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Exclusive Feature Papers in Macromolecular Chemistry

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Macromolecular Chemistry".

Deadline for manuscript submissions: 31 December 2024 | Viewed by 13091

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Guest Editor
The Michael M. Szwarc Polymer Research Institute, State University of New York – ESF, Syracuse, NY 13210, USA
Interests: synthesis and characterization of polymers with novel macromolecular architectures: Linear, dendritic, linear-dendritic, star-dendritic, cyclo-dendritic, dendronized, hyperbranched and linear-hyperbranched; biocompatible and biodegradable polymers, novel polymeric systems for drug delivery and diagnosis (theranostics materials); “living” polymerization methods; macromolecular self-assembly and interfacial transport; polymer-supported biocatalysis and “green” chemistry, semi-artificial enzymes
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Special Issue Information

Dear Colleagues,

We are pleased to announce a Special Issue entitled “Exclusive Feature Papers in Macromolecular Chemistry”. This is a collection of important high-quality papers (original research articles or comprehensive review papers) published in open access format by prominent scholars invited by the Editorial Office and Guest Editors.

This Special Issue aims to discuss new knowledge or cutting-edge developments in the Macromolecular Chemistry research field through selected works, in the hope of making a great contribution to the community. We intend for this issue to be the best forum for disseminating excellent research findings as well as sharing innovative ideas in the field.

Prof. Dr. Ivan Gitsov
Associate Section Editor-in-Chief

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Published Papers (8 papers)

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Research

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23 pages, 13534 KiB  
Article
Benchmark Study of Epoxy Coatings with Selection of Bio-Based Phenalkamine versus Fossil-Based Amine Crosslinkers
by Pieter Samyn, Joey Bosmans and Patrick Cosemans
Molecules 2023, 28(11), 4259; https://doi.org/10.3390/molecules28114259 - 23 May 2023
Cited by 2 | Viewed by 1704
Abstract
The phenalkamines (PK) derived from cardanol oil can be used as a bio-based crosslinker for epoxy coatings as an alternative for traditional fossil amines (FA). First, the reaction kinetics of an epoxy resin with four PK and FA crosslinkers are compared by differential [...] Read more.
The phenalkamines (PK) derived from cardanol oil can be used as a bio-based crosslinker for epoxy coatings as an alternative for traditional fossil amines (FA). First, the reaction kinetics of an epoxy resin with four PK and FA crosslinkers are compared by differential scanning calorimetry, illustrating a fast reaction rate and higher conversion of PK at room temperature in parallel with a moderate exothermal reaction. Second, the performance of coatings with various concentrations of PK and PK/FA ratios indicates good mixing compatibility between crosslinkers resulting in higher hardness, scratch resistance, hydrophobicity, and abrasive wear resistance of coatings with PK. The superior performance is confirmed over a broad range of resin/crosslinker ratios, facilitating the processing with viscosity profiles depending on the PK type. Although fossil- and bio-based crosslinkers have different chemical structures, the unique linear relationships between intrinsic mechanical properties (i.e., ductility and impact resistance) and coating performance indicate that the degree of crosslinking is a primary parameter controlling coating performance, where PK simultaneously provides high hardness and ductility. In conclusion, the optimization of the processing range for bio-based PK as a crosslinker for epoxy coatings delivers suitable processing conditions and superior mechanical performance compared to traditional amine crosslinkers. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Macromolecular Chemistry)
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12 pages, 5815 KiB  
Article
Co-Crystallization between Aliphatic Polyesters through Co-Inclusion Complexation with Small Molecule
by Jia-Yao Chen, Xue-Wen Zhang, Tian-Yu Wu and Hai-Mu Ye
Molecules 2023, 28(10), 4091; https://doi.org/10.3390/molecules28104091 - 15 May 2023
Viewed by 907
Abstract
Crystalline/crystalline blends of polymer have shown advantages in the preparation of new polymeric materials. However, the regulation of co-crystallization in a blend is still full of challenges due to the preferential self-crystallization driven by thermodynamics. Here, an inclusion complex approach is proposed to [...] Read more.
Crystalline/crystalline blends of polymer have shown advantages in the preparation of new polymeric materials. However, the regulation of co-crystallization in a blend is still full of challenges due to the preferential self-crystallization driven by thermodynamics. Here, an inclusion complex approach is proposed to facilitate the co-crystallization between crystalline polymers, because the crystallization process displays a prominent kinetics advantage when polymer chains are released from the inclusion complex. Poly(butylene succinate) (PBS), poly(butylene adipate) (PBA) and urea are chosen to form co-inclusion complexes, where PBS and PBA chains play as isolated guest molecules and urea molecules construct the host channel framework. The coalesced PBS/PBA blends are obtained by fast removing the urea framework and systematically investigated by differential scanning calorimetry, X-ray diffraction, proton nuclear magnetic resonance and Fourier transformation infrared spectrometry. It is demonstrated that PBA chains are co-crystallized into PBS extended-chain crystals in the coalesced blends, while such a phenomenon has not been detected in simply co-solution-blended samples. Though PBA chains could not be totally accommodated in the PBS extended-chain crystals, their co-crystallized content increases with the initial feeding ratio of PBA. Consequently, the melting point of the PBS extended-chain crystal gradually declines from 134.3 °C to 124.2 °C with an increasing PBA content. The PBA chains playing as defects mainly induce lattice expansion along the a-axis. In addition, when the co-crystals are soaked in tetrahydrofuran, some of the PBA chains are extracted out, leading to damage to the correlative PBS extended-chain crystals. This study shows that co-inclusion complexation with small molecules could be an effective way to promote co-crystallization behavior in polymer blends. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Macromolecular Chemistry)
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18 pages, 5492 KiB  
Article
The Synergistic Effect of Triazine and Phosphaphenanthrene Units on the Physico-Chemical Behavior of Polyimides
by Irina Butnaru and Mariana-Dana Damaceanu
Molecules 2023, 28(10), 4072; https://doi.org/10.3390/molecules28104072 - 13 May 2023
Cited by 1 | Viewed by 1084
Abstract
With the aim to develop polymers with appealing, multifunctional characteristics, a series of polyimides were designed by anchoring 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) units on the main polymer chains containing 1,3,5-triazine and several flexible moieties, such as ether, hexafluoroisopropylidene, or isopropylidene. A detailed study was [...] Read more.
With the aim to develop polymers with appealing, multifunctional characteristics, a series of polyimides were designed by anchoring 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) units on the main polymer chains containing 1,3,5-triazine and several flexible moieties, such as ether, hexafluoroisopropylidene, or isopropylidene. A detailed study was conducted to establish structure–property correlations, with a focus on the synergistic effectiveness of triazine and DOPO moieties on the overall features of polyimides. The results evidenced good solubility of the polymers in organic solvents, their amorphous nature with short-range regular-packed polymer chains, and high thermal stability with no glass transition temperature below 300 °C. Spectrophotometric measurements revealed the existence of a strong charge transfer complex in these polymers that led to a “black” appearance, which generated broad absorption bands spanning on the overall visible range. Nevertheless, these polymers displayed green light emission associated with 1,3,5-triazine emitter. The electrochemical characteristics of the polyimides in solid state demonstrated their strong n-type doping character induced by three different structural elements with electron-acceptance capability. The useful properties of these polyimides, including optical, thermal, electrochemical, aesthetics, and opaqueness, endow them with several possible applications in the microelectronic field, such as protecting layers for the inner circuits against UV light deterioration. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Macromolecular Chemistry)
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12 pages, 4672 KiB  
Article
Rational Design of Disulfide Bridges in BbPETaseCD for Enhancing the Enzymatic Performance in PET Degradation
by Dongjian Huang, Lin Zhang and Yan Sun
Molecules 2023, 28(8), 3528; https://doi.org/10.3390/molecules28083528 - 17 Apr 2023
Cited by 5 | Viewed by 1684
Abstract
Polyethylene terephthalate (PET) is one of the most prevalent transparent thermoplastics. It is commonly utilized due to its low cost and high durability. With the massive accumulation of waste PET, however, serious environmental pollution has become a global problem. Compared to traditional chemical [...] Read more.
Polyethylene terephthalate (PET) is one of the most prevalent transparent thermoplastics. It is commonly utilized due to its low cost and high durability. With the massive accumulation of waste PET, however, serious environmental pollution has become a global problem. Compared to traditional chemical degradation, biodegradation of PET catalyzed by PET hydrolase (PETase) is more environmentally friendly and energy-efficient. BbPETaseCD from the Burkholderiales bacterium is a PETase that shows favorable properties for application in the biodegradation of PET. To enhance the enzymatic performance of this enzyme, this work focuses on the rational design of disulfide bridges in BbPETaseCD. We utilized two computational algorithms to predict the probable disulfide-bridge mutations in BbPETaseCD, and five variants were acquired from the computations. Among these, the N364C/D418C variant with one additional disulfide bond showed higher expression than the wild-type enzyme (WT) and the best enzymatic performance. The melting temperature (Tm) of the N364C/D418C variant presented an increase of 14.8 °C over that of WT (56.5 °C), indicating that the additional disulfide bond significantly raised the thermodynamic stability of the enzyme. Kinetic experiments at different temperatures also demonstrated the thermal stability increase of the variant. The variant also showed significantly increased activity over WT when using bis(hydroxyethyl) terephthalate (BHET) as the substrate. More remarkably, the N364C/D418C variant exhibited approximately an 11-fold increase over the WT enzyme in the long-term (14 days) degradation of PET films. The results prove that the rationally designed disulfide bond significantly improved the enzymatic performance of the enzyme for PET degradation. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Macromolecular Chemistry)
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16 pages, 4112 KiB  
Article
Hydrogel-Film-Fabricated Fluorescent Biosensors with Aggregation-Induced Emission for Albumin Detection through the Real-Time Modulation of a Vortex Fluidic Device
by Qi Hu, Xuan Luo, Damian Tohl, Anh Tran Tam Pham, Colin Raston and Youhong Tang
Molecules 2023, 28(7), 3244; https://doi.org/10.3390/molecules28073244 - 05 Apr 2023
Viewed by 1439
Abstract
Hydrogels have various promising prospects as a successful platform for detecting biomarkers, and human serum albumin (HSA) is an important biomarker in the diagnosis of kidney diseases. However, the difficult-to-control passive diffusion kinetics of hydrogels is a major factor affecting detection performance. This [...] Read more.
Hydrogels have various promising prospects as a successful platform for detecting biomarkers, and human serum albumin (HSA) is an important biomarker in the diagnosis of kidney diseases. However, the difficult-to-control passive diffusion kinetics of hydrogels is a major factor affecting detection performance. This study focuses on using hydrogels embedded with aggregation-induced emission (AIE) fluorescent probe TC426 to detect HSA in real time. The vortex fluidic device (VFD) technology is used as a rotation strategy to control the reaction kinetics and micromixing during measurement. The results show that the introduction of VFD could significantly accelerate its fluorescence response and effectively improve the diffusion coefficient, while VFD processing could regulate passive diffusion into active diffusion, offering a new method for future sensing research. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Macromolecular Chemistry)
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Review

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33 pages, 10171 KiB  
Review
Enzymes in “Green” Synthetic Chemistry: Laccase and Lipase
by Dieter M. Scheibel, Ioan Pavel Ivanov Gitsov and Ivan Gitsov
Molecules 2024, 29(5), 989; https://doi.org/10.3390/molecules29050989 - 24 Feb 2024
Viewed by 706
Abstract
Enzymes play an important role in numerous natural processes and are increasingly being utilized as environmentally friendly substitutes and alternatives to many common catalysts. Their essential advantages are high catalytic efficiency, substrate specificity, minimal formation of byproducts, and low energy demand. All of [...] Read more.
Enzymes play an important role in numerous natural processes and are increasingly being utilized as environmentally friendly substitutes and alternatives to many common catalysts. Their essential advantages are high catalytic efficiency, substrate specificity, minimal formation of byproducts, and low energy demand. All of these benefits make enzymes highly desirable targets of academic research and industrial development. This review has the modest aim of briefly overviewing the classification, mechanism of action, basic kinetics and reaction condition effects that are common across all six enzyme classes. Special attention is devoted to immobilization strategies as the main tools to improve the resistance to environmental stress factors (temperature, pH and solvents) and prolong the catalytic lifecycle of these biocatalysts. The advantages and drawbacks of methods such as macromolecular crosslinking, solid scaffold carriers, entrapment, and surface modification (covalent and physical) are discussed and illustrated using numerous examples. Among the hundreds and possibly thousands of known and recently discovered enzymes, hydrolases and oxidoreductases are distinguished by their relative availability, stability, and wide use in synthetic applications, which include pharmaceutics, food and beverage treatments, environmental clean-up, and polymerizations. Two representatives of those groups—laccase (an oxidoreductase) and lipase (a hydrolase)—are discussed at length, including their structure, catalytic mechanism, and diverse usage. Objective representation of the current status and emerging trends are provided in the main conclusions. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Macromolecular Chemistry)
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18 pages, 2329 KiB  
Review
Selenium in Peptide Chemistry
by Özge Pehlivan, Mateusz Waliczek, Monika Kijewska and Piotr Stefanowicz
Molecules 2023, 28(7), 3198; https://doi.org/10.3390/molecules28073198 - 04 Apr 2023
Cited by 8 | Viewed by 2235
Abstract
In recent years, researchers have been exploring the potential of incorporating selenium into peptides, as this element possesses unique properties that can enhance the reactivity of these compounds. Selenium is a non-metallic element that has a similar electronic configuration to sulfur. However, due [...] Read more.
In recent years, researchers have been exploring the potential of incorporating selenium into peptides, as this element possesses unique properties that can enhance the reactivity of these compounds. Selenium is a non-metallic element that has a similar electronic configuration to sulfur. However, due to its larger atomic size and lower electronegativity, it is more nucleophilic than sulfur. This property makes selenium more reactive toward electrophiles. One of the most significant differences between selenium and sulfur is the dissociation of the Se-H bond. The Se-H bond is more easily dissociated than the S-H bond, leading to higher acidity of selenocysteine (Sec) compared to cysteine (Cys). This difference in acidity can be exploited to selectively modify the reactivity of peptides containing Sec. Furthermore, Se-H bonds in selenium-containing peptides are more susceptible to oxidation than their sulfur analogs. This property can be used to selectively modify the peptides by introducing new functional groups, such as disulfide bonds, which are important for protein folding and stability. These unique properties of selenium-containing peptides have found numerous applications in the field of chemical biology. For instance, selenium-containing peptides have been used in native chemical ligation (NCL). In addition, the reactivity of Sec can be harnessed to create cyclic and stapled peptides. Other chemical modifications, such as oxidation, reduction, and photochemical reactions, have also been applied to selenium-containing peptides to create novel molecules with unique biological properties. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Macromolecular Chemistry)
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17 pages, 2544 KiB  
Review
Antifoaming Agent for Lubricating Oil: Preparation, Mechanism and Application
by Chenfei Ren, Xingxing Zhang, Ming Jia, Chenming Ma, Jiaxin Li, Miaomiao Shi and Yunyin Niu
Molecules 2023, 28(7), 3152; https://doi.org/10.3390/molecules28073152 - 31 Mar 2023
Cited by 3 | Viewed by 2542
Abstract
In the process of using lubricating oil, it is inevitable that bubbles will be produced, which can not only accelerate the oil’s oxidation and shorten the oil change cycle but also reduce its fluidity and lubricity, aggravate the wear of mechanical parts and [...] Read more.
In the process of using lubricating oil, it is inevitable that bubbles will be produced, which can not only accelerate the oil’s oxidation and shorten the oil change cycle but also reduce its fluidity and lubricity, aggravate the wear of mechanical parts and produce an air lock that interrupts the oil pump supply and causes an oil shortage accident. This paper mainly and comprehensively discusses the foaming process and its harm, the defoaming mechanism and defoaming method of lubricating oil, more specifically, the synthesis, application, advantages, disadvantages and current situation of three kinds of chemical defoaming agents, namely silicone defoaming agent, non-silicone defoaming agent and compound defoaming agent. Finally, the paper looks forward to the future development of special defoaming agents for lubricating oil. Full article
(This article belongs to the Special Issue Exclusive Feature Papers in Macromolecular Chemistry)
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