Deterministic Synthesis

The synthesis of fluorene oligomers is intensive in terms of number of steps, but the unique properties and the new insight into structure-property relationships are well worth the effort. A number of approaches have been developed from the initial brute force fractionation of polydisperse systems to the more elegant deterministic synthesis of monodisperse systems. 

Scheme 6.2 Deterministic synthesis of cholesteric and nematic GLCs via a bicyclic intermediate with anhydride and acid chloride functionalities. DMAP 4-dimethylamino pyridine...

Scheme 6.3 Deterministic synthesis of cholesteric GLCs starting with monohydrolysis of a 1,3,5-cyclohexanetricarboxylic acid trimethyl ester with pig liver enzyme, PLE and b 1,3,5-benzenetricarboxylic acid trimethyl ester...

Scheme 6.4 Deterministic synthesis of a cholesteric GLCs consisting of hybrid chiral-nematic pendant groups...

In view of the unique roles of cholesteric GLCs in material synthesis and device application, the commonly practiced statistical synthesis and the continuing effort in deterministic synthesis are highlighted. All factors considered, a hybrid chiral-nematic precursor is much preferred over separate chiral and nematic precursors in terms of synthesis and subsequent product separation and purification. 

H.M.P. Chen, D. Katsis, S.H. Chen, Deterministic synthesis and optical properties of glassy chiral-nematic liquid crystals. Chem. Mater. 15, 2534—2542 (2003)... 

Reaction Scheme I. Deterministic synthesis hf glassy cholesterics. 

Finally, the methods of tasks A, C, D are non-deterministic, but finite. This means that choice-points are created there, and that the made selections may be reconsidered later, either because synthesis fails, or because synthesis succeeds and the specifier wants more algorithms. Only Task A could possibly fail, namely if there is no parameter of an inductive type. Do not mix up non-deterministic synthesis and a non-deterministic synthesized algorithm. The latter would feature either mutually nonexclusive cases or predicates that are non-deterministic. The logic algorithm synthesized at Step 2 is deterministic, because the two cases are mutually exclusive by construction, and because the introduced predicates are deterministic. 

Serra, 1989] Serra, X. (1989). A System for Sound Analysis/Transformation/Synthesis Based on a Deterministic Plus Stochastic Decomposition. PhD thesis, CCRMA, Department of Music, Stanford University. 

The analysis/synthesis system which corresponds to the deterministic/stochastic model is similar to the baseline sine-wave analysis/synthesis system. The primary differences he in the frequency matching stage for extraction of the deterministic component, in the subtraction operation to obtain the residual (stochastic component), and in the synthesis of the stochastic component. 

Serra and Smith, 1989] Serra, X. and Smith, J. (1989). Spectral modeling synthesis A sound analysis/synthesis system based on a deterministic plus stochastic decomposition. In Proc. oflnt. Computer Music Conf., pages 281-284, San Francisco, CA. 

HT synthesis and testing supported by deterministic (molar group contributions) and statistical (probabilistic regression) analyses were successfully used to develop novel, functional, transparent plastics from commodity starting materials that satisfy the stringent flammability requirements for use in aircraft cabin interiors. 

The various fields that make up a science tend naturally to integrate, and with time such a process can lead to a true synthesis. Physics was the first science to achieve a synthesis of its disciplines, and it may be useful to compare that experience with its biological counterpart. The first unification occurred between mechanics and thermodynamics, in the first half of the nineteenth century, and the second came shortly afterwards, with the integration of electromagnetism. The result was the imposing edifice of classical physics, a conceptual system that described all reality in terms of particles and waves, with equations that seemed perfect because they were perfectly deterministic. The common denominator of all branches of classical physics was in fact the concept of determinism, and nodoby doubted, in the nineteenth century, that that was the true logic of the universe. 

More recently a hybrid approach to computer-assisted catalyst synthesis, based on a microkinetic analysis of the catalytic reaction, has been put forward which comprises essentially deterministic but also some non-deterministic features. For the synthesis of a catalyst with high activity and selectivity for a given reaction, the application of a microkinetic analysis has been suggested by Dumesic and co-workers [43-45]. The derivation of the microkinetics is not necessarily based on detailed kinetic experimentation but, by analogy, to similarities with other known catalytic processes. In an ideal situation, the microkinetics of a catalytic reaction are completely defined according to Dumesic and his collaborators when ... 

If a linear hexapeptide solution existed, it must have been present in Geysen s library (provided the synthesis worked perfectly, which is a separate issue). There are no additional umepresented sequences, and mathematically such libraries are called NP-complete (NP = non-deterministic polynomial time). Such NP-complete libraries are actually quite rare in combinatorial chemistry. Although there are infinite numbers of peptides, for Geysen s epitope mapping, he needed to examine only natural amino acids. This reduces the complexity for a sequence of length n to 20", a number that increases exponentially with n but nevertheless remains finite. 

A simplification of the glycolytic and respiratory routes considered in the deterministic model to represent bioethanol synthesis is shown below by stoichiometric expressions. More details of the kinetics can be found in Stremel [8]. 

A deterministic mathematical model for simulating the biotechnological synthesis of acrylic acid was developed in a previous study [3] to explore an alternative process. The proposed... 

K, compare stochastic and deterministic formulas (6-13) and (6-15) for the probability of the adiabatic channel of reaction (6-2) limiting the Zeldovich mechanism of NO synthesis in plasma. Explain the difference in temperature dependences of the probabilities for the stochastic and deterministic approaches. 

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