Derivatives drawbacks

The main drawback of the chister-m-chister methods is that the embedding operators are derived from a wavefunction that does not reflect the proper periodicity of the crystal a two-dimensionally infinite wavefiinction/density with a proper band structure would be preferable. Indeed, Rosch and co-workers pointed out recently a series of problems with such chister-m-chister embedding approaches. These include the lack of marked improvement of the results over finite clusters of the same size, problems with the orbital space partitioning such that charge conservation is violated, spurious mixing of virtual orbitals into the density matrix [170], the inlierent delocalized nature of metallic orbitals [171], etc. 

One drawback is that, as a result of the time-dependent potential due to the LHA, the energy is not conserved. Approaches to correct for this approximation, which is valid when the Gaussian wavepacket is narrow with respect to the width of the potential, include that of Coalson and Karplus [149], who use a variational principle to derive the equations of motion. This results in replacing the function values and derivatives at the central point, V, V, and V" in Eq. (41), by values averaged over the wavepacket. 

Gelemter and Rose [25] used machine learning techniques Chapter IX, Section 1.1 of the Handbook) to analyze the reaction center. Based on the functionalities attached to the reaction center, the method of conceptual clustering derived the features a reaction needed to possess for it to be assigned to a certain reaction type. A drawback of this approach was that it only used topological features, the functional groups at the reaction center, and its immediate environment, and did not consider the physicochemical effects which are so important for determining a reaction mechanism and thus a reaction type. 

A drawback of this approach is that it typically generates enormous and imwieldy synthesis trees which contain a large number of dead-end branches which are not worth further consideration. Furthermore, the chemist is forced to follow a rigid scheme during the planning process, alternating between the application of transforms, the derivation of new precursors, and again the application of further transforms to these precursors. 

One of the drawbacks of the multicanonical method is that, during the simulations tc derive the weight factor, the energy distribution in H(E) can oscillate rather than steadilj approaching a limiting distribution. Another drawback is that it can fail to properlj... 

A drawback of the SCRF method is its use of a spherical cavity molecules are rarely exac spherical in shape. However, a spherical representation can be a reasonable first apprc mation to the shape of many molecules. It is also possible to use an ellipsoidal cavity t may be a more appropriate shape for some molecules. For both the spherical and ellipsoi cavities analytical expressions for the first and second derivatives of the energy can derived, so enabling geometry optimisations to be performed efficiently. For these cavil it is necessary to define their size. In the case of a spherical cavity a value for the rad can be calculated from the molecular volume ... 

Integration of the peaks for the two diastereomers accurately quantifies the relative amounts of each enantiomer within the mixture. Such diastereometic derivatives may also be analy2ed by more accurate methods such as gc or hplc. One drawback to diastereometic detivatization is that it requites at least 15 mg of material, which is likely to be material painstakingly synthesized, isolated, and purified. The use of analytical chiral chromatographic methods allows for the direct quantification of enantiomeric purity, is highly accurate to above 99.8% ee, and requites less than one milligram of material. 

A protonic acid derived from a suitable or desired anion would seem to be an ideal initiator, especially if the desired end product is a poly(tetramethylene oxide) glycol. There are, however, a number of drawbacks. The protonated THF, ie, the secondary oxonium ion, is less reactive than the propagating tertiary oxonium ion. This results in a slow initiation process. Also, in the case of several of the readily available acids, eg, CF SO H, FSO H, HCIO4, and H2SO4, there is an ion—ester equiUbrium with the counterion, which further reduces the concentration of the much more reactive ionic species. The reaction is illustrated for CF SO counterion as follows ... 

The Bts derivative is formed from the sulfonyl chloride, either using apro-tic conditions for simple amines or by the Schotten-Baumann protocol for amino acids (87-97% yield). The primary drawback of this reagent is that its stability depends on its quality. It can on occasion rapidly and exothermically lose SO2 to give 2-chlorobenzothiazole. ... 

The detailed first principles study of the three stable polymorphs has been performed recently using the LCAO technique The main drawback of that work is that no cell optimization was performed for anatase or brookite. The energy-volume curves that were used to calculate the bulk modulus, B, and its pressure derivative, B, have been produced by varying the volume with the c/a ratio and fractional atomic coor nates being fixed at experimental values which makes results unreliable. 

Since these assumptions are not always justifiable when applied to plastics, the classic equations cannot be used indiscriminately. Each case must be considered on its merits, with account being taken of such factors as the time under load, the mode of deformation, the service conditions, the fabrication method, the environment, and others. In particular, it should be noted that the traditional equations are derived using the relationship that stress equals modulus times strain, where the modulus is a constant. From the review in Chapter 2 it should be clear that the modulus of a plastic is generally not a constant. Several approaches have been used to allow for this condition. The drawback is that these methods can be quite complex, involving numerical techniques that are not attractive to designers. However, one method has been widely accepted, the so-called pseudo-elastic design method. 

A major drawback of vectors derived from prototypic retroviruses is that they can only transduce dividing cells. Therefore, these vectors cannot be used for gene transfer in many nondividing cells (e.g., muscle and brain cells). 

The Suzuki-Miyaura and Heck reactions were recently also reported under conventional heating conditions [39,40]. A variety of 3-chloro pyrazinones were reacted with commercially available (hetero)aryl boronic acids or the alkyl-9-BBN derivatives under either classical or slightly modified Suzuki conditions to generate the 3-substituted analogues, however having the drawback of longer reaction times of up to 12 h of reflux. 

The analysis of pentaerythritols and brominated derivatives, which are fire retardants, may be performed by a number of techniques, some of which will be discussed here. Each procedure suffers from different drawbacks. The method chosen must answer the specific need of the analysis. We use the following abbreviations. 

A number of drawbacks in the application of the 0PA/2-ME reagent system include the instability of the fluorescent isoindole derivative (5-7) the use of the noisome reagent 2-mercaptoethanol the low and solvent-dependent fluorescence efficiencies (8,9) of the isoindole and—perhaps the most limiting—the effective restriction of the OPA assay to primary aliphatic amines and to amino acids. 

We have also investigated other oxalate esters as a potential means to improve the efficiency. The most commonly used oxalates are the 2,4,6-trichlorophenyl (TCPO) and 2,4-dinitrophenyl (DNPO) oxalates. Both have severe drawbacks namely, their low solubility in aqueous and mixed aqueous solvents and quenching of the acceptor fluorescence. To achieve better solubility and avoid the quenching features of the esters and their phenolic products, we turned to difluorophenyl oxalate (DFPO) derivatives 5 and 6 (Figure 14). Both the 2,4- and the 2,6-difluoro esters were readily synthesized and were shown to be active precursors to DPA chemiluminescence. In fact, the overall efficiency of the 2,6-difluorophenyl oxalate 5 is higher than for TCPO in the chemical excitation of DPA under the conditions outlined earlier. Several other symmetrical and unsymmet-rical esters were also synthesized, but all were less efficient than either TCPO or 2,6-DFPO (Figure 14). 

Dansyl chloride does have some drawbacks when used with reverse-phase HPLC. One of these is that the quantum yield of fluorescence varies greatly with the polarity of the solvent for dansyl derivatives (10,11). As the polarity of the solvent increases, the... 

---