ABSTRACT
We report the helix-sense-selective memory polymerization (HSMP) of achiral biphenylylacetylenes bearing carboxy and amino pendant groups in the presence of basic and acidic chiral guests in water, respectively. The HSMP proceeds in a highly helix-sense-selective manner driven by noncovalent chiral ionic interactions between the monomers and guests under kinetic control, producing the one-handed helical polymers with a static memory of helicity in one-pot during the polymerization in a very short time, accompanied by amplification of asymmetry. The carboxy-bound helicity-memorized polymer self-assembles into a cholesteric liquid crystal in concentrated water, in which a variety of basic achiral fluorophores further co-assembles to form supramolecular helical aggregates that exhibit an induced circularly polarized luminescence in a color tunable manner.
ABSTRACT
A 72-year-old man with chronic obstructive pulmonary disease (COPD) was admitted for coronavirus disease 2019 (COVID-19). He was discharged on day 30; however, he was readmitted 6 days later due to a left lung organizing pneumonia secondary to COVID-19. After methylprednisolone treatment, the patient was discharged on day 15. One year later, computed tomography showed shrinkage of emphysematous lesions, and both total lung capacity measured using computed tomography and fraction of low attenuation volume decreased in the left lung compared to that before COVID-19. Here, we report a rare case of autobullectomy with COVID-19 in a patient with COPD.
ABSTRACT
We report unique coordination-driven supramolecular helical assemblies of a series of dirhodium(II) tetracarboxylate paddlewheels bearing chiral phenyl- or methyl-substituted amide-bound m-terphenyl residues with triethylene glycol monomethyl ether (TEG) or n-dodecyl tails through a 1:1 complexation with 1,4-diazabicyclo[2.2.2]octane (DABCO). The chiral dirhodium complexes with DABCO in CHCl3/n-hexane (1:1) form one-handed helical coordination polymers with a controlled propeller chirality at the m-terphenyl groups, which are stabilized by intermolecular hydrogen-bonding networks between the adjacent amide groups at the periphery mainly via a cooperative nucleation-elongation mechanism as supported by circular dichroism (CD), vibrational CD, and variable-temperature (VT) absorption and CD analyses. The VT visible-absorption titrations revealed the temperature-dependent changes in the degree of polymerization. The columnar supramolecular helical structures were elucidated by X-ray diffraction and atomic force microscopy. The helix sense of the homopolymer carrying the bulky phenyl and n-dodecyl substituents is opposite those of other chiral homopolymers despite having the same absolute configuration at the pendants. A remarkably strong "sergeants and soldiers" (S&S) effect was observed in most of the chiral/achiral copolymers, while the copolymers of the bulky chiral phenyl-substituted dirhodium complexes with n-dodecyl chains displayed an "abnormal" S&S effect accompanied by an inversion of the helix sense, which could be switched to a "normal" S&S effect by changing the solvent composition. A nonracemic dirhodium complex of 20% enantiomeric excess bearing the less bulky chiral methyl substituents with n-dodecyl chains assembled with DABCO to form an almost one-handed helix (the "majority rule" (MR) effect), whereas the three other nonracemic copolymers showed a weak MR effect.
ABSTRACT
Two novel poly(biphenylylacetylene)s (PBPAs) bearing achiral alkylphenyl groups at the 4'-position of the biphenyl pendant through ester linkers with different sequences were synthesized by the rhodium-catalyzed polymerization of the corresponding monomers. The influence of the alkylphenyl pendants and the ester sequences on the macromolecular helicity induction and subsequent static helicity memory was investigated. In addition, the chiral recognition ability as chiral stationary phases for high-performance liquid chromatography of the helicity-memorized PBPAs was also examined. Both polymers formed almost perfect right- and left-handed helical conformations through noncovalent chiral interactions with enantiomeric alcohols, and their induced macromolecular helicities were completely retained ("memorized") after removal of the helix inducer. A PBPA bearing a 4-n-butylphenoxycarbonyl pendant group with a static helicity memory showed a remarkably high chiral recognition ability toward a wide variety of chiral aromatics, including simple point chiral compounds, axially chiral biaryls, a chiral spiro compound, helicenes, and planar chiral cyclophanes, particularly under the reversed-phase conditions.
Subject(s)
Polymers , Chromatography, High Pressure Liquid/methods , Molecular Conformation , Polymerization , Polymers/chemistry , StereoisomerismABSTRACT
A racemic monomer-based optically inactive polyacetylene folds into a one-handed helix assisted by a nonracemic alcohol, which can separate various enantiomers as a chiral stationary phase in chromatography. The chiral-resolving power is virtually identical to that of the enantiopure monomer-based one-handed helical polyacetylene. Because of its unique static memory of the induced helicity, the original racemic polyacetylene expresses an auto-evolution of its helical handedness over time, and at the same time, chirality of the nonracemic alcohol is discriminated accompanied by successive enhancement of its optical purity enantioselectively adsorbed on the helical polyacetylene owing to the chiral filter effect as directly monitored by NMR, which contributes to further enhancing the helix-sense-excess of the helical polyacetylene.
