Rigid Backbone Research Articles

Recent progress on covalent organic frameworks for photocatalytic hydrogen generationviawater splitting

Covalent organic frameworks (COFs) with permanent porosity, long-range order and rigid backbones offer a promising material platform for photocatalytic water splitting for hydrogen production.

Porous organic cages as inhibitors of Aβ42 peptide aggregation: a simulation study.

The aggregation of Aβ monomers into oligomers with β-sheet structures is an important cause of Alzheimer's disease (AD), while the Aβ42 peptide is more toxic and prone to aggregate. It is of great significance to study the inhibition mechanism of Aβ42 monomer aggregation and find excellent inhibitors for the treatment of AD. Research in recent years has focused on small molecule compounds and nanoparticles, but they all have certain limitations. As a new type of porous material, a porous organic cage (POC) has potential application feasibility in the biomedical field due to its unique physicochemical properties. In this work, molecular dynamics simulations were used for the first time to explore the interaction and conformational transformation of the Aβ42 peptide in CC3 crystals with different morphologies (planar and spherical). The results show that the adsorption of the Aβ42 peptide on different CC3 crystals is mainly achieved through strong van der Waals forces. During the simulations, the Aβ42 peptide undergoes various degrees of structural changes. Compared to that in water, this binding induces more irregular structures, such as turns and 3-helices, and inhibits the production of β-sheets, while enhancing the overall backbone rigidity of the Aβ42 peptide. The transformation analysis of peptide conformation is further complemented by free energy landscape and cluster analysis. These findings provide a strong basis for CC3 crystals as novel inhibitors to inhibit the toxicity and aggregation of the Aβ42 peptide.

A high performance, stable anion exchange membrane for alkaline redox flow batteries

The development of cost-effective, safe, and low-corrosion alkaline aqueous redox flow batteries, such as alkaline zinc-iron flow batteries, has motivated the research of hydrocarbon-based anion exchange membranes. These membranes, characterized by their positively charged functional groups, facilitate the transport of hydroxide anions (OH−) in alkaline environments, rendering them as potential alternatives to conventional proton exchange membranes in emerging alkaline redox flow batteries. Herein, a facilely synthesized anion exchange membrane (AEM) with superior chemical stability in alkaline media and outstanding ion conductivity has been developed for use in an alkaline redox flow battery. The membrane consists of a partially imidazolium substituted poly (vinylbenzyl chloride) polymer matrix and low molecular weight polyethylene glycol (PEG) additive. The membrane provides positively charged polymer backbone with hydroxide anion as counter ions. The additive PEG not only augments membrane flexibility through interaction with the rigid polymer backbone, but also enhances the conductivity through conducting ions by the alkalized-ether functionality. The optimized anion exchange membrane demonstrates better ionic conductivity of 58.2 mS cm−1 and comparable permeability compared with commercially Nafion117 membrane, enabling promoted energy efficiency (83.5 %), coulombic efficiency (99.85 %) and excellent stability (280 cycles with negligible capacity degradation) of a zinc-iron flow battery at 80 mA cm−2.

Discriminating and recording different types of mechanical force by distinct turn-on responses of a T-shape luminescent compound

Smart mechano-responsive luminescent (SMRL) materials that can discriminate different types of mechanical force have attracted extensive research interest. However, the reported few SMRL materials were limited in low sensitivity (pressure ≥ GPa) and transient record. Herein, a T-shape compound (T2) combination with a flexible alkyl chain and a rigid backbone of slightly twisted conjugate has been demonstrated. It presents sensitively distinct luminescence turn-on responses to grinding (red, λem = 622 nm) and pressing (near-infrared, λem = 696 nm), with pressure threshold as low as 1 MPa. More importantly, the resulted luminescent information of mechanical forces can be maintained and recorded for several days, after removing the external stimuli. It is revealed that the loose grid-like-stack assembly formed by T2 was destroyed by grinding but pressed into compact interlaced-stack by pressing. This study paves a new way for realizing SMRL materials on the basis of T-shape compound combing rigidity and flexibility, with turn-on response for sensitively discriminating and long-term recording mechanical forces.

Synthesis and Metal‐Complexation of a Trimer of Dendrimers with Bipyridine Cores in the Center of Conjugated Chains

AbstractTwo types of dendrimers with a bipyridine unit in the center of their rigid backbones were prepared. One dendrimer has two azide groups and the other has one ethynyl terminal. These dendrimers were coupled by the copper‐mediated Hüisgen 1,3‐dipolar cycloadditions of the ethynyl and azide terminals to afford a trimer with three bipyridine cores. The addition of Fe(II) to a solution of the trimer resulted in an absorption change characteristic of the formation of tris(bipyridine)Fe(II) complexes. The structural properties of the tris(bipyridine)Fe(II) core are likely reflected in the conformation of the timer because the bipyridine units are attached to the rigid backbones.

Microphase separation structures facilitated by dipole molecules and hydrogen bonding in poly (biphenyl piperidine-isatin) anion exchange membranes

The anion exchange membranes (AEMs) have the important function of blocking fuel and conducting OH− to make the cell form a circuit, so its alkali stability directly affects the performance of alkaline fuel cells. Currently, AEMs face a “trade-off” between ionic conductivity and stability. In order to solve this problem, we optimize the alkali resistance and conductivity of AEMs by introducing dipole-interacting side chains and hydrophilic hydroxyl side chains acting simultaneously on a rigid polymer backbone. By adopting the design strategy of “1 + 1>2″, the ion channel efficiency also makes a high-speed leap from a “two-wheeled bicycle” to a “four-wheeled car”. This effective microscopic modulation is clearly demonstrated by transmission electron microscope (TEM), where the AEMs after molecular design carry out a more obvious microphase separation structure at 200 nm. Through the PBP-54-IS- [OPD-100-OH-0] membrane, the maximum ionic conductivity is 100.62 mS cm−1 at 80 °C. After 1000 h at 80 °C, the retention rate of OH− conductivity of all AEMs was over 88.24 %. We also test its fuel cell performance for analysis. When the temperature of the two poles is 75 °C/72 °C, the power density is 147.28 mW cm−2. These are in line with the inherent requirements of AEMs for fuel cell applications.

Stretchable Semiconducting Polymers with Hydrogen-Bonding-Capable Conjugation Breakers: Synthesis and Application in Organic Thin-Film Transistors.

Diketopyrrolopyrrole (DPP)-based conjugated copolymers are important organic semiconductors for applications in high-efficiency organic thin-film transistors (OTFTs). However, the direct application of these polymers with rigid backbones in stretchable devices has limitations. In this study, we designed and synthesized three kinds of DPPBT-based copolymers, DPPBT-A1, DPPBT-A3, and DPPBT-A5, which have amide-coupled alkylene conjugation breakers capable of hydrogen bonding. Linkers with different segment lengths were copolymerized with DPP and bithiophene (BT) backbone units. A DPP-based copolymer with alternating BT moieties, DPPBT, was synthesized as a reference fully conjugated copolymer. The synthesized polymers with freely rotational backbone linkers have sufficient flexibility to develop ordered phase domains, even in thin films, in comparison to the reference copolymer. However, the introduction of the conjugation breakers, which disconnect the intramolecular π-π overlapping, tends to decrease the hole mobility (μ) from 0.76 to 0.20 cm2 V-1 s-1 in the corresponding OTFT devices. The TFT fabricated using DPPBT-A3 showed a mobility of 0.50 cm2 V-1 s-1, and the mobility value did not show a significant change even when elongated by more than 50%. Therefore, the molecular design strategy of introducing amide-coupled alkylene conjugation breakers into conjugated polymer chains can contribute significantly to the development of high-mobility stretchable conjugated polymers in future.

π-Extended Helical Multilayer Nanographenes with Layer-Dependent Chiroptical Properties.

Helical nanographenes (NGs) have attracted increasing attention recently because of their intrinsic chirality and exotic chiroptical properties. However, the efficient synthesis of extended helical NGs featuring a multilayer topology is still underdeveloped, and their layer-dependent chiroptical properties remain elusive. In this study, we demonstrate a modular synthetic strategy to construct a series of novel helical NGs (1-3) with a multilayer topology through a consecutive Diels-Alder reaction and regioselective cyclodehydrogenation from the readily accessible phenanthrene-based precursors bearing ethynyl groups. The resultant NGs exhibit bilayer, trilayer, and tetralayer structures with elongated π extension and rigid helical backbones, as unambiguously confirmed by single-crystal X-ray or electron diffraction analysis. We find that the photophysical properties of these helical NGs are notably influenced by the degree of π extension, which varies with the number of layers, leading to obvious redshifted absorption, a fast rising molar extinction coefficient (ε), and markedly boosted fluorescence quantum yield (Φf). Moreover, the embedded [7]helicene subunits in these NGs result in stable chirality, enabling both chiral resolution and exploration of their layer-dependent chiroptical properties. Profiting from the good alignment of electric and magnetic dipole moments determined by the multilayer structure, the resultant NGs exhibit excellent circular dichroism and circularly polarized luminescence response with unprecedented high CPL brightness up to 168 M-1 cm-1, rendering them promising candidates for CPL emitters.

Rational Design of DNA Hydrogels Based on Molecular Dynamics of Polymers.

In recent years, DNA has emerged as a fascinating building material to engineer hydrogel due to its excellent programmability, which has gained considerable attention in biomedical applications. Understanding the structure-property relationship and underlying molecular determinants of DNA hydrogel is essential to precisely tailor its macroscopic properties at molecular level. In this review, the rational design principles of DNA molecular networks based on molecular dynamics of polymers on the temporal scale, which can be engineered via the backbone rigidity and crosslinking kinetics, are highlighted. By elucidating the underlying molecular mechanisms and theories, it is aimed to provide a comprehensive overview of how the tunable DNA backbone rigidity and the crosslinking kinetics lead to desirable macroscopic properties of DNA hydrogels, including mechanical properties, diffusive permeability, swelling behaviors, and dynamic features. Furthermore, it is also discussed how the tunable macroscopic properties make DNA hydrogels promising candidates for biomedical applications, such as cell culture, tissue engineering, bio-sensing, and drug delivery.

Local stability of spheres via the convex hull and the radical Voronoi diagram.

Jamming is an emergent phenomenon wherein the local stability of individual particles percolates to form a globally rigid structure. However, the onset of rigidity does not imply that every particle becomes rigid, and indeed some remain locally unstable. These particles, if they become unmoored from their neighbors, are called rattlers, and their identification is critical to understanding the rigid backbone of a packing, as these particles cannot bear stress. The accurate identification of rattlers, however, can be a time-consuming process, and the currently accepted method lacks a simple geometric interpretation. In this manuscript, we propose two simpler classifications of rattlers in hard sphere systems based on the convex hull of contacting neighbors and the maximum inscribed sphere of the radical Voronoi cell, each of which provides geometric insight into the source of their instability. Furthermore, the convex hull formulation can be generalized to explore stability in hyperstatic soft sphere packings, spring networks, nonspherical packings, and mean-field non-central-force potentials.

Probing conformational properties of conjugated polymers in dilute solutions under variable solvent quality via coarse‐grained modeling

AbstractConjugated polymers (CPs), characterized by rigid conjugation backbones and flexible peripheral side chains, hold significant promise in various organic optoelectronic applications. In this study, we employ coarse‐grained molecular dynamics (CG‐MD) simulations to investigate the intricate interplay of solvent quality, temperature, and chain architecture (e.g., side‐chain length and molecular mass) on the conformational behaviors of CPs in dilute solutions. Our research uncovers distinctive conformational behaviors under varying solvent conditions, highlighting the versatile nature of polymer chains, which can adopt extended configurations in good solvents and transition to aggregated states in poor solvents. Additionally, the mass scaling exponent , a robust structural descriptor, consistently described CPs behavior across diverse architectures and solvent conditions. Furthermore, our study shows that a CP with longer side‐chain exhibits improved solubility, which is further confirmed by experimental observations. Moreover, our analysis of the shape descriptor provided valuable insights into the symmetry and dimensionality of CPs under varying solvent conditions. These findings offer a comprehensive understanding of conformational behaviors of CPs in dilute solution, which are helpful in guiding the conformational design of polymer for specific applications.

Wholly sustainable graft copolymers derived from cellulose, lignin, and hemicellulose for high-performance elastomers, adhesives, and UV-blocking materials

Sustainable elastomers derived from renewable biobased resources with excellent mechanical properties and varied functions are highly pursued to substitute traditional petroleum-based polymers yet challenging due to their limited macroscopic performance. In this work, we designed a series of wholly biobased cellulose-graft-poly(vanillin acrylate-co-tetrahydrofurfuryl acrylate) (Cell-g-P(VA-co-THFA) copolymer elastomers with cellulose as the rigid backbone, sustainable VA derived from lignin and soft THFA derived from hemicellulose as the hard and soft segments in the rubbery side chains. Moreover, the grafted side chains can be cross-linked to introduce an additional dynamic network structure via Schiff-base chemistry between the aldehyde and amino groups. The mechanical properties of Cell-g-P(VA-co-THFA) copolymer elastomers, including tensile strength, extensibility, elasticity, and toughness can be facilely manipulated by the VA/THFA feed ratio, cellulose content, and cross-linking density. These Cell-g-P(VA-co-THFA) copolymer elastomers are thermally stable and possess outstanding adhesion behavior and prominent UV-shielding performance. Besides dramatically enhanced mechanical properties, the cross-linked Cell-g-P(VA-co-THFA) counterparts exhibit remarkable shape memory behavior. This work provides a robust and convenient strategy for developing strong and versatile sustainable elastomers with different application demands by integrating different biomass feedstocks via elaborate molecular design.

Dopant‐Free Polymeric Hole Transport Materials with a DA’D–A Backbone for Efficient and Stable Inverted Perovskite Solar Cells

Dopant‐free hole transport layers (HTLs) play a crucial role in achieving high‐efficiency and stable perovskite solar cells (PSCs). However, only a limited number of these HTLs have demonstrated power conversion efficiencies (PCEs) surpassing 21%. Herein, the design and synthesis of two polymeric HTLs with a novel DA’D–A backbone are presented. The incorporation of two A units (benzothiazole and imide functionalized aromatics) in the polymer imparts a rigid backbone, high mobility, appropriate film morphology, excellent thermal stability, and a deeper highest occupied molecular orbital energy level, crucial for achieving a more suitable energy‐level alignment between HTL and perovskite layer. Notably, the champion PSC based on our HTLs exhibits a remarkable PCE of 22.02% with minimal hysteresis and excellent thermal stability, surpassing the performance of devices based on the benchmark polymeric HTL PTAA under identical conditions. These findings underscore the immense potential of our DA’D‐A backbone strategy in developing high‐performance dopant‐free polymer HTLs for enhancing the PCE of PSCs.

Vinyl-Addition Homopolymeization of Norbornenes with Bromoalkyl Groups.

Vinyl-addition polynorbornenes are of great interest as versatile templates for the targeted design of polymer materials with desired properties. These polymers possess rigid and saturated backbones, which provide them with high thermal and chemical stability as well as high glass transition temperatures. Vinyl-addition polymers from norbornenes with bromoalkyl groups are widely used as precursors of anion exchange membranes; however, high-molecular-weight homopolymers from such monomers are often difficult to prepare. Herein, we report the systematic study of vinyl-addition polymerization of norbornenes with various bromoalkyl groups on Pd-catalysts bearing N-heterocyclic carbene ligands ((NHC)Pd-systems). Norbornenes with different lengths of hydrocarbon linker (one, two, and four CH2 groups) between the bicyclic norbornene moiety and the bromine atom were used as model monomers, while single- and three-component (NHC)Pd-systems were applied as catalysts. In vinyl-addition polymerization, the reactivity of the investigated monomers varied substantially. The relative reactivity of these monomers was assessed in copolymerization experiments, which showed that the closer the bromine is to the norbornene double-bond, the lower the monomer's reactivity. The most reactive monomer was the norbornene derivative with the largest substituent (with the longest linker). Tuning the catalyst's nature and the conditions of polymerization, we succeeded in synthesizing high-molecular-weight homopolymers from norbornenes with bromoalkyl groups (Mn up to 1.4 × 106). The basic physico-chemical properties of the prepared polymers were studied and considered together with the results of vinyl-addition polymerization.

Combination of Backbone Rigidity and Richness in Aryl Structures Enables Direct Membrane Translocation of Polymer Scaffolds for Efficient Gene Delivery.

The development of cell-penetrating polymers with endocytosis-independent cell uptake pathways has emerged as a prominent strategy to enhance the transfection efficiency. Inspired by the rigid α-helical structure that endows polypeptides with cell-penetrating ability, we propose that a rigid backbone can facilitate the corresponding polymer vector's performance in gene delivery by bypassing the difficult endosomal escape process. Meanwhile, the installation of aromatic domains, as a way to promote gene transfection efficiency, is employed through the construction of a poly(benzyl ether) (PBE)-based scaffold in this work. We demonstrate that the direct membrane translocation capability of the synthesized PBE contributes to its enhanced transfection performance and excellent biocompatibility profile, rendering the imidazolium-functionalized PBE scaffold with higher activity and biocompatibility. Molecular details of the PBE-lipid interaction are also revealed in molecular dynamics simulations, indicating the important roles of individual structural elements on the polymeric scaffold in the membrane penetration process.

Thermoresponsive Helical Dendronized Poly(phenylacetylene)s: Remarkable Stabilization of Their Helicity via Photo-Dimerization of the Dendritic Pendants.

Dynamic helical polymers can change their helicity according to external stimuli due to the low helix-inversion barriers, while helicity stabilization for polymers is important for applications in chiral recognition or chiral separations. Here, we present a convenient methodology to stabilize dynamic helical conformations of polymers through intramolecular cross-linking. Thermoresponsive dendronized poly(phenylacetylene)s (PPAs) carrying 3-fold dendritic oligoethylene glycol pendants containing cinnamate moieties were synthesized. These polymers exhibit typical features of dynamic helical structures in different solvents, that is, racemic contracted conformations in less polar organic solvents and predominantly one-handed stretched helical conformations in highly polar solvents. This dynamic helicity can be enhanced through selective solvation by increasing the polarity of the organic solvents or simply via their thermally mediated dehydration in water. However, through photocycloaddition of the cinnamate moieties between the neighboring pendants via UV irradiation, these dendronized PPAs adopt stable helical conformations either below or above their phase transition temperatures in water, and their helical conformations can even be retained in less polar organic solvents. Spectroscopic and atomic force microscopy measurements demonstrate that photocycloaddition between the cinnamate moieties occurs on the individual molecular level, and this is found to be helpful in restraining the photodegradation of the PPA backbones. Molecular dynamics simulations reveal that the spatial orientation of the pendants along the rigid polyene backbone is crucial for the photodimerization of cinnamates within one helix pitch.

Relating the length of a magnetic filament with solvophobic, superparamagnetic colloids to its properties in applied magnetic fields.

The idea of creating polymer-like structures by crosslinking magnetic nanoparticles (MNPs) opened an alternative perspective on controlling the rheological properties of magnetoresponsive systems, because unlike suspensions of self-assembled MNPs, whose cluster sizes are sensitive to temperature, magnetic filaments (MFs) preserve their initial topology. Considering the length scales characteristic of single-domain nanoparticles used to create MFs, the MNPs can be both ferro- and superparamagnetic. Moreover, steric or electrostatic stabilization might not fully screen van der Waals interactions. In this paper, using coarse-grained molecular dynamics simulations, we investigate the influence of susceptibility of superparamagnetic MNPs-their number and central attraction forces between them-on the polymeric, structural, and magnetic properties of MFs with varied backbone rigidity. We find that, due to the general tendency of MFs with superparamagnetic monomers to bend, reinforced for colloids with a high susceptibility, properties of MFs vary greatly with chain length.

A novel phosphorylated hyper-crosslinked porous polymer for efficient uranium adsorption in water

As the nuclear resource industry rapidly progresses, efficient adsorbents play a vital role in separating and eliminating uranium from aqueous solutions. Herein, 9,9-dimethyl-fluorenylphosphonic acid was designed as a phosphate functional monomer and the triptycene as a rigid backbone monomer. Through the “knitting” strategy, a novel triptycene-based phosphorylated hyper-crosslinked porous polymer (TPP-DFP) was obtained by the above monomers. The resulted polymer TPP-DFP has a high BET surface area of 1397.62 m2/g with a rich porosity. The porous polymer TPP-DFP was the first time used for uranium adsorption from water and showed outstanding adsorption performance. The maximum uranium adsorption capacity of TPP-DFP was 414.26 mg/g, which was higher than that of most of other porous adsorbents. In the presence of impurity ions such as Ca2+, Mg2+, Al3+, Co2+, Ni2+, V5+, NO3−, CO32− etc., TPP-DFP exhibited high selectivity (Su up to 99%) for uranium. In addition, TPP-DFP has excellent reusability, and the removal percentage of uranium can reach more than 95% after 5 adsorption–desorption cycles. According to the XPS experiment, the mechanism of interaction between TPP-DFP and U(VI) was mainly due to the complex formed by the phosphate functional groups and U(VI). The theory DFT calculation indicated a 1:2 ratio of U(VI) and phosphate functional group on the two-distinct graft chain, which was consistent with the experimental results. Accordingly, the “knitting” polymerization technique showed potential for preparation effective adsorbents for uranium extraction from water.

Non-fullerene acceptors with thiazole π-bridge for organic solar cells

Intramolecular noncovalent conformational locks (NoCLs) have been found to be effective in increasing the rigidity and planarity of the molecular backbone. This, in turn, leads to reduced recombination energy and improved intramolecular charge transport mobility, resulting in significant enhancements in the photovoltaic performance of organic solar cell (OSC) devices. To take advantage of this effect, we designed and synthesized two small molecule non-fullerene acceptors (NFAs) with A-π-D-π-A structures using thiazole (Tz): IDTz-IC4F and IDTz-IC4Cl. With the synergistic assistance of NoCLs and halogenated end groups, the NFAs IDTz-IC4F and IDTz-IC4Cl exhibited power conversion efficiencies (PCEs) of 6.20 % and 6.06 %, respectively. This study presents a strategy for enhancing the PCE of OSCs by incorporating cooperative NoCLs and halogen end groups, providing an exciting avenue for designing high-performance non-fullerene materials in the future.

Synthesis, characterization, and photophysical properties of dicyanoarylamine‐based semi‐aromatic polymers

AbstractIntroductionFluorescent high‐performance polymers have been extensively used in designing optoelectronic devices due to their low cost, excellent thermal stability, high mechanical strength, low flammability, good chemical and radiation resistance, and good electronic properties. While conventional organic luminophores fluoresce strongly in dilute solutions, they suffer from undesirable aggregation‐caused quenching in concentrated solutions and in the solid state due to extensive π‐π stacking interactions and formation of delocalized excitons or excimers. This phenomenon leads to non‐radiative decay thus, decreased fluorescence emission of the material in the solid film state, which significantly limits their real‐world application as solid light‐emitting materials.ObjectivesTo develop new high‐performance polymers with high photo luminescent efficiency, good processability, film‐forming properties, which could potentially be used in the fabrication of optoelectronic devices.MethodsThe preparation of the polyimide DiCN‐PI was carried out by a one‐step, high‐temperature solution imidization method. In this procedure, 1,2,4,5‐cyclohexanetetracarboxylic dianhydride and the diamine were polymerized in 1‐methyl‐2‐pyrrolidinone and γ‐butyrolactone co‐solvent at 180°C for 15 hours in the presence of isoquinoline as catalyst. On the other hand, polyamide DiCN‐PA was synthesized according to the direct phosphorylation polycondensation technique described by Yamazaki from diamine and trans‐1,4‐cyclohexanedicarboxylic acid using triphenyl phosphite and pyridine as condensing agents.Results and DiscussionBoth polymers were soluble in several polar aprotic solvents and exhibited useful levels of thermal stability. The polymers were emissive with PL emission bands around 555 (bluish‐green) and 498 (cyan) nm in dilute 1‐methyl‐2‐pyrrolidinone solutions for polyimide and polyamide, respectively. In the solid film state, the polymers emit light green and yellow colors, which simulate the PL behavior of their aggregated states, thereby demonstrating aggregation‐induced fluorescence changes.ConclusionsThese results indicate that the incorporation of bulky dicyanoarylamine moiety and alicyclic monomer units into the rigid polymer backbones effectively disrupted the planarity of the chain packing which resulted to the fluorescent high‐performance polymers with desired properties for potential optoelectronic applications.