Linear Monomers Research Articles

Methane Formation Induced via Face-to-Face Orientation of Cyclic Fe Porphyrin Dimer in Photocatalytic CO2 Reduction.

Iron porphyrins are known to provide CH4 as an eight-electron reduction product of CO2 in a photochemical reaction. However, there are still some aspects of the reaction mechanism that remain unclear. In this study, we synthesized iron porphyrin dimers and carried out the photochemical CO2 reduction reactions in N,N-dimethylacetamide (DMA) containing a photosensitizer in the presence of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as an electron donor. We found that, despite a low catalytic turnover number, CH4 was produced only when these porphyrins were facing each other. The close proximity of the cyclic dimers, distinguishing them from a linear Fe porphyrin dimer and monomers, induced multi-electron CO2 reduction, emphasizing the unique role of their structural arrangement in CH4 formation.

Wood consolidation through an epoxy‐acrylic gamma‐crosslinked three‐dimensional system

AbstractEmerging technologies based on polymeric materials are progressively developed in order to preserve and consolidate cultural heritage artifacts. In this study, we aimed to obtain a hybrid polymer reliant on two types of thermosets that undergo irreversible crosslinking via ionizing radiation‐induced polymerization, the polymer's structure and characteristics being tailored using specific dose rates, doses, linear energy transfer and monomers ratio, in order to achieve the established performance requirements. Here, we demonstrate a covalently bonded 3D hybrid diepoxy‐triacrylic polymer that is chemically and dimensionally stable, intending to use it as a consolidant of highly degraded wooden artifacts in order to mitigate oxygen inhibition from radical chain reactions, to increase chemical and thermal stability, as well as to obtain a stiffer consolidated artifact, therefore more resistant to deformation. Various types of analytical techniques such as Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy, Mass Spectrometry or Thermal analysis were performed in order to support our strategy and predictions regarding the synergistic effect given by gamma irradiation‐driven crosslinking through simultaneous cationic and radical chain growth polymerization reaction mechanisms. We achieved a homogenous polymeric formulation and wood‐polymer composite materials with high modulus of elasticity, therefore providing up to a twofold increase in Young's modulus in the consolidated wood, a good chemical resistance to various solvents and outstanding thermal resistance up to 381°C. Consequently, the consolidation methodology, as well as mechanical testing, analytical and morphological characterization of the resulted composite will be discussed. Apart from consolidating cultural heritage wooden artifacts, this synthetic route and impregnation methodology provide opportunities for wood‐polymer composites in a wealth of applications as reinforced wood‐based materials.

Solid Polymer Electrolyte (SPE) from Corn Starch and Aluminum Nitrate Salt Composites for Aluminum - ​​Ion Battery

The increasing of need for portable electrical energy makes the demand for rechargeable batteries high. Aluminum-ion battery with Solid Polymer Electrolyte (SPE) produced from the natural polymer corn starch with salt additive has the potential to be developed. The flexibility and resilience of SPE are enhanced by glycerol (C3H8O3). Throughing gelatinization of the linear monomer chains to become amorphous, the space for the ions in it is more free so that the ionic conductivity is high. By means of solution casting, heating temperature of 50°C for 9 hours found SPE with a strong structure. With the same concentration CS-Al has a higher conductivity with σ = 4.93 x 10-5 S/cm than CS-Na whose value is σ = 2,92 x 10-5 S/cm. This is due to the SPE CS-Al show more amorphous structure which allow more flexible ionic segmental motion. This is in accordance with XRD resulting which shows that the addition of aluminum nitrate salt is more amorphous than sodium acetate; the shift in peak pattern is also greater due to cation intercalation Al3+ with corn starch. FTIR is the result found that nitrate fixed by corn starch, indicated a change in the hydroxyl group of corn starch amylopectin. SEM photo of result also showed aluminum nitrate salt ion more easily in overcoming than sodium acetate. The indicate of SPE was more homogeneous because corn starch was already intercalated. They are combined to Al3+ and NO3- ions. With this value it can be an appropriate reference for developing SPE on Aluminum-ion batteries with aluminum nitrate salts have higher performance and environment friendly Keywords: Aluminum-ion battery, Solid Polymer Electrolyte, corn starch, ionic conductivity, and Amorphous

Narrow-Pore Engineering of Vinylene-Linked Covalent Organic Frameworks with Weak Interaction-Triggered Multiple Responses.

Vinylene-linked covalent organic frameworks (COFs) are emerging as promising crystalline materials, but their narrow pore engineering is severely impeded by the weak reversibility of the carbon-carbon double bond formation reaction, which has led to less exploration of their ultramicroporous structures and properties. Herein, we developed a single aromatic ring-based tetratopic monomer, tetramethylpyrazine, which undergoes a smooth Knoevenegal condensation at its four arylmethly carbon atoms with linear aromatic dialdehyde monomers upon the self-catalyzed activation of pyridine nitrogen-containing monomers in the presence of an organic anhydride. This has resulted in the formation of two vinylene-linked COFs, which both crystallized in orthorhombic lattices, and layered in AA stacking fashions along the vertical directions. They exhibit high surface areas and well-tailored ultramicropore sizes up to 0.5 nm. The unique cross-linking mode at two pairs of para-positions of each pyrazine unit through carbon-carbon double bonds afford them with π-extended conjugation over the in-plane backbones and substantial semiconducting characters. The resultant COFs can be well-dispersed in water to form stable sub-microparticles with negative charges (zeta potentials: ca. -30 mV), and exhibiting tunable aggregation behaviors through protonation/deprotonation. As a consequence, they exhibit pore-size-dependent colorimetric responses to various anions with different pKa values in high selectivity.

Narrow‐Pore Engineering of Vinylene‐Linked Covalent Organic Frameworks with Weak Interaction‐Triggered Multiple Responses

AbstractVinylene‐linked covalent organic frameworks (COFs) are emerging as promising crystalline materials, but their narrow pore engineering is severely impeded by the weak reversibility of the carbon‐carbon double bond formation reaction, which has led to less exploration of their ultramicroporous structures and properties. Herein, we developed a single aromatic ring‐based tetratopic monomer, tetramethylpyrazine, which undergoes a smooth Knoevenegal condensation at its four arylmethly carbon atoms with linear aromatic dialdehyde monomers upon the self‐catalyzed activation of pyridine nitrogen‐containing monomers in the presence of an organic anhydride. This has resulted in the formation of two vinylene‐linked COFs, which both crystallized in orthorhombic lattices, and layered in AA stacking fashions along the vertical directions. They exhibit high surface areas and well‐tailored ultramicropore sizes up to 0.5 nm. The unique cross‐linking mode at two pairs of para‐positions of each pyrazine unit through carbon‐carbon double bonds afford them with π‐extended conjugation over the in‐plane backbones and substantial semiconducting characters. The resultant COFs can be well‐dispersed in water to form stable sub‐microparticles with negative charges (zeta potentials: ca. −30 mV), and exhibiting tunable aggregation behaviors through protonation/deprotonation. As a consequence, they exhibit pore‐size‐dependent colorimetric responses to various anions with different pKa values in high selectivity.

High-Throughput Characterization and Optimization of Polyamide Hydrolase Activity Using Open Port Sampling Interface Mass Spectrometry.

Enzymatic biodegradation of polymers, such as polyamides (PA), has the potential to cost-effectively reduce plastic waste, but enhancements in degradation efficiency are needed. Engineering enzymes through directed evolution is one pathway toward identification of critical domains needed for improving activity. However, screening such enzymatic libraries (100s-to-1000s of samples) is time-consuming. Here we demonstrate the use of robotic autosampler (PAL) and immediate drop on demand technology (I.DOT) liquid handling systems coupled with open-port sampling interface-mass spectrometry (OPSI-MS) to screen for PA6 and PA66 hydrolysis by 6-aminohexanoate-oligomer endo-hydrolase (nylon hydrolase, NylC) in a high-throughput (8-20 s/sample) manner. The OPSI-MS technique required minimal sample preparation and was amenable to 96-well plate formats for automated processing. Enzymatic hydrolysis of PA characteristically produced soluble linear oligomer products that could be identified by OPSI-MS. Incubation temperatures and times were optimized for PA6 (65 °C, 24 h) and PA66 (75 °C, 24 h) over 108 experiments. In addition, the I.DOT/OPSI-MS quantified production of PA6 linear dimer (8.3 ± 1.6 μg/mL) and PA66 linear monomer (13.5 ± 1.5 μg/mL) by NylC with a lower limit of detection of 0.029 and 0.032 μg/mL, respectively. For PA6 and PA66, linear oligomer production corresponded to 0.096 ± 0.018% and 0.204 ± 0.028% conversion of dry pellet mass, respectively. The developed methodology is expected to be utilized to assess enzymatic hydrolysis of engineered enzyme libraries, comprising hundreds to thousands of individual samples.

Enhanced Liposomal Drug Delivery Via Membrane Fusion Triggered by Dimeric Coiled-Coil Peptides.

An ideal nanomedicine system improves the therapeutic efficacy of drugs. However, most nanomedicines enter cells via endosomal/lysosomal pathways and only a small fraction of the cargo enters the cytosol inducing therapeutic effects. To circumvent this inefficiency, alternative approaches are desired. Inspired by fusion machinery found in nature, synthetic lipidated peptide pair E4/K4 is used to induce membrane fusion previously. Peptide K4 interacts specifically with E4, and it has a lipid membrane affinity and resulting in membrane remodeling. To design efficient fusogens with multiple interactions, dimeric K4 variants are synthesized to improve fusion with E4-modified liposomes and cells. The secondary structure and self-assembly of dimers are studied; the parallel PK4 dimer forms temperature-dependent higher-order assemblies, while linear K4 dimers form tetramer-like homodimers. The structures and membrane interactions of PK4 are supported by molecular dynamics simulations. Upon addition of E4, PK4 induced the strongest coiled-coil interaction resulting in a higher liposomal delivery compared to linear dimers and monomer. Using a wide spectrum of endocytosis inhibitors, membrane fusion is found to be the main cellular uptake pathway. Doxorubicin delivery results in efficient cellular uptake and concomitant antitumor efficacy. These findings aid the development of efficient delivery systems of drugs into cells using liposome-cell fusion strategies.

A novel clover-like COFs membrane fabricated via one-step interfacial polymerization for dye/salt separation

Covalent organic frameworks (COFs) membranes have exhibited great applications in wastewater treatment due to their highly ordered porous architecture. Currently, numerous studies have focused on the hexagonal-structured COFs synthesized with linear C2 and C3 precursor. However, the C2 monomer is limited-variety and high-cost. Herein, a novel clover-like structure COFs membrane is successfully fabricated for the first time. Meta-position monomer m-phenylenediamine (MPD) and 1,3,5-triformylbenzene (TFB) are used to synthesize the clover-like COFs membrane by interfacial polymerization (IP) method on the nylon substrate directly. The optimized MPD-TFB/Nylon membrane shows excellent water permeance of 94.4 L m−2 h−1 bar−1, which is higher than hexagonal-structured COFs membrane, in Congo red (CR) and NaCl mixed solution The rejections are 98.6% for CR and 2.9% for NaCl. This work opens a novel route for designing the COFs membrane with clover-like channels, manifesting the usage of linear C2 monomers is unnecessary. Besides, it has been found that the unique clover-like structure can improve the water molecular transport path under the same dye molecules deposition situation compared with hexagonal structure COFs membrane.

Vanillin-Derived Thermally Reprocessable and Chemically Recyclable Schiff-Base Epoxy Thermosets.

The paradigm shift from traditional petroleum-based non-recyclable thermosets to biobased repeatedly recyclable materials is required to move toward circular bioeconomy. Here, two mechanically and chemically recyclable extended vanillin-derived epoxy thermosets are successfully fabricated by introduction of Schiff-base/imine covalent dynamic bonds. Thermoset 1 (T1) is based on linear monomer 1 (M1) with two alcohol end groups and one imine bond, while thermoset 2 (T2) is based on branched monomer 2 (M2) with three alcohol end-groups and three imine-groups. Thermosets are obtained by reaction of monomer 1 (M1) and monomer 2 (M2) with trimethylolpropane triglycidyl ether. The structure of the monomers and thermosets is confirmed by nuclear magnetic resonance and Fourier transform infrared spectroscopic techniques. Both thermosets exhibit good thermal and mechanical properties and they are stable in common organic solvents. Furthermore, they can be thermally reprocessed through compression molding with good recovery of the mechanical properties. Last but not least, the fabricated thermosets can be rapidly and completely chemically recycled to water-soluble aldehydes and amines by imine hydrolysis at room temperature in 0.1m HCl solution. This is promising for development of future materials with multiple circularity by different routes.

The effect of thread-like monomer structure on the synthesis of poly[n]catenanes from metallosupramolecular polymers.

The main-chain poly[n]catenane consists of a series of interlocked rings that resemble a macroscopic chain-link structure. Recently, the synthesis of such intriguing polymers was reported via a metallosupramolecular polymer (MSP) template that consists of alternating units of macrocyclic and linear thread-like monomers. Ring closure of the thread components has been shown to yield a mixture of cyclic, linear, and branched poly[n]catenanes. Reported herein are studies aimed at accessing new poly[n]catenanes via this approach and exploring the effect the thread-like monomer structure has on the poly[n]catenane synthesis. Specifically, the effect of the size of the aromatic linker and alkenyl chains of the thread-like monomer is investigated. Three new poly[n]catenanes (with different ring sizes) were prepared using the MSP approach and the results show that tailoring the structure of the thread-like monomer can allow the selective synthesis of branched poly[n]catenanes.

Long and Covalently Conjugated Branched DNA Structures for in Situ Gelation in Vivo

Long and Covalently Conjugated Branched DNA Structures for in Situ Gelation in Vivo

Segmental Motion Adjustment of the Polycarbonate Electrolyte for Lithium-Metal Batteries.

Carbonyl oxygen atoms are the primary active sites to solvate Li salts that provide a migration site for Li ions conducting in a polycarbonate-based polymer electrolyte. We here exploit the conductivity of the polycarbonate electrolyte by tuning the segmental motion of the structural unit with carbonyl oxygen atoms, while its correlation to the mechanical and electrochemical stability of the electrolyte is also discussed. Two linear alkenyl carbonate monomers are designed by molecular engineering to combine methyl acrylate (MA) and the commonly used ethylene carbonate (EC), w/o dimethyl carbonate (DMC) in the structure. The integration of the DMC structural unit in the side chain of the in situ constructed polymer (p-MDE) releases the free motion of the terminal EC units, which leads to a lower glass-transition temperature and higher ionic conductivity. While pure polycarbonates are normally fragile with high Young's modulus, such a prolonged side chain also manipulates the flexibility of the polymer to provide a mechanical stable interface for Li-metal anode. Stable long-term cycling performance is achieved at room temperature for both LiFePO4 and LiCoO2 electrodes based on the p-MDE electrolyte incorporated with a solid plasticizer.

3D Carbon Nanonetwork Coated Composite Electrode with Multi-Heteroatom Doping for High-Rate Vanadium Redox Flow Batteries.

With the advantages of benign mechanical property, electrochemical stability, and low cost, graphite fibers (GFs) have been widely used as electrodes for vanadium redox flow batteries (VRFBs). However, GFs usually possess inferior electrochemical activity and ion diffusion kinetics for electrode reaction, vastly limiting their application in VRFBs. Here, a 3D carbon nanonetwork coated GFs with multi-heteroatom doping was constructed for application in VRFBs via low temperature polymerization between linear polymer monomer and phytic acid, and subsequent carbonization (900 °C) on the GFs (GF@PCNs-900). Benefiting from the 3D structural features and multi-heteroatom doping (O, N and P), the composite electrode displayed sufficient diffusion of vanadium ions, rapid electron conduction, and highly enhanced electrochemical activity of reactive site on the electrodes. As a result, the GF@PCNs-900 delivered a high discharge capacity of 21 Ah L-1 and energy efficiency of above 70% with extraordinary stability during 200 cycles at 200 mA cm-2. Even at a huge current density of 400 mA cm-2, the GF@PCNs-900 still maintained a discharge capacity of 5.0 Ah L-1, indicating an excellent rate of performance for VRFBs. Such design strategy opens up a clear view for further development of energy storage field.

Venomics survey of six myrmicine ants provides insights into the molecular and structural diversity of their peptide toxins

Among ants, Myrmicinae represents the most speciose subfamily. The venom composition previously described for these social insects is extremely variable, with alkaloids predominant in some genera while, conversely, proteomics studies have revealed that some myrmicine ant venoms are peptide-rich. Using integrated transcriptomic and proteomic approaches, we characterized the venom peptidomes of six ants belonging to the different tribes of Myrmicinae. We identified a total of 79 myrmicitoxins precursors which can be classified into 38 peptide families according to their mature sequences. Myrmicine ant venom peptidomes showed heterogeneous compositions, with linear and disulfide-bonded monomers as well as dimeric toxins. Several peptide families were exclusive to a single venom whereas some were retrieved in multiple species. A hierarchical clustering analysis of precursor signal sequences led us to divide the myrmicitoxins precursors into eight families, including some that have already been described in other aculeate hymenoptera such as secapin-like peptides and voltage-gated sodium channel (NaV) toxins. Evolutionary and structural analyses of two representatives of these families highlighted variation and conserved patterns that might be crucial to explain myrmicine venom peptide functional adaptations to biological targets.

Development of LCEs with 100% Azobenzene Moieties: Thermo-Mechanical Phenomena and Behaviors.

Azobenzene is one of the most investigated photo-responsive liquid crystalline molecules. It can isomerize between two different isoforms, trans (E) and cis (Z) configurations, when stimulated by light. It is used as a molecular engine in photo-mobile materials (PMPs). The use of liquid crystals (LCs) as building blocks enhances the mechanical properties of the PMPs. It is not easy to obtain PMPs with monodomain configurations when the LCs are 100% azobenzene. In this work, we studied three LC mixtures, describing the thermo/mechanical phenomena that regulate the actuation of such materials. The nematic temperature of the LC elastomers was measured and the PMPs carefully characterized for their bending and speed capability. Our finding suggests that the ratio between linear and cross-linker monomer greatly influences the nematic temperature of the mixture. Furthermore, 100% azobenzene materials polymerized using dicumyl peroxide can be useful to design polarization-selective switches.

Effect of different monomers on the electro-optical properties of reverse-mode polymer stabilized liquid crystal

Reverse-mode polymer-stabilized liquid crystal (RPSLC) plays an important role in optical display field and becomes one of the research hotspots because of its normal transparent state without driving voltage. The concentration and type of polymer monomer has a great influence on the electro-optical properties of the RPSLC, so the optimization of the polymer monomer can reduce the driving voltage and hysteresis, and improve the contrast ratio of the RPSLC. In this paper, two kinds of V-type and two kinds of linear type monomers with bi-functional group, and a mesogenic monomer were used, the effect of the concentration and type of non-mesogenic monomers on electro-optical properties of RPSLC were studied with the fixed concentration of mesogenic monomer in experiment. The results show that the electro-optical properties of the RPSLC can be improved more when the suitable ratio of a V-type monomer is added. The maximum and minimum transmittances are 85.9% and 3.1%, the contrast ratio is 27.6, the threshold and saturation voltages are 6.4 V and 11.6 V, and the hysteresis is less than 1 V. Combined with the scanning electron microscopy morphology of polymer network, the mechanism of the influence of non-mesogenic monomer on the electro-optical properties of RPSLC is revealed. These experimental results will be of great significance for the research of RPSLC.

Monomeric prefusion structure of an extremophile gamete fusogen and stepwise formation of the postfusion trimeric state

Here, we study the gamete fusogen HAP2 from Cyanidioschyzon merolae (Cyani), an extremophile red algae that grows at acidic pH at 45 °C. HAP2 has a trimeric postfusion structure with similarity to viral class II fusion proteins, but its prefusion structure has been elusive. The crystal structure of a monomeric prefusion state of Cyani HAP2 shows it is highly extended with three domains in the order D2, D1, and D3. Three hydrophobic fusion loops at the tip of D2 are each required for postfusion state formation. We followed by negative stain electron microscopy steps in the process of detergent micelle-stimulated postfusion state formation. In an intermediate state, two or three linear HAP2 monomers associate at the end of D2 bearing its fusion loops. Subsequently, D2 and D1 line the core of a trimer and D3 folds back over the exterior of D1 and D2. D3 is not required for formation of intermediate or postfusion-like states.

Benzimidazole-based N-heterocyclic carbene silver complexes as catalysts for the formation of carbonates from carbon dioxide and epoxides

A series of left-to-right inequivalent 1,3-disubstituted benzimidazolium halide pro-ligands having the general formula [RBNHCCH2OxMe][X] (R = 3-Me-Bn, 3,5-Me2-Bn, 2,4,6-Me3-Bn, 2,3,5,6-Me4-Bn, 2,3,4,5,6-Me5-Bn, 3,4,5-(OMe)3-Bn, or 4-tBu-Bn; X = Cl, Br) were synthesized by the alkylation of 1-((3-methyloxetan-3-yl)methyl)benzimidazole. The corresponding Ag complexes, (RBNHCCH2OxMe)AgX, were prepared following pro-ligand addition to Ag2O. These compounds were characterized using spectroscopic techniques such as FT-IR, NMR spectroscopy, and single-crystal X-ray diffraction. The solid-state structure of (3-Me-BnBNHCCH2OxMe)AgCl revealed a linear monomer while [(2,4,6-Me3-BnBNHCCH2OxMe)AgCl]2 was found to exist as a dimer with pseudo trigonal planar geometry about each metal center. The synthesized (RBNHCCH2OxMe)AgX complexes were found to be efficient for the addition of carbon dioxide to epoxides to yield value-added cyclic carbonates at ambient pressure. Amongst the investigated complexes, the bimetallic complex [(2,4,6-Me3-BnBNHCCH2OxMe)AgCl]2 was found to be the most active for CO2 insertion, exhibiting favorable activity when compared to known NHC complexes.

Mechanochemistry‐Driven Construction of Aza‐fused π‐Conjugated Networks Toward Enhanced Energy Storage

AbstractThe current approaches toward synthesis of conjugated microporous polymers (CMPs) functionalized by aza‐fused functionalities are still limited to solution‐based procedures or ionothermal polymerizations, which requires monomers with rigid/high steric hindrance structures and multiple reactive sites and extra arene‐based cross‐linkers, and generated CMPs with low content of aza‐fused functionalities. Herein, a facile mechanochemistry‐driven procedure is developed capable of affording a series of CMPs composed of abundant aza‐fused functionalities via a homocoupling process. Simple and linear aromatic bromide monomers with phenanthroline or bipyridine cores are deployed as the starting materials, which can coordinate on the metal surface to form 3D assembly and be polymerized in the presence of catalytic amount of magnesium powder driven by mechanochemical treatment under solvent‐ and additive‐free conditions. CMPs composed of solely phenanthroline or bipyridine moieties being connected by C–C bonds are afforded with high surface areas (up to 789 m2 g‐1), permanent and hierarchical porous architectures (micro‐ and mesopores), abundant aza‐fused moieties, and π‐conjugated networks. All these unique features made them promising candidates as supercapacitors, which exhibit outstanding electrocapacitive performance with a capacitance of 296 F g‐1 at 0.3 A g‐1 and capacitance retention of 103% for 5000 cycles at 5 A g‐1.

Towards high performance semi-interpenetrating phase change materials networks via linear polyethylene glycol-based multimerization effect

Semi-interpenetrating polymer network (semi-IPN)-based phase change materials (PCMs) with linear polyethylene glycol (PEG)-based multimer intends to enhance the encapsulation fraction, shape stability and mechanical strength in a synergetic way relative to semi-IPN-based PCMs with linear PEG monomer. Herein, semi-IPN-based PCMs comprised of PEG-based multimers and covalent crosslinking polyester network were successfully synthesized via efficient esterification reaction between eco-friendly citric acid and multiple aziridine ring-containing species. The linear PEG-based multimers with various PEG unit number were formed by the reaction between polyethylene glycol and toluene diisocyanate in various molar ratio. With increasing PEG unit number of linear PEG-based multimers from 1 to 6, the PEG weight fraction of PCMs increases by 48.91% (from 60 wt% to 89.35 wt%) and the storage modulus (G′) of PCMs rises (from G′ = 12390 Pa for PCM-2–0.6 at 1 Hz at 90 °C while to G′ = 12780 Pa for PCM-6–0.6 at 1 Hz at 125 °C) when PEG weight fraction is nearly 60 wt%. The maximum latent heat reaches up to 141.0 J/g with the maximum PEG weight fraction of 89.35% in PCMs with linear PEG-based multimers encapsulated. The PCMs feature shape-stable form even at 140 °C, efficient photothermal effect by introducing carbon black and degradation ability resulting from hydrolysis effect of ester structure. The enhanced comprehensive performance of semi-IPN-based PCMs is due to the introduction of linear PEG-based multimers instead of pristine PEGs, which is denoted as multimerization effect, and the semi-IPN-based PCMs with multimerization effect will broaden the application of PCMs.