Crosslinking ionic oligomers as conformable precursors to calcium carbonate

Liu, Zhaoming; Shao, Changyu; Jin, Biao; Zhang, Zhisen; Zhao, Yueqi; Xu, Xurong; Tang, Ruikang

doi:10.1038/s41586-019-1645-x

Cited by 209 publications

(223 citation statements)

References 55 publications

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“…Alg is additionally used as a chemical bridge to combine PVA and HAP by its abundant carboxyl functional groups, which can interact with both PVA and HAP. To prepare SSF‐like fibers by biomimetic mineralization, ultrasmall amorphous calcium phosphate (CaP) nanoclusters (≈1.64 nm in diameter, Figure S1, Supporting Information) are used as the precursor mineral phase and benefit the organic–inorganic incorporation process at the nanoscale . The steps used to fabricate the PVA/Alg/HAP hybrid macrofibers by self‐assembly are presented in Figure a.…”

Section: Resultsmentioning

confidence: 99%

Biomimetic Mineralized Organic–Inorganic Hybrid Macrofiber with Spider Silk‐Like Supertoughness

Zhao

et al. 2019

Adv Funct Materials

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Spider silk fibers (SSF) have a hierarchical structure composed of proteins with highly repetitive sequences and biomineralization is sophisticated in hierarchical organic-inorganic constructions. By using inorganic hydroxyapatite (HAP) and organic polyvinyl alcohol (PVA) to simulate the rigid crystalline and flexible amorphous protein blocks of SSF, respectively, biomimetic mineralization is herein attempted for the large-scale preparation of SSF-like macrofibers with a hierarchical ordered structure, a superhigh tensile strength of 949 ± 38 MPa, a specific toughness of 296 ± 12 J g −1 , and a stretch ability of 80.6%. The hybrid macrofibers consist of microfibers, and their outstanding performance (e.g., extreme tolerance to temperatures ranging from −196 to 80 °C and superior ability to inhibit the transverse growth of cracks) is attributed to the hierarchical arrangement as well as the organic-inorganic integrated structure within the oriented mineralized polymer chains. The biomineralization-inspired technique provides a promising tactic that can be used to synthesize functional organicinorganic fibers that are structurally complex and, furthermore, industrially manufacture SSF-like artificial fibers with a supertoughness.

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Section: Resultsmentioning

confidence: 99%

Biomimetic Mineralized Organic–Inorganic Hybrid Macrofiber with Spider Silk‐Like Supertoughness

Zhao

et al. 2019

Adv Funct Materials

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“…Thet riethylamine (TEA)-stabilized inorganic CPO precursors are prepared as our established protocol (see more details in the Supporting Information). [7] Thed ynamic lightscattering (DLS) measurement on CPO confirms that the average size is 0.88 AE 0.27 nm ( Figure 1a), and no calcium phosphate particle is precipitated. Then the electron spray ionization mass spectrometry (ESI-MS) analysis is used to reveal more detailed composition of CPO ( Figure 1b).…”

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confidence: 72%

“…[5] Polymer materials are of great importance in our world owing to their easy and moldable fabrication, which can generate large-sized bulk materials with continuous structure. [6] Inspired by organic polymerization processes, we recently reported inorganic oligomers (such as calcium carbonate and calcium phosphate) and their polymerization/ crosslinking, [7] which can produce inorganic mineral monoliths.T his achievement arises from af usion of classic inorganic and polymer chemistry by employing the same pathway for materials manufacturing. Furthermore,s uch an achievement would open aw indow to produce homogenous organic-inorganic hybrid materials by using copolymerization of organic and inorganic monomers/oligomers as conformable precursors.…”

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confidence: 99%

“…Then the electron spray ionization mass spectrometry (ESI-MS) analysis is used to reveal more detailed composition of CPO ( Figure 1b). As the TEA is evaporated during MS measurement, [7] the result directly shows the molecular weight of CPO,which is around 620-930. It implies that each CPO contains 2or3[Ca 3 (PO 4 ) 2 ] units,w hich fits with the DLS result.…”

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confidence: 99%

“…[16] As ac onclusion, the CPO can be expressed as [Ca 3 (PO 4 ) 2 ] m (C 6 H 15 N) n ,where m = 2-3 and n represents for the number of multiple TEA molecules.I ti sa lso demonstrated experimentally that the crosslinking of CPO by avolatilization-induced TEA removal can result in the formation of amorphous calcium phosphate (CaP) bulk, which is in agreement with our previous finding. [7,16] Figure 1d illustrates anew composite fabrication by copolymerization of organic AM and inorganic CPO precursors.N ,N-methylene bisacrylamide (MBAA), ammonium persulfate (APS), and N,N,N',N'-tetramethylethylenediamine (TEMED) are used as the crosslinker,i nitiator,a nd accelerator,r espectively,t og enerate PA Mf rom AM via af ree radical polymerization. [17] By mixing AM, TEAstabilized CPO and the crosslinking molecules together,t he organic-inorganic copolymerization can be initiated as the follows:A Mm onomers are polymerized by free-radical polymerization and connected by covalent bonds;w hile the volatilization-induced TEA removal leads to the polymerization of CPO via ionic bonds;s ynchronously,C PO are polymerized with AM monomers via hydrogen bonds between the inorganic phosphate and the organic NH 2 groups.F ollowing this process,t he ultrasmall CPO can incorporate well into PA Mc hemically at molecular level.…”

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confidence: 99%

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Organic–Inorganic Copolymerization for a Homogenous Composite without an Interphase Boundary

Yu¹,

Zhao²,

Jin³

et al. 2019

Angewandte Chemie

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Ionic oligomers and their crosslinking implies ap ossibility to produce novel organic-inorganic composites by copolymerization. Using organic acrylamide monomers and inorganic calcium phosphate oligomers as precursors, uniformly structured polyacrylamide (PAM)-calcium phosphate copolymer is prepared by an organic-inorganic copolymerization. In contrast to the previous PAM-based composites by mixing inorganic components into polymers,t he copolymerized material has no interphase boundary owing to the homogenous incorporation of the organic and inorganic units at molecular level, resulting in ac omplete and continuous hybrid network. The participation of the ionic binding effect in the crosslinking process can substantially improve the mechanical strength;the copolymer can reachamodulus and hardness of 35.14 AE 1.91 GPaa nd 1.34 AE 0.09 GPa, respectively,w hich are far superior to any other PAM-based composites.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

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Improved Quantum Yield and Excellent Luminescence Stability of Europium‐Incorporated Polymeric Hydrogen‐Bonded Heptazine Frameworks Due to an Efficient Hydrogen‐Bonding Effect

Yang

Folens

Laing

et al. 2020

Adv Funct Materials

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Two of the most persistent challenges for the high-end application of luminescent lanthanide (Ln) compounds are a low quantum yield and luminescence quenching caused by a liquid medium. In this work, a type of polymeric hydrogen-bonded heptazine framework is developed incorporating trivalent europium ions (P-HHF-Eu) via a low-cost and facile low-temperature thermal condensation reaction. Structural characterization clearly reveals that the solid-phase pyrolyzation reaction results in the formation of P-HHF-Eu. Using time-resolved and steady state photoluminescence (PL) spectroscopies, the photophysics and photochemistry of P-HHF-Eu at different hydration degrees are investigated and the role of hydrogen bonding in the significant enhancement of the emission properties is demonstrated. Furthermore, the P-HHF-Eu particles suspended in polyvinyl alcohol hydrogel exhibit excellent luminescence stability with a high PL quantum yield of up to ≈46% and wavelength responsive color-tunable emission, which holds potential for security applications.

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Crosslinking ionic oligomers as conformable precursors to calcium carbonate

Cited by 209 publications

References 55 publications

Biomimetic Mineralized Organic–Inorganic Hybrid Macrofiber with Spider Silk‐Like Supertoughness

Biomimetic Mineralized Organic–Inorganic Hybrid Macrofiber with Spider Silk‐Like Supertoughness

Organic–Inorganic Copolymerization for a Homogenous Composite without an Interphase Boundary

Improved Quantum Yield and Excellent Luminescence Stability of Europium‐Incorporated Polymeric Hydrogen‐Bonded Heptazine Frameworks Due to an Efficient Hydrogen‐Bonding Effect

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