Polymer Solvent Research Articles

Bactericidal Chitosan Derivatives and Their Superabsorbent Blends with ĸ-Carrageenan.

The aim of this work is research dedicated to the search for new bactericidal systems for use in cosmetic formulations, dermocosmetics, or the production of wound dressings. Over the last two decades, chitosan, due to its special biological activity, has become a highly indispensable biopolymer with very wide application possibilities. Reports in the literature on the antibacterial effects of chitosan are very diverse, but our research has shown that they can be successfully improved through chemical modification. Therefore, in this study, results on the synthesis of new chitosan-based Schiff bases, dCsSB-SFD and dCsSB-PCA, are obtained using two aldehydes: sodium 4-formylbenzene-1,3-disulfonate (SFD) and 2-pyridine carboxaldehyde (PCA), respectively. Chitosan derivatives synthesized in this way demonstrate stronger antimicrobial activity. Carrying out the procedure of grafting chitosan with a caproyl chain allowed obtaining compatible blends of chitosan derivatives with κ-carrageenan, which are stable hydrogels with a high swelling coefficient. Furthermore, the covalently bounded poly(ε-caprolactone) (PCL) chain improved the solubility of obtained polymers in organic solvents. In this respect, the Schiff base-containing polymers obtained in this study, with special hydrogel and antimicrobial properties, are very promising materials for potential use as a controlled-release formulation of both hydrophilic and hydrophobic drugs in cosmetic products for skin health.

Electrochemical Characterization of Diffusion in Polymeric vs. Monomeric Solvents.

Polymer electrolyte was used as a medium for testing the performance of microband electrodes under conditions of linear diffusion. Cyclic voltammetry (CV) and chronoamperometry (CA) experiments were performed in a highly viscous medium, where diffusion rates are much slower than in fluid solutions. The log i vs. log v (CV) or log i vs. log t (CA) relationships with the current equation confirmed the existence of such conditions, yielding slope values that were lower than the expected 0.5. This could indicate an impure linear diffusion profile, i.e., some contribution from radial diffusion (edge effects). However, the desired value of 0.5 was obtained when performing these tests in monomeric solvents of similar viscosities, such as glycerol or propylene glycol. These results led to the conclusion that the current equations, which are based on Fick's laws, may not be applicable for polymer electrolytes, where various obstructions to free diffusion result in a more complicated process than for monomeric solvents.

A Unified Model for Non-Fickian Diffusion and Anomalous Swelling of Glassy Polymer Gels.

A sheet of glassy polymers placed in a solvent shows swelling behaviors quite different from that of soft polymers (rubbers and gels). (1) Non-Fickian diffusion (called case II diffusion): As solvent permeates into the sample, a sharp front is created between the swollen part and the glassy part, and it moves toward the center at constant speed. (2) Nonmonotonous swelling: The thickness of the sample first increases and then decreases toward the equilibrium value. Here we propose a theory to explain such anomalous behavior by extending the previous theory for swelling of soft gels. We regard the material as a continuum mixture of a glassy polymer network and solvent. We assume that the polymer network is a viscoelastic gel of glassy polymers, and its relaxation time depends strongly on solvent concentration. We show that this theory explains the above two characteristics of glassy polymers in a simple and unified framework. The theory predicts how the permeation speed of the solvent and the characteristic times of the swelling process depend on material parameters and experimental conditions, which can be checked experimentally.

Coherent structures in elastic turbulent planar jets

At low Reynolds numbers, the flow of a Newtonian planar jet remains laminar, thus easy to characterize. In contrast, the presence of elasticity (e.g., attained dissolving polymers in a Newtonian solvent) enables a highly-complex turbulent-like behavior termed elastic turbulence. In this work, we run data-driven modal decomposition algorithms on high-fidelity data collected from the simulation of an elastic turbulent planar jet. The large-scale motions are expressed as a finite expansion of modes that condense the dominant dynamics. The modes associated with lower frequencies weight the most on the reconstruction of the original data, thus they are further decomposed in space to investigate their implications on the sustainment of the elastic turbulent state. Our findings suggest that slower dynamics are crucial for the sustainment of elastic turbulence, which is connected to the interaction of spanwise-coherent structures, steady in space, with spanwise-periodic traveling waves, causing the breakdown of the structures close to the inlet.

Light-Responsive Organic-Inorganic Hydrogel Functionalized with MoO3 Composites of Poly(Vinyl Alcohol) and Choline Chloride-Based Polymeric Deep Eutectic Solvent

Light-Responsive Organic-Inorganic Hydrogel Functionalized with MoO3 Composites of Poly(Vinyl Alcohol) and Choline Chloride-Based Polymeric Deep Eutectic Solvent

Toward Sustainability in All‐Printed Accumulation Mode Organic Electrochemical Transistors

AbstractThis study reports on the first all‐printed vertically stacked organic electrochemical transistors (OECTs) operating in accumulation mode; the devices, relying on poly([4,4′‐bis(2‐(2‐(2‐methoxyethoxy)ethoxy)ethoxy)‐2,2′‐bithiophen‐5,5′‐diyl]‐alt‐[thieno[3,2‐b]thiophene‐2,5‐diyl]) (pgBTTT) as the active channel material, are fabricated via a combination of screen and inkjet printing technologies. The resulting OECTs (W/L ≈5) demonstrate good switching performance; gm, norm ≈13 mS cm−1, µC* ≈21 F cm−1 V−1 s−1, ON–OFF ratio > 104 and good cycling stability upon continuous operation for 2 h. The inkjet printing process of pgBTTT is established by first solubilizing the polymer in dihydrolevoglucosenone (Cyrene), a non‐toxic, cellulose‐derived, and biodegradable solvent. The resulting ink formulations exhibit good jettability, thereby providing reproducible and stable p‐type accumulation mode all‐printed OECTs with high performance. Besides the environmental and safety benefits of this solvent, this study also demonstrates the assessment of how the solvent affects the performance of spin‐coated OECTs, which justifies the choice of Cyrene as an alternative to commonly used harmful solvents such as chloroform, also from a device perspective. Hence, this approach shows a new possibility of obtaining more sustainable printed electronic devices, which will eventually result in all‐printed OECT‐based logic circuits operating in complementary mode.

18.63% Efficiency of Ternary Organic Solar Cells Achieved via Nonhalogenated Solvent and Hot Spin‐Coating Process

AbstractThe solubility problem of conjugated polymers in nonhalogenated solvents limits the application of nonhalogenated solvents in Organic solar cells (OSCs). By combining with a hot spin‐coating process, efficient PM6:BTP‐BO‐4F:GS‐ISO ternary OSCs are prepared by employing o‐xylene as a solvent. After adding 10 wt% content of GS‐ISO to PM6:BTP‐BO‐4F, the surface morphology in the active layers is improved and the charge extraction, transport, and collection in OSCs are enhanced. Compared with the efficiency of PM6:BTP‐BO‐4F OSCs (16.25%), an efficiency of 18.63% is achieved for PM6:BTP‐BO‐4F:GS‐ISO ternary OSCs. Moreover, PM6:BTP‐BO‐4F:GS‐ISO ternary OSCs with an efficiency of 14.13% are prepared in air. The work provides a new strategy for preparing efficient and environmentally friendly OSCs using green solvents.

Highly Permeable Ultrafiltration Membranes Based on Polyphenylene Sulfone with Cardo Fragments.

For the first time, copolymers of polyphenylene sulfone (PPSU) with cardo fragments of phenolphthalein (PP) were synthesized to develop highly permeable flat-sheet ultrafiltration membranes. By introducing cardo fragments into the polymer chain, we achieved a mechanical strength 1.3 times higher than the strength of commercial PPSU. It is shown that the introduction of the cardo monomer significantly increases the solubility of the polymer in aprotic solvents. The highest solubility is observed at the concentration of PP 50 mol.%. It is found that reduced viscosity of cardo polymer solutions leads to an increase in the coagulation rate. The permeance of asymmetric ultrafiltration membranes increases with PP concentration from 17.5 L/(m2·h·bar) (10 mol.% PP) to 85.2 L/(m2·h·bar) (90 mol.% PP). These data are in agreement with the results of a study of the coagulation rate of polymer solutions. Thus, for ultrafiltration membranes with 1.5-8 times higher permeance in comparison with PPSU due to the introduction of cardo fragments in the polymer chain, possessing high rejection of the model dye Blue Dextran (MW = 70,000 g/mol), more than 99.2%, as well as high strength characteristics, were achieved.

Increasing the Dissolution Rate of Polystyrene Waste in Solvent-Based Recycling.

Solvent-based recycling of plastic waste is a promising approach for cleaning polymer chains without breaking them. However, the time required to actually dissolve the polymer in a lab environment can take hours. Different factors play a role in polymer dissolution, including temperature, turbulence, and solvent properties. This work provides insights into bottlenecks and opportunities to increase the dissolution rate of polystyrene in solvents. The paper starts with a broad solvent screening in which the dissolution times are compared. Based on the experimental results, a multiple regression model is constructed, which shows that within several solvent properties, the viscosity of the solvent is the major contributor to the dissolution time, followed by the hydrogen, polar, and dispersion bonding (solubility) parameters. These results also indicate that cyclohexene, 2-pentanone, ethylbenzene, and methyl ethyl ketone are solvents that allow fast dissolution. Next, the dissolution kinetics of polystyrene in cyclohexene in a lab-scale reactor and a baffled reactor are investigated. The effects of temperature, particle size, impeller speed, and impeller type were studied. The results show that increased turbulence in a baffled reactor can decrease the dissolution time from 40 to 7 min compared to a lab-scale reactor, indicating the importance of a proper reactor design. The application of a first-order kinetic model confirms that dissolution in a baffled reactor is at least 5-fold faster than that in a lab-scale reactor. Finally, the dissolution kinetics of a real waste sample reveal that, in optimized conditions, full dissolution occurs after 5 min.

Nonmonotonic polymer translocation kinetics through nanopores under changing surface-polymer interactions.

Understanding the dynamics of polymers in confined environments is pivotal for diverse applications ranging from polymer upcycling to bioseparations. In this study, we develop an entropic barrier model using self-consistent field theory that considers the effect of attractive surface interactions, solvation, and confinement on polymer kinetics. In this model, we consider the translocation of a polymer from one cavity into a second cavity through a single-segment-width nanopore. We find that, for a polymer in a good solvent (i.e., excluded volume, u0 > 0), there is a nonmonotonic dependence of mean translocation time (τ) on surface interaction strength, ɛ. At low ɛ, excluded volume interactions lead to an energetic penalty and longer translocation times. As ɛ increases, the surface interactions counteract the energetic penalty imposed by excluded volume and the polymer translocates faster through the nanopore. However, as ɛ continues to increase, an adsorption transition occurs, which leads to significantly slower kinetics due to the penalty of desorption from the first cavity. The ɛ at which this adsorption transition occurs is a function of the excluded volume, with higher u0 leading to an adsorption transition at higher ɛ. Finally, we consider the effect of translocation across different size cavities. We find that the kinetics for translocation into a smaller cavity speeds up while translocation to a larger cavity slows down with increasing ɛ due to higher surface contact under stronger confinement.

On the Swelling of Polymer Network Strands.

Large scale computer simulations are employed to analyze the conformations of network strands in polymer networks at preparation conditions (characterized by a polymer volume fraction of ϕ0) and when swollen to equilibrium (characterized by a polymer volume fraction ϕ < ϕ0). Network strands in end-linked model networks are weakly stretched and partially swollen at preparation conditions as compared to linear polymers in the same solvent at ϕ0. Equilibrium swelling causes non-ideal chain conformations characterized by an effective scaling exponent approaching 7/10 on intermediate length scales for increasing overlap of the chains. The chain size in a network consists of a fluctuating and a time average "elastic" contribution. The elastic contribution swells essentially affinely ∝(ϕ0/ϕ)2/3, whereas the swelling of the fluctuating part lies between the expected swelling of the entanglement constraints and the swelling of non-cross-linked chains in a comparable semi-dilute solution. The total swelling of chain size results from the changes of both fluctuating and non-fluctuatingcontributions.

A Unified Picture of Aggregate Formation in a Model Polymer Semiconductor during Solution Processing

AbstractOne grand challenge for printed organic electronics is the development of a knowledge platform that describes how polymer semiconductors assemble from solution, which requires a unified picture of the complex interplay of polymer solubility, mass transport, nucleation and, e.g., vitrification. One crucial aspect, thereby, is aggregate formation, i.e., the development of electronic coupling between adjacent chain segments. Here, it is shown that the critical aggregation temperatures in solution (no solvent evaporation allowed) and during film formation (solvent evaporation occurring) are excellent pointers to i) establish reliable criteria for polymer assembly into desired aggregates, and ii) advance mechanistic understanding of the overall polymer assembly. Indeed, important insights are provided on why aggregation occurs via a 1‐ or 2‐step process depending on polymer solubility, deposition temperature and solvent evaporation rate; and the selection of deposition temperatures for specific scenarios (e.g., good vs bad solvent) is demystified. Collectively, it is demonstrated that relatively straightforward, concurrent in situ time‐resolved absorbance and photoluminescence spectroscopies to monitor aggregate formation lead to highly useful and broadly applicable criteria for processing functional plastics. In turn, improved control over their properties and device performance can be obtained toward manufacturing sensors, energy‐harvesting devices and, e.g., bioelectronics systems at high yield.

Preparation of PLGA Microspheres Using the Non-Toxic Glycofurol as Polymer Solvent by a Modified Phase Inversion Methodology.

Poly(D,L-lactide-co-glycolide is a biodegradable copolymer that can release pharmaceuticals. These pharmaceuticals can provide local therapy and also avert the clinical issues that occur when a drug must be given continuously and/or automatically. However, the drawbacks of using poly(D,L-lactide-co-glycolide include the kinetics and duration of time of poly(D,L-lactide-co-glycolide drug release, the denaturing of the drug loaded drug, and the potential clinical side effects. These drawbacks are mainly caused by the volatile organic solvents needed to prepare poly(D,L-lactide-co-glycolide spheres. Using the non-toxic solvent glycofurol solvent instead of volatile organic solvents to construct poly(D,L-lactide-co-glycolide microspheres may deter the issues of using volatile organic solvents. Up to now, preparation of such glycofurol spheres has previously met with limited success. We constructed dexamethasone laden poly(D,L-lactide-co-glycolide microspheres utilizing glycofurol as the solvent within a modified phase inversion methodology. These prepared microspheres have a higher drug load and a lower rate of water diffusion. This prolongs drug release compared to dichloromethane constructed spheres. The glycofurol-generated spheres are also not toxic to target cells as is the case for dichloromethane-constructed spheres. Further, glycofurol-constructed spheres do not denature the dexamethasone molecule and have kinetics of drug release that are more clinically advantageous, including a lower drug burst and a prolonged drug release.

The impact of polypyrrole:carboxymethyl cellulose composite nanostructure on conductivity and capacitance

Polypyrrole is a popular conjugated polymer that becomes highly conductive in its p-doped state. The intrinsically non-polar nature of the conjugated bond network limits the processing options of such polymers. Surfactants and polyanions help increase dispersity of conductive polymer in suitable solvents for processing. However, while such dispersions can be highly stable, they are formed by complex nanostructures that significantly impact the conducting polymer composite’s bulk properties. Similarly, complex nanostructures can be formed when surfactants or polyelectrolytes serve as templates during the polymerization of the conducting polymer precursor. Following the report of polypyrrole:carboxymethyl cellulose composites in battery electrodes as conductive binders, we are here investigating the role that nanostructure control can have in optimizing their performance. Using methyl orange as a structural template, we can control the composite’s nanoscopic shape between nanospheres and nanofibers. In the bulk material, the latter gives rise to significantly increased electronic conductivity and capacitance in battery use conditions, underlining the opportunities for improved performance of conducting polymer composites by controlling synthesis conditions.

Comment on "Effects of topological constraints on linked ring polymers in solvents of varying quality" by Z. A. Dehaghani, I. Chubak, C. N. Likos and M. R. Ejtehadi, Soft Matter, 2020, 16, 3029.

This comment critically evaluates the work of Dehaghani et al., who investigated the conformational behavior of catenated polymers under diverse solvent conditions using coarse-grained molecular dynamics simulations. While their study provides valuable insights into the scaling behavior of poly[n]catenane's radius of gyration in a good solvent, significant discrepancies arise, particularly concerning the reported θ-temperature trends. The validity of their methodology in determining θ-temperatures for linear and ring polymers is questioned, given observed disparities in chosen number of bead ranges that imply varying molecular weights. This comment underscores the need for a meticulous reassessment of the methodologies and interpretations presented in Dehaghani et al.'s study, emphasizing the importance of rigorous considerations in the investigation of the physical properties of catenated polymers.

Reply to the 'Comment on "Effects of topological constraints on linked ring polymers in solvents of varying quality"' by M. Tsige and H. Guo, Soft Matter, 2024, 20, DOI: 10.1039/D3SM01614E.

In the preceding Comment, Drs Tsige and Guo compare their findings about the θ-temperatures of linear chains, ring polymers and poly[n]catenanes with those of previous work by us [Z. A. Dehaghani, I. Chubak, C. N. Likos and M. R. Ejtehadi, Soft Matter, 2020, 16, 3029-3038] and point out that the ordering they obtain for these three quantities is, for large degrees of polymerisation, the reverse of the one we had found in our own investigations. We thank the authors of the Comment for their remarks and we appreciate their detailed investigations, which emphasise the importance of understanding the properties of topological polymers and their behaviour under varying solvent quality. We point out, however, that the discrepancy found by Tsige and Guo is only apparent because it pertains to the Θ-temperature of rings and poly[n]catenanes with the same overall molecular weight, whereas in our work we compared the Θ-temperature of a constituent ring of the poly[n]catenane with that of the entire mechanically linked macromulecule.

Protection coatings for corrosion control of mild steel using phenolic polymeric deep eutectic solvents

Phenolic polymeric deep eutectic solvents form coloured complexes with iron surfaces which can be used as protection coatings for corrosion control of mild steel.

Redox-active, photoluminescent porous polymers based on spirofluorene-bridged N-heterotriangulenes and their feasibility as organic cathode materials.

Novel microporous polymers were synthesized through Yamamoto polymerization of selectively brominated spirofluorene-bridged N-heterotriangulenes. Extensive characterization, including combustion analysis, ToF-SIMS, IR, and Raman spectroscopy, confirmed the elemental composition and integrity of the polymers. The amorphous polymers, observed by scanning electron microscopy as globular particles aggregating into larger structures, exhibited remarkable thermal stability (decomposition temperatures > 400 °C) and BET surface areas up to 690 m2 g-1. Dispersions of the tert-butyl-substituted polymer in different solvents displayed bathochromically shifted emission with remarkable solvatochromism. The polymer is reversibly oxidized at +3.81 V (vs. Li/Li+) in composite electrodes with carbon black and reaches specific capacities up to 26 mA h g-1 and excellent cycling stability when implemented as cathode material in lithium-ion batteries. Our results highlight the potential of spirofluorene-bridged N-heterotriangulenes as versatile building blocks for the development of functional redox-active porous polymers.

Grafting photochromic spiropyran polymer brushes on graphene oxide surfaces via surface-initiated ring-opening metathesis polymerization.

A practical "grafting-from" strategy is described to grow photochromic polymer brushes bearing spiropyran (SP) functional groups on graphene oxide (GO) surfaces via surface-initiated ring-opening metathesis polymerization (SI-ROMP). The Grubbs II catalyst was fixed on the GO surface, and the norbornene derivatives functionalized using spiropyran were synthesized from this active site via the ROMP method. The results indicated that the spiropyran-modified polymer brushes were obtained on the GO surface in the form of thin films. The solubility of GO modified by spiropyran polymers (GO-SPs) in organic solvents was significantly improved. The GO-SPs exhibited excellent photochromic properties, including fast coloration/decoloration. The modified GO with an isomeric structure was colored in 90 s under ultraviolet irradiation and decolored in 360 s under white light. The fading kinetic rate in the dark was slow and the kinetic attenuation curve followed bi-exponential decay. The GO-SP composite materials took more than 2 h to return to thermodynamically stable forms. The reversible change in the water contact angle reached 8° after continuous cycling with ultraviolet and visible light. GO-SP maintained its photochromic performance and possessed excellent fatigue resistance after more than six successive UV/light cycles. This work describes a practical strategy for the preparation of photochromic polymer brush modified GO composite materials and extends the applications of GO in photochromic materials.

Dynamics of polymers in coarse-grained nematic solvents.

Polymers are a primary building block in many biomaterials, often interacting with anisotropic backgrounds. While previous studies have considered polymer dynamics within nematic solvents, rarely are the effects of anisotropic viscosity and polymer elongation differentiated. Here, we study polymers embedded in nematic liquid crystals with isotropic viscosity via numerical simulations to explicitly investigate the effect of nematicity on macromolecular conformation and how conformation alone can produce anisotropic dynamics. We employ a hybrid multi-particle collision dynamics and molecular dynamics technique that captures nematic orientation, thermal fluctuations and hydrodynamic interactions. The coupling of the polymer segments to the director field of the surrounding nematic elongates the polymer, producing anisotropic diffusion even in nematic solvents with isotropic viscosity. For intermediate coupling, the competition between background anisotropy and macromolecular entropy leads to hairpins - sudden kinks along the backbone of the polymer. Experiments of DNA embedded in a solution of rod-like fd viruses qualitatively support the role of hairpins in establishing characteristic conformational features that govern polymer dynamics. Hairpin diffusion along the backbone exponentially slows as coupling increases. Better understanding two-way coupling between polymers and their surroundings could allow the creation of more biomimetic composite materials.