Influence of Network Structure on the Crystallization Behavior in Chemically Crosslinked Hydrogels

Zhang, Zhenfang; Li, Qian; Yesildag, Cigdem; Bartsch, Christoph; Zhang, Xiaoyuan; Liu, Wei; Loebus, Axel; Su, Zhiqiang; Lensen, Marga C.

doi:10.3390/polym10090970

Cited by 18 publications

(17 citation statements)

References 41 publications

(49 reference statements)

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“…PEG is a semicrystalline polymer with crystals acting as additional cross-links. However, in this case, one has to consider the possibility that the crystallization of the polymer is affected by the network topology or even inhibited. , On the other hand, increasing the length of polymer chains is a way to increase the distance between the ionomeric microstructures that are responsible for the improvement in the mechanical properties.…”

Section: Introductionmentioning

confidence: 99%

Heterogeneous Local Dynamics in Mussel-Inspired Elastomers

et al. 2023

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Materials with increased mechanical strength and toughness bearing mussel-inspired iron–catechol complexes and network architectures exhibit several dynamic features, e.g., high and broad glass-“transition” temperature, not explored so far. By combining differential scanning calorimetry and dielectric spectroscopy, the latter as a function of temperature and pressure, we have explored the increase in the glass temperature, T g, and the concomitant increase in the breath of T g in bioinspired networks bearing one (covalent) or two (covalent and coordination) types of cross-links. Cross-linked networks experience heterogeneous segmental dynamics that are responsible for the broad T g range observed in the thermal measurements. The two distinct dynamics reflect the relaxation of segments in the vicinity versus more distant cross-linked units. The various topologies are shown to have different fragilities and tend to form stronger glasses with increasing network topology. In addition, the ionic conductivity is influenced by the segmental dynamics and the increased T g in the networks. These features (reduced specific heat step, Δc p, at T g and “strong” dynamic behavior) are also found in permanently cross-linked polymers with dynamic network topology known as vitrimers. The similarities in the two network systems are discussed.

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Section: Introductionmentioning

confidence: 99%

Heterogeneous Local Dynamics in Mussel-Inspired Elastomers

et al. 2023

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“…Very recently, a new class of eight-armed star-shaped PEG-based hydrogels (8PEG-NH 3 ) has been developed in our lab [ 40 ], in which ammonium solution (NH 3 ) serves as the crosslinker. They were formed by an amine Michael-type addition reaction between unsaturated carbon–carbon double bonds (acrylate end groups) and reactive amine species.…”

Section: Resultsmentioning

confidence: 99%

One-Pot, In-Situ Synthesis of 8-Armed Poly(Ethylene Glycol)-Coated Ag Nanoclusters as a Fluorescent Sensor for Selective Detection of Cu2+

Zhang

Wei

et al. 2020

Biosensors

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Fluorescent nanomaterials, such as quantum dots, have developed rapidly in recent years and have been significantly developed. Herein, we demonstrate a facile, one-pot, and in-situ synthesis strategy to obtain fluorescent silver nanoclusters (AgNCs) coated with eight-armed poly (ethylene glycol) polymers (8PEG-AgNCs) via a direct gel-mediated process. During the synthesis, ammonium (NH3) served as the crosslinker for the gel formation via a amine-type Michael addition reaction. This hydrogel can be used as a template to synthesize AgNCs using its volume-limiting effect. The in-situ generation of AgNCs takes place inside the nanocages of the formed gels, which guarantees the homogenous distribution of AgNCs in the gel matrix, as well as the efficient coating of PEG on the nanoclusters. After the degradation of gels, the released 8PEG-AgNCs nanohybrids showed strong blue fluorescence and exhibited long-term stability in aqueous solution for nearly one year. Results showed that the fabricated sensor revealed excellent fluorescent sensitivity for the selective detection of Cu2+ with a detection limit of 50 nM and a wide linear detection range of 5–100 μM. It is proposed that the greater cross-linking density leads to smaller gel pores and allows the synthesis of AgNCs with fluorescent properties. These results indicate that this novel hydrogel with certain biodegradation has the potential to be applied as a fluorescent sensor for catalytic synthesis, fluorescence tracing in cells, and fluorescence detection fields. Meanwhile, the novel design principle has a certain versatility to accelerate the development and application of other kinds of metal nanoclusters and quantum dots.

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“…This results in nonuniform aggregation of molecules and the associated increase of semicrystalline anisotropy. , Then, electromagnetic refractions occur at the boundary of crystalline and amorphous domains in the fiber. Since λ 0 is less sensitive to the δ of polymer materials, the δ is assumed to be primarily a function of t fiber ,, and crystallinity ( X C ). An intensity-based retardation exposure model for lithographic 2-D image plane can be expressed as follows , where α is the correction factor.…”

Section: Theoretical Basismentioning

confidence: 99%

Fiber Lithography: A Facile Lithography Platform Based on Electromagnetic Phase Modulation Using a Highly Birefringent Electrospun Fiber

Kim

Shin

Chang

2020

ACS Appl. Mater. Interfaces

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Lithography plays a key role in advancing manufacturing as well as the semiconductor industry. However, the currently available state-of-the-art lithography methods still require access to expensive tools and facilities. Herein, we suggest a novel lithography method based on electromagnetic phase modulation of ultraviolet using a highly birefringent electrospun fiber to overcome such limitations. The optical birefringent effect, by which the phase of incident ultraviolet electromagnetic fields is retarded when passing through optically anisotropic media, is combined with semicrystalline poly(ethylene oxide) (PEO)− poly(ethylene glycol) (PEG) polymeric microfibers patterned in a programmable form using near-field electrospinning. By positioning the mask between two linear polarizers that are perpendicular to each other, only the UV waves that are passing through the fibers can be selectively utilized to exhibit lithographic property. Therefore, the UV intensity on the photoresist (PR) surface follows the shape of the fiber pattern, enabling precisely controlled patterning of the photoresist. Zero-to two-dimensional key features of lithography are achieved, including straight, curved, array, and isolated patterns. Facile optical alignments without using dedicated alignment marks are successfully demonstrated, as well as various applications including micro-to macroscale serpentine, tree, and antenna circuit patterns on a flexible substrate. The presented approach, packed in a table-top scale, is expected to provide a practical and affordable lithography solution by leveraging the directwriting capability and tunable optical functionality of polymers, scalability, and the simple optical alignment method.

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Influence of Network Structure on the Crystallization Behavior in Chemically Crosslinked Hydrogels

Cited by 18 publications

References 41 publications

Heterogeneous Local Dynamics in Mussel-Inspired Elastomers

Heterogeneous Local Dynamics in Mussel-Inspired Elastomers

One-Pot, In-Situ Synthesis of 8-Armed Poly(Ethylene Glycol)-Coated Ag Nanoclusters as a Fluorescent Sensor for Selective Detection of Cu2+

Fiber Lithography: A Facile Lithography Platform Based on Electromagnetic Phase Modulation Using a Highly Birefringent Electrospun Fiber

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