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12 pages, 3488 KiB

Open AccessArticle

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://doi.org/10.3390/molecules27020364 - 7 Jan 2022

Cited by 3 | Viewed by 2879

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://doi.org/10.3390/molecules27010087 - 24 Dec 2021

Cited by 3 | Viewed by 3434

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://doi.org/10.3390/molecules26237344 - 3 Dec 2021

Cited by 2 | Viewed by 2328

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://doi.org/10.3390/molecules26195882 - 28 Sep 2021

Cited by 7 | Viewed by 3415

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://doi.org/10.3390/molecules26144345 - 18 Jul 2021

Cited by 5 | Viewed by 2404

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://doi.org/10.3390/molecules26144154 - 8 Jul 2021

Viewed by 2470

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://doi.org/10.3390/molecules26134096 - 5 Jul 2021

Cited by 6 | Viewed by 3175

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://doi.org/10.3390/molecules26134058 - 2 Jul 2021

Cited by 3 | Viewed by 2759

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://doi.org/10.3390/molecules26061560 - 12 Mar 2021

Cited by 5 | Viewed by 2909

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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19 pages, 7838 KiB

Open AccessArticle

Hydroxyapatite-poly(d,l-lactide) Nanografts. Synthesis and Characterization as Bone Cement Additives

by Kristina L. Goranova, Anne Kathrine Kattenhøj Sloth Overgaard and Ivan Gitsov

Molecules 2021, 26(2), 424; https://doi.org/10.3390/molecules26020424 - 15 Jan 2021

Cited by 9 | Viewed by 2531

Abstract

This paper reports the creation of hydroxyapatite/polyester nanografts by “graft-from” polymerization of d,l-lactide with [Ca₅(OH)(PO₄)₃]₂ as the initiator and tin(II)-2-ethylhexanoate as the catalyst. Model polymerizations were performed with cyclooctanol as initiator to confirm [...] Read more.

This paper reports the creation of hydroxyapatite/polyester nanografts by “graft-from” polymerization of d,l-lactide with [Ca₅(OH)(PO₄)₃]₂ as the initiator and tin(II)-2-ethylhexanoate as the catalyst. Model polymerizations were performed with cyclooctanol as initiator to confirm the grafting on the surface of the hydroxyapatite nanocrystals. Polymers with the highest molecular mass (M_n) between 4250 Da (cyclooctanol) and 6100 Da (hydroxyapatite) were produced. In both cases the molecular mass distributions of the polymers formed were monomodal. The materials obtained were characterized by size-exclusion chromatography, NMR and FT-IR spectroscopy, and thermal methods. Their suitability as additives for commercial bone cement (Simplex P Speedset, Stryker Orthopaedics) has been confirmed by thermal analysis techniques and mechanical testing. The results obtained show that addition of the hydroxyapatite/ polyester nanografts improved both thermal and mechanical properties of the bone cement. Full article

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

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12 pages, 2661 KiB

Open AccessArticle

Lectin and E. coli Binding to Carbohydrate-Functionalized Oligo(ethylene glycol)-Based Microgels: Effect of Elastic Modulus, Crosslinker and Carbohydrate Density

by Fabian Schröer, Tanja J. Paul, Dimitri Wilms, Torben H. Saatkamp, Nicholas Jäck, Janita Müller, Alexander K. Strzelczyk and Stephan Schmidt

Molecules 2021, 26(2), 263; https://doi.org/10.3390/molecules26020263 - 7 Jan 2021

Cited by 5 | Viewed by 2890

Abstract

The synthesis of carbohydrate-functionalized biocompatible poly(oligo(ethylene glycol) methacrylate microgels and the analysis of the specific binding to concanavalin A (ConA) and Escherichia coli (E. coli) is shown. By using different crosslinkers, the microgels’ size, density and elastic modulus were varied. Given [...] Read more.

The synthesis of carbohydrate-functionalized biocompatible poly(oligo(ethylene glycol) methacrylate microgels and the analysis of the specific binding to concanavalin A (ConA) and Escherichia coli (E. coli) is shown. By using different crosslinkers, the microgels’ size, density and elastic modulus were varied. Given similar mannose (Man) functionalization degrees, the softer microgels show increased ConA uptake, possibly due to increased ConA diffusion in the less dense microgel network. Furthermore, although the microgels did not form clusters with E. coli in solution, surfaces coated with mannose-functionalized microgels are shown to bind the bacteria whereas galactose (Gal) and unfunctionalized microgels show no binding. While ConA binding depends on the overall microgels’ density and Man functionalization degree, E. coli binding to microgels’ surfaces appears to be largely unresponsive to changes of these parameters, indicating a rather promiscuous surface recognition and sufficiently strong anchoring to few surface-exposed Man units. Overall, these results indicate that carbohydrate-functionalized biocompatible oligo(ethylene glycol)-based microgels are able to immobilize carbohydrate binding pathogens specifically and that the binding of free lectins can be controlled by the network density. Full article

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

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18 pages, 6219 KiB

Open AccessArticle

Structural Characterization of Act c 10.0101 and Pun g 1.0101—Allergens from the Non-Specific Lipid Transfer Protein Family

by Andrea O’Malley, Swanandi Pote, Ivana Giangrieco, Lisa Tuppo, Anna Gawlicka-Chruszcz, Krzysztof Kowal, Maria Antonietta Ciardiello and Maksymilian Chruszcz

Molecules 2021, 26(2), 256; https://doi.org/10.3390/molecules26020256 - 6 Jan 2021

Cited by 7 | Viewed by 2773

Abstract

(1) Background: Non-specific lipid transfer proteins (nsLTPs), which belong to the prolamin superfamily, are potent allergens. While the biological role of LTPs is still not well understood, it is known that these proteins bind lipids. Allergen nsLTPs are characterized by significant stability and [...] Read more.

(1) Background: Non-specific lipid transfer proteins (nsLTPs), which belong to the prolamin superfamily, are potent allergens. While the biological role of LTPs is still not well understood, it is known that these proteins bind lipids. Allergen nsLTPs are characterized by significant stability and resistance to digestion. (2) Methods: nsLTPs from gold kiwifruit (Act c 10.0101) and pomegranate (Pun g 1.0101) were isolated from their natural sources and structurally characterized using X-ray crystallography (3) Results: Both proteins crystallized and their crystal structures were determined. The proteins have a very similar overall fold with characteristic compact, mainly α-helical structures. The C-terminal sequence of Act c 10.0101 was updated based on our structural and mass spectrometry analysis. Information on proteins’ sequences and structures was used to estimate the risk of cross-reactive reactions between Act c 10.0101 or Pun g 1.0101 and other allergens from this family of proteins. (4) Conclusions: Structural studies indicate a conformational flexibility of allergens from the nsLTP family and suggest that immunoglobulin E binding to some surface regions of these allergens may depend on ligand binding. Both Act c 10.0101 and Pun g 1.0101 are likely to be involved in cross-reactive reactions involving other proteins from the nsLTP family. Full article

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

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12 pages, 3815 KiB

Open AccessArticle

Intercalated Poly (2-acrylamido-2-methyl-1-propanesulfonic Acid) into Sulfonated Poly (1,4-phenylene ether-ether-sulfone) Based Proton Exchange Membrane: Improved Ionic Conductivity

by Murli Manohar, Prem P. Sharma and Dukjoon Kim

Molecules 2021, 26(1), 161; https://doi.org/10.3390/molecules26010161 - 31 Dec 2020

Cited by 9 | Viewed by 2545

Abstract

A series of hybrid proton exchange membranes were synthesized via in situ polymerization of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) PMPS with sulfonated poly (1,4-phenylene ether-ether-sulfone) (SPEES). The insertion of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) PMPS, between the rigid skeleton of SPEES plays a reinforcing role to enhance [...] Read more.

A series of hybrid proton exchange membranes were synthesized via in situ polymerization of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) PMPS with sulfonated poly (1,4-phenylene ether-ether-sulfone) (SPEES). The insertion of poly (2-acrylamido-2-methyl-1-propanesulfonic acid) PMPS, between the rigid skeleton of SPEES plays a reinforcing role to enhance the ionic conductivity. The synthesized polymer was chemically characterized by fourier-transform infrared spectroscopy (FT-IR) and nuclear magnetic resonance ¹H NMR spectroscopy to demonstrate the successful grafting of PMPS with the pendent polymer chain of SPEES. A variety of physicochemical properties were also investigated such as ion exchange capacity (IEC), proton conductivity, water uptake and swelling ratio to characterize the suitability of the formed polymer for various electrochemical applications. SP-PMPS-03, having the highest concentration of all PMPS, shows excellent proton conductivity of 0.089 S cm⁻¹ at 80 °C which is much higher than SPEES which is ~0.049 S cm⁻¹. Optimum water uptake and swelling ratio with high conductivity is mainly attributed to a less ordered arrangement polymer chain with high density of the functional group to facilitate ionic transport. The residual weight was 93.35, 92.44 and 89.56%, for SP-PMPS-01, 02 and 03, respectively, in tests with Fenton’s reagent after 24 h. In support of all above properties a good chemical and thermal stability was also achieved by SP-PMPS-03, owing to the durability for electrochemical application. Full article

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

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18 pages, 5110 KiB

Open AccessArticle

Dendrons and Dendritic Terpolymers: Synthesis, Characterization and Self-Assembly Comparison

by Sofia Rangou, Dimitrios Moschovas, Ioannis Moutsios, Gkreti-Maria Manesi, Konstantina Tsitoni, Polina V. Bovsunovskaya, Dimitri A. Ivanov, Edwin L. Thomas and Apostolos Avgeropoulos

Molecules 2020, 25(24), 6030; https://doi.org/10.3390/molecules25246030 - 19 Dec 2020

Cited by 5 | Viewed by 2674

Abstract

To the best of our knowledge, this is the very first time that a thorough study of the synthetic procedures, molecular and thermal characterization, followed by structure/properties relationship for symmetric and non-symmetric second generation (2-G) dendritic terpolymers is reported. Actually, the synthesis of [...] Read more.

To the best of our knowledge, this is the very first time that a thorough study of the synthetic procedures, molecular and thermal characterization, followed by structure/properties relationship for symmetric and non-symmetric second generation (2-G) dendritic terpolymers is reported. Actually, the synthesis of the non-symmetric materials is reported for the first time in the literature. Anionic polymerization enables the synthesis of well-defined polymers that, despite the architecture complexity, absolute control over the average molecular weight, as well as block composition, is achieved. The dendritic type macromolecular architecture affects the microphase separation, because different morphologies are obtained, which do not exhibit long range order, and various defects or dislocations are evident attributed to the increased number of junction points of the final material despite the satisfactory thermal annealing at temperatures above the highest glass transition temperature of all blocks. For comparison reasons, the initial dendrons (miktoarm star terpolymer precursors) which are connected to each other in order to synthesize the final dendritic terpolymers are characterized in solution and in bulk and their self-assembly is also studied. A major conclusion is that specific structures are adopted which depend on the type of the core connection between the ligand and the active sites of the dendrons. Full article

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

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14 pages, 1457 KiB

Open AccessFeature PaperArticle

Self-Assembly of Low-Molecular-Weight Asymmetric Linear Triblock Terpolymers: How Low Can We Go?

by Christina Miskaki, Ioannis Moutsios, Gkreti-Maria Manesi, Konstantinos Artopoiadis, Cheng-Yen Chang, Egor A. Bersenev, Dimitrios Moschovas, Dimitri A. Ivanov, Rong-Ming Ho and Apostolos Avgeropoulos

Molecules 2020, 25(23), 5527; https://doi.org/10.3390/molecules25235527 - 25 Nov 2020

Cited by 3 | Viewed by 3273

Abstract

The synthesis of two (2) novel triblock terpolymers of the ABC type and one (1) of the BAC type, where A, B and C are chemically different segments, such as polystyrene (PS), poly(butadiene) (PB_1,4) and poly(dimethylsiloxane) (PDMS), is reported; moreover, their [...] Read more.

The synthesis of two (2) novel triblock terpolymers of the ABC type and one (1) of the BAC type, where A, B and C are chemically different segments, such as polystyrene (PS), poly(butadiene) (PB_1,4) and poly(dimethylsiloxane) (PDMS), is reported; moreover, their corresponding molecular and bulk characterizations were performed. Very low dimensions are evident from the characterization in bulk from transmission electron microscopy studies, verified by small-angle X-ray data, since sub-16 nm domains are evident in all three cases. The self-assembly results justify the assumptions that the high Flory–Huggins parameter, χ, even in low molecular weights, leads to significantly well-ordered structures, despite the complexity of the systems studied. Furthermore, it is the first time that a structure/properties relationship was studied for such systems in bulk, potentially leading to prominent applications in nanotechnology and nanopatterning, for as low as sub-10 nm thin-film manipulations. Full article

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

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10 pages, 2978 KiB

Open AccessArticle

High Performance Redox Initiating Systems Based on the Interaction of Silane with Metal Complexes: A Unique Platform for the Preparation of Composites

by Ahmad Arar, Haifaa Mokbel, Frédéric Dumur and Jacques Lalevée

Molecules 2020, 25(7), 1602; https://doi.org/10.3390/molecules25071602 - 31 Mar 2020

Cited by 6 | Viewed by 3084

Abstract

Currently, Redox Initiating Systems (RISs) of Free Radical Polymerization (FRP) are mainly based on the interaction of aromatic amines with peroxides (e.g., dibenzoyl peroxide (BPO)) that can be both toxic and unstable. In the present work, we aim to replace these hazardous substances [...] Read more.

Currently, Redox Initiating Systems (RISs) of Free Radical Polymerization (FRP) are mainly based on the interaction of aromatic amines with peroxides (e.g., dibenzoyl peroxide (BPO)) that can be both toxic and unstable. In the present work, we aim to replace these hazardous substances in new RIS that can be peroxide-free and amine-free. Our redox two components (2K) initiating system is based on diphenylsilane (DPS) as reducing agent combined with different metal complexes (Mn(acac)₂, Cu(AAEMA)₂ or Fe(acac)₃) as oxidizing agents. For the new proposed RIS, an excellent reactivity is found for the polymerization of benchmark methacrylate monomers under mild conditions (redox polymerization done under air and at room temperature); remarkably, it is also possible to finely control the gel time. Different techniques (optical pyrometry, Real-Time FTIR spectroscopy, Cyclic Voltammetry and Electron Spin Resonance (ESR)) were used to follow the polymerization processes but also to shed some light on the new redox chemical mechanisms. Full article

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

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17 pages, 5235 KiB

Open AccessFeature PaperReview

Design Strategies of Conductive Hydrogel for Biomedical Applications

by Junpeng Xu, Yu-Liang Tsai and Shan-hui Hsu

Molecules 2020, 25(22), 5296; https://doi.org/10.3390/molecules25225296 - 13 Nov 2020

Cited by 81 | Viewed by 9525

Abstract

Conductive hydrogel, with electroconductive properties and high water content in a three-dimensional structure is prepared by incorporating conductive polymers, conductive nanoparticles, or other conductive elements, into hydrogel systems through various strategies. Conductive hydrogel has recently attracted extensive attention in the biomedical field. Using [...] Read more.

Conductive hydrogel, with electroconductive properties and high water content in a three-dimensional structure is prepared by incorporating conductive polymers, conductive nanoparticles, or other conductive elements, into hydrogel systems through various strategies. Conductive hydrogel has recently attracted extensive attention in the biomedical field. Using different conductivity strategies, conductive hydrogel can have adjustable physical and biochemical properties that suit different biomedical needs. The conductive hydrogel can serve as a scaffold with high swelling and stimulus responsiveness to support cell growth in vitro and to facilitate wound healing, drug delivery and tissue regeneration in vivo. Conductive hydrogel can also be used to detect biomolecules in the form of biosensors. In this review, we summarize the current design strategies of conductive hydrogel developed for applications in the biomedical field as well as the perspective approach for integration with biofabrication technologies. Full article

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

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