Tyrosine Derivative Regulated Enzyme Catalytic Pathway for Controllable Synthesis of Functional Melanin★

doi:10.6023/A23050240

Acta Chimica Sinica ›› 2023, Vol. 81 ›› Issue (11): 1486-1492.DOI: 10.6023/A23050240 Previous Articles Next Articles

Special Issue: 庆祝《化学学报》创刊90周年合辑

Article

酪氨酸衍生物调控酶催化路径可控合成功能黑色素^★

苏东芮^a^,^b, 任小康^b, 于沄淏^b, 赵鲁阳^b^,^*(), 王天宇^a^,^*(), 闫学海^b^,^c^,^d^,^*()

a 北京科技大学化学与生物工程学院功能分子与晶态材料科学与应用北京市重点实验室北京 100083
b 中国科学院过程工程研究所生化工程国家重点实验室北京 100083
c 中国科学院大学化学工程学院北京 100049
d 中国科学院过程工程研究所介尺度科学研究中心北京 100083

投稿日期:2023-05-19 发布日期:2023-07-28
作者简介:
^★庆祝《化学学报》创刊90周年.
基金资助:
国家自然科学基金(22025207); 国家自然科学基金(22232006); 国家自然科学基金(22077122); 国家自然科学基金(22072004)

Tyrosine Derivative Regulated Enzyme Catalytic Pathway for Controllable Synthesis of Functional Melanin^★

Dongrui Su^a^,^b, Xiaokang Ren^b, Yunhao Yu^b, Luyang Zhao^b(), Tianyu Wang^a(), Xuehai Yan^b^,^c^,^d()

a Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, School of Chemistry and Chemical Engineering, University of Science and Technology Beijing, Beijing 100083
b State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100083
c School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049
d Center for Mesoscience, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100083

Received:2023-05-19 Published:2023-07-28
Contact: *E-mail: yanxh@ipe.ac.cn (X. Y.); zhaoly@ipe.ac.cn (Y. Z.); twang@ustb.edu.cn (T. W.)
About author:
^★Dedicated to the 90th anniversary of Acta Chimica Sinica.
Supported by:
National Natural Science Foundation of China(22025207); National Natural Science Foundation of China(22232006); National Natural Science Foundation of China(22077122); National Natural Science Foundation of China(22072004)

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Abstract

Construction of biomacromolecules via enzyme-mediated catalytic assembly from small biomolecules is fascinating for preparing functional biological materials. The challenge remains on how to control the structure and functions of biomacromolecules through substrate regulation. A sequence of crucial biomacromolecules, melanin, were prepared via simple substrate derivation, which controls the key polymerization sites in enzyme catalyzed self-assembly process. In detail, we designed three tyrosine derivatives, namely, 3-fluorotyrosine [Tyr(F)], N-acetyltyrosine [Tyr(N-Ac)], and tyrosine ethyl ester [Tyr(OEt)]. The three substrates corresponded to the blockage of different tyrosinase-mediated polymerization active site, and tyrosine was used as the reference. The above small molecules as substrates (1.0 mmol/L) and tyrosinase (2 U) were mixed in phosphate buffer (pH=8.5, 0.10 mol/L, 2.0 mL), which was stirred in an air environment of 25 ℃. After 24 h, the reaction was quenched and the mixture was centrifuged to obtain different melanin nanoparticle products (MNPs). Characterizations from transmission electron microscopy (TEM), infrared spectroscopy (IR), and X-ray photoelectron spectroscopy (XPS) showed that all the melanin products had eumelanin-like skeleton, but were different in the degree of polymerization and microscopic chemical structures. These structure-modified MNPs showed overall absorption in the ultraviolet-visible-near infrared (UV-vis-NIR) region, thus enabling photothermal conversion in the NIR-I region. The photothermal conversion efficiency of MNP, MNP(F), and MNP(OEt) (3 mg•mL^-1) was measured to be 46.6%, 37.0%, and 25.8% [laser 808 nm, 1.5 W, where MNP(N-Ac) was not available due to rather low temperature increase]. Interestingly, in vitro experiment showed that MNP(OEt) exhibited better photothermal cytotoxicity than MNP, and this was probably because MNP(OEt) had a smaller particle size and less negative ζ-potential, which could ease cell endocytosis. This work demonstrated the feasibility to regu-late enzyme-mediated catalytic pathway via simple substrate derivation. It provides insights for the construction of new functional melanin materials and for revealing the relationship between biological macromolecular structure and function.

Key words: melanin, tyrosinase, enzyme-mediated catalyztic assembly, tyrosine derivative, photothermal material

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Dongrui Su, Xiaokang Ren, Yunhao Yu, Luyang Zhao, Tianyu Wang, Xuehai Yan. Tyrosine Derivative Regulated Enzyme Catalytic Pathway for Controllable Synthesis of Functional Melanin^★[J]. Acta Chimica Sinica, 2023, 81(11): 1486-1492.

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Fig. & Tab. 6

Figure 1. (a) Mechanism of tyrosinase catalysis from tyrosine (Tyr) substrate to melanin product, (b) active site of tyrosine reaction polymerization and the structure of tyrosine derivatives used in this work, (c) schematic diagram of tyrosinase-mediated melanin production by regulating the active polymerization site through the derivatization of tyrosine substrates, and (d) images of melanin solution samples prepared from different substrates [from left to right: MNP, MNP(OEt), MNP(F), and MNP(N-Ac) corresponding to Tyr, Tyr(OEt), Tyr(F), and Tyr(N-Ac)]

Figure 2. Morphology and structural characterizations of melanin products (a~d) TEM images of MNP, MNP(F), MNP(N-Ac) and MNP(OEt), respectively; (e) infrared spectra of four types of melanin, where the feature peaks (1) indicated catechol and quinone groups, respectively; (f) XPS spectra of four types of melanin

Figure 3. Structural diagram of molecular docking simulation of different tyrosine substrates with energy minima in the tyrosinase activity pocket. The substrates (a~d) are Tyr, Tyr(F), Tyr(N-Ac), and Tyr(OEt), respectively. The substrate (omitting nonactive hydrogen atoms) is represented by a ball stick model, the amino acid residues within 3 ? of the substrate are represented by a colored stick model, and the oxo-dicopper catalytic core is represented by a ball model

Figure 4. Characterization of the photothermal conversion effect of four types of melanins (a) UV-Vis-NIR absorption spectra of four types of melanins; (b) temperature rise-fall cycles of four types of melanin under laser irradiation (the concentration of melanin sample is 3.0 mg?mL–1, the laser is 808 nm, and the laser power density is 1.5 W?cm–2. The curve segments in the yellow area are taken for photothermal efficiency calculation)

	[(Q_NP+Q_dis)/ξ+T₀]^a/K	C₀^a/K	(–ξ/C_p)^a/s^–1	A^b	ξ/(W•K^–1)	Q_NP/W	η	R²^c
MNP	49.5	–19.8	–0.00751	1.073	0.031	0.650	0.473	1.000
MNP(F)	50.7	–18.2	–0.00432	1.959	0.018	0.386	0.260	1.000
MNP(OEt)	51.4	–18.4	–0.00610	1.431	0.026	0.572	0.396	0.999

Table 1. Photothermal conversion efficiency calculation parameters of MNP, MNP(F), and MNP(OEt)

Figure 5. MTT assay of 4T1 cell vialibity after exposure to different concentrations of (a) MNP, (b) MNP(F), (c) MNP(N-Ac), and (d) MNP(OEt) with or without 808 nm laser irradiation (1.5 W?cm–2) for 3 min [error bars represent the standard deviation (n=6)]

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酪氨酸衍生物调控酶催化路径可控合成功能黑色素^★

Tyrosine Derivative Regulated Enzyme Catalytic Pathway for Controllable Synthesis of Functional Melanin^★

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酪氨酸衍生物调控酶催化路径可控合成功能黑色素★

Tyrosine Derivative Regulated Enzyme Catalytic Pathway for Controllable Synthesis of Functional Melanin★

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Supporting Info.

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References 39

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酪氨酸衍生物调控酶催化路径可控合成功能黑色素^★

Tyrosine Derivative Regulated Enzyme Catalytic Pathway for Controllable Synthesis of Functional Melanin^★