Metallohydrogel with Tunable Fluorescence, High Stretchability, Shape-Memory, and Self-Healing Properties

Tang, Liuyan; Liao, Shanshan; Qu, Jinqing

doi:10.1021/acsami.9b06177

Cited by 37 publications

(23 citation statements)

References 49 publications

(75 reference statements)

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“…Coordination of alkali/ transition/lanthanide metal ions to appropriately designed ligands produces metallogels which may demonstrate the unique optical/fluorescent as well as other metal associated properties . Due to appearance of unique fluorescence property in metallogels, these materials could be utilized for sensing, cell imaging, security writing, etc .…”

Section: Introductionmentioning

confidence: 99%

Investigation of the Mechanism Behind Conductive Fluorescent and Multistimuli‐responsive Li⁺‐enriched Metallogel Formation

Shukla

Kumar

Dixit

et al. 2020

Chemistry An Asian Journal

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A fluorescent metallogel (2.6 % w/v) has been obtained from two non-fluorescent components viz. phenylsuccinic acid derived pro-ligand H 2 PSL and LiOH (2 equiv.) in DMF. Li + ion not only plays a crucial role in gelation through aggregation, but also contributed towards enhancement of fluorescence by imposing restriction over excited state intramolecular proton transfer (ESIPT) followed by origin of chelation enhanced fluorescence (CHEF) phenomenon. Further, the participation of CHEF followed by aggregationcaused quenching (ACQ) and aggregation-induced emission (AIE) in the gelation process have been well established by fluorescence experiments. Transmission electron microscopy (TEM) analysis disclosed the sequential creation of nanonuclei followed by nanoballs and their alignment towards the generation of fibers of about 3, 31 and 40 nm diameter, respectively. The presence of a long-range fibrous morphology inside the metallogel was further attested by scanning electron microscopy (SEM). Rheological studies on the metallogel showed its true gel-phase material nature. Nyquist impedance study shows a resistance value of 7.4 kΩ for the metallogel which upon applying ultrasound increased to 8.5 kΩ, while an elevated temperature of 70°C caused reduction in the resistance value to 4.8 kΩ. The mechanism behind metallogel formation has been well established by using FTIR, UV-vis, SEM, TEM, PXRD, 1 H NMR, fluorescence and ESI-MS.

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Section: Introductionmentioning

confidence: 99%

Investigation of the Mechanism Behind Conductive Fluorescent and Multistimuli‐responsive Li⁺‐enriched Metallogel Formation

Shukla

Kumar

Dixit

et al. 2020

Chemistry An Asian Journal

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“…The band from 1200 to 1400 cm −1 of PAAc corresponds to the hydrogen bonds between carboxylates. This band of D50A50 significantly decreased compared to pure PAAc, which proves the deformation of the hydrogen bonds by carboxylate‐Al 3+ coordination . The characteristic absorption peak at 1591 cm −1 of DETA (NH 2 bending) shifted to the peak at 1530 cm −1 in the spectrum of D50A50 hydrogel (NH 3 + and NH 2 + stretching vibration), manifesting the formation of ionic bonds between amines of DETA and carboxylates of PAAc .…”

Section: Resultsmentioning

confidence: 84%

Bioinspired Strategy to Reinforce Hydrogels via Cooperative Effect of Dual Physical Cross‐Linkers

Liang

Zhou

et al. 2020

Macro Chemistry & Physics

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including ionic bond, [4][5][6][7][8][9] hydrogen bond, [10][11][12][13][14][15] coordination, [16][17][18] microcrystalline, [19][20][21] and hydrophobic interaction. [22][23][24][25] Although these non-covalent bonds can significantly improve the extensibility and self-recovery of hydrogels, they usually dramatically reduce the toughness. Covalent cross-linkers are always required for reaching high toughness, whereas the permanent fracture of covalent cross-links will lead to irreversible structure damage and significant decline of toughness and mechanical strength. Without the help from covalent cross-linkers, what kind of multiple physical cross-linker system can endow mono-network hydrogels with both rapid self-recovery and high toughness still remains a challenge.Our strategy is inspired by the nacre of abalone shell, which is constituted by alternating layers of CaCO 3 and biopolymers. The hard CaCO 3 layer provides strength and hardness and the soft biopolymer layer provides adhesion and ductility. The cooperative effect of two components leads to eminent strength and toughness. [26,27] This naturally suggests a new strategy to construct high toughness materials via combining both weak and strong non-covalent cross-linkers in one polymeric network. Polyacrylic acid will be an appropriate candidate for the versatile functions of carboxyl group to realize two different interactions in one polymeric network. First, carboxyl groups are able to form ionic bond with alkaline group, such as primary amine and pyridine. [28] Second, carboxyl groups can coordinate with metal ions, such as Al 3+ and Fe 3+ . [29] In this work, we present a new class of polyacrylic acid hydrogels cross-linked by coordinate bonds with Al 3+ and ionic bonds with triamine (diethylenetriamine, DETA). Compared to Al 3+ or DETA cross-linked hydrogels, this dual physically cross-linked hydrogel become super tough and the toughness of hydrogels can be recovered rapidly. In addition, the mechanical properties can be tuned over a wide range by using different molar ratios of cross-linkers. Experimental Section MaterialsDETA, acrylic acid (AAc), ammonium persulfate (APS), and aluminum chloride (AlCl 3 ) were purchased from Aladdin Many biological tissues including cartilage and tendons are composed of polymeric hydrogels, which exhibit high toughness and rapid self-recovery. However, developing hydrogels with both high toughness and rapid recovery remains a challenge. Inspired by the nacre of abalone shell, two non-covalent cross-linkers (Al 3+ and diethylenetriamine [DETA]) with different relaxation times are introduced into a polyacrylic acid network. Compared with mono cross-linked hydrogels, the dual physical cross-linked hydrogel exhibits both high toughness (work of extension at fracture up to 8.0 MJ m −3 ) and rapid self-recovery ability without loss of extensibility. Strong carboxylate-DETA ionic cross-links with longer relaxation time endow the hydrogels with high strength and help to localize the reformation of carboxylate-Al 3+ coordi...

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“…[ 19 ] However, for less nucleophilic acyl hydrazides [ 20 ] a catalyst is desirable to conduct the reaction under mild conditions. Thus, in a typical procedure, acyl hydrazide–aldehyde condensation proceeds either in the absence of any catalyst (20–82 °C; 0.33–24 h), [ 21 ] or in the presence of catalytic amount of a Brønsted acid (HCl, 20 °C, 1–72 h; [ 22 ] or AcOH, 82 °C, 12–24 h [ 23 ] ). Tetrabromomethane has never been applied to enhance this condensation and, after preliminary experiments when we established its activity, our idea was to verify the potential and/or limitations of CBr 4 functioning as an organic catalyst in the Schiff reaction.…”

Section: Resultsmentioning

confidence: 99%

Tetrabromomethane as an Organic Catalyst: a Kinetic Study of CBr₄‐Catalyzed Schiff Condensation

et al. 2020

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Tetrabromomethane functions as an organic catalyst for non‐redox reactions of carbonyl species and, in particular, it enhances the aldehyde–acyl hydrazide condensation to give N‐acyl hydrazones. This simple, inexpensive, and commercially available halomethane provides up to 14‐fold acceleration of the Schiff reaction; the kinetic data indicate that the studied condensation exhibits the first order on CBr4. The catalytic activity of CBr4 is significantly higher than the activity of other halogen‐containing species, such as CHX3 or ArX (X = Cl, Br, I).

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Metallohydrogel with Tunable Fluorescence, High Stretchability, Shape-Memory, and Self-Healing Properties

Cited by 37 publications

References 49 publications

Investigation of the Mechanism Behind Conductive Fluorescent and Multistimuli‐responsive Li⁺‐enriched Metallogel Formation

Investigation of the Mechanism Behind Conductive Fluorescent and Multistimuli‐responsive Li⁺‐enriched Metallogel Formation

Bioinspired Strategy to Reinforce Hydrogels via Cooperative Effect of Dual Physical Cross‐Linkers

Tetrabromomethane as an Organic Catalyst: a Kinetic Study of CBr₄‐Catalyzed Schiff Condensation

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Metallohydrogel with Tunable Fluorescence, High Stretchability, Shape-Memory, and Self-Healing Properties

Cited by 37 publications

References 49 publications

Investigation of the Mechanism Behind Conductive Fluorescent and Multistimuli‐responsive Li+‐enriched Metallogel Formation

Investigation of the Mechanism Behind Conductive Fluorescent and Multistimuli‐responsive Li+‐enriched Metallogel Formation

Bioinspired Strategy to Reinforce Hydrogels via Cooperative Effect of Dual Physical Cross‐Linkers

Tetrabromomethane as an Organic Catalyst: a Kinetic Study of CBr4‐Catalyzed Schiff Condensation

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Investigation of the Mechanism Behind Conductive Fluorescent and Multistimuli‐responsive Li⁺‐enriched Metallogel Formation

Investigation of the Mechanism Behind Conductive Fluorescent and Multistimuli‐responsive Li⁺‐enriched Metallogel Formation

Tetrabromomethane as an Organic Catalyst: a Kinetic Study of CBr₄‐Catalyzed Schiff Condensation