Preparation and Characterization of Solvent-Free Adhesive Based on Phenylalanine

doi:10.19894/j.issn.1000-0518.250031

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (11): 1489-1499.DOI: 10.19894/j.issn.1000-0518.250031

• Full Papers • Previous Articles Next Articles

Preparation and Characterization of Solvent-Free Adhesive Based on Phenylalanine

Xiao-Ming XIE¹(), Jia-He LIU¹, Ze-Hao MA¹, Yu-Lian JIANG¹, Xing-Yu XU¹, Zhi-Yuan MA³, Wen LI²()

^1.Department of Chemistry，Xinzhou Teachers University，Xinzhou 034000，China
^2.College of Chemistry，Jilin University，Changchun 130000，China
^3.School of Chemical Engineering，Dalian University of Technology，Dalian 116081，China

Received:2025-01-16 Accepted:2025-08-25 Published:2025-11-01 Online:2025-12-05
Contact: Xiao-Ming XIE,Wen LI
About author:wenli@jlu.edu.cn
xiexm0910@163.com
Supported by:
the National Natural Science Foundation of China(22172059);the Natural Science Foundation of Shanxi Province, China(20210302124339)

1. .pdf(1493KB)

Abstract

Abstract:

Solvent-free adhesives are indispensable auxiliary materials in the fields of food and pharmaceutical packaging， electronic devices， automotive manufacturing and aerospace due to their advantages of eco-friendliness， ease of use， and wide applicability. Herein， we have screened inexpensive phenylalanine as building blocks and successfully prepared a series of new solvent-free adhesives through a simple heat-assisted process. This solvent-free adhesive can be bonded to a variety of natural and artificial substrates， the adhesion strength can reach up to 1.84 MPa； Excellent durable adhesion （＞15 days）， cyclic adhesion （＞10 cycles） and non-polar solvent tolerance； A wide operating temperature （-196~80 ℃）， can be injected into different shapes of microtubes and crafts for repair， and adhere to biological tissues and exhibit good biocompatibility. Notably， this solvent-free adhesive can be easily achieved for kilogram-scale preparation by a simple heat-assisted process. The work in this paper provides a reliable basis and guidance for promoting green manufacturing and sustainable development of adhesive materials.

Key words: Phenylalanine, Solvent-free, Temperature tolerance, Adhesive

CLC Number:

O648.1

Xiao-Ming XIE, Jia-He LIU, Ze-Hao MA, Yu-Lian JIANG, Xing-Yu XU, Zhi-Yuan MA, Wen LI. Preparation and Characterization of Solvent-Free Adhesive Based on Phenylalanine[J]. Chinese Journal of Applied Chemistry, 2025, 42(11): 1489-1499.

Figures/Tables 6

Fig.1 Schematic illustration of the solvent-free adhesive based on Phe via thermal-assisted method （Phe： phenylalanine， CA： citric acid）

Fig.2 （A） FT-IR spectra of PNSA， Phe and CA；（B） PXRD patterns of PNSA， Phe and CA；（C） 1H NMR spectra of PNSA， Phe and CA；（D） 13C NMR spectra of PNSA， Phe and CA；（E） SEM and corresponding elemental mapping images of PNSA adhesive；（F） Photographs of the weights bonded by PNSA adhesive and the PNSA adhesive obtained in kilogram scale

Fig.3 （A） Adhering various substrates： wood， ceramic， glass， plastic， SS， carnelian （scale bar： 1 cm）；（B） The force vs displacement curves of different substrates adhered by the PNSA adhesive；（C） Adhesion strengths of PNSA adhesive on various substrates；（D） Cyclic adhesion strengths of PNSA adhesive on Al substrate；（E） Adhesion strengths of PNSA adhesive tolerating a mass of ~1 kg on Al substrate before and after 15 days

Fig.4 （A） Images of transfusing the PNSA adhesive into different shapes of glass tubes （scale bar： 1 cm）；（B） Images of repairing a fractured “Monkey” statue by PNSA adhesive （scale bar： 1 cm）；（C） Frequency sweep analysis at a constant strain of 1%；（D） Strain sweep at the frequency of 5 rad/s；（E） Dynamic rheology behavior over time （γ=1%） after PNSA adhesive is broken by applying a 100% strain amplitude sweep；（F） Viscosity versus shear rate for PNSA adhesive

Fig.5 （A） Adhesion strengths of PNSA adhesive with different mass ratios；（B） Adhesion strengths of PNSA， VNSA and GNSA adhesives；（C） Adhesion strengths of PNSA1， VNSA1 and GNSA1 adhesives；（D） Adhesion strengths of PNSA and PNSA2 adhesives；（E） TGA curves of PNSA adhesive；（F） DSC spectra of PNSA adhesive， Phe and CA

Fig.6 （A） Macroscopic adhesion tests of PNSA adhesive in liquid nitrogen （scale bar， 1 cm）；（B） Adhesion strengths of PNSA adhesive on Al substrates at various temperatures；（C） Cycling tests of the PNSA adhesive at low temperature；（D） Macroscopic adhesion behavior of PNSA adhesive on porcine skin （scale bar， 1 cm）；（E） Adhesion strength of PNSA adhesive on porcine skin；（F） Hemolytic activity of the PNSA adhesive；（G） Photographs of the red blood cells incubating with PNSA adhesive， 0.9% NaCl （saline）， and deionized water for 6 h （scale bar， 1 cm）；（H） Confocal fluorescence microscopic images of L-929 cells （mouse fibroblasts） incubating with PNSA adhesive （2 mg/mL） for 3 days （scale bar， 50 μm）

References 41

[1]	YANG G， GONG Z， LUO X， et al. Bonding wood with uncondensed lignins as adhesives［J］. Nature， 2023， 621（7979）： 511-515.
[2]	DENG T， GAO D， SONG X， et al. A natural biological adhesive from snail mucus for wound repair［J］. Nat Commun， 2023， 14（1）： 396.
[3]	NAM S， MOONEY D. Polymeric tissue adhesives［J］. Chem Rev， 2021， 121（18）： 11336-11384.
[4]	XIE X， JIANG Y， YAO X， et al. A solvent-free processed low-temperature tolerant adhesive［J］. Nat Commun， 2024， 15（1）： 5017.
[5]	YAO G， LI F， DONG S. Solvent-free bulk soft material with low-temperature tolerance： transparency， flexibility， stretchability， and adhesion［J］. Chem Eng Sci， 2023， 281（5）： 119164.
[6]	LIU L， WEI M， LI H， et al. Polyvinyl alcohol solvent-free adhesives for biomass bonding via rapid water activation and heat treatment［J］. Green Chem， 2024， 26（24）： 11873-11884.
[7]	YIN L， CHOLEWINSKI A， ZHAO B. Solvent-free urethane-based prepolymer as a versatile underwater adhesive material［J］. Chem Eng J， 2024， 481： 148487.
[8]	WU S， CAI C， LI F， et al. Deep eutectic supramolecular polymers： bulk supramolecular materials［J］. Angew Chem Int Ed， 2020， 59（29）： 11871-11875.
[9]	LI W， BOUZIDI L， NARINE S. Current research and development status and prospect of hot-melt adhesives： a review［J］. Ind Eng Chem Res， 2008， 47（20）： 7524-7532.
[10]	MARQUE E A S， DA SLIVA L F M， BANEA M D， et al. Adhesive joints for low- and high-temperature use： an overview［J］. The J Adhesion， 2015， 91（7）： 556-585.
[11]	BEHNOOD A， MODIRI G. Morphology， rheology， and physical properties of polymer-modified asphalt binders［J］. Eur Polym J， 2019， 112： 766-791.
[12]	PARK S， JU H， PARK S， et al. New possibilities in polymer binder jetting additive manufacturing via infiltration and warm isostatic pressing［J］. Mater Des， 2023， 231： 112045.
[13]	ZHANG J， WANG W， ZHANG Y， et al. Small-molecule ionic liquid-based adhesive with strong room-temperature adhesion promoted by electrostatic interaction［J］. Nat Commun， 2022， 13（1）： 5214.
[14]	LIANG Y， WANG K， LI J， et al. Low-molecular-weight supramolecular adhesives based on non-covalent self-assembly of a small molecular gelator［J］. Mater Horiz， 2022， 9（6）： 1700.
[15]	WANG Y， LIU G， ZHAO J， et al. Mechanically interlocked ［an］ daisy chain adhesives with simultaneously enhanced interfacial adhesion and cohesion［J］. Angew Chem Int Ed， 2024， 63（42）： e202409705.
[16]	SUN P， LI Y， QIN B， et al. Super strong and multi-reusable supramolecular epoxy hot melt adhesives［J］. ACS Mater Lett， 2021， 3（7）： 1003-1009.
[17]	BEDNARCZYK P， MOZELEWSKA K， CZECH Z. Influence of the UV crosslinking method on the properties of acrylic adhesive［J］. Int J Adhes， 2020， 102： 102652.
[18]	ZHANG Q， DENG Y， SHI C， et al. Dual closed-loop chemical recycling of synthetic polymers by intrinsically reconfigurable poly（disulfides）［J］. Matter， 2021， 4（4）： 1352-1364.
[19]	MU C， DU Z， LI W. Taming of heteropoly acids into adhesive electrodes using amino acids for the development of flexible two-dimensional supercapacitors［J］. Polyoxometalates， 2024， 3（3）： 9140062.
[20]	XU J， LI X， LI J， et al. Wet and functional adhesives from one-step aqueous self-assembly of natural amino acids and polyoxometalates［J］. Angew Chem Int Ed， 2017， 56（30）： 8731 -8735.
[21]	LI X， DU Z， SONG Z， et al. Bringing heteropolyacid based underwater adhesive as printable cathode coating for self-powered electrochromic aqueous batteries［J］. Adv Funct Mater， 2018， 28（23）： 1800599.
[22]	HU Y， LIANG P， WANG Z， et al. Developing amino acid-citric acid-based deep eutectic solvent for food applications： preparation， characterization， antibacterial activity， biosafety， and formation mechanism exploration［J］. Sustainable Chem Pharm， 2023， 36： 101317.
[23]	XIE X， MENG F， ZHANG Z， et al. Self-assembled peptide-based nanoblocks for drug delivery［J］. New J Chem， 2023， 47（40）： 18721-18728.
[24]	CHEN C， YANG X， LI S， et al. Tannic acid-thioctic acid hydrogel： a novel injectable supramolecular adhesive gel for wound healing［J］. Green Chem， 2021， 23（4）： 1794-1804.
[25]	XIE X， XU X， JIANG Y. Hydrogen-bonding interaction-driven catechin assembly into solvent-free supramolecular adhesive with antidrying and antifreezing properties［J］. ACS Appl Polym Mater， 2022， 4（6）： 4319-4328.
[26]	解晓明，张嘉琦. 氢键作用驱动原花青素构筑水基抗菌黏合剂［J］. 应用化学， 2022， 39（10）： 1533-1542
	XIE X M， ZHANG J Q. Hydrogen bond interaction driven procyanidine assembly into underwater adhesive with antibacterial activity［J］. Chin J Appl Chem， 2022， 39（10）： 1533-1542.
[27]	LAI J， HUANG S， WU S， et al. Adhesion behaviour of bulk supramolecular polymers via pillar［5］arene-based molecular recognition［J］. Chem Commun， 2021， 57（98）： 13317-13320.
[28]	MA C， SUN J， LI B， et al. Ultra-strong bio-glue from genetically engineered polypeptides［J］. Nat Commun， 2021， 12（1）： 3613.
[29]	WANG Z， GU X， LI B， et al. Molecularly engineered protein glues with superior adhesion performance［J］. Adv Mater， 2022， 34（41）： 2204590.
[30]	CHEN S， SHEN B， ZHANG F， et al. Mussel-inspired graphene film with enhanced durability as a macroscale solid lubricant［J］. ACS Appl Mater Interfaces， 2019， 11（34）： 31386-31392.
[31]	LI J， EJIMA H， YOSHIE N. Seawater-assisted self-healing of catechol polymers via hydrogen bonding and coordination interactions［J］. ACS Appl Mater Interfaces， 2016， 8（29）： 19047-19053.
[32]	DENG X， TANG J， GUAN W， et al. Strong dynamic interfacial adhesion by polymeric ionic liquids under extreme conditions［J］. ACS Nano， 2022， 16（4）： 5303-5315.
[33]	LIU X， MA Z， NIE J， et al. Exploiting redox-complementary peptide/polyoxometalate coacervates for spontaneously curing into antimicrobial adhesives［J］. Biomacromolecules， 2022， 23（3）： 1009-1019.
[34]	WAMG X， LIU X， MA Z， et al. Photochromic and photothermal hydrogels derived from natural amino acids and heteropoly acids［J］. Soft Matter， 2021， 17（44）： 10140-10148.
[35]	CHEM J， DONG Z， LI M， et al. Ultra-strong and proton conductive aqua-based adhesives from facile blending of polyvinyl alcohol and tungsten oxide clusters［J］. Adv Funct Mater， 2022， 32（33）： 2111892.
[36]	GUO H， ZENG M， LI X， et al. Multifunctional enhancement of proton-conductive， stretchable， and adhesive performance in hybrid polymer electrolytes by polyoxometalate nanoclusters［J］. ACS Appl Mater Interfaces， 2021， 13（25）： 30039-30050.
[37]	SALIHU R， ABD RAZAK S I， AHMAD N， et al. Citric acid： a green cross-linker of biomaterials for biomedical applications［J］. Eur Polym J， 2021， 146， 110271.
[38]	PRESTI M， RIZZO G， FARINOLA G， et al. Bioinspired biomaterial composite for all-water-based high-performance adhesives［J］. Adv Sci， 2021， 8（16）： 2004786.
[39]	LIU X， JIANG Q， YIN Y， et al. Phe-phe-based macroscopic supramolecular hydrogel construction strategies and biomedical applications［J］. Chem Bio Eng， 2024， 1（8）： 664-677.
[40]	KE X， TANG S， DONG Z， et al. An instant， repeatable and universal supramolecular adhesive based on natural small molecules for dry/wet environments［J］. Chem Eng J， 2022， 442（15）： 136206.
[41]	MA Z， LIU X， NIE J， et al. Nano-antimicrobial peptides based on constitutional isomerism-dictated self-assembly［J］. Biomacromolecules， 2022， 23（3）： 1302-1313.

Preparation and Characterization of Solvent-Free Adhesive Based on Phenylalanine

RichHTML

PDF

Supplement

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 6

References 41

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Wen-Qiang MAO, Jia-Peng LI, Dong-Dong WANG, Yan-Xiong PAN, Xiang-Ling JI, Wei JIANG. Preparation and Properties of Chlorinated Poly（Propylene Carbonate）/ Poly（Butylene Succinate） Blends Modified with Epoxy Chain Extender ADR-4468 [J]. Chinese Journal of Applied Chemistry, 2025, 42(2): 201-211.
[2]	Jia-Hui LIU, Bai-Chao AN, Qiu-Yan YAN, Shi-Fang LUAN. Preparation and Properties of Mussel-Inspired Antibacterial Bone Adhesive [J]. Chinese Journal of Applied Chemistry, 2023, 40(9): 1258-1266.
[3]	Jia-Cheng ZHOU, Dong-Dong WANG, Yun-Bao GAO, Jing JIN, Wei JIANG. Rheological Properties and Bonding Properties of Modified Poly（Propylene Carbonate） Pressure-sensitive Adhesive [J]. Chinese Journal of Applied Chemistry, 2023, 40(6): 871-878.
[4]	Bi-Ru SHI, Hao-Hao WU, Hao-Pu XIE, Xin-Xin TIAN, Ying-Lu SUN, Xiang-Dong LIU, Yu-Ming YANG. Preparation and Properties of Self-healing Polyurethane Adhesives with Diels-Alder Bonds [J]. Chinese Journal of Applied Chemistry, 2023, 40(2): 277-287.
[5]	Feng-Shuo LIU, Qian DONG, Zhong-Fu ZHAO, Wei LIU, Chun-Qing ZHANG. Structure and Performance Modulation of Self‑Adhesive SIS/C5 Electrospun Membranes for Transdermal Drug Delivery [J]. Chinese Journal of Applied Chemistry, 2022, 39(10): 1523-1532.
[6]	Xiao-Ming XIE, Jia-Qi ZHANG. Hydrogen Bond Interaction Driven Procyanidine Assembly into Underwater Adhesive with Antibacterial Activity [J]. Chinese Journal of Applied Chemistry, 2022, 39(10): 1533-1542.
[7]	WU Zhi-Qiang, HAN Xin-Ning, LIU Yang, WANG Gang, ZHAN Hai-Juan, LIU Wan-Yi. Research Progress on Synthesis of Bis(indolyl)methanes under Aqueous or Solvent-free Catalysis [J]. Chinese Journal of Applied Chemistry, 2021, 38(8): 881-896.
[8]	XU Bing, WU Zhongkui, MIAO Linhui, WANG Zhenkun, DAI Siyu, ZHU Zhe. Properties of Acrylate Pressure Sensitive Adhesive [J]. Chinese Journal of Applied Chemistry, 2020, 37(7): 778-784.
[9]	SUN Liping, XIA Ran. Synthesis of α-Adenine Arabinoside under Solvent-and Catalyst-Free Conditions [J]. Chinese Journal of Applied Chemistry, 2019, 36(3): 300-305.
[10]	WANG Wenxu,HUANG Bingyu,TAN Licheng,HAN Jihui,CHEN Lie,XU Haitao,CHEN Yiwang. Research Progress of Addition Type Liquid Silicone Rubber [J]. Chinese Journal of Applied Chemistry, 2018, 35(9): 1005-1012.
[11]	TANG Zuwu,LU Shengchang,LIN Xinxing,WU Hui,HUANG Liulian,CHEN Lihui. Research Progress on Catechol-Containing Polymers [J]. Chinese Journal of Applied Chemistry, 2018, 35(12): 1399-1410.
[12]	LIU Jianjian, CHENG Hui, LIN Faquan, LUO Xuan, WANG Lisheng, LIN Cuiwu. One-pot Synthesis of L-Phenylalanine Derivatives and Their Anti/Pro-coagulational Properties [J]. Chinese Journal of Applied Chemistry, 2017, 34(2): 139-145.
[13]	XU Zhaohui,LIU Deyong,TU Yuanhong. Efficient Solvent-free Synthesis of Spiro Heterobicyclic Derivatives with Boric Acid as Catalyst [J]. Chinese Journal of Applied Chemistry, 2015, 32(9): 999-1004.
[14]	XU Zhaohui. SnO Catalyzed Solvent-Free Synthesis of Dimethyl 2-[(Indol-3-yl)-methyl]malonate Derivatives [J]. Chinese Journal of Applied Chemistry, 2015, 32(7): 759-764.
[15]	ZHAO Zhouxing. One-pot Synthesis of Aroyl Cyanides Under Solvent-free and Catalyst-free Conditions [J]. Chinese Journal of Applied Chemistry, 2014, 31(08): 943-946.