Helix-Sense-Selective Permeation of Racemic Helical Oligoacetylenes through One-Handed Helical Channels in Polymer Membranes.

Helix-sense-selective permeation (HSSPerm) of racemic helical oligoacetylenes through one-handed helical channels has been realized. The one-handed helical channels were created in the one-handed helical polyacetylene membranes by the helix-sense-selective decomposition (HSS-SCAT) of the corresponding racemic helical polyacetylene membranes, followed by removing the formed oligomers. Since the HSS-SCAT reaction proceeds with just circularly polarized visible light with no reagents, no catalysts, no solvent, and high selectivity, the chiral channel-containing membrane with high purity was obtained easily.

Synthesis and Direct Observation of Molecules of 2D Polymers: With High Molecular Weights, Large Areas, Small Micropores, Solubility, Membrane Forming Ability, and High Oxygen Permselectivity.

If ideal 2D polymer (2DP) macromolecules with small pores that are similar in size to gas molecules, large areas, small thickness, and excellent membrane-forming ability are synthesized, ultimate gas separation membranes would be obtained. However, as far it is known, such ideal well-characterized 2DP macromolecules are not isolated. In this study, an ideal 2DP macromolecule is synthesized by using the successive three reactions (Glaser coupling, SCAT reaction, and the introduction of octyl groups), in which the conjugated framework structure is maintained, from a fully conjugated 1D polymer.

Novel highly efficient absolute optical resolution method by serial combination of two asymmetric reactions from acetylene monomers having racemic substituents.

For general optical resolution, an optical resolution agent is necessary, and the best agent should be selected for each racemic compound. In this study, we will report that a novel optical resolution method by circularly polarized light (CPL) without any optical resolution agents has been developed by serially connecting two enantioselective reactions. These reactions we developed are the enantiomer-selective helix-sense-selective polymerization (ES-HSSP) and helix-sense-selective highly selective photocyclic aromatization (SCAT) by CPL (HS-SCAT).

Macromolecular Design for Oxygen/Nitrogen Permselective Membranes-Top-Performing Polymers in 2020.

Oxygen/nitrogen permselective membranes play particularly important roles in fundamental scientific studies and in a number of applications in industrial chemistry, but have not yet fulfilled their full potential. Organic polymers are the main materials used for such membranes because of the possibility of using sophisticated techniques of precise molecular design and their ready processability for making thin and large self-supporting membranes. However, since the difference in the properties of oxygen and nitrogen gas molecules is quite small, for example, their kinetic diameters are 3.

Synthesis of Cis-Cisoid or Cis-Transoid Poly(Phenyl-Acetylene)s Having One or Two Carbamate Groups as Oxygen Permeation Membrane Materials.

Three new phenylacetylene monomers having one or two carbamate groups were synthesized and polymerized by using (Rh(norbornadiene)Cl) as an initiator. The resulting polymers had very high average molecular weights () of 1.4-4.

Helix-Sense-Selective Polymerization of 3,5-bis(hydroxymethyl)phenylacetylene Rigidly Bearing Galvinoxyl Residues and Their Chiroptical Properties.

Four kinds of newly synthesized achiral phenylacetylenes bearing a phenylhydrogalvinoxyl residue at 4-position were polymerized by using a chiral rhodium catalyst system, [Rh(nbd)B(CH)] or [Rh(nbd)Cl] catalysts in the presence of chiral ()-(+)- or ()-(-)-1-phenylethylamine (()- or ()-PEA) cocatalysts. Poly(-HGDHPA) and poly(-HGTHPA) in THF showed Cotton signals at the absorption regions of the main chain and hydrogalvinoxyl in the circular dichroism (CD) spectra. It indicated that excess of one-handed helical polyacetylene backbone was induced by helix-sense-selective polymerization (HSSP) under the asymmetric conditions despite the achiral monomer, and the hydrogalvinoxyl moieties were also arranged to form one-handed helical structure.

New Synthetic Methods of Novel Nanoporous Polycondensates and Excellent Oxygen Permselectivity of Their Composite Membranes.

Two kinds of novel nanoporous polycondensates (sc()) have been synthesized by two new preparation methods consisting of polycondensation and highly selective photocyclicaromataization of 1/3 helical cis-cis polyphenylacetylenes with polymerizable groups. By the original methods, new well-defined sheet polymers having nanopores or nanospaces have been synthesized for the first time. Their composite membranes, containing small amounts (1.

Helix-Sense-Selective Polymerization of Phenylacetylenes Having a Porphyrin and a Zinc-Porphyrin Group: One-Handed Helical Arrangement of Porphyrin Pendants.

Newly synthesized two kinds of achiral phenylacetylenes having a free-base- or a zinc-porphyrin ( and , respectively) were polymerized by using a chiral rhodium catalyst system, Rh⁺(nbd)[(⁶-C₆H₅)B(C₆H₅)₃] catalyst and ()-(+)- or ()-(⁻)-1-phenylethylamine (()- or ()-PEA, respectively) cocatalyst. Poly() and poly() in THF showed a Cotton signal at the absorption region of the porphyrin and the main chain in the circular dichroism (CD) spectra. This result suggests that poly() and poly() exist in a conformation with an excess of one-handed helix sense and the porphyrin moiety arranged in chiral helical fashion.

Synthesis of soluble oligsiloxane-end-capped hyperbranched polyazomethine and their application to CO/N separation membranes.

Three soluble hyperbranched polyazomethines containing oligosiloxane end group were successfully synthesized. were used as modifiers of ethyl cellulose (EC) and polysulfone (PS) membranes. Blend membranes, /EC and /PS were prepared by blending the THF solution of with ethanol solution of EC and dichloromethane solution of PS, respectively.

Synthesis of Two Well-Defined Quadruple-Stranded Copolymers having Two Kinds of Backbones by Postpolymerization of a Helical Template Polymer.

A brand new, soluble quadruple-stranded copolymer is synthesized by using a self-template polymer from a new monomer. In addition, another very unique quadruple-stranded copolymer having a π-π stacking supramolecular polymer main chain is synthesized by selective photocyclic aromatization of the quadruple-stranded copolymer. The two quadruple-stranded copolymers gave self-standing membranes.

Synthesis of One-Handed Helical Block Copoly(substituted acetylene)s Consisting of Dynamic and Static Block: Chiral Teleinduction in Helix-Sense-Selective Polymerization Using a Chiral Living Polymer as an Initiator.

By using a living one-handed helical poly(chiral substituted phenylacetylene) as a polymer initiator (poly()), helix-sense-selective polymerization () of an achiral phenylacetylene having two hydroxy groups successfully afforded a diblock copoly(phenylacetylene) (copoly(/)) consisting of a dynamic one-handed helical block and a static one-handed helical block. The formation of the diblock structure was confirmed by consumption of the chiral initiator, appearance of characteristic CD indicating the one-handed helical block, and occurrence of the selective photocylic aromatization reaction in the block. Therefore, has been achieved by using the chiral alkenyl groups in the initiator as a chiral source for the first time.

Highly Emissive, Optically Active Poly(diphenylacetylene) Having a Bulky Chiral Side Group.

A highly emissive, optically active poly(diphenylacetylene) derivative, NpSi*-PDPA, was synthesized by introducing a bulky chiral pendant group into the polymer chain. NpSi*-PDPA exists in a glassy state having a highly disordered and amorphous structure. Hence, the fractional free volume is quite high, i.

A Helical Polyphenylacetylene Having Amino Alcohol Moieties Without Chiral Side Groups as a Chiral Ligand for the Asymmetric Addition of Diethylzinc to Benzaldehyde.

One-handed helical polyphenylacetylenes having achiral amino alcohol moieties, but no chiral side groups, were synthesized by the helix-sense-selective copolymerization of an achiral phenylacetylene having an amino alcohol side group with a phenylacetylene having two hydroxyl groups. Since the resulting helical copolymers were successfully utilized as chiral ligands for the enantioselective alkylation of benzaldehyde with diethylzinc, we can conclude that the main-chain chirality based on the one-handed helical conformation is useful for the chiral catalysis of an asymmetric reaction for the first time. The enantioselectivities of the reaction were controlled by the optical purities of the helical polymer ligands.

Synthesis of a Fluorine-Containing Cis-Cisoidal One-Handed Helical Polyphenylacetylene and Application of Highly Selective Photocyclic Aromatization Product on Oxygen Permselective Membrane.

A novel phenylacetylene monomer having a perfluorinated alkyl group (M-F) was synthesized and polymerized in a chiral catalytic system to yield a one-handed helical polymer. The ability and efficiency of the chiral induction of the fluorine-containing monomer in the helix-sense-selective polymerization (HSSP) was much higher than those of a monomer having the corresponding alkyl group (M-H) we reported before. The resulting polymer showed cis-cisoidal one-handed helical conformation, and was suitable for highly selective photocyclic aromatization (SCAT) to give a 2D surface modifier ().

Chiral amplification during asymmetric-induced copolymerization of phenylacetylenes with tight cis-cisoidal main chains.

A novel phenylacetylene (1) having two hydroxyl groups and a chiral pinanyl group together with the other three related phenylacetylenes has been synthesized and (co)polymerized by using an achiral catalytic system. Among the four monomers, only 1 is suitable to the asymmetric-induced polymerization (AIP). Chiral amplification phenomenon is only observed in the copolymerization of 1 with an achiral phenylacetylene having two hydroxyl groups (3).

Top-down preparation of self-supporting supramolecular polymeric membranes using highly selective photocyclic aromatization of cis-cisoid helical poly(phenylacetylene)s in the membrane state.

A novel, highly selective photocyclic aromatization (SCAT) of π-conjugated polymers from phenylacetylene having two hydroxyl groups to exclusively yield a 1,3,5-trisubstituted benzene derivative was developed, and its success was confirmed by (1)H NMR, GPC, and TOF-MS. The SCAT reaction has many unique characteristics. (1) It is a quantitative reaction: it gave only the corresponding cyclic trimer, i.

Helix-Sense-Selective Polymerization of Achiral Phenylacetylenes with Two -Alkylamide Groups to Generate the One-Handed Helical Polymers Stabilized by Intramolecular Hydrogen Bonds.

In this study, we investigated the helix-sense-selective polymerizations of newly synthesized achiral phenylacetylenes having two -alkylamide groups, such as 3,5-bis(dodecylamide)phenylacetylene (), 3,5-bis(octylamide)phenylacetylene (), and 3,5-bis(butylamide)phenylacetylene (), by using a chiral rhodium catalyst system ([Rh(nbd)Cl]-()-(+)-1-phenylethylamine [()-PEA]). Poly() was insoluble in any solvents. On the other hand, poly() and poly() were soluble in toluene, THF, and CHCl, and the obtained polymers showed intense circular dichroism signals at the absorption region of the main chain in the UV-vis region.

Pseudo helix-sense-selective polymerisation of achiral substituted acetylenes.

Pseudo helix-sense-selective polymerisation of a wide range of achiral substituted acetylenes having dynamic covalent bonds has been realised to yield static one-handed helical polymers without any other chiral moieties.

Synthesis of stable and soluble one-handed helical homopoly(substituted acetylene)s without the coexistence of any other chiral moieties via two-step polymer reactions in membrane state: molecular design of the starting monomer.

A soluble and stable one-handed helical poly(substituted phenylacetylene) without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer followed by two-step polymer reactions in membrane state: (1) removing the chiral groups (desubstitution); and (2) introduction of achiral long alkyl groups at the same position as the desubstitution to enhance the solubility of the resulting one-handed helical polymer (resubstitution). The starting chiral monomer should have four characteristic substituents: (i) a chiral group bonded to an easily hydrolyzed spacer group; (ii) two hydroxyl groups; (iii) a long rigid hydrophobic spacer between the chiral group and the polymerizing group; (iv) a long achiral group near the chiral group. As spacer group a carbonate ester was selected.

Enzymatic treatment of estrogens and estrogen glucuronide.

Natural and synthetic estrogens from sewage treatment systems are suspected to influence the reproductive health of the animals in the rivers. In this article, we investigated the enzymatic treatment of three estrogens (estrone, 17beta-estradiol, and 17alpha-ethynyletstradiol) by a fungal laccase which oxidize phenolic compounds with dissolved oxygen. The elimination of the estrogenic activities by enzymatic oxidation was demonstrated by medaka vitellogenin assay.

Electrochemical and photosensitized redox reactions of a prussian blue film layered on a WO3/[Ru(bpy)3]2+/polymer hybrid film.

A hybrid film of WO(3)/tris(2,2'-bipyridine)ruthenium(II) ([Ru(bpy)(3)](2+))/poly(sodium 4-styrenesulfonate) (PSS) (denoted as a WRP hybrid film) was prepared as a base layer on an indium tin oxide electrode substrate by cathodic electrodeposition from a colloidal ternary solution containing peroxotungstic acid, [Ru(bpy)(3)](2+), and PSS. Prussian blue, Fe(III) (4)[Fe(II)(CN)(6)](3) (Fe(II)-Fe(III)) was cathodically electrodeposited on the WRP hybrid film from a Berlin brown (Fe(III)-Fe(III)) colloidal solution to give a WRP/Fe(II)-Fe(III) bilayer film. Spectrocyclic voltammetry measurement of the WRP/Fe(II)-Fe(III) bilayer film reveals that Prussian white (Fe(II)-Fe(II)) is oxidized to Fe(II)-Fe(III) by electrogenerated Ru(III), and Fe(II)-Fe(III) is re-reduced to Fe(II)-Fe(II) by electrogenerated H(x)WO(3).

Analysis and regulation of unusual adsorption of phthalocyanine zinc(II) into a Nafion film as investigated by UV-vis spectroscopic techniques.

Phthalocyanine zinc(II) (ZnPc) was found to be adsorbed well into a Nafion (Nf) film. The kinetic analysis suggested that the adsorption of ZnPc into the Nf film is controlled by its diffusion in the Nf film with a diffusion coefficient of D = 1.9 x 10(-6) cm(2) s(-1) that is higher than those (10(-9)-10(-12) cm(2) s(-1)) of cationic redox molecules in the Nf film by 3-6 orders of magnitude.

Helix-sense-selective polymerization of phenylacetylene having two hydroxy groups using a chiral catalytic system.

We have found a simple and novel synthetic method for obtaining a chiral polymer from an achiral monomer by using a chiral catalytic system. The chirality of the polymer was caused only by a one-handed helical backbone, and the polymer had no other chiral structures in the side groups. In addition, the helical conformation was stable in solution by itself.

Ladderlike ferromagnetic spin coupling network on a pi-conjugated pendant polyradical.

A poly(9,10-anthryleneethynylene)-based polyradical with two pendant stable phenoxyls in one anthracene skeleton was newly synthesized via polymerization of the corresponding bromoethynylanthracene monomer using a Pd(0) catalyst. The average molecular weight of the polymer reached M(n) = 5 x 10(3) and was soluble in common organic solvents. The polyradical was prepared from the corresponding hydroxyl precursor polymer and was appropriately stable at room temperature.