Triethylenetetramine-Based Semiconducting Fe(III) Metallogel: Effective Catalyst for Aryl–S Coupling

Dhibar, Subhendu; Dey, Arka; Ghosh, Debidas; Majumdar, Santanu; Dey, Arun K.; Ray, Partha Pratim; Dey, Biswajit

doi:10.1021/acsomega.9b03194

Cited by 45 publications

(24 citation statements)

References 95 publications

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“…The values of the optical nonlinear absorption coefficients (β eff ) at intensity 283 GW/cm 2 of the metallohydrogels BSA@CuA and BSA@CuCl are (0.0662 ± 0.0002) cm/GW and (0.0540 ± 0.0001) cm/GW, respectively, which indicates that BSA@CuA is showing higher nonlinear absorption than BSA@CuCl. Because UV–visible absorption spectra (see Figure S8 in the Supporting Information) show that the absorption is maximum at ∼ 275 nm for BSA-CuA and ∼290 nm for BSA-CuCl, following the literature − and by analysis of UV–Vis absorption data, the optical band gap for BSA-CuA and BSA-CuCl is calculated. The calculated optical band gap of BSA-CuA and BSA-CuCl is ∼2.37 and ∼2.82 eV, respectively.…”

Section: Resultsmentioning

confidence: 99%

Protein-Based Self-Healing Cu(II)-Metallohydrogels: Efficient Third-Order Nonlinear Optical Materials in Terms of an Intensity-Dependent Refractive Index and Two-Photon Absorption

Majumdar

Singha

Dhibar

et al. 2020

ACS Appl. Electron. Mater.

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Two protein-based self-healing Cu(II)-metallohydrogels named BSA-CuA and BSA-CuCl have been synthesized by mixing acetate and chloride salts of Cu(II) distinctly with the protein bovine serum albumin (BSA) in water medium. Experimentally investigated rheological parameters of both synthesized metallohydrogels not only expose the viscoelastic semi solid nature and mechanical toughness but also reveal the self-healing properties of both metallohydrogel materials. Counteranion-directed morphological variations of these metallohydrogels are visualized through field-emission scanning electron microscopic images. The third-order optical nonlinear susceptibility x (3) of these synthesized metallohydrogels has been studied using the Z-scan technique at a wavelength of 550 nm under the femtosecond regime in the excitation intensity range from 66 to 283 GW/cm 2 . BSA-CuA and BSA-CuCl metallohydrogels exhibit a high value of the positive nonlinear refractive index n 2 I and two-photon absorption coefficient β eff , which are very important for all-optical switching, optical limiting, and other photonic applications. The polarity possibly associated with the self-healing property of these two synthesized metallohydrogels has been justified through the experimentally measured high value of optical nonlinearity. At 88 GW/cm 2 intensity of the excitation beam, the n 2 I values for BSA-CuA and BSA-CuCl are (14.40 ± 0.16) × 10 −7 cm 2 /GW and (10.99 ± 0.15) × 10 −7 cm 2 /GW, respectively, and at 283 GW/cm 2 intensity, the β eff values are (0.0662 ± 0.0002) cm/GW and (0.0540 ± 0.0001) cm/GW, respectively. The (x (3) ) of BSA@CuA and BSA@CuCl at 283 GW/cm 2 is (1.757 ± 0.018) (esu ×10 −14 ) and (1.560 ± 0.017) (esu ×10 −14 ), respectively.

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Section: Resultsmentioning

confidence: 99%

Protein-Based Self-Healing Cu(II)-Metallohydrogels: Efficient Third-Order Nonlinear Optical Materials in Terms of an Intensity-Dependent Refractive Index and Two-Photon Absorption

Majumdar

Singha

Dhibar

et al. 2020

ACS Appl. Electron. Mater.

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“…These metallogels, along with their implementations in different applications, are now also being shown as an intriguing platform for studying novel catalytic reactions. − After the first report on peroxidase mimicking activity by Fe 3 O 4 nanoparticles, wide varieties of other nanomaterials have been also explored for studies on artificial enzymatic activities . Majorly, these nanomaterials enjoy their intrinsic enzymatic catalytic properties and hence imitate the activity of natural enzymes to catalyze the same biocatalytic reaction.…”

Section: Introductionmentioning

confidence: 99%

Cu(II)-Based Nanofibrous Metallogel for Phenoxazinone Synthase-like Activity

Sarkar

Maji

Dutta

et al. 2021

ACS Appl. Nano Mater.

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Metallogel formation by an individual ligand is well known, but simultaneous need of two ligands in selective metallogelation is relatively less common. In our present study, we have shown that disodium succinate and hexamethylenetetramine, when allowed to react simultaneously with CuCl 2 in an aqueous medium, instantaneously form a greenish metallogel. The gelation is not attainable in the absence of any of the two ligands, which ascertains the cooperativity of the ligands to successfully achieve the metallogelation. Different microanalytical studies [Fourier transform infrared (FTIR), powder X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, rheology, and so on] have been performed for complete characterizations of the gel sample. The gel shows a nanodimensional entangled network morphology. Metal−ligand coordination in association with solventmediated hydrogen bonding interactions becomes a part-and-parcel in making the nanoscale fibrillar network of the metallogel. Different related ligands and metal ions were also reviewed in lieu of the above two ligands and the Cu(II) ion, but none of the alternatives was able to result in the gel formation. Thus, both the ligands were highly specific for the said metallogelation with Cu(II) only. The effect of counter anions of the Cu(II) salt was also studied. The gel also exhibits its stimuli-responsive nature toward different interfering chemical parameters such as pH, selective anions, selective complexing agents, and so forth. Finally, the robust Cu(II) metallogel was deliberately exploited as a heterogeneous catalyst for successful oxidative conversion of 2-aminophenol (OAPH) to phenoxazinone hiring atmospheric oxygen and thereby conferring its role as a biomimetic nanozyme catalyst. The catalytic conversion has been followed spectrophotometrically. The detailed kinetics for the reaction was performed with varied reaction parameters. The Michaelis−Menten model was applied to analyze the results. Based on the experimental results (e.g., FTIR, XRD, thermogravimetric analysis, and electrospray ionization−mass spectrometry), a mechanistic approach has also been anticipated to establish the catalytic process. Finally, recyclability of the catalyst was also verified. This nanozymatic phenoxazinone synthase-like activity of a nanodimensional metallogel is hitherto unknown and thus suggests its enzyme mimicking feature.

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“…Self-assembled soft materials made up of small molecules or low molecular weight gelators (LMWGs), via various noncovalent interactions are highly topical. [1] Among various soft materials, metallogels [1c] that incorporate the metal ions into the supramolecular gel endowed the gels with various unique features [1] and new application potentials in luminescence, [2] sensing, [3] molecular recognition, [4] catalysis, [5] drug-delivery, [1g,6] adsorption, [7] antibacterial [8] and ion conductivity [9] etc. Metallogels are formed when discrete metal complexes or welldefined coordination polymers are self-assembled through noncovalent interactions such as hydrogen bonding, π-π stacking, hydrophobic interactions and Van der Waals interactions resulting in suitable networks for immobilizing solvent molecules.…”

Section: Introductionmentioning

confidence: 99%

Silver‐Ion‐Selective Gelation of Simple Pyridine‐Naphthalimide Conjugates with Multiple Applications: Sensing, Drug Delivery, Dye Adsorption and Ion Conductivity

et al. 2021

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Naphthalimide‐based compounds 1–4, which show excellent gelation from semi aqueous solvents in the presence of Ag+ ions over a series of other metal ions have been synthesized. While compounds 1–3 form gel in the presence of Ag+ ion in DMF‐H2O (1 : 1, v/v), compound 4, devoid of pyridine, acts as non gelator under identical conditions. The gels reveal rock and fibrous like morphologies and show good viscoelastic response as established from rheological study. Ag‐gels of 1–3 exhibit excellent ion conduction property along with other attributes in material chemistry. Ion transport properties within the gels are analyzed by evaluating the different electrical parameters viz. ion conductivity, ion diffusivity and concentration of mobile ions at different temperatures using impedance spectroscopy. Despite identical concentration of metal ion precursor within the gels, a strong gelator‐dependent conduction property is observed. Furthermore, the Ag‐gels as soft functional materials discriminate L‐ cysteine from other amino acids and show good response in drug delivery and dye adsorption from wastewater.

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Triethylenetetramine-Based Semiconducting Fe(III) Metallogel: Effective Catalyst for Aryl–S Coupling

Cited by 45 publications

References 95 publications

Protein-Based Self-Healing Cu(II)-Metallohydrogels: Efficient Third-Order Nonlinear Optical Materials in Terms of an Intensity-Dependent Refractive Index and Two-Photon Absorption

Protein-Based Self-Healing Cu(II)-Metallohydrogels: Efficient Third-Order Nonlinear Optical Materials in Terms of an Intensity-Dependent Refractive Index and Two-Photon Absorption

Cu(II)-Based Nanofibrous Metallogel for Phenoxazinone Synthase-like Activity

Silver‐Ion‐Selective Gelation of Simple Pyridine‐Naphthalimide Conjugates with Multiple Applications: Sensing, Drug Delivery, Dye Adsorption and Ion Conductivity

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