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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. Because this exfoliated 2DP is soluble, the macromolecular structure can be fully characterized by 1 H-NMR, GPC, SEM, AFM, and its dense membrane with no defects can be fabricated by the solvent cast method. This soluble 2DP macromolecule has very small micropores (6.0 Å) inside the macromolecule, a large area (30 × 68 nm by SEM and AFM), high molecular weight (Mn = 2.80 × 105 by GPC), and a small thickness (4.4 Å by AFM). This membrane shows the highest oxygen permselectivity exceeding Robeson's upper line because of the high molecular sieving effect of the controlled small micropores.
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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). Since this significantly unique EPHS method (EPHS = ES-HSSP + HS-SCAT) does not need any optical resolution agents, any cocatalysts, and solvents for the selective decomposition reaction (HS-SCAT), this process is quite simple and convenient. Since this process does not include any decomposition of the target racemates themselves, both enantiomers could be obtained. The optical yields for isolated compounds that were enantiomerically separated by the EPHS method were very high, for example, 78%ee, 93%ee, and 85%ee for menthol, phenethyl alcohol, and 2-butanol, respectively. In addition, their chemical yields were around 85% to 94%. Therefore, the EPHS method was found to show an excellent performance and can be applied to actual optical resolution for a wide range of racemic compounds. This is the first absolute optical resolution by CPL showing high optical and chemical yields and expected to become a practical optical resolution method.
Assuntos
Acetileno , EstereoisomerismoRESUMO
A substituted poly(phenylacetylene) derivative (PPAHB ) with two hydroxymethyl groups at the meta position of the side phenyl ring was examined as a conformation-switchable helical spring polymer that responds to solvent and heat stimuli in a precisely controlled manner. Intramolecular hydrogen bonds, which cause the helical structure of the polymer, were broken and re-formed by adjusting the hydrogen-bonding strength values (pKHB ) of various combinations of solvents or by varying the temperature. In this process, a reversible conformational change from cis-cisoid to cis-transoid, accompanied by a phase transition in the form of a helix-coil transformation occurred, with the polymer exhibiting critical changes of color fading and recovery in specific environments. These results demonstrate that PPAHB can be used as either a pKHB indicator or a thermometer. The color changes of the polymer solution are described in detail based on spectroscopic analyses and thermodynamic considerations.
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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.
Assuntos
Substâncias Macromoleculares/síntese química , Membranas Artificiais , Polímeros/síntese química , Substâncias Macromoleculares/química , Estrutura Molecular , Polímeros/químicaRESUMO
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. In addition, the polymer ligands could be easily recovered by precipitation after the reaction.
Assuntos
Acetileno/análogos & derivados , Amino Álcoois/química , Benzaldeídos/química , Compostos Organometálicos/química , Acetileno/química , EstereoisomerismoRESUMO
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 (). Oxygen permselectivity through a base polymer membrane was highly enhanced from 1.83 to 2.36 by adding a small amount (1-5 wt%) of the 2D surface modifier . The improvement was thought to be caused by improvement of solution selectivity on the membrane surface which the 2D surface modifier effectively covered.
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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. This membrane could separate racemic helical oligoacetylenes enantioselectively in up to 30%ee. To our knowledge, this is the first example of HSSPerm.
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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.e., a 1,3,5-trisubstituted benzene derivative, quantitatively (100%). No byproducts were produced under the best conditions. (2) It is an intramolecular reaction: it occurred between three adjacent monomer units in one macromolecule. (3) It is a stereospecific and topochemical or template reaction: the reactivity strongly depended on the configuration and conformation of the starting polymer substrates. (4) It is a photoreaction: high selectivity (100%) was observed only by the use of visible light irradiation, not by heating. (5) It is a solid-state reaction: high selectivity (100%) was observed only in the solid state, not in solution. In addition, (6) the resulting cyclic trimers could form a self-supporting membrane, despite their low molecular weights. This new approach resulted in a new class of supramolecular polymers consisting of a 1,3,5-trisubstituted benzene derivative, numbers of which were linearly linked by hydrogen bonds and stacked benzene derivatives. Since SCAT has such high selectivities and is useful for the preparation of a self-supporting supramolecular polymer membrane, many applications can be expected.
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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). The tight helical cis-cisoidal main chain formed by making intramolecular hydrogen bonds between the hydroxyl groups in the copoly(1/3) enhances the efficiency of chiral induction and as a result chiral amplification phenomenon is observed during the copolymerization.
Assuntos
Acetileno/análogos & derivados , Acetileno/química , Catálise , Dicroísmo Circular , Ligação de Hidrogênio , Conformação Molecular , Polimerização , EstereoisomerismoRESUMO
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. The two hydroxyl groups formed intramolecular hydrogen bonds stabilizing a one-handed helical structure in solution before and after the two-step polymer reactions in membrane state. The rigid long hydrophobic spacer, a phenylethynylphenyl group, enhanced the solubility of the starting polymer, and realized effective chiral induction from the chiral side groups to the main chain in the asymmetric-induced polymerization. The long alkyl group near the chiral group avoided shrinkage of the membrane and kept the reactivity of resubstitution in membrane state after removing the chiral groups. The g value (g = ([θ]/3,300)/ε) for the CD signal assigned to the main chain in the obtained final polymer was almost the same as that of the starting polymer in spite of the absence of any other chiral moieties. Moreover, since the one-handed helical structure was maintained by the intramolecular hydrogen bonds in a solution, direct observation of the one-handed helicity of the final homopolymer has been realized in CD for the solution for the first time.
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Acetileno/análogos & derivados , Membranas Artificiais , Polimerização , Acetileno/síntese química , Acetileno/química , Acetileno/isolamento & purificação , Dicroísmo Circular , Ligação de Hidrogênio , Conformação Molecular , Espectrofotometria Infravermelho , Espectrofotometria Ultravioleta , EstereoisomerismoRESUMO
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 3.46 Å and 3.64 Å, respectively, the architectures of the membrane macromolecules should be designed precisely. It has been reported often that oxygen permeability (PO2) and oxygen permselectivity (α = PO2/PN2) have trade-off relationships for symmetric membranes made from pure polymers. Some empirical upper bound lines have been reported in (ln α - ln PO2) plots since Robeson reported an upper bound line in 1991 for the first time. The main purpose of this review is to discuss suitable macromolecular structures that produce excellent oxygen/nitrogen permselective membranes. For this purpose, we first searched extensively and intensively for papers which had reported α and PO2 values through symmetric dense membranes from pure polymers. Then, we examined the chemical structures of the polymers showing the top performances in (ln α - ln PO2) plots, using their aged performances. Furthermore, we also explored progress in the molecular design in this field by comparing the best polymers reported by 2013 and those subsequently found up to now (2020) because of the rapid outstanding growth in this period. Finally, we discussed how to improve α and PO2 simultaneously on the basis of reported results using not only symmetric membranes of pure organic polymers but also composite asymmetric membranes containing various additives.
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Noncovalent chemistry may offer diversity in the functions and applications for artificial polymers by allowing various ordered-disordered phase transitions in a precisely controlled manner. To verify this notion from a fundamental perspective, we examined an achiral poly(phenylacetylene) derivative with an α-helical structure as a helical-spring polymer for revealing phase changes through control of intramolecular hydrogen bonding with the chiral solvent and temperature. When an amine capable of hydrogen bonding was used as the chiral solvent, either an irreversible helix-helix or a reversible helix-coil phase change occurred in an optically dissymmetric manner according to the amount of the chiral solvent added and ambient temperature. Considering the hydrogen-bonding strength values of the solvent mixture and the thermodynamic parameters, we could predict if the optical-dissymmetry phase changes would occur and, if so, how they occur. Our results were similar to those see for the denaturation of proteins, induced by solvent and temperature, based on helix-coil phase transition.
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Polímeros , Ligação de Hidrogênio , Conformação Molecular , Solventes , TemperaturaRESUMO
Three new phenylacetylene monomers having one or two carbamate groups were synthesized and polymerized by using (Rh(norbornadiene)Cl)2 as an initiator. The resulting polymers had very high average molecular weights (Mw) of 1.4-4.8 × 106, with different solubility and membrane-forming abilities. The polymer having two carbamate groups and no hydroxy groups in the monomer unit showed the best solubility and membrane-forming ability among the three polymers. In addition, the oxygen permeability coefficient of the membrane was more than 135 times higher than that of a polymer having no carbamate groups and two hydroxy groups in the monomer unit with maintaining similar oxygen permselectivity. A better performance in membrane-forming ability and oxygen permeability may be caused by a more extended and flexible cis-transoid conformation and lower polarity. On the other hand, the other two new polymers having one carbamate group and two hydroxy groups in the monomer unit showed lower performances in membrane-forming abilities and oxygen permeabilities. It may be caused by a very tight cis-cisoid conformation, which was maintained by intramolecular hydrogen bonds.
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Newly synthesized two kinds of achiral phenylacetylenes having a free-base- or a zinc-porphyrin (1 and Zn1, respectively) were polymerized by using a chiral rhodium catalyst system, Rhâº(nbd)[(η6-C6H5)Bâ»(C6H5)3] catalyst and (R)-(+)- or (S)-(â»)-1-phenylethylamine ((R)- or (S)-PEA, respectively) cocatalyst. Poly(1) and poly(Zn1) 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(1) and poly(Zn1) exist in a conformation with an excess of one-handed helix sense and the porphyrin moiety arranged in chiral helical fashion. The one-handed helical structure of poly(1) could be sustained in a mixture of THF/HMPA (10/2, v/v) due to stabilizing by stacking effect of porphyrin moieties along the main chain. This is the first example about helix-sense-selective polymerization by using Rhâº(nbd)[(η6-C6H5)Bâ»(C6H5)3] catalyst. Additionally, poly(Zn1) showed about 10 times larger CD intensity in comparison with poly(1). This result suggests the regularity of arrangement of the porphyrin in poly(Zn1) is higher compared with poly(1). Spatial arrangement of porphyrins was achieved by utilizing a one-handed helical poly(phenylacetylenes) as a template.
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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(C6H5)4] or [Rh(nbd)Cl]2 catalysts in the presence of chiral (R)-(+)- or (S)-(-)-1-phenylethylamine ((R)- or (S)-PEA) cocatalysts. Poly(m-HGDHPA) and poly(m-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. However, there was no Cotton effect for poly(p-HGDHPA) and poly(p-HGTHPA) because the intramolecular hydrogen bonding did not act well to stabilize the helical conformation. The hydrogalvinoxyl units of poly(m-HGDHPA) and poly(m-HGTHPA) were converted to the corresponding galvinoxyl radicals after treatment with PbO2. In the CD spectra of the polyradicals, the Cotton effects decreased depending on their static stability of helical conformation, suggesting that reversal conformation of the polymer chain arose.
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Two kinds of novel nanoporous polycondensates (sc(Rf)) 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 (1.0 wt%) of sc(Rf), had ultrahigh oxygen permeability (Po2 > 1000 barrer), and their plots were beyond the Robeson's upper bound line in the graph of oxygen permselectivity (α = Po2/PN2) versus Po2. Both α and Po2 values were enhanced by adding only small amounts (1.0 wt%) of sc(Rf). One of the sc(Rf)s synthesized on the base membrane surface showed the best performance, i.e., Po2 = 5300 barrer and α = 2.5. The membrane surface was effectively covered by sc(Rf), judging from the contact angle values. It is thought that nanopores and nanospaces created in and between sc(Rf) molecules played an important role for the enhancement of both α and Po2/PN2.
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Three soluble hyperbranched polyazomethines containing oligosiloxane end group HBP-PAZ-SiOn were successfully synthesized. HBP-PAZ-SiOns were used as modifiers of ethyl cellulose (EC) and polysulfone (PS) membranes. Blend membranes, HBP-PAZ-SiOn /EC and HBP-PAZ-SiOn /PS were prepared by blending the THF solution of HBP-PAZ-SiOn with ethanol solution of EC and dichloromethane solution of PS, respectively. Surprisingly, the permeabilities for CO2 of the blend membranes were more than 15-16 times higher than those of pure EC and PS membranes without any drop of pemselectivity to N2. This unusual improvement has been achieved by both enhancement of diffusivity for carbon dioxide and nitrogen by the oligosiloxane groups and enhancement of affinity of the amino groups with carbon dioxide at the end groups of HBP-PAZ-SiOn .
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The [Rh(L-alaninate)(cod)] (cod = 1,5-Cyclooctadiene) complex was synthesized and characterized. Asymmetric polymerizations of achiral phenylacetylene with two hydroxyl groups and a dodecyl group (DoDHPA) were performed by using the rhodium complex as the catalyst to provide polymers with a higher molecular weight (>105) than the polymers obtained using the [Rh(cod)Cl]2 initiator systems. The resulting polymers showed circular dichroism (CD) signals at approximately 310 and 470 nm, indicating that they have a preferential one-handed helical structure. The helix sense in the polymer main chain was controlled by the sign of the catalyst chirality. These findings suggest that the rhodium complex with a chiral amine is the true active species for the helix-sense-selective polymerization of DoDHPA. The [Rh(L-alaninate)(cod)] complex also exhibits high catalytic activity in the polymerization of phenylacetylene (PA) to give a high yield and molecular weight. All these results demonstrate that this Rh complex is an excellent catalyst for the polymerization of phenylacetylene monomers.
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The importance of capnometry and end-tidal carbon dioxide (ETCO2) has been underscored in recent years by guidelines as a method to continuously monitor adequacy of ventilation during sedation and anesthesia. Guidelines for cardiopulmonary resuscitation (CPR) recommend attempts to improve CPR quality if ETCO2 is lower than 10 mmHg. ETCO2 is thus a time-critical parameter that may benefit from being delivered in real time to health care providers. We performed a pilot study to investigate whether the addition of audible capnometric cues after each breath enhanced providers' ability to maintain appropriate ventilation over conventional capnography. The addition of audible cues was confirmed to enhance control of ETCO2 during manual ventilation. We subsequently developed five distinct audible capnometric cues corresponding to different levels of ETCO2. We performed a study using ten random simulated test cases to confirm whether changes between levels as well as the direction of change could be distinguished using these audible cues. Audible cues were found to be easily distinguishable. 16 evaluators correctly identified presence and direction of change in ETCO2 with an average pass rate of 89%. It is anticipated that this "ETCO2 Audible Cue" feature will be able to improve the quality of patient monitoring, as well help improve the quality of CPR.
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Monitorização Fisiológica , Capnografia , Dióxido de Carbono , Sinais (Psicologia) , Humanos , Projetos Piloto , Volume de Ventilação PulmonarRESUMO
By using a living one-handed helical cis-transoidal poly(chiral substituted phenylacetylene) as a polymer initiator (poly(1n)), helix-sense-selective polymerization (HSSP) of an achiral phenylacetylene 2 having two hydroxy groups successfully afforded a diblock copoly(phenylacetylene) (copoly(1n/2m)) consisting of a dynamic one-handed helical cis-transoidal block and a static one-handed helical cis-cisoidal block. The formation of the diblock structure was confirmed by consumption of the chiral initiator, appearance of characteristic CD indicating the one-handed helical cis-cisoidal block, and occurrence of the selective photocylic aromatization reaction in the cis-cisoidal block. Therefore, HSSP has been achieved by using the chiral alkenyl groups in the initiator as a chiral source for the first time. In addition, since the HSSP was achieved in spite of the long distance between the chiral initiation site and the propagating site, chiral teleinduction through the rigid and static one-handed helical cis-cisoidal block based on domino effects was confirmed.