Research

12 pages, 3488 KiB

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Alkaline Stable Anion Exchange Membranes Based on Cross-Linked Poly(arylene ether sulfone) Bearing Dual Quaternary Piperidines for Enhanced Anion Conductivity at Low Water Uptake

by Prem P. Sharma, Yeeun Jeon and Dukjoon Kim

Molecules 2022, 27(2), 364; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27020364 - 07 Jan 2022

Cited by 2 | Viewed by 2295

Abstract

Alkaline stable anion exchange membranes based on the cross-linked poly(arylene ether sulfone) grafted with dual quaternary piperidine (XPAES-DP) units were synthesized. The chemical structure of the synthesized PAES-DP was validated using ¹H-NMR and FT-IR spectroscopy. The physicochemical, thermal, and mechanical properties of [...] Read more.

Alkaline stable anion exchange membranes based on the cross-linked poly(arylene ether sulfone) grafted with dual quaternary piperidine (XPAES-DP) units were synthesized. The chemical structure of the synthesized PAES-DP was validated using ¹H-NMR and FT-IR spectroscopy. The physicochemical, thermal, and mechanical properties of XPAES-DP membranes were compared with those of two linear PAES based membranes grafted with single piperidine (PAES-P) unit and conventional trimethyl amine (PAES-TM). XPAES-DP membrane showed the ionic conductivity of 0.021 S cm⁻¹ at 40 °C which was much higher than that of PAES-P and PAES-TM because of the possession of more quaternary ammonium groups in the cross-linked structure. This cross-linked structure of the XPAES-DP membrane resulted in a higher tensile strength of 18.11 MPa than that of PAES-P, 17.09 MPa. In addition, as the XPAES-DP membrane shows consistency in the ionic conductivity even after 96 h in 3 M KOH solution with a minor change, its chemical stability was assured for the application of anion exchange membrane fuel cell. The single-cell assembled with XPAES-DP membrane displayed a power density of 109 mWcm⁻² at 80 °C under 100% relative humidity. Full article

(This article belongs to the Special Issue Exclusive Contributions by the Editorial Board Members (EBMs) of the Macromolecular Chemistry Section of Molecules 2021)

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17 pages, 4480 KiB

Open AccessArticle

Purification, Characterization, and Structural Studies of a Sulfatase from Pedobacter yulinensis

by Caleb R. Schlachter, Andrea O’Malley, Linda L. Grimes, John J. Tomashek, Maksymilian Chruszcz and L. Andrew Lee

Molecules 2022, 27(1), 87; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules27010087 - 24 Dec 2021

Cited by 3 | Viewed by 2869

Abstract

Sulfatases are ubiquitous enzymes that hydrolyze sulfate from sulfated organic substrates such as carbohydrates, steroids, and flavones. These enzymes can be exploited in the field of biotechnology to analyze sulfated metabolites in humans, such as steroids and drugs of abuse. Because genomic data [...] Read more.

Sulfatases are ubiquitous enzymes that hydrolyze sulfate from sulfated organic substrates such as carbohydrates, steroids, and flavones. These enzymes can be exploited in the field of biotechnology to analyze sulfated metabolites in humans, such as steroids and drugs of abuse. Because genomic data far outstrip biochemical characterization, the analysis of sulfatases from published sequences can lead to the discovery of new and unique activities advantageous for biotechnological applications. We expressed and characterized a putative sulfatase (PyuS) from the bacterium Pedobacter yulinensis. PyuS contains the (C/S)XPXR sulfatase motif, where the Cys or Ser is post-translationally converted into a formylglycine residue (FGly). His-tagged PyuS was co-expressed in Escherichia coli with a formylglycine-generating enzyme (FGE) from Mycobacterium tuberculosis and purified. We obtained several crystal structures of PyuS, and the FGly modification was detected at the active site. The enzyme has sulfatase activity on aromatic sulfated substrates as well as phosphatase activity on some aromatic phosphates; however, PyuS did not have detectable activity on 17α-estradiol sulfate, cortisol 21-sulfate, or boldenone sulfate. Full article

(This article belongs to the Special Issue Exclusive Contributions by the Editorial Board Members (EBMs) of the Macromolecular Chemistry Section of Molecules 2021)

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14 pages, 2838 KiB

Open AccessArticle

Engineered Bacteriorhodopsin May Induce Lung Cancer Cell Cycle Arrest and Suppress Their Proliferation and Migration

by Chui-Wei Wong, Ling-Ning Ko, Hung-Jin Huang, Chii-Shen Yang and Shan-hui Hsu

Molecules 2021, 26(23), 7344; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26237344 - 03 Dec 2021

Cited by 2 | Viewed by 1867

Abstract

Highly expressible bacteriorhodopsin (HEBR) is a light-triggered protein (optogenetic protein) that has seven transmembrane regions with retinal bound as their chromophore to sense light. HEBR has controllable photochemical properties and regulates activity on proton pumping. In this study, we generated HEBR protein and [...] Read more.

Highly expressible bacteriorhodopsin (HEBR) is a light-triggered protein (optogenetic protein) that has seven transmembrane regions with retinal bound as their chromophore to sense light. HEBR has controllable photochemical properties and regulates activity on proton pumping. In this study, we generated HEBR protein and incubated with lung cancer cell lines (A549 and H1299) to evaluate if there was a growth-inhibitory effect with or without light illumination. The data revealed that the HEBR protein suppressed cell proliferation and induced the G₀/G₁ cell cycle arrest without light illumination. Moreover, the migration abilities of A549 and H1299 cells were reduced by ~17% and ~31% after incubation with HEBR (40 μg/mL) for 4 h. The Snail-1 gene expression level of the A549 cells was significantly downregulated by ~50% after the treatment of HEBR. In addition, HEBR significantly inhibited the gene expression of Sox-2 and Oct-4 in H1299 cells. These results suggested that the HEBR protein may inhibit cell proliferation and cell cycle progression of lung cancer cells, reduce their migration activity, and suppress some stemness-related genes. These findings also suggested the potential of HEBR protein to regulate the growth and migration of tumor cells, which may offer the possibility for an anticancer drug. Full article

(This article belongs to the Special Issue Exclusive Contributions by the Editorial Board Members (EBMs) of the Macromolecular Chemistry Section of Molecules 2021)

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12 pages, 1956 KiB

Open AccessArticle

Photoredox-Catalyzed Reduction of Halogenated Arenes in Water by Amphiphilic Polymeric Nanoparticles

by Fabian Eisenreich, Tom H. R. Kuster, David van Krimpen and Anja R. A. Palmans

Molecules 2021, 26(19), 5882; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26195882 - 28 Sep 2021

Cited by 6 | Viewed by 2858

Abstract

The use of organic photoredox catalysts provides new ways to perform metal-free reactions controlled by light. While these reactions are usually performed in organic media, the application of these catalysts at ambient temperatures in aqueous media is of considerable interest. We here compare [...] Read more.

The use of organic photoredox catalysts provides new ways to perform metal-free reactions controlled by light. While these reactions are usually performed in organic media, the application of these catalysts at ambient temperatures in aqueous media is of considerable interest. We here compare the activity of two established organic photoredox catalysts, one based on 10-phenylphenothiazine (PTH) and one based on an acridinium dye (ACR), in the light-activated dehalogenation of aromatic halides in pure water. Both PTH and ACR were covalently attached to amphiphilic polymers that are designed to form polymeric nanoparticles with hydrodynamic diameter D_H ranging between 5 and 11 nm in aqueous solution. Due to the hydrophobic side groups that furnish the interior of these nanoparticles after hydrophobic collapse, water-insoluble reagents can gather within the nanoparticles at high local catalyst and substrate concentrations. We evaluated six different amphiphilic polymeric nanoparticles to assess the effect of polymer length, catalyst loading and nature of the catalyst (PTH or ACR) in the dechlorination of a range of aromatic chlorides. In addition, we investigate the selectivity of both catalysts for reducing different types of aryl-halogen bonds present in one molecule, as well as the activity of the catalysts for C-C cross-coupling reactions. We find that all polymer-based catalysts show high activity for the reduction of electron-poor aromatic compounds. For electron-rich compounds, the ACR-based catalyst is more effective than PTH. In the selective dehalogenation reactions, the order of bond stability is C-Cl > C-Br > C-I irrespective of the catalyst applied. All in all, both water-compatible systems show good activity in water, with ACR-based catalysts being slightly more efficient for more resilient substrates. Full article

(This article belongs to the Special Issue Exclusive Contributions by the Editorial Board Members (EBMs) of the Macromolecular Chemistry Section of Molecules 2021)

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13 pages, 3339 KiB

Open AccessArticle

Free-Standing, Flexible Nanofeatured Polymeric Films Prepared by Spin-Coating and Anodic Polymerization as Electrodes for Supercapacitors

by Guillem Ruano, Brenda G. Molina, Juan Torras and Carlos Alemán

Molecules 2021, 26(14), 4345; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26144345 - 18 Jul 2021

Cited by 4 | Viewed by 1973

Abstract

Flexible and self-standing multilayered films made of nanoperforated poly(lactic acid) (PLA) layers separated by anodically polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) conducting layers have been prepared and used as electrodes for supercapacitors. The influence of the external layer has been evaluated by comparing the charge storage [...] Read more.

Flexible and self-standing multilayered films made of nanoperforated poly(lactic acid) (PLA) layers separated by anodically polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) conducting layers have been prepared and used as electrodes for supercapacitors. The influence of the external layer has been evaluated by comparing the charge storage capacity of four- and five-layered films in which the external layer is made of PEDOT (PLA/PEDOT/PLA/PEDOT) and nanoperforated PLA (PLA/PEDOT/PLA/PEDOT/PLA), respectively. In spite of the amount of conducting polymer is the same for both four- and five-layered films, they exhibit significant differences. The electrochemical response in terms of electroactivity, areal specific capacitance, stability, and coulombic efficiency was greater for the four-layered electrodes than for the five-layered ones. Furthermore, the response in terms of leakage current and self-discharge was significantly better for the former electrodes than for the latter ones. Full article

(This article belongs to the Special Issue Exclusive Contributions by the Editorial Board Members (EBMs) of the Macromolecular Chemistry Section of Molecules 2021)

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10 pages, 1794 KiB

Open AccessArticle

Side-Arm Assisted Anilido-Imine Based Rare-Earth Metal Complexes for Isoprene Stereoselective Polymerization

by Yi Wu, Xinli Liu and Dongmei Cui

Molecules 2021, 26(14), 4154; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26144154 - 08 Jul 2021

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Abstract

Anilido-imine ligands o-C₆H₄(NHAr₁)(CH=NAr₂), in which Ar₁ is 2,6-diisopropylbenzyl group and Ar₂ contains fluorine (HL₁) or methoxyl (HL₂) group on ortho-position of phenyl substituent, were synthesized for constructing rare-earth [...] Read more.

Anilido-imine ligands o-C₆H₄(NHAr₁)(CH=NAr₂), in which Ar₁ is 2,6-diisopropylbenzyl group and Ar₂ contains fluorine (HL₁) or methoxyl (HL₂) group on ortho-position of phenyl substituent, were synthesized for constructing rare-earth metals based complexes of 1a–1c (HL₁ based Sc, Lu, Y) and 2a–2c (HL₂ based Sc, Lu, Y). Based on their NMR spectra and X-ray single-crystal structures, the side-arm group of -F and -OMe is identified to chelate to the corresponding central metal. The twisted angles between two planes formed by chelated heteroatoms (N, N, F for HL₁ and N, N, O for HL₂) are observed, in which the largest dihedral angle (53.3°) for HL₁-Y and the smallest dihedral angle (44.32°) for HL₂-Sc are detected. After being activated by AlⁱBu₃ and [Ph₃C][B(C₆F₅)₄], these catalysts showed great activity for isoprene polymerization. Bearing the same ligand HL₁, smaller scandium based complex 1a and middle size of lutetium based 1b provided lower cis-1,4-selectivity (57.3% and 64.2%), larger yttrium complex 1c displayed high cis-1,4-selectivity (84%). Chelating by crowded HL₂, small size of scandium complex 2a provided impressive trans-1,4-selectivity (93.0%), middle lutetium based 2b displayed non-selectivity and larger yttrium complex 2c showed clear cis-1,4-selectivity (83.3%). Moreover, 2a/AlⁱBu₃ system showed the quasi-living chain transfer capability. Full article

(This article belongs to the Special Issue Exclusive Contributions by the Editorial Board Members (EBMs) of the Macromolecular Chemistry Section of Molecules 2021)

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10 pages, 3830 KiB

Open AccessArticle

Additive Effects of Lithium Salts with Various Anionic Species in Poly (Methyl Methacrylate)

by Asae Ito and Koh-hei Nitta

Molecules 2021, 26(13), 4096; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26134096 - 05 Jul 2021

Cited by 5 | Viewed by 2766

Abstract

We report that lithium salts in lithium-ion batteries effectively modify the physical properties of poly (methyl methacrylate) (PMMA). The glass transition temperature (T_g) is an indicator of the heat resistance of amorphous polymers. The anionic species of the salts strongly [...] Read more.

We report that lithium salts in lithium-ion batteries effectively modify the physical properties of poly (methyl methacrylate) (PMMA). The glass transition temperature (T_g) is an indicator of the heat resistance of amorphous polymers. The anionic species of the salts strongly affected the glass transition behavior of PMMA. We focused on the additive effects of various lithium salts, such as LiCF₃SO₃, LiCOOCF₃, LiClO₄, and LiBr, on the T_g of PMMA. The large anions of the former three salts caused them to form macroscopic aggregates that acted as fillers in the PMMA matrix and to combine the PMMA domains, increasing T_g. On the other hand, LiBr salts dispersed microscopically in the PMMA matrix at the molecular scale, leading to the linking of the PMMA chains. Thus, the addition of LiBr to PMMA increased T_g as well as the relaxation time in the range of glass to rubber transition. Full article

(This article belongs to the Special Issue Exclusive Contributions by the Editorial Board Members (EBMs) of the Macromolecular Chemistry Section of Molecules 2021)

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12 pages, 2996 KiB

Open AccessArticle

High-Solids, Solvent-Free Modification of Engineered Polysaccharides

by Athanasios Porfyris, Constantine D. Papaspyrides, Natnael Behabtu, Cristian Lenges and Alexander Kopatsis

Molecules 2021, 26(13), 4058; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26134058 - 02 Jul 2021

Cited by 3 | Viewed by 2357

Abstract

The nature-identical engineered polysaccharide α-(1,3) glucan, produced by the enzymatic polymerization of sucrose, was chemically modified by acylation with succinic anhydride. This modification reaction was initially performed at the micro scale in a TGA reactor to access a range of reaction conditions and [...] Read more.

The nature-identical engineered polysaccharide α-(1,3) glucan, produced by the enzymatic polymerization of sucrose, was chemically modified by acylation with succinic anhydride. This modification reaction was initially performed at the micro scale in a TGA reactor to access a range of reaction conditions and to study the mechanism of the reaction. Subsequently, the best performing conditions were reproduced at the larger laboratory scale. The reaction products were characterized via coupled TGA/DSC analysis, FT-IR spectroscopy, solution viscosity and pH determination. The acylation path resulted in partially modifying the polysaccharide by altering its behavior in terms of thermal properties and solubility. The acylation in a solvent-free approach was found promising for the development of novel, potentially melt-processable and fully bio-based and biodegradable ester compounds. Full article

(This article belongs to the Special Issue Exclusive Contributions by the Editorial Board Members (EBMs) of the Macromolecular Chemistry Section of Molecules 2021)

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21 pages, 2853 KiB

Open AccessArticle

Poly(Pyridinium Salt)s Containing 2,7-Diamino-9,9′-Dioctylfluorene Moieties with Various Organic Counterions Exhibiting Both Lyotropic Liquid-Crystalline and Light-Emitting Properties

by Pradip K. Bhowmik, Tae S. Jo, Jung J. Koh, Jongwon Park, Bidyut Biswas, Ronald Carlo G. Principe, Haesook Han, András F. Wacha and Matti Knaapila

Molecules 2021, 26(6), 1560; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26061560 - 12 Mar 2021

Cited by 5 | Viewed by 2407

Abstract

A series of poly(pyridinium salt)s-fluorene main-chain ionic polymers with various organic counterions were synthesized by using ring-transmutation polymerization and metathesis reactions. Their chemical structures were characterized by Fourier Transform Infrared (FTIR), proton (¹H), and fluorine 19 (¹⁹F) nuclear magnetic [...] Read more.

A series of poly(pyridinium salt)s-fluorene main-chain ionic polymers with various organic counterions were synthesized by using ring-transmutation polymerization and metathesis reactions. Their chemical structures were characterized by Fourier Transform Infrared (FTIR), proton (¹H), and fluorine 19 (¹⁹F) nuclear magnetic resonance (NMR) spectrometers. These polymers showed a number-average molecular weight (M_ns) between 96.5 and 107.8 kg/mol and polydispersity index (PDI) in the range of 1.12–1.88. They exhibited fully-grown lyotropic phases in polar protic and aprotic solvents at different critical concentrations. Small-angle X-ray scattering for one polymer example indicates lyotropic structure formation for 60–80% solvent fraction. A lyotropic smectic phase contains 10 nm polymer platelets connected by tie molecules. The structure also incorporates a square packing motif within platelets. Thermal properties of polymers were affected by the size of counterions as determined by differential scanning calorimetry and thermogravimetric analysis measurements. Their ultraviolet-visible (UV-Vis) absorption spectra in different organic solvents were essentially identical, indicating that the closely spaced π-π* transitions occurred in their conjugated polymer structures. In contrast, the emission spectra of polymers exhibited a positive solvatochromism on changing the polarity of solvents. They emitted green lights in both polar and nonpolar organic solvents and showed blue light in the film-states, but their λ_em peaks were dependent on the size of the counterions. They formed aggregates in polar aprotic and protic solvents with the addition of water (v/v, 0–90%), and their λ_em peaks were blue shifted. Full article

(This article belongs to the Special Issue Exclusive Contributions by the Editorial Board Members (EBMs) of the Macromolecular Chemistry Section of Molecules 2021)

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