionic phosphorus site adds directly to the carbonyl center. While the initial efforts concerned with the "Pudovik reaction"259 were directed toward the use of sodium salts of the simple dialkyl phosphites, as shown in Equation 3.17,260 266 with a, 5-unsaturated carbonyl systems (vide infra) competition between sites for addition can occur. Addition at the carbonyl carbon site is the kinetically favored route.267-270... 

Michael addition in the absence of any catalytic agent has been reported for dialkyl and diaryl phosphites and thiophosphites with a-cyanoacrylate esters and a-cyanoacrylic acid.444 Yields of the conjugate addition products were moderate to good. The regiochemistry of this process is the opposite of that previously reported for similar additions to ketene acetals, the latter presumably proceeding by initial protonation of the distal olefinic carbon site.445... 

Classical Michaelis-Arbuzov or Michaelis-Becker approaches toward formation of C-P bonds involving aromatic carbon sites are (understandably) not generally feasible. Nucleophilic substitution reactions on aromatic carbon proceed only under particular circumstances relating to the nature of attendant additional substituents, and then often with mechanisms quite different from those observed in... 

For example, in the instance of 9-chloroacridine, the attachment of the halogen (leaving group) at a suitably electrophilic carbon site allows the occurrence of a replacement reaction, presumably occurring via an addition-elimination procedure for phosphorus attachment, followed by the common nucleophilic displacement (ester cleavage) of the Michaelis-Arbuzov process (Figure 6.1).4... 

The addition of phosphorus reagents, either trialkyl phosphites or dialkyl phosphite anions, to the P-carbon atom of a,P-unsaturated carbonyl systems has been studied extensively. (This is the fundamental hydrophosphinylation reaction as considered in Chapter 3.) An interesting situation arises when the P-carbon site also bears a... 

A two-step mechanism and resulting rate law can be developed as follows. Reactive carbon sites, C (total number Nc,), are assumed to exist on the surface of the solid. These can be oxidized reversibly by water vapor ... 

Fig. 3. Contour plot of the proton-detected local field (PDLF) spectrum of a static 5CB sample. The traces taken parallel to for each carbon site show distinct doublets that are related to individual C-H couplings. (Reproduced by permission of American Chemical Society.)...

The above spectral densities can be modified for the occurence of chain flexibility, and for the director being oriented at dLD w.r.t. the external BQ field in the L frame. For CD bonds located in the flexible chain, the effect of DF is reduced due to an additional averaging of the time dependent factor (/f g) by conformational transitions in the chain. Consequently, the spectral densities given in Eqs. (60)-(62) are modified by replacing Soc%0(Pm,q) by the segmental order parameter YCD of the C-D bond at a particular carbon site on the chain.146,147 As observed experimentally,148,149 the spectral densities in a flexible chain show a SqD dependence when DF dominate the relaxation rates. The general expression of Jm(co 0LD) due to DF in uniaxial nematic phases is given by... 

Chirality (or a lack of mirror symmetry) plays an important role in the LC field. Molecular chirality, due to one or more chiral carbon site(s), can lead to a reduction in the phase symmetry, and yield a large variety of novel mesophases that possess unique structures and optical properties. One important consequence of chirality is polar order when molecules contain lateral electric dipoles. Electric polarization is obtained in tilted smectic phases. The reduced symmetry in the phase yields an in-layer polarization and the tilt sense of each layer can change synclinically (chiral SmC ) or anticlinically (SmC)) to form a helical superstructure perpendicular to the layer planes. Hence helical distributions of the molecules in the superstructure can result in a ferro- (SmC ), antiferro- (SmC)), and ferri-electric phases. Other chiral subphases (e.g., Q) can also exist. In the SmC) phase, the directions of the tilt alternate from one layer to the next, and the in-plane spontaneous polarization reverses by 180° between two neighbouring layers. The structures of the C a and C phases are less certain. The ferrielectric C shows two interdigitated helices as in the SmC) phase, but here the molecules are rotated by an angle different from 180° w.r.t. the helix axis between two neighbouring layers. 

Bot these C atoms provides a site for optical isomerism. Each such site can exhibit either d- or /-type isomerism which depends on whether the R group is located below the plane of carbon-carbon chain or above. The regularity or the order in which the successive asymmetric carbon sites, C, exhibit their d-or /- form leads to three different types of isomeric structure in the polymer molecule. The structures shown in figure below. 

In situ reactive barriers Treat contaminated water as it passes through a physical barrier containing reactive chemicals, organisms, or activated carbon Site specific Slow process... 

In heterogeneous catalytic hydrogenations suprafacial (as) addition of hydrogen would be expected, as the transfer of hydrogen atoms from the catalyst surface to the reactant is usually assumed. However, in some Pt catalyzed reactions antarafacial (trans) addition of hydrogen is also observed. The ratio of diastereomeric products formed is determined by the chemisorption equilibrium of the surface intermediates and by the relative rates of hydrogen entrance to the different unsaturated carbon sites. Both effects are influenced by steric factors. 

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