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

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논문

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

학술지

Materials

저자명

Baptista, Rosa M. F.; Gomes, Clara S. B.; Silva, Bruna; Oliveira, Joã o; Almeida, Bernardo; Castro, Cidá lia; Rodrigues, Pedro V.; Machado, Ana; Freitas, Ruben B.; Rodrigues, Manuel J. L. F.; de Matos Gomes, Etelvina; Belsley, Michael

초록

<P>A polymorph of glycyl-L-alanine HI.H<SUB>2</SUB>O 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.H<SUB>2</SUB>O polymorph is determined at room temperature and indicates that the space group is polar (P2<SUB>1</SUB>), with two molecules per unit cell and unit cell parameters a = 7.747 &Aring;, b = 6.435 &Aring;, c = 10.941 &Aring;, &alpha; = 90&deg;, &beta; = 107.53(3)&deg;, &gamma; = 90&deg; and V = 520.1(7) &Aring;<SUP>3</SUP>. 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.H<SUB>2</SUB>O 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 &micro;C/m<SUP>2</SUP>K 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.H<SUB>2</SUB>O 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 [FORMULA OMISSION], when embedded into electrospun polymer fibers, indicating its suitability as an active system for energy harvesting.</P>

발행연도

2023

발행기관

MDPI

ISSN

1996-1944

16

10

페이지

pp.3690

주제어

glycyl-L-alanine iodide; polymorphism; crystal structure; cyclic dipeptides; optical second harmonic generation; pyroelectricity

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1 2023-12-11

논문; 2023-05-12

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