Bioinspired Cyclic Dipeptide Functionalized Nanofibers for Thermal Sensing and Energy Harvesting

Santos, Daniela Lopes dos; Batista, Rosa Maria Ferreira; Handa, Adelino; Almeida, Bernardo; Rodrigues, Pedro V.; Torres, Ana Raquel Rosas; Machado, Ana Lúcia; Belsley, M.; Gomes, E. de Matos

doi:10.20944/preprints202302.0365.v1

Cited by 6 publications

(1 citation statement)

References 30 publications

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“…This inherent ability to self-assemble is particularly important, as it opens the door to the creation of a wide range of nanostructured materials with potential applications in several fields [16,17]. 2 The electrospinning technique has emerged as a powerful tool for producing fibers from a polymer solution doped with active molecules, namely dipeptides [18][19][20][21][22]. This involves applying a strong electric field between the tip of a syringe and a collector, resulting in the formation of fibers with diameters on the micro or nanometer scale [23,24].…”

Section: Introductionmentioning

confidence: 99%

Electrospun Microstructured Biopolymer Fibers Containing Self-Assembled Boc-Phe-Ile Dipeptide: Dielectric and Energy Harvesting Properties

Handa,

Baptista,

Santos

et al. 2023

Preprint

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Hybrid biomaterials were engineered using the electrospinning technique, incorporating the dipeptide Boc-L-phenylalanyl-L-Isoleucine into microfibers composed of biocompatible polymers. The examination by scanning electron microscopy affirmed the morphology of the microfibers, exhibiting diameters ranging between 0.9 to 1.8 µm. The dipeptide self-assemblies into spheres with a hydrodynamic size between 0.18 to 1.26 µm. The dielectric properties of these microfibers were characterized through impedance spectroscopy, where variations in both temperature and frequency were systematically studied. The investigation revealed a noteworthy rise in the dielectric constant and AC electric conductivity with increasing temperature, attributable to augmented charge mobility within the material. The successful integration of the dipeptide was substantiated through the observation of Maxwell-Wagner interfacial polarization, affirming the uniform dispersion within the microfibers. In-depth insights into electric permittivity and activation energies were garnered using the Havriliak-Negami model and the AC conductivity behavior. Very importantly, these engineered fibers exhibited pronounced pyroelectric and piezoelectric responses, with Boc-Phe-Ile@PLLA microfibers standing out with the highest piezoelectric coefficient, calculated to be 56 pC/N. These discoveries help us understand how dipeptide nanostructures embedded into electrospun nano/microfibers can greatly affect their pyroelectric and piezoelectric properties. They also point out that polymer fibers could be used as highly efficient piezoelectric energy harvesters, with promising applications in portable and wearable devices.

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Section: Introductionmentioning

confidence: 99%

Electrospun Microstructured Biopolymer Fibers Containing Self-Assembled Boc-Phe-Ile Dipeptide: Dielectric and Energy Harvesting Properties

Handa,

Baptista,

Santos

et al. 2023

Preprint

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A Polymorph of Dipeptide Halide Glycyl-L-Alanine Hydroiodide Monohydrate: Crystal Structure, Optical Second Harmonic Generation, Piezoelectricity and Pyroelectricity

et al. 2023

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A polymorph of glycyl-L-alanine HI.H2O is synthesized from chiral cyclo-glycyl-L-alanine dipeptide. The dipeptide is known to show molecular flexibility in different environments, which leads to polymorphism. The crystal structure of the glycyl-L-alanine HI.H2O polymorph is determined at room temperature and indicates that the space group is polar (P21), with two molecules per unit cell and unit cell parameters a = 7.747 Å, b = 6.435 Å, c = 10.941 Å, α = 90°, β = 107.53(3)°, γ = 90° and V = 520.1(7) Å3. Crystallization in the polar point group 2, with one polar axis parallel to the b axis, allows pyroelectricity and optical second harmonic generation. Thermal melting of the glycyl-L-alanine HI.H2O polymorph starts at 533 K, close to the melting temperature reported for cyclo-glycyl-L-alanine (531 K) and 32 K lower than that reported for linear glycyl-L-alanine dipeptide (563 K), suggesting that although the dipeptide, when crystallized in the polymorphic form, is not anymore in its cyclic form, it keeps a memory of its initial closed chain and therefore shows a thermal memory effect. Here, we report a pyroelectric coefficient as high as 45 µC/m2K occurring at 345 K, one order of magnitude smaller than that of semi-organic ferroelectric triglycine sulphate (TGS) crystal. Moreover, the glycyl-L-alanine HI.H2O polymorph displays a nonlinear optical effective coefficient of 0.14 pm/V, around 14 times smaller than the value from a phase-matched inorganic barium borate (BBO) single crystal. The new polymorph displays an effective piezoelectric coefficient equal to deff=280 pCN−1, when embedded into electrospun polymer fibers, indicating its suitability as an active system for energy harvesting.

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Nanostructured Electrospun Fibers with Self-Assembled Cyclo-L-Tryptophan-L-Tyrosine Dipeptide as Piezoelectric Materials and Optical Second Harmonic Generators

et al. 2023

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The potential use of nanostructured dipeptide self-assemblies in materials science for energy harvesting devices is a highly sought-after area of research. Specifically, aromatic cyclo-dipeptides containing tryptophan have garnered attention due to their wide-bandgap semiconductor properties, high mechanical rigidity, photoluminescence, and nonlinear optical behavior. In this study, we present the development of a hybrid system comprising biopolymer electrospun fibers incorporated with the chiral cyclo-dipeptide L-Tryptophan-L-Tyrosine. The resulting nanofibers are wide-bandgap semiconductors (bandgap energy 4.0 eV) consisting of self-assembled nanotubes embedded within a polymer matrix, exhibiting intense blue photoluminescence. Moreover, the cyclo-dipeptide L-Tryptophan-L-Tyrosine incorporated into polycaprolactone nanofibers displays a strong effective second harmonic generation signal of 0.36 pm/V and shows notable piezoelectric properties with a high effective coefficient of 22 pCN−1, a piezoelectric voltage coefficient of geff=1.2 VmN−1 and a peak power density delivered by the nanofiber mat of 0.16μWcm−2. These hybrid systems hold great promise for applications in the field of nanoenergy harvesting and nanophotonics.

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Bioinspired Cyclic Dipeptide Functionalized Nanofibers for Thermal Sensing and Energy Harvesting

Cited by 6 publications

References 30 publications

Electrospun Microstructured Biopolymer Fibers Containing Self-Assembled Boc-Phe-Ile Dipeptide: Dielectric and Energy Harvesting Properties

Electrospun Microstructured Biopolymer Fibers Containing Self-Assembled Boc-Phe-Ile Dipeptide: Dielectric and Energy Harvesting Properties

A Polymorph of Dipeptide Halide Glycyl-L-Alanine Hydroiodide Monohydrate: Crystal Structure, Optical Second Harmonic Generation, Piezoelectricity and Pyroelectricity

Nanostructured Electrospun Fibers with Self-Assembled Cyclo-L-Tryptophan-L-Tyrosine Dipeptide as Piezoelectric Materials and Optical Second Harmonic Generators

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