Polymers In Solid State Research Articles

Solid-State Fluorescent Organic Polymers for Visual Detection and Elimination of Heavy Metals in Water.

Selective sensing and removal of toxic heavy metals from water are highly essential since their presence poses significant health and environmental hazards. Herein, we designed and synthesized a novel fluorescent nonconjugated organic polymer by strategically incorporating two key functional groups, namely, a dansyl fluorophore and dithiocarbamate (DTC). Different characterization techniques, including 1H nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray analysis (EDAX), Fourier transform infrared (FTIR), and fluorescence spectroscopy, were performed to understand its structure and material properties. The quantum yield of 4.72% and its solid-state fluorescence indicate that it has potential for various applications in several technological and scientific domains. In this study, we investigated a specific application involving the detection and elimination of heavy metals from water. Interestingly, the presence of dansyl and DTC moieties demonstrated remarkable selectivity toward Cu2+, Co2+, Ni2+, Fe3+, and Fe2+ sensing, displaying distinct color changes specific to each metal. Cu2+ resulted in a yellow color, Co2+ showed a green color, Ni2+ displayed a pale yellowish-green color, and Fe2+/Fe3+ exhibited a brown color. The LOD (limit of detection) for each metal was obtained in the nanomolar range by using a fluorescence spectrometer and the micromolar range from UV-visible spectra: 13.27 nM and 0.518 μM for Cu2+, 8.27 nM and 0.581 μM for Co2+, 14.36 nM and 0.140 μM for Ni2+, 14.95 nM and 0.174 μM for Fe2+, and 15.54 nM and 0.33 μM for Fe3+. Moreover, the DTC functionality on its backbone facilitates effective interaction with the aforementioned heavy metals, subsequently removing them from water (except Fe2+ and Fe3+), validating its dual functionality as both an indicator and a purifier for heavy metals in water. The polymer exhibited a maximum adsorption capacity of 192.30 mg/g for Cu2+, 159.74 mg/g for Co2+, and 181.81 mg/g for Ni2+. Furthermore, this approach exhibits versatility in crafting fluorescent polymers with adjustable attributes that are suitable for a wide range of applications.

Structural, Ionic, and Electronic Properties of Solid-State Phthalimide-Containing Polymers for All-Organic Batteries

Structural, Ionic, and Electronic Properties of Solid-State Phthalimide-Containing Polymers for All-Organic Batteries

Computational approach inspired advancements of solid-state electrolytes for lithium secondary batteries: from first-principles to machine learning.

The increasing demand for high-security, high-performance, and low-cost energy storage systems (EESs) driven by the adoption of renewable energy is gradually surpassing the capabilities of commercial lithium-ion batteries (LIBs). Solid-state electrolytes (SSEs), including inorganics, polymers, and composites, have emerged as promising candidates for next-generation all-solid-state batteries (ASSBs). ASSBs offer higher theoretical energy densities, improved safety, and extended cyclic stability, making them increasingly popular in academia and industry. However, the commercialization of ASSBs still faces significant challenges, such as unsatisfactory interfacial resistance and rapid dendrite growth. To overcome these problems, a thorough understanding of the complex chemical-electrochemical-mechanical interactions of SSE materials is essential. Recently, computational methods have played a vital role in revealing the fundamental mechanisms associated with SSEs and accelerating their development, ranging from atomistic first-principles calculations, molecular dynamic simulations, multiphysics modeling, to machine learning approaches. These methods enable the prediction of intrinsic properties and interfacial stability, investigation of material degradation, and exploration of topological design, among other factors. In this comprehensive review, we provide an overview of different numerical methods used in SSE research. We discuss the current state of knowledge in numerical auxiliary approaches, with a particular focus on machine learning-enabled methods, for the understanding of multiphysics-couplings of SSEs at various spatial and time scales. Additionally, we highlight insights and prospects for SSE advancements. This review serves as a valuable resource for researchers and industry professionals working with energy storage systems and computational modeling and offers perspectives on the future directions of SSE development.

BINOL induces chirality in polyfluorene-based electroluminescent polymers in solid state

Nowadays circularly polarized luminescence (CPL) gains much attraction because it can be applied to a variety of fields. An efficient method to achieve CPL is blending achiral emissive polymers with chiral small-molecule additives as a chiral inducer. In this work, we demonstrate that 1,1′-Bi-2-naphthol (BINOL) acts as a chiral-inducer for poly (9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) in a thin film. In the thin films of F8BT/BINOL before annealing, only circular dichroism (CD) signals of BINOL were observed. After the annealing at 120 °C, clear CD signals of F8BT were observed indicating that the chiroptical property was induced on the F8BT thin films. The CD signal intensity was enhanced by increasing the annealing temperature up to 200 °C. By optimizing the concentration of BINOL and the annealing temperature, we obtained a dissymmetry CD value of 0.012. Photoluminescence quantum yield of the F8BT/BINOL thin films was also increased after the annealing.

Molecular Photoswitching of Main-Chain α-Bisimines in Solid-State Polymers.

Photoisomerization of chromophores usually shows significantly less efficiency in solid polymers than in solution as strong intermolecular interactions lock their conformation. Herein, we establish the impact of macromolecular architecture on the isomerization efficiency of main-chain-incorporated chromophores (i.e., α-bisimine) in both solution and the solid state. We demonstrate that branched architectures deliver the highest isomerization efficiency for the main-chain chromophore in the solid state─remarkably as high as 70% compared to solution. The macromolecular design principles established herein for efficient solid-state photoisomerization can serve as a blueprint for enhancing the solid-state isomerization efficiency for other polymer systems, such as those based on azobenzenes.

Solid-State Surface Patterning on Polymer Using the Microcellular Foaming Process

This study proposes a novel process that integrates the molding and patterning of solid-state polymers with the force generated from the volume expansion of the microcellular-foaming process (MCP) and the softening of solid-state polymers due to gas adsorption. The batch-foaming process, which is one of the MCPs, is a useful process that can cause thermal, acoustic, and electrical characteristic changes in polymer materials. However, its development is limited due to low productivity. A pattern was imprinted on the surface using a polymer gas mixture with a 3D-printed polymer mold. The process was controlled with changing weight gain by controlling saturation time. A scanning electron microscope (SEM) and confocal laser scanning microscopy were used to obtain the results. The maximum depth could be formed in the same manner as the mold geometry (sample depth: 208.7 μm; mold depth: 200 μm). Furthermore, the same pattern could be imprinted as a layer thickness of 3D printing (sample pattern gap and mold layer gap: 0.4 mm), and surface roughness was increased according to increase in the foaming ratio. This process can be used as a novel method to expand the limited applications of the batch-foaming process considering that MCPs can impart various high-value-added characteristics to polymers.

Generalization of the post-collision interaction effect from gas-phase to solid-state systems demonstrated in thiophene and its polymers

We demonstrate experimentally and theoretically the presence of the post-collision interaction (PCI) effect in sulfur ${\mathrm{KL}}_{2,3}{\mathrm{L}}_{2,3}$ Auger electron spectra measured in the gas-phase thiophene and in solid-state organic polymers: polythiophene (PT) and poly(3-hexylthiophene-2,5-diyl), commonly known as P3HT. PCI manifests itself through a distortion and a blueshift of the normal Auger S ${\mathrm{KL}}_{2,3}{\mathrm{L}}_{2,3}$ spectrum when S $1s$ ionization occurs close to the ionization threshold. Our investigation shows that the PCI-induced shift of the Auger spectra is stronger in the solid-state polymers than in the gas-phase organic molecule. Theoretical modeling within the framework of the eikonal approximation provides good agreement with the experimental observations. In a solid medium, two effects influence the interaction between the photoelectron and the Auger electron. In detail, stronger PCI in the polymers is attributed to the photoelectron scattering in the solid, which overcompensates the polarization screening of electron charges which causes a reduction of the interaction. Our paper demonstrates the general nature of the PCI effect occurring in different media.

Selective modulation of energy levels of frontier orbitals in solid-state luminescent boron-fused azomethine polymers with orthogonal orientations to the main chains

We demonstrate that the energy levels of π-conjugated polymers for luminescent films can be controlled by selecting their fused structure.

Effect of the cyano group on colour-tunability of aryl-substituted buta-1,3-diene based solid-state emissive copolymers

Solid-state emissive copolymers with varying cyano groups have been developed and are utilised for the PLED device applications to demonstrate the effect of acceptor strength.

Factors Controlling Degradation of Biologically Relevant Synthetic Polymers in Solution and Solid State.

The field of biodegradable synthetic polymers, which is central for regenerative engineering and drug delivery applications, encompasses a multitude of hydrolytically sensitive macromolecular structures and diverse processing approaches. The ideal degradation behavior for a specific life science application must comply with a set of requirements, which include a clinically relevant kinetic profile, adequate biocompatibility, benign degradation products, and controlled structural evolution. Although significant advances have been made in tailoring materials characteristics to satisfy these requirements, the impacts of autocatalytic reactions and microenvironments are often overlooked resulting in uncontrollable and unpredictable outcomes. Therefore, roles of surface versus bulk erosion, in situ microenvironment, and autocatalytic mechanisms should be understood to enable rational design of degradable systems. In an attempt to individually evaluate the physical state and form factors influencing autocatalytic hydrolysis of degradable polymers, this Review follows a hierarchical analysis that starts with hydrolytic degradation of water-soluble polymers before building up to 2D-like materials, such as ultrathin coatings and capsules, and then to solid-state degradation. We argue that chemical reactivity largely governs solution degradation while diffusivity and geometry control the degradation of bulk materials, with thin "2D" materials remaining largely unexplored. Following this classification, this Review explores techniques to analyze degradation in vitro and in vivo and summarizes recent advances toward understanding degradation behavior for traditional and innovative polymer systems. Finally, we highlight challenges encountered in analytical methodology and standardization of results and provide perspective on the future trends in the development of biodegradable polymers.

Efficient Strategy for Investigating the Third-Order Nonlinear Optical (NLO) Properties of Solid-State Coordination Polymers.

The investigation of third-order nonlinear optical (NLO) properties of coordination polymers (CPs) based on solid samples is very difficult but is crucial for practical applications. Herein, we show a method for preparing high optical quality CP films in a polymer matrix to study the third-order NLO performance of solid-state CPs. Two novel azobenzene-based CPs, [CdL(DMAc)(H2O)]n (1) and {[CuL(4,4'-azobpy)]·3H2O}n (2) (H2L = 5-((4-(phenyldiazenyl)phenoxy)methyl)isophthalic acid), were selected as study subjects. The corresponding microcrystals with a grain size of around 3 μm were doped into poly(vinyl alcohol) (PVA), forming CP films (1-MC/PVA and 2-MC/PVA). 1-MC/PVA and 2-MC/PVA exhibit NLO absorption switching behavior from saturable absorption (SA) to reverse saturable absorption (RSA) with increasing pulse energy. Moreover, their NLO properties can also be efficiently modulated by photostimulation energy due to the trans → cis isomerization of an azobenzene moiety. The density functional theory (DFT) results show that the narrower the band gap between the conduction band minimum and the valence band maximum, the denser the electron density distribution in the central mental and coordination atoms, which is beneficial to exhibit better third-order NLO performance. This work provides a feasible method for the wider practical application of solid materials with excellent third-order NLO performance.

Thermal Behavior of Polymers in Solid-State

A variety of potential polymers with chemical and physical stability characteristics and abundant availability lead to the rapid application of polymers in various fields. One of the crucial things that are crucial to be discussed from such polymers is the characteristic of thermal behavior. Each type of polymer such as natural and synthetic has different thermal characteristics, including Tc, Tg, Tm, and Td which can be the determining factor of polymer selection of processing and application temperature. The thermal properties will also affect molecular interactions, physical stability in manufacturing, distribution, and storage. Therefore, in this article will appoint a study on the thermal characteristics of natural and synthetic polymers, the effect of modification on the thermal properties of polymers, efforts to increase the stability of thermal, and polymer applications in the field of pharmaceutical technology.

Macrocycle-Based Solid-State Supramolecular Polymers.

Supramolecular polymers, generated by connecting monomers through noncovalent interactions, have received considerable attention over the past years, as they provide versatile platforms for developing diverse aesthetically pleasing polymeric structures with promising applications in a variety of fields, such as medicine, catalysis, and sensing. In the development of supramolecular polymers, macrocyclic hosts play a very important role. Benefiting from their abundant host-guest chemistry and self-assembly characteristics, macrocycles themselves or their host-guest complexes can self-assemble to form well-ordered supramolecular polymeric architectures including pseudopolyrotaxanes and polyrotaxanes. The integration of these topological structures into supramolecular polymeric materials also imbues them with some unforeseen functions. Current interest in macrocycle-based supramolecular polymers is mostly focused on the development of supramolecular soft materials in solution or gel-state, in which the dynamic nature of noncovalent interactions endows supramolecular polymers with a wealth of "smart" properties, such as multiresponsiveness and self-repair capabilities. While preparation of macrocycle-derived supramolecular polymers in the solid state is a relatively challenging but intriguing prospect, they are an important part of the field of supramolecular polymers. On one hand, the construction of macrocycle-based solid-state supramolecular polymers enables us to obtain new materials with novel properties and functions such as mechano-responsiveness. On the other hand, the molecular structures and arrangements in these materials are well-identified by X-ray crystallography techniques, offering a direct visual representation of the supramolecular polymerization process. The analysis of the role of noncovalent interactions in these architectures allows us to design more sophisticated and elegant supramolecular polymers in a highly rationalized and controllable manner. This Account serves to summarize the research progress on macrocycle-based solid-state supramolecular polymers (MSSPs), including the contributions toward this field made by our group. For constructing MSSPs, the key point is to control noncovalent interactions. Thus, in this Account, we primarily classify these MSSPs by different noncovalent interactions involved to connect the monomers, including metal-ligand interactions, host-guest interactions, π···π stacking, and halogen bonding. These noncovalent interactions are highly associated with the structures and functions of the resultant MSSPs. For instance, using metal-ligand interactions as driving forces, metal clusters can be introduced in MSSPs which afford systems with solid-state luminescence or proton conduction properties; supramolecular polymerization using macrocycle-based host-guest interactions can modulate the molecular arrangement of some specific molecules in the solid state, which further influences their solid-state properties; π···π stacking interactions and halogen bonding give chemists more choice to design MSSPs with various elements. The role of macrocyclic hosts in MSSPs is also revealed in these descriptions. Finally, the remaining challenges are identified for further development of future prospects. We hope that this Account can inspire new discoveries in the realm of supramolecular functional systems and offer new opportunities for the construction of supramolecular architectures and solid-state materials.

Dual Reactivity Induced Structure Transformation of Coordination Polymers in Solid State

Structure transformation of dual reactive coordination polymers in solid state is unique but rarely reported. In this work, dual reactive Znbpe was successfully prepared, whose solid-state structure transformation was realized by UV light and ozone on the same crystal with different order. The products of structure transformation from Znbpe, Znbpe-OL and Znbpe-LO, exhibit similar rod-like morphology and crystal structure. And their corresponding calcination product show better photocatalytic activities in terms of Rhodamine-B degradation than Znbpe’s.

Vapochromic Behaviors of A Solid-State Supramolecular Polymer Based on Exo-Wall Complexation of Perethylated Pillar[5]arene with 1,2,4,5-Tetracyanobenzene.

The research for the solid-state supramolecular polymers with specific functions accelerates the development of supramolecular and materials sciences. Herein, we discover the different complexation modes of perethylated pillar[5]arene (EtP5) with 1,2,4,5-tetracyanobenzene (TCNB) in various solvents. Driven by charge-transfer interaction, TCNB is enclosed in the cavity of EtP5 in CHCl3 , while TCNB complexes with EtP5 at the exo-wall of EtP5 in CH2 Cl2 . This is because the size of CH2 Cl2 matches the cavity of EtP5, forcing TCNB to complex with the exo-wall of EtP5. Furthermore, we fabricate a vapochromic solid-state supramolecular polymer by exploiting the exo-wall complexation, which turns from brown to reddish brown or black after adsorption of alkyl aldehyde vapors. The adsorptive nature for alkyl aldehyde vapors comes from the unoccupied cavity of EtP5 based on C-H⋅⋅⋅π interactions. The vapochromic property is attributed to the change of the charge-transfer interaction caused by molecular rearrangement induced by vapor-capture in the solid-state supramolecular polymer.

Synthesis, processability and photoluminescence of pyrene-containing polyimides

Summary Four different contents of pyrene group were introduced in polyimide (PI) backbone via one step polycondensation procedure. The chemical structure, thermal property, process ability, and photophysical performance of polymers were characterized and analyzed. The obtained PIs exhibited high glass-transition temperatures from 270 to 285 °C, and weight remainder rates of PIs were all above 50% at 800 °C in N2. Fluorescence detection of metal ions was taken by adding Cu2+, Pb2+, Cr3+, Cd2+, Fe3+, Co2+, and Ni2+ to polymer solutions. It was interesting to found that the polymer exhibited significant luminescence emission “turn-on” response to Cu2+ and fluorescence emission quenching to Fe3+. Furthermore, the uniform morphologies of pyrene-containing PI fibers were prepared via electrospinning technique for investigating their optical properties in solid state. The fluorescent images and optical photographs indicated that the luminescence stability of polymers in fiber solid state was decided by both the chromophore in macromolecular chain and effective draft of polymer chains during spinning process. This study provided a facility strategy for controlling the morphology structure of materials and keeping the PL emission intensity in flexible devices.

Pillar[5]arene-Based Solid-State Supramolecular Polymers with Suppressed Aggregation-Caused Quenching Effects and Two-Photon Excited Emission.

Herein we develop a new pillar[5]arene-mediated supramolecular polymerization strategy to control the assembly of dyes 4,7-di-2-thienyl-2,1,3-benzothiadiazole and 4,7-di-2-thienyl-2,1,3-benzoselenadiazole in the solid state. The resulting supramolecular polymeric structures drive the dye aggregates in the solid state from parallel alignments to highly ordered "head-to-tail" structures, which effectively suppresses excimer formation and thus aggregation-caused quenching effects and enhances the solid-state emission efficiency by almost 1 order of magnitude. This, together with two-photon excited emission, endows these solid-state polymers with exciting potential in optoelectronic, photonic, and bioimaging applications.

Selective and rapid detection of nerve agent simulants by polymer fibers with a fluorescent chemosensor in gas phase

Nerve agents (NAs) are the most feared and unpredictable chemical warfare agents (CWAs) on the battlefield and in the hands of terrorists. To cope with chemical terrorism or chemical warfare, it is urgent to establish a rapid and reliable detection method for NAs. In this work, we have developed two 6-aminoquinolin-2-yl-methanols (AQmol-1 and AQmol-2), which can selectively detect two nerve agent simulants, diisopropylfluorophosphate (DFP) and diethylchlorophosphate (DCP), over other organophosphate compunds. In this sensing reaction, the hydroxy group of two sensors is phosphorylated by DFP/DCP and simulanutaus protonation of nitrigen of the quinoline to form a stronger electron donor-acceptor (DA) molecule over the sensor molecule, giving corresponding fluorescence response. Therein, AQmol-2 diplays ratiometirc fluorescence response towards DFP/DCP with a lower limit of detection (LOD) 0.18 μM or 0.16 μM, respectively. Furthermore, two AQmol-2 embedded solid polymers, membrane and fibers (the diameter <1 μm), were fabricated for detection of DFP/DCP vapor. Both AQmol-2-embedded solid-state polymers can detect DFP/DCP vapor more rapidly over those (about 30 min) in solutions. The polymer fibers from an electrospaning technology give more rapid response toward DCP (within 20 s) over that (3 min) of the membrane. Therefore, AQmol-2-embedded polymer nanofibrosis is promissing way for selective and rapid detection of nerve agents in gas phase.

ATRP Initiators Based on Proton Transfer Benzazole Dyes: Solid-State Photoactive Polymer with Very Large Stokes Shift

This work presents the synthesis, photophysical characterization, and application of ATRP polymerization initiators to produce photoactive solid-state fluorescent polystyrene-based polymers. These ...

Modeling of pvT behavior of semi-crystalline polymer based on the two-domain Tait equation of state for injection molding

The absence of the influence of cooling rate in the pressure–specific volume–temperature (pvT) models makes them inadequate in the process simulation of injection molding. This work derived new equations of state (EoS) from the traditional two-domain Tait model that describes the pvT behavior of semi-crystalline polymers in both molten and solid state. Especially, the cooling rate was considered. The second aim of this work is to solve the discontinuity problem of the traditional two-domain Tait model. A continuous two-domain Tait EoS was developed. A good agreement between the calculations and experimental results was achieved. The new pvT models were successfully applied in the prediction of specific volume as a function of temperature, pressure and cooling rate during injection molding. A higher value of the specific volume was predicted when the cooling rate was considered. Combining the continuous two-domain Tait EoS, more accurate results can be obtained especially at the transition phase from melt to solid of the semi-crystalline polymer.