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Keywords = polydiacetylenes

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18 pages, 12270 KiB  
Article
Sulfonate Thiacalixarene-Modified Polydiacetylene Vesicles as Colorimetric Sensors for Lead Ion Detection
by Angelina A. Fedoseeva, Indira Yespanova, Elza D. Sultanova, Bulat Kh. Gafiatullin, Regina R. Ibragimova, Klara Kh. Darmagambet, Marina A. Il’ina, Egor O. Chibirev, Vladimir G. Evtugyn, Nurbol O. Appazov, Vladimir A. Burilov, Svetlana E. Solovieva and Igor S. Antipin
Colloids Interfaces 2025, 9(2), 20; https://doi.org/10.3390/colloids9020020 - 28 Mar 2025
Viewed by 646
Abstract
We report the first synthesis of zwitterionic thiacalixarenes featuring imidazolium and sulfonate groups on the upper rim and alkyl (butyl or octyl) fragments on the lower rim of the platform. Despite their amphiphilic structure, these macrocycles exhibit limited water solubility. However, dynamic light [...] Read more.
We report the first synthesis of zwitterionic thiacalixarenes featuring imidazolium and sulfonate groups on the upper rim and alkyl (butyl or octyl) fragments on the lower rim of the platform. Despite their amphiphilic structure, these macrocycles exhibit limited water solubility. However, dynamic light scattering detected the formation of associates for derivatives with octyl moieties at a concentration of 0.1 mM. To develop stable materials for aqueous environments and to investigate the functionality of zwitterionic sulfonate-imidazolium groups along with the thiacalixarene platform, mixed organo-organic systems based on polydiacetylene polymer were created. Characterization of the modified polydiacetylene systems through various analytical methods revealed a significant colorimetric response to lead ions in aqueous media, surpassing that of the unmodified polydiacetylene polymer. Additionally, the modified polymers demonstrated efficacy in purifying aqueous media from lead ions, as evidenced by anodic stripping voltammetry (ASV) and microwave plasma atomic emission spectroscopy (MP AES). Full article
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18 pages, 5657 KiB  
Article
Orientation of Conjugated Polymers in Single Crystals: Is It Really Unusual for the Polydiacetylene Backbone to Be Aligned Almost Perpendicular to the Hydrogen Bond Network?
by Pierre Baillargeon, Mathieu Desnoyers-Barbeau, Marc-Olivier Pouliot, Émile Gaouette, Rose Champoux, Myriam Veillette, Félix-Antoine Lemieux, Valentina Rojas Riano, Simone Picard, Ophélie Théberge, Jakob Boulanger, Sabrina Cissé, Daniel Fortin and Tarik Rahem
Solids 2025, 6(1), 12; https://doi.org/10.3390/solids6010012 - 9 Mar 2025
Viewed by 2092
Abstract
We report the topochemical solid-state polymerization of different series of symmetrical diacetylenes (DAs) and asymmetrical chlorodiacetylenes (ClDAs), whose members differ in their alkyl spacing lengths of one to four methylene units (n = 1, 2, 3, 4) between the diyne and carbamate [...] Read more.
We report the topochemical solid-state polymerization of different series of symmetrical diacetylenes (DAs) and asymmetrical chlorodiacetylenes (ClDAs), whose members differ in their alkyl spacing lengths of one to four methylene units (n = 1, 2, 3, 4) between the diyne and carbamate functionalities. Structure determination by single-crystal X-Ray diffraction (SCXRD) confirms that in each of these series, at least 50% of the analyses show monomers with a particular stacking pattern presenting two potential directions of polymerization simultaneously. An organization of a crystalline polydiacetylene (PDA) with an oblique chain orientation with respect to the network of cooperatives hydrogen bonds is rather rare in the literature (only two cases), and here we have obtained two more examples of this type of structural motif (supported by SCXRD analysis of the polymer). Orientation control is essential to optimize the performance of conjugated polymers, and a spacer length modification strategy presents a potential way to achieve this in the case of PDA. Full article
(This article belongs to the Special Issue Young Talents in Solid-State Sciences)
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18 pages, 3039 KiB  
Article
Nanoscale “Chessboard” Pattern Lamellae in a Supramolecular Perylene-Diimide Polydiacetylene System
by Ian J. Martin, Francis Kiranka Masese, Kuo-Chih Shih, Mu-Ping Nieh and Rajeswari M. Kasi
Molecules 2025, 30(6), 1207; https://doi.org/10.3390/molecules30061207 - 7 Mar 2025
Cited by 1 | Viewed by 761
Abstract
The rational design of ordered chromogenic supramolecular polymeric systems is critical for the advancement of next-generation stimuli-responsive, optical, and semiconducting materials. Previously, we reported the design of a stimuli-responsive, lamellar self-assembled platform composed of an imidazole-appended perylene diimide of varying methylene spacer length [...] Read more.
The rational design of ordered chromogenic supramolecular polymeric systems is critical for the advancement of next-generation stimuli-responsive, optical, and semiconducting materials. Previously, we reported the design of a stimuli-responsive, lamellar self-assembled platform composed of an imidazole-appended perylene diimide of varying methylene spacer length (n = 3, 4, and 6) and a commercially available diacid-functionalized diacetylene monomer, 10, 12 docosadiynedioic acid, in a 1:1 molar ratio. Herein, we expound on the importance of the composition of the imidazole-appended perylene diimide of varying methylene spacer length (n = 3, 4, and 6) and 10, 12 docosadiynedioic acid in the ratio of 2:1 to the supramolecular self-assembly, final morphology, and properties. Topochemical polymerization of the drop-cast films by UV radiation yielded blue-phase polydiacetylene formation, and subsequent thermal treatment of the films produced a thermoresponsive blue-to-red phase transformation. Differential scanning calorimetry (DSC) studies revealed a dual dependence of the methylene spacer length and stimuli treatment (UV and/or heat) on the thermal transitions of the films. Furthermore, small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) showed well-defined hierarchical semiconducting nanostructures with interconnected “chessboard”-patterned lamellar stacking. Upon doping with an ionic liquid, the 2:1 platform showed higher ionic conductivity than the previous 1:1 one. The results presented here illustrate the importance of the composition and architecture to the ionic domain connectivity and ionic conductivity, which will have far-reaching implications for the rational design of semiconducting polymers for energy applications including fuel cells, batteries, ion-exchange membranes, and mixed ionic conductors. Full article
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20 pages, 9193 KiB  
Review
Polydiacetylene (PDA) Embedded Polymer-Based Network Structure for Biosensor Applications
by Huisoo Jang, Junhyeon Jeon, Mingyeong Shin, Geonha Kang, Hyunil Ryu, Sun Min Kim and Tae-Joon Jeon
Gels 2025, 11(1), 66; https://doi.org/10.3390/gels11010066 - 15 Jan 2025
Cited by 2 | Viewed by 2356
Abstract
Biosensors, which combine physical transducers with biorecognition elements, have seen significant advancement due to the heightened interest in rapid diagnostic technologies across a number of fields, including medical diagnostics, environmental monitoring, and food safety. In particular, polydiacetylene (PDA) is gaining attention as an [...] Read more.
Biosensors, which combine physical transducers with biorecognition elements, have seen significant advancement due to the heightened interest in rapid diagnostic technologies across a number of fields, including medical diagnostics, environmental monitoring, and food safety. In particular, polydiacetylene (PDA) is gaining attention as an ideal material for label-free colorimetric biosensor development due to its unique color-changing properties in response to external stimuli. PDA forms through the self-assembly of diacetylene monomers, with color change occurring as its conjugated backbone twists in response to stimuli such as temperature, pH, and chemical interactions. This color change enables the detection of biomarkers, metal ions, and toxic compounds. Moreover, the combination of PDA with polymeric structures including hydrogels further enhances the sensitivity and structural stability of PDA-based biosensors, making them reliable and effective in complex biological and environmental conditions. This review comprehensively examines recent research trends and applications of PDA–polymeric structure hybrid biosensors, while discussing future directions and potential advancements in this field. Full article
(This article belongs to the Special Issue Recent Progress of Hydrogel Sensors and Biosensors)
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22 pages, 2504 KiB  
Article
Fluorogenic Biosensing with Tunable Polydiacetylene Vesicles
by John S. Miller, Tanner J. Finney, Ethan Ilagan, Skye Frank, Ye Chen-Izu, Keishi Suga and Tonya L. Kuhl
Biosensors 2025, 15(1), 27; https://doi.org/10.3390/bios15010027 - 7 Jan 2025
Cited by 1 | Viewed by 1385
Abstract
Polydiacetylenes (PDAs) are conjugated polymers that are well known for their colorimetric transition from blue to red with the application of energetic stimulus. Sensing platforms based on polymerized diacetylene surfactant vesicles and other structures have been widely demonstrated for various colorimetric biosensing applications. [...] Read more.
Polydiacetylenes (PDAs) are conjugated polymers that are well known for their colorimetric transition from blue to red with the application of energetic stimulus. Sensing platforms based on polymerized diacetylene surfactant vesicles and other structures have been widely demonstrated for various colorimetric biosensing applications. Although less studied and utilized, the transition also results in a change from a non-fluorescent to a highly fluorescent state, making polydiacetylenes useful for both colorimetric and fluorogenic sensing applications. Here, we focus on the characterization and optimization of polydiacetylene vesicles to tune their sensitivity for fluorogenic sensing applications. Particularly, we look at how the structure of the diacetylene (DA) hydrocarbon tail and headgroup affect the self-assembled vesicle size and stability, polymerization kinetics, and the fluorogenic, blue to red phase transition. Longer DA acyl tails generally resulted in smaller and more stable vesicles. The polymerization kinetics and the blue to red transition were a function of both the DA acyl tail length and structure of the headgroup. Decreasing the acyl tail length generally led to vesicles that were more sensitive to energetic stimuli. Headgroup modifications had different effects depending on the structure of the headgroup. Ethanolamine headgroups resulted in vesicles with potentially increased stimuli responsivity. The lower energy stimulus to induce the chromatic transition was attributed to an increase in headgroup hydrogen bonding and polymer backbone strain. Boronic-acid headgroup functionalization led to vesicles that were generally unstable, only weakly polymerized, and unable to fully transform to the red phase due to strong polar, aromatic headgroup interactions. This work presents the design of PDA vesicles in the context of biosensing platforms and includes a discussion of the past, present, and future of PDA biosensing. Full article
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17 pages, 3150 KiB  
Review
Exploring the Origins of Low-Temperature Thermochromism in Polydiacetylenes
by Magdalena Wilk-Kozubek, Bartłomiej Potaniec, Patrycja Gazińska and Joanna Cybińska
Polymers 2024, 16(20), 2856; https://doi.org/10.3390/polym16202856 - 10 Oct 2024
Cited by 5 | Viewed by 2518
Abstract
This review article delves into the intriguing phenomenon of low-temperature thermochromism, whereby materials change color in response to temperature variations, with a particular focus on its applications in temperature-sensitive fields like medical storage. By closely examining thermochromic materials, this article highlights their potential [...] Read more.
This review article delves into the intriguing phenomenon of low-temperature thermochromism, whereby materials change color in response to temperature variations, with a particular focus on its applications in temperature-sensitive fields like medical storage. By closely examining thermochromic materials, this article highlights their potential to offer innovative solutions for monitoring and preserving thermolabile products that require strict temperature control. This leads to a special emphasis on polydiacetylenes (PDAs), a class of conjugated polymers with unique low-temperature thermochromic properties, positioning them as promising candidates for reliable temperature indicators. This article then explores the underlying mechanisms for fine-tuning the thermochromic behavior of PDAs, particularly discussing recent advancements in PDA design, such as structural alterations of monomers to achieve low-temperature thermochromism. These modifications, influenced by factors like side-chain length, hydrogen-bonding interactions, and the use of copolymers, are intended to result in irreversible color transitions at specific low temperatures, which is crucial to maintaining the integrity of thermally sensitive products. Finally, this article discusses the potential applications of PDAs as thermochromic sensors in tissue biobanking, where their ability to provide visual indications of temperature fluctuations could significantly enhance the monitoring and management of biological samples. Full article
(This article belongs to the Special Issue Advances in Functional Polymers and Composites)
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10 pages, 3717 KiB  
Article
A Color-Detectable Vitamin C Controlled-Release System Fabricated Using Electrospinning
by Min Jae Shin
Polymers 2024, 16(10), 1347; https://doi.org/10.3390/polym16101347 - 9 May 2024
Cited by 1 | Viewed by 1663
Abstract
This study develops a vitamin C controlled-release system, trackable via color changes as a function of vitamin C release. The system is composed of coaxial microfibers prepared via coaxial electrospinning, with a core of poly(ethylene oxide) (PEO) incorporating vitamin C, and a shell [...] Read more.
This study develops a vitamin C controlled-release system, trackable via color changes as a function of vitamin C release. The system is composed of coaxial microfibers prepared via coaxial electrospinning, with a core of poly(ethylene oxide) (PEO) incorporating vitamin C, and a shell composed of polycaprolactone (PCL) containing polydiacetylene (PDA) as the color-changing material. The shell thickness is controlled by adjusting the amount of PCL ejected during electrospinning, allowing regulation of the release rate of vitamin C. When vitamin C added to PEO penetrates the PCL layer, the color of PDA changes from blue to red, indicating a color change. The results of this study can be applied to devices that require immediate detection of vitamin C release levels. Full article
(This article belongs to the Section Smart and Functional Polymers)
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12 pages, 1901 KiB  
Article
Sprayable Diacetylene-Containing Amphiphile Coatings for Visual Detection of Gas-Phase Hydrogen Peroxide
by Priyanka Shiveshwarkar and Justyn Jaworski
Chemosensors 2024, 12(5), 71; https://doi.org/10.3390/chemosensors12050071 - 1 May 2024
Cited by 1 | Viewed by 1805
Abstract
Colorimetric chemical sensing of target gases, such as hydrogen peroxide vapors, is an evolving area of research that implements responsive materials that undergo molecule-specific interaction, resulting in a visible color change. Due to the intuitive nature of an observable color change, such sensing [...] Read more.
Colorimetric chemical sensing of target gases, such as hydrogen peroxide vapors, is an evolving area of research that implements responsive materials that undergo molecule-specific interaction, resulting in a visible color change. Due to the intuitive nature of an observable color change, such sensing systems are particularly desirable as they can be widely deployed at low cost and without the need for complex analytical instrumentation. In this work, we describe our development of a new spray-on sensing material that can provide a colorimetric response to the presence of a gas-phase target, specifically hydrogen peroxide vapor. By providing a cumulative response over time, we identified that part per million concentrations of hydrogen peroxide vapor can be detected. Specifically, we make use of iron chloride-containing formulations to enable the catalysis of hydrogen peroxide to hydroxyl radicals that serve to initiate polymerization of the diacetylene-containing amphiphile, resulting in a white to blue color transition. Due to the irreversible nature of the color change mechanism, the cumulative exposure to hydrogen peroxide over time is demonstrated, enabling longitudinal assessment of target exposure with the same coatings. The versatility of this approach in generating a colorimetric response to hydrogen peroxide vapor may find practical applications for environmental monitoring, diagnostics, or even industrial safety. Full article
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12 pages, 2046 KiB  
Article
Wearable Device for Cumulative Chlorobenzene Detection and Accessible Mitigation Strategies
by Aryan Mago, Yeon-Suk Yang, Jae-Hyuck Shim and Aijaz Ahmad John
Sensors 2023, 23(18), 7904; https://doi.org/10.3390/s23187904 - 15 Sep 2023
Cited by 2 | Viewed by 2477
Abstract
Chronic exposure to low concentrations of volatile organic compounds (VOCs), such as chlorobenzene, is not being monitored in industrializing countries, although VOC exposure is associated with carcinogenic, organ-toxic, and endocrine-disrupting effects. Current VOC-sensing technologies are inaccessible due to high cost, size, and maintenance [...] Read more.
Chronic exposure to low concentrations of volatile organic compounds (VOCs), such as chlorobenzene, is not being monitored in industrializing countries, although VOC exposure is associated with carcinogenic, organ-toxic, and endocrine-disrupting effects. Current VOC-sensing technologies are inaccessible due to high cost, size, and maintenance or are ineffective due to poor sensitivity or reliability. In particular, marginalized individuals face barriers to traditional prescription VOC treatments due to cost, lack of transportation, and limited access to physicians; thus, alternative treatments are needed. Here, we created a novel cumulative wearable color-changing VOC sensor with a paper-based polydiacetylene sensor array for chlorobenzene. With a single smartphone picture, the sensor displays 14 days of logged chlorobenzene exposure data, interpreted by machine-learning (ML) techniques, including principal component analysis. Further, we explored the efficacy of affordable and accessible treatment options to mitigate a VOC’s toxic effects. Vitamin D and sulforaphane are naturally found in cruciferous vegetables, like broccoli, and can be used to treat chlorobenzene-mediated bone degradation. Our platform combines these components into a smartphone app that photographs the sensor’s colorimetric data, analyzes the data via ML techniques, and offers accessible treatments based on exposure data. Full article
(This article belongs to the Section Chemical Sensors)
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13 pages, 1866 KiB  
Article
Spray-On Colorimetric Sensors for Distinguishing the Presence of Lead Ions
by Priyanka Shiveshwarkar and Justyn Jaworski
Chemosensors 2023, 11(6), 327; https://doi.org/10.3390/chemosensors11060327 - 2 Jun 2023
Cited by 3 | Viewed by 2724
Abstract
Sprayable stimuli-responsive material coatings represent a new class of detection system which can be quickly implemented to transform a surface into a color-responsive sensor. In this work, we describe a dipicolylamine-terminated diacetylene-containing amphiphile formulation for spray coating on to a simple paper substrate [...] Read more.
Sprayable stimuli-responsive material coatings represent a new class of detection system which can be quickly implemented to transform a surface into a color-responsive sensor. In this work, we describe a dipicolylamine-terminated diacetylene-containing amphiphile formulation for spray coating on to a simple paper substrate to yield disposable test strips that can be used to detect the presence of lead ions in solution. We find the response to be very selective to only lead ions and that the sensitivity can be modulated by altering the UV curing time after spraying. Sensitive detection to at least 0.1 mM revealed a clear color change from a blue to red phase. This represents the first demonstration of a spray-on sensor system capable of detection of lead ions in solution. Full article
(This article belongs to the Special Issue Chemosensors for Ion Detection)
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15 pages, 2484 KiB  
Article
Targeted Anticancer Agent with Original Mode of Action Prepared by Supramolecular Assembly of Antibody Oligonucleotide Conjugates and Cationic Nanoparticles
by Victor Lehot, Patrick Neuberg, Manon Ripoll, François Daubeuf, Stéphane Erb, Igor Dovgan, Sylvain Ursuegui, Sarah Cianférani, Antoine Kichler, Guilhem Chaubet and Alain Wagner
Pharmaceutics 2023, 15(6), 1643; https://doi.org/10.3390/pharmaceutics15061643 - 2 Jun 2023
Cited by 4 | Viewed by 3407
Abstract
Despite their clinical success, Antibody-Drug Conjugates (ADCs) are still limited to the delivery of a handful of cytotoxic small-molecule payloads. Adaptation of this successful format to the delivery of alternative types of cytotoxic payloads is of high interest in the search for novel [...] Read more.
Despite their clinical success, Antibody-Drug Conjugates (ADCs) are still limited to the delivery of a handful of cytotoxic small-molecule payloads. Adaptation of this successful format to the delivery of alternative types of cytotoxic payloads is of high interest in the search for novel anticancer treatments. Herein, we considered that the inherent toxicity of cationic nanoparticles (cNP), which limits their use as oligonucleotide delivery systems, could be turned into an opportunity to access a new family of toxic payloads. We complexed anti-HER2 antibody-oligonucleotide conjugates (AOC) with cytotoxic cationic polydiacetylenic micelles to obtain Antibody-Toxic-Nanoparticles Conjugates (ATNPs) and studied their physicochemical properties, as well as their bioactivity in both in vitro and in vivo HER2 models. After optimising their AOC/cNP ratio, the small (73 nm) HER2-targeting ATNPs were found to selectively kill antigen-positive SKBR-2 cells over antigen-negative MDA-MB-231 cells in serum-containing medium. Further in vivo anti-cancer activity was demonstrated in an SKBR-3 tumour xenograft model in BALB/c mice in which stable 60% tumour regression could be observed just after two injections of 45 pmol of ATNP. These results open interesting prospects in the use of such cationic nanoparticles as payloads for ADC-like strategies. Full article
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20 pages, 6918 KiB  
Article
Stimuli-Responsive and Antibacterial Cellulose-Chitosan Hydrogels Containing Polydiacetylene Nanosheets
by Edwin Shigwenya Madivoli, Justine Veronique Schwarte, Patrick Gachoki Kareru, Anthony Ngure Gachanja and Katharina M. Fromm
Polymers 2023, 15(5), 1062; https://doi.org/10.3390/polym15051062 - 21 Feb 2023
Cited by 28 | Viewed by 3708
Abstract
Herein, we report a stimuli-responsive hydrogel with inhibitory activity against Escherichia coli prepared by chemical crosslinking of carboxymethyl chitosan (CMCs) and hydroxyethyl cellulose (HEC). The hydrogels were prepared by esterification of chitosan (Cs) with monochloroacetic acid to produce CMCs which were then chemically [...] Read more.
Herein, we report a stimuli-responsive hydrogel with inhibitory activity against Escherichia coli prepared by chemical crosslinking of carboxymethyl chitosan (CMCs) and hydroxyethyl cellulose (HEC). The hydrogels were prepared by esterification of chitosan (Cs) with monochloroacetic acid to produce CMCs which were then chemically crosslinked to HEC using citric acid as the crosslinking agent. To impart a stimuli responsiveness property to the hydrogels, polydiacetylene-zinc oxide (PDA-ZnO) nanosheets were synthesized in situ during the crosslinking reaction followed by photopolymerization of the resultant composite. To achieve this, ZnO was anchored on carboxylic groups in 10,12-pentacosadiynoic acid (PCDA) layers to restrict the movement of the alkyl portion of PCDA during crosslinking CMCs and HEC hydrogels. This was followed by irradiating the composite with UV radiation to photopolymerize the PCDA to PDA within the hydrogel matrix so as to impart thermal and pH responsiveness to the hydrogel. From the results obtained, the prepared hydrogel had a pH-dependent swelling capacity as it absorbed more water in acidic media as compared to basic media. The incorporation of PDA-ZnO resulted in a thermochromic composite responsive to pH evidenced by a visible colour transition from pale purple to pale pink. Upon swelling, PDA-ZnO-CMCs-HEC hydrogels had significant inhibitory activity against E. coli attributed to the slow release of the ZnO nanoparticles as compared to CMCs-HEC hydrogels. In conclusion, the developed hydrogel was found to have stimuli-responsive properties and inhibitory activity against E. coli attributed to zinc nanoparticles. Full article
(This article belongs to the Special Issue Advanced Stimuli-Responsive Polymer Composites)
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16 pages, 2721 KiB  
Article
Supramolecular Optimization of Sensory Function of a Hemicurcuminoid through Its Incorporation into Phospholipid and Polymeric Polydiacetylenic Vesicles: Experimental and Computational Insight
by Bulat S. Akhmadeev, Olga O. Retyunskaya, Sergey N. Podyachev, Sergey A. Katsyuba, Aidar T. Gubaidullin, Svetlana N. Sudakova, Victor V. Syakaev, Vasily M. Babaev, Oleg G. Sinyashin and Asiya R. Mustafina
Polymers 2023, 15(3), 714; https://doi.org/10.3390/polym15030714 - 31 Jan 2023
Cited by 3 | Viewed by 2137
Abstract
This work presents the synthesis of a new representative of hemicurcuminoids with a nonyloxy substituent (HCur) as a fluorescent amphiphilic structural element of vesicular aggregates based on phosphatidylcholine (PC), phosphatidylserine (PS), and 10,12-pentacosadiynoic acid (PCDA). Both X-ray diffraction analysis of the [...] Read more.
This work presents the synthesis of a new representative of hemicurcuminoids with a nonyloxy substituent (HCur) as a fluorescent amphiphilic structural element of vesicular aggregates based on phosphatidylcholine (PC), phosphatidylserine (PS), and 10,12-pentacosadiynoic acid (PCDA). Both X-ray diffraction analysis of the single crystal and 1H NMR spectra of HCur in organic solvents indicate the predominance of the enol-tautomer of HCur. DFT calculations show the predominance of the enol tautomer HCur in supramolecular assemblies with PC, PS, and PCDA molecules. The results of the molecular modeling show that HCur molecules are surrounded by PC and PS with a rather weak exposure to water molecules, while an exposure of HCur molecules to water is enhanced under its supramolecular assembly with PCDA molecules. This is in good agreement with the higher loading of HCur into PC(PS) vesicles compared to PCDA vesicles converted into polydiacetylene (PDA) ones by photopolymerization. HCur molecules incorporated into HCur-PDA vesicles exhibit greater planarity distortion and hydration effect in comparison with HCur-PC(PS) ones. HCur-PDA is presented as a dual fluorescence-chromatic nanosensor responsive to a change in pH within 7.5–9.5, heavy metal ions and polylysine, and the concentration-dependent fluorescent response is more sensitive than the chromatic one. Thus, the fluorescent response of HCur-PDA allows for the distinguishing between Cd2+ and Pb2+ ions in the concentration range 0–0.01 mM, while the chromatic response allows for the selective sensing of Pb2+ over Cd2+ ions at their concentrations above 0.03 mM. Full article
(This article belongs to the Special Issue Eco-Friendly Supramolecular Polymeric Materials)
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44 pages, 19950 KiB  
Review
Hybridization of Wide-Angle X-ray and Neutron Diffraction Techniques in the Crystal Structure Analyses of Synthetic Polymers
by Kohji Tashiro, Katsuhiro Kusaka, Hiroko Yamamoto, Takaaki Hosoya, Shuji Okada and Takashi Ohhara
Polymers 2023, 15(2), 465; https://doi.org/10.3390/polym15020465 - 16 Jan 2023
Cited by 5 | Viewed by 3503
Abstract
The development in the crystal structure analysis of synthetic polymers using the hybridized combination of wide-angle X-ray and neutron diffraction (WAXD and WAND, respectively) techniques has been reviewed with many case studies performed by the authors. At first, the technical development was reviewed, [...] Read more.
The development in the crystal structure analysis of synthetic polymers using the hybridized combination of wide-angle X-ray and neutron diffraction (WAXD and WAND, respectively) techniques has been reviewed with many case studies performed by the authors. At first, the technical development was reviewed, in which the usage of high-energy synchrotron X-ray source was emphasized for increasing the total number of the observable diffraction peaks, and several examples were introduced. Secondly, the usage of the WAND method was introduced, in which the successful extraction of hydrogen atomic positions was described. The third example is to show the importance for the hybrid combination of these two diffraction methods. The quantitative WAXD data analysis gave the crystal structures of at-poly(vinyl alcohol) (at-PVA) and at-PVA-iodine complex. However, the thus-proposed structure models were found not to reproduce the observed WAND data very much. The reason came from the remarkable difference in the atomic scattering powers of the constituting atomic species between WAXD and WAND phenomena. The introduction of statistical disorder solved this serious problem, which reproduced both of the observed WAXD and WAND data consistently. The more systematic combination of WAXD and WAND methods, or the so-called X-N method, was applied also to the quantitative evaluation of the bonded electron density distribution along the skeletal chains, where the results about polydiacetylene single crystals were presented as the first successful study. Finally, the application of WAND technique in the trace of structural changes induced under the application of external stress or temperature was described. The future perspective is described for the development of structural science of synthetic polymers on the basis of the combined WAXD/WAND techniques. Full article
(This article belongs to the Special Issue State-of-the-Art Polymer Science and Technology in Japan (2021,2022))
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12 pages, 4596 KiB  
Article
Fabrication of High-Performance Colorimetric Membrane by Incorporation of Polydiacetylene into Polyarylene Ether Nitriles Electrospinning Nanofibrous Membranes
by Pan Wang, Xidi Liu, Yong You, Mengxue Wang, Yumin Huang, Ying Li, Kui Li, Yuxin Yang, Wei Feng, Qiancheng Liu, Jiaqi Chen and Xulin Yang
Nanomaterials 2022, 12(24), 4379; https://doi.org/10.3390/nano12244379 - 8 Dec 2022
Cited by 5 | Viewed by 1835
Abstract
Polyarylene ether nitrile (PEN) is a novel high-performance engineering plastic with various applications, particularly in thermoresistance-required fields. In this study, a well-known stimuli-response polydiacetylene monomer, 10, 12-pentacosadiynoic acid (PCDA), was encapsulated within electrospun PEN nanofibers to fabricate a colorimetric membrane with satisfactory thermal [...] Read more.
Polyarylene ether nitrile (PEN) is a novel high-performance engineering plastic with various applications, particularly in thermoresistance-required fields. In this study, a well-known stimuli-response polydiacetylene monomer, 10, 12-pentacosadiynoic acid (PCDA), was encapsulated within electrospun PEN nanofibers to fabricate a colorimetric membrane with satisfactory thermal and corrosion resistance. To optimize the compatibility with PCDA, two PENswith distinct molecular chains were utilized: PEN−PPL and PEN−BPA. The chemical structure and elemental mapping analysis revealed that the PCDA component was successfully incorporated into the PEN fibrous. The PCDA bound significantly better to the PEN−PPL than to the PEN−BPA; due to the carboxyl groups present on the side chains of PEN−PPL, the surface was smooth and the color changed uniformly as the temperature rose. However, owing to its poor compatibility with PEN−BPA, the PCDA formed agglomerations on the fibers. The thermal analysis demonstrated that the membranes obtained after PCDA compounding maintained their excellent heat resistance. The 5% weight loss temperatures of composite nanofibrous membranes manufactured by PEN−PPL and PEN−BPA were 402 °C and 506 °C, respectively, and their glass transition temperatures were 219 °C and 169 °C, respectively, indicating that the blended membranes can withstand high temperatures. The evaluation of application performance revealed that the composite membranes exhibited good dimensional stability upon high thermal and corrosive situations. Specifically, the PEN−P−PCDA did not shrink at 170 °C. Both composite membranes were dimensionally stable when exposed to the alkali aqueous solution. However, PEN−P−PCDA is more sensitive to OH, exhibiting color transition at pH > 8, whereas PEN−B−PCDA exhibited color transition at high OH concentrations (pH ≥ 13), with enhanced alkali resistance stability owing to its nanofibrous architecture. This exploratory study reveals the feasibility of PEN nanofibers functionalized using PCDA as a desirable stimulus-response sensor even in high-temperature and corrosive harsh environments. Full article
(This article belongs to the Special Issue Hybrid Nanofibers: Fabrication, Properties and Applications)
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