Purposely tailored

The mobile Jt-electrons of unsaturated systems, responsible for the stabilization of the carbocations, provide equally efficient stabilization for carbanions. Consequently, a retrosynthetic cleavage of a benzylic, allylic, or propargylic C-C bond has additional merits since the resulting fragments can be visualized as either an electrophile or a nucleophile. The dual synthetic value of the allylic moiety has been extensively utilized in the synthesis of a large number of natural acyclic isoprenoids. The structures of many of these compounds look like they were purposely tailored for this type of retrosynthetic analysis. In fact, the 1,5-diene system, usually present in their structure (Scheme 2.19), immediately suggests the cleavage of its central C-3-C-4 bond, which leads to two allylic precursors. 

The reported examples convincingly support that using a purposely tailored diblock copolymer is a powerful tool of generating new, or at least improved, multiphase polymeric materials. Quite interestingly, the interfacial activity of diblock copolymers is not exclusively confined to immiscible polymer blends but it can be fruitfully extended to dispersions of fine solid particles in either a liquid phase or a polymeric matrix, as illustrated hereafter. 

Dispersion of solid particles in a polymeric matrix is another target that can be reached successfully using a purposely tailored diblock copolymer. 

A lot of work has been devoted to the elaboration of more and more purposely tailored monomers, followed by electropolymerization, in order to improve a given property of the resulting polymer, e.g., a low bandgap. Approaches have also been made to synthesize oligomers, in order to prepare a better-defined polymer with improved properties. However, little work has been published outside the three main families, namely thiophene (especially EDOT), pyrrole, and aniline derivatives. In this section, we will only recall which kind of approach in monomer tailoring has been followed, and focus on some examples where the electrochemical behavior of the monomers has been found different from what could be expected. 

The matrix may be purposely tailored to impart the appropriate solubility to the final product (in most cases water solubility), and/or to be selectively localized in the body. This is usually obtained by adding to the active units suitable hydrophylic units which are by themselves pharmacologically inert, and/or preparing block copolymers in which "active blocks are coupled with "directing" blocks... 

Furthermore, a trend in direction of coupling TLC with spectroscopic methods (e.g. FTIR, RAMAN, SERS, and MS) is recognizable to enlarge the analytical possibilities. For this purpose tailor-made precoated layers are in preparation. 

On the other hand, PBEO (like aU the standard density functionals) exhibits important failures in describing zero-overlap CT transitions. In these cases, a check using purposely tailored functionals (CAM-B3LYP, M06-2X, LCcu-PBE) is highly recommended. 

In order to take vibrational averaging effects into proper account, we resorted to classical treatment with a purposely tailored force field using a new accurate force field obtained by extending the ff99SB force field [88] with a reliable... 

Structural properties were obtained by means of quantum mechanical calculations performed to find the minimum energy geometry of the molecule, evaluate the magnetic tensors, and calculate the internal potential [44]. On the basis of a previous study [87], the alkyl chain of TP was replaced by an ethyl group. Internal torsional potentials and magnetic tensors were then evaluated by the PBEO hybrid functional [88] and the purposely tailored N06 basis set. Solvent effects were taken into account by our anisotropic version of the polarizable continuum model [87]. 

Feasible computations of spectroscopic properties for even larger systems can be faciUtated thanks to the set up of relatively small, purposely tailored basis sets, that allow to reach an accuracy similar to that obtainable with much larger basis sets (e.g., aug-cc-pVTZ) even for difficult properties such as Raman intensities [132] or rotatory strengths [133]. An example is provided by the recently introduced spectroscopic aug-N07D/SNSD basis set [49, 94, 134]), developed also for some metallic atoms (Li, Be, B, Na, Mg, Al, Zn). The SNSD [120, 134] basis set is an improved version of the polarized double- N07D basis set [94-96,... 

Abstract Gas polymer interactions play a pivotal role in the formation of different molecular organizations/reorganizations of polymeric structures. Such structural modifications can have a negative impact on the material properties and should be understood in order to prevent them or these modifications are of engineering interest and they should be purposely tailored and properly controlled. Two newly developed techniques, gas-sorption/solubility and scanning transitiometry, are shown to be well adapted to provide the necessary (key) data to better understand and monitor the polymeric modifications observed under the triple constraints of temperature, elevated pressure, and gas sorption. This article illustrates the major contribution of gas polymer interactions in different intercoimected applied and engineering fields of the petroleum industry, polymer science, and microelectronics. 

The synthesis of poly(amido-amine) block and graft copolymers was performed starting from poly(amido-amines) having purposely tailored end groups. Most of our studies have been performed starting from poly(amido-amine) VI (see Table 1), deriving from the... 

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