Chiral Units (chiral + unit)

Distribution by Scientific Domains


Selected Abstracts


Counterintuitive influence of microscopic chirality on helical order in polymers

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 9 2004
Kap Soo Cheon
Abstract Studies of copolymers of chiral and achiral units forming a helical array correlate to statistical physical predictions of the influence of the chiral units on the helical sense taken by the array. In the absence of conflict among the chiral units for helical sense control, the sergeants and soldiers experiment, a larger chiral bias leads to increased control. However, when conflict exists among the chiral units for helical sense control, the majority rule experiment, a larger chiral bias leads to decreased control of the helical sense and therefore a smaller optical activity. Changing the achiral units in the majority rule experiment can change the nature of the statistical physics between statistical and thermal randomness. In general, the experiments quantitatively demonstrate that the effect of chirality is not an intrinsic property of the chiral moiety but rather depends on the molecular environment. Copyright © 2004 John Wiley & Sons, Ltd. [source]


Preparation, characterization, and chiral recognition of optically active polymers containing pendent chiral units via reversible addition-fragmentation chain transfer polymerization

JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 16 2007
Jian Wang
Abstract Optically active polymers bearing chiral units at the side chain were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization in the presence of 2,2,-azobisisobutyronitrile (AIBN)/benzyl dithiobenzoate (BDB), using a synthesized 6- O - p -vinylbenzyl-1,2:3,4-Di- O -isopropylidene- D -galactopyranose (VBPG) as the monomer. The experimental results suggested that the polymerization of the monomer proceeded in a living fashion, providing chiral group polymers with narrow molecular weight distributions. The optically active nature of the obtained poly (6- O - p -vinylbenzyl-1,2:3,4-Di- O -isopropylidene- D -galactopyranose) (PVBPG) was studied by investigating the dependence of specific rotation on the molecular weight of PVBPG and the concentration of PVBPG in tetrahydrofuran (THF). The results showed the specific rotation of PVBPG increased greatly with the decrease of the concentration of the PVBPG homopolymer. In addition, the effect of block copolymers of PVBPG on the optically active nature was also investigated by preparing a series of diblock copolymers of poly(methyl methacrylate) (PMMA)- b -PVBPG, polystyrene (PS)- b -PVBPG, and poly(methyl acrylate) (PMA)- b -PVBPG. It was found that both the homopolymer and the diblock copolymers possessed specific rotations. Finally, the ability of chiral recognition of the PVBPG homopolymer was investigated via an enantiomer-selective adsorption experiment. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3788,3797, 2007 [source]


Synthesis and chiroptical properties of liquid crystalline copolymers containing azobenzene chromophores

POLYMER INTERNATIONAL, Issue 6 2007
Zhi Zheng
Abstract A series of new liquid crystalline copolymers, poly[((S)-2-methyl-1-butyl methacrylate)- co -(6-(4-(4-cyanophenylazo)phenoxy)hexyl methacrylate)], with different contents of chiral units of 17, 36, 54 and 78 mol% were synthesized. The structures and properties of the copolymers were characterized and evaluated using infrared, 1H NMR and UV spectroscopy, differential scanning calorimetry, gel permeation chromatography and circular dichroism (CD). The CD results suggested that absorptions of azobenzene chromophores were observed in films of copolymer containing 17, 36 or 54 mol% chiral units, but not in the film of copolymer containing 78 mol% chiral units. Also, CD values of the copolymeric films decreased with increasing chiral content. After irradiation with linear polarized light at 442 nm, CD values were changed in all the copolymeric films, and the CD values increased with decreasing chiral content in a nonlinear way, while the photoinduced change of chirality of the copolymers increased in a linear way with decreasing chiral content. The results are discussed in terms of interactions between structures and chiroptical properties. Copyright © 2007 Society of Chemical Industry [source]


Co-Metal-Free Enantioselective Conjugate Addition Reactions of Zinc Reagents

CHEMISTRY - A EUROPEAN JOURNAL, Issue 36 2008
Sefer Ay Dipl.-Chem.
Abstract Asymmetric conjugate addition of diethylzinc to cinnamaldehyde in a co-metal-free fashion by using N,O-ligands with planar and central chirality is described. Different modulations of the ligand structure, including several combinations of the chiral units, indicate that a [2.2]paracyclophane backbone is essential for the activity and the enantioselectivity of the generated active catalyst. By using the optimized ligand, an isolated yield of 90,% was obtained with up to 99,%,ee. [source]