Sains Malaysiana 55(2)(2026): 257-270

http://doi.org/10.17576/jsm-2026-5502-06

 

Quaternized Ionic Poly(2-(dimethylamino)ethyl methacrylate) Exhibiting Chain Length and Amphiphilicity Dependent Thermal and Enzymatic Degradation

(Poli(2-(dimetilamino)etil metakrilat) Ion Terkuaternisasi yang Menunjukkan Degradasi Terma dan Enzim Bergantung pada Panjang Rantai dan Amfifilisiti)

 

NORAFIZAH AHMAD SHAYUTI1, AINA AQILA ARMAN ALIM2,
SITI FATAHIYAH MOHAMAD5, NORAZIAH MOHAMAD ZIN3, NUR HAZLIN HAZRIN-CHONG4 & RUSLI DAIK1,*

1Department of Chemical Sciences, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia
2Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia
3Center of Diagnostics, Therapeutics & Investigations, Faculty of Health Sciences, Universiti Kebangsaan Malaysia, Jalan Raja Muda Abdul Aziz, 50300 Kuala Lumpur, Malaysia
4Department of Biological Sciences and Biotechnology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia 
5Radiation Processing and Technology Division, Malaysia Nuclear Agency, 43000 Bangi, Selangor, Malaysia

Received: 25 September 2025/Accepted: 4 February 2026

 

Abstract

Amphiphilic polymers derived from quaternized 2-(N, N-dimethylamino)ethyl methacrylate (DMAEMA) were synthesized via radical polymerization to achieve a balance between hydrophilic and hydrophobic segments for antibacterial applications. Quaternization with bromoalkane compounds introduced alkyl side chains, thereby enhancing amphiphilicity and enabling tunable physicochemical properties. The polymers obtained exhibited molecular weights ranging from 1600 to 50600 Da, providing a wide distribution suitable for correlating chain length with performance characteristics. Thermogravimetric analysis confirmed that all samples maintained stability up to 400 °C, indicating robust thermal resistance. Enzymatic degradation studies demonstrated time-dependent surface erosion, with pore formation observed on polymer surfaces beginning at day 5, accompanied by progressive weight reduction. Structural and morphological analyses were performed using Fourier-transform infrared spectroscopy (FTIR), which verified successful functional group modification; meanwhile, scanning electron microscopy (SEM) showed distinct topographical changes associated with amphiphilic behavior and biodegradability of the polymer. Collectively, the findings highlight the successful design of amphiphilic DMAEMA-based polymers with promising thermal stability, controlled degradability, and structural versatility, underscoring their potential utility in antibacterial material development.

Keywords: Amphiphilic polymer; biodegradability; thermal behavior

 

Abstrak

Polimer amfifilik yang diperoleh daripada kuaternisasi 2-(N, N-dimethylamino)etil metakrilat (DMAEMA) telah disintesis melalui pempolimeran radikal yang bertujuan untuk mencapai keseimbangan antara segmen hidrofilik dan hidrofobik sebagai aplikasi antibakteria. Kuaternisasi dengan sebatian bromoalkana dengan penambahan rantai sisi alkil dapat meningkatkan polimer amfifilik dan membolehkan sifat fizikokimia yang boleh dilaras. Polimer yang diperoleh menunjukkan berat molekul antara 1600 hingga 50600 Da, memberikan taburan luas yang sesuai untuk mengaitkan panjang rantai dengan ciri prestasi. Analisis termogravimetri mengesahkan bahawa semua sampel mengekalkan kestabilan sehingga suhu 400 °C, menunjukkan rintangan haba yang baik. Kajian degradasi berenzim menunjukkan hakisan permukaan polimer, dengan pembentukan liang diperhatikan pada permukaan polimer bermula pada hari ke-5, disertai dengan pengurangan jisim polimer yang progresif. Analisis struktur dan morfologi telah dilakukan menggunakan spektroskopi inframerah transformasi Fourier (FTIR) yang mengesahkan pengubahsuaian kumpulan berfungsi telah berjaya manakala mikroskop elektron pengimbasan (SEM) menunjukkan perubahan topografi berbeza yang dikaitkan dengan sifat amfifilik dan kebolehuraian polimer. Secara keseluruhan, kajian ini berjaya mereka bentuk polimer berasaskan DMAEMA dengan sifat amfifilik dengan kestabilan haba yang baik, penguraian terkawal dan kepelbagaian struktur, menggariskan potensi utilitinya dalam pembangunan bahan antibakteria.

Kata kunci: Kebolehuraian; polimer amfifilik; tingkah laku haba

REFERENCES

Abdelaziz, A.I.E., Elsaeed, S.M., Zaki, E.G., Aboaly, M.M., Abdel-Raouf, M.E.S. & Al-Sabagh, A.M. 2021. Preparation and characterization of a new family of bio-interpenetrating network hydrogel based on a green method. Egyptian Journal of Chemistry 64(12): 7451-7464.

Acik, G. 2020. Preparation of antimicrobial and biodegradable hybrid soybean oil and poly (ʟ -lactide) based polymer with quaternized ammonium salt. Polymer Degradation and Stability 181: 109317.

Aina Aqila Arman Alim, Siti Salwa Mohammad Shirajuddin & Farah Hannan Anuar. 2022. A review of nonbiodegradable and biodegradable composites for food packaging application. Journal of Chemistry 2022: Article ID. 7670819.

Aina Aqila Arman Alim, Azizah Baharum, Siti Salwa Mohammad Shirajuddin & Farah Hannan Anuar. 2023. Blending of low-density polyethylene and poly(butylene succinate) (LDPE/PBS) with polyethylene–graft–maleic anhydride (PE–g–MA) as a compatibilizer on the phase morphology, mechanical and thermal properties. Polymers 15(2): 261.

Albayati, S.H., Masomian, M., Ishak, S.N.H., Ali, M.S.B.M., Thean, A.L., Shariff, F.B.M., Noor, N.D.B.M. & Rahman, R.N.Z.R.A. 2020. Main structural targets for engineering lipase substrate specificity. Catalysts 10(7): 747.

Ali, M., Garg, A., Srivastava, A. & Arora, P.K. 2025. The role of antimicrobial peptides in overcoming antibiotic resistance. Microbe (Netherlands) 7: 100337.

Bednarz, S., Błaszczyk, A., Błazejewska, D. & Bogdał, D. 2014. Free-radical polymerization of itaconic acid in the presence of choline salts: Mechanism of persulfate decomposition. Catalysis Today 257: 297-304.

Bixenmann, L., Stickdorn, J. & Nuhn, L. 2020. Amphiphilic poly(esteracetal)s as dual pH-and enzyme-responsive micellar immunodrug delivery systems. Polymer Chemistry 11(13): 2441-2456.

Bomfim, J.A.S., Mincheva, R., Beigbeder, A., Persenaire, O. & Dubois, P. 2009. (Quaternized/betainized) amino-based amphiphilic block copolymers: Quantitative composition characterization via FTIR and thermogravimetry. E-Polymers 9(1): 035.

Casanova, M., Olleik, H., Hdiouech, S., Roblin, C., Cavalier, J.F., Point, V., Jeannot, K., Caron, B., Perrier, J., Charriau, S., Lafond, M., Guillaneuf, Y., Canaan, S., Lefay, C. & Maresca, M. 2023. Evaluation of the efficiency of random and diblock methacrylate-based amphiphilic cationic polymers against major bacterial pathogens associated with cystic fibrosis. Antibiotics 12(1): 120.

Cazotti, J.C., Fritz, A.T., Garcia-Valdez, O., Smeets, N.M.B., Dubé, M.A. & Cunningham, M.F. 2020. Graft modification of starch nanoparticles with pH-responsive polymers via nitroxide-mediated polymerization. Journal of Polymer Science 58(16): 2211-2220.

Chandra, P., Enespa, Singh, R. & Arora, P.K. 2020. Microbial lipases and their industrial applications: A comprehensive review. Microbial Cell Factories 19(1): 169.

Chaudhary, A.K. & Vijayakumar, R.P. 2020. Studies on biological degradation of polystyrene by pure fungal cultures. Environment, Development and Sustainability 22(5): 4495-4508.

Chen, J., Wu, Z., Yang, L., Zhang, Q., Sun, J., Shi, Y., Xia, L. & Kaetsu, I. 2007. Grafting copolymerization of N,N-dimethyacrylaminoethylmethacrylate (DMAEMA) onto preirradiated polypropylene films. Radiation Physics and Chemistry 76(8-9): 1367-1370.

Cook-Chennault, K., Anaokar, S., Medina Vázquez, A.M. & Chennault, M. 2024. Influence of high strain dynamic loading on HEMA–DMAEMA hydrogel storage modulus and time dependence. Polymers 16(13): 1797.

Dalhatu, S.N., Modu, K.A., Mahmoud, A.A., Adamu, H.M. & Murtala, R. 2021. Ultrasonic assisted synthesis and characterization of chitosan graf with 2- (dimethylaminoethylmethacrylate) (DMAEMA) Cs-G-PDMAEMA. Journal of Physical Sciences 3(1): 1-10.

Danielsen, S.P.O., Beech, H.K., Wang, S., El-Zaatari, B.M., Wang, X., Sapir, L., Ouchi, T., Wang, Z., Johnson, P.N., Hu, Y., Lundberg, D.J., Stoychev, G., Craig, S.L., Johnson, J.A., Kalow, J.A., Olsen, B.D. & Rubinstein, M. 2021. Molecular characterization of polymer networks. Chemical Reviews 121(8): 5042-5092.

Fu, X., Zhang, Y., Jia, X., Wang, Y. & Chen, T. 2022. Research progress on typical quaternary ammonium salt polymers. Molecules 27(4): 1267.

Gaytán, I., Burelo, M. & Loza-Tavera, H. 2021. Current status on the biodegradability of acrylic polymers: Microorganisms, enzymes and metabolic pathways involved. Applied Microbiology and Biotechnology 105(3): 991-1006.

Guo, H., Ma, L., Yan, C. & Ma, X. 2021. A study on the preparation of polycation gel polymer electrolyte for supercapacitors. RSC Advances 11(40): 24995-25003.

Im, D., Gavande, V., Lee, H.Y. & Lee, W.K. 2023. Influence of molecular weight on the enzymatic degradation of PLA isomer blends by a Langmuir system. Materials 16(14): 5087.

Kalita, N.K., Bhasney, S.M., Kalamdhad, A. & Katiyar, V. 2020. Biodegradable kinetics and behavior of bio-based polyblends under simulated aerobic composting conditions. Journal of Environmental Management 261: 110211.

Kang, Y., Zhang, Z., Li, S., Wang, C., Chang, T., Hao, Y. & Liu, J. 2026. Engineered alkyl-chain functionalized hyper-crosslinked polymers as robust lipase hosts for synthesis fatty esters in aqueous solution. Fuel 405: 136769.

Kong, D.C., Yang, M.H., Zhang, X.S., Du, Z.C., Fu, Q., Gao, X.Q. & Gong, J.W. 2021. Control of polymer properties by entanglement: A review. Macromolecular Materials and Engineering 306(12): 2100536.

Kong, Z., Wu, X., Wei, J., Zhang, H. & Cui, L. 2016. Preparation and characterization of hydrophilicity fibers based on 2-(dimethylamino)ethyl methacrylate grafted polypropylene by UV- irradiation for removal of Cr(VI) and as(V). Journal of Polymer Research 23: 1-9.

Koufakis, E., Manouras, T., Anastasiadis, S.H. & Vamvakaki, M. 2020. Film properties and antimicrobial efficacy of quaternized PDMAEMA brushes: Short vs long alkyl chain length. Langmuir 36(13): 3482-3493.

Koutsougera, M.F., Adamopoulou, S., Druvari, D., Vlamis-Gardikas, A., Iatridi, Z. & Bokias, G. 2025. Multifunctional amphiphilic biocidal copolymers based on N-(3-(Dimethylamino)propyl)methacrylamide Exhibiting pH-, thermo-, and CO2-sensitivity. Polymers 17(14): 1896.

Kupczak, M., Mielanczyk, A. & Neugebauer, D. 2021a. The influence of polymer composition on the hydrolytic and enzymatic degradation of polyesters and their block copolymers with PDMAEMA. Materials 14(13): 3636.

Kupczak, M., Mielańczyk, A. & Neugebauer, D. 2021b. PDMAEMA/polyester miktopolymers: Synthesis via in-out approach, physicochemical characterization and enzymatic degradation. Materials 14(5): 1277.

Leggieri, M.R.T., Kaldéus, T., Johansson, M. & Malmström, E. 2023. PDMAEMA from α to ω chain ends: Tools for elucidating the structure of poly(2-(dimethylamino)ethyl methacrylate). Polymer Chemistry 14(11): 1241-1253.

Li, M., Jin, E., Qiao, Z. & Zhao, R. 2018. Effects of alkyl chain length of aliphatic dicarboxylic ester on degradation properties of aliphatic-aromatic water-soluble copolyesters for warp sizing. Fibers and Polymers 19(3): 538-547.

Liu, G.L. & Kazarian, S.G. 2022. Recent advances and applications to cultural heritage using ATR-FTIR spectroscopy and ATR-FTIR spectroscopic imaging. Analyst 147(9): 1777-1797.

Lu, G., Wu, D. & Fu, R. 2007. Studies on the synthesis and antibacterial activities of polymeric quaternary ammonium salts from dimethylaminoethyl methacrylate. Reactive and Functional Polymers 67(4): 355-366.

Luo, X., Ye, X., Ding, L., Zhu, W., Yi, P., Zhao, Z., Gao, H., Shu, Z., Li, S., Sang, M., Wang, J., Zhong, W. & Chen, Z. 2021. Fine-tuning of alkaline residues on the hydrophilic face provides a non-toxic cationic α-helical antimicrobial peptide against antibiotic-resistant ESKAPE pathogens. Frontiers in Microbiology 12: 684591.

Manouras, T., Platania, V., Georgopoulou, A., Chatzinikolaidou, M. & Vamvakaki, M. 2021. Responsive quaternized PDMAEMA copolymers with antimicrobial action. Polymers 13(18): 3051.

Mathew, M.E., Ahmad, I., Thomas, S., Daik, R. & Kassim, M. 2018. Synthesis and characterization of poly (benzyl trimethyl ammonium chloride) ionic polymer. AIP Conference Proceedings. p. 1940.

Mousavi, S.M., Babazadeh, M., Nemati, M., Esʼhaghi, M. & Babazadeh, M. 2024. Fabrication of graphene oxide nanocomposite based on poly(3-hydroxybutyrate)-chitosan as a useful drug carrier. Karaj Branch Journal of Applied Chemical Research 18(1): 41-59.

Mushtaq, S., Ahmad, N.M., Mahmood, A. & Iqbal, M. 2021. Antibacterial amphiphilic copolymers of dimethylamino ethyl methacrylate and methyl methacrylate to control biofilm adhesion for antifouling applications. Polymers 13(2): 216.

Neelamegan, H., Yang, D.K., Lee, G.J., Anandan, S., Sorrentino, A. & Wu, J.J. 2020. Synthesis of magnetite-based polymers as mercury and anion sensors using single electron transfer-living radical polymerization. ACS Omega 5(13): 7201-7210.

Okten, N.S., Canakci, C.C. & Orakdogen, N. 2019. Hertzian elasticity and triggered swelling kinetics of poly(amino ester)-based gel beads with controlled hydrophilicity and functionality: A mild and convenient synthesis via dropwise freezing into cryogenic liquid. European Polymer Journal 114(February): 176-188.

Omer, A.M., Tamer, T.M., Khalifa, R.E., Eltaweil, A.S., Agwa, M.M., Sabra, S., Abd-Elmonem, M.S., Mohy-Eldin, M.S. & Ziora, Z.M. 2021. Formulation and antibacterial activity evaluation of quaternized aminochitosan membrane for wound dressing applications. Polymers 13(15): 2428.

Park, S., Thanakkasaranee, S., Shin, H., Lee, Y., Tak, G. & Seo, J. 2021. PET/bio-based terpolyester blends with high dimensional thermal stability. Polymers 13(5): 728.

Rahman, M.S., Brown, J., Murphy, R., Carnes, S., Carey, B., Averick, S., Konkolewicz, D. & Page, R.C. 2021. Polymer modification of lipases, substrate interactions, and potential inhibition. Biomacromolecules 22(2): 309-318.

Rauschkolb, J.C., Ribeiro, B.C., Feiden, T., Fischer, B., Weschenfelder, T.A., Cansian, R.L. & Junges, A. 2022. Parameter estimation of Mark-Houwink equation of polyethylene glycol (PEG) using molecular mass and intrinsic viscosity in water. Biointerface Research in Applied Chemistry 12(2): 1778-1790.

Ren, N., Yu, C. & Zhu, X. 2021. Topological effect on macromonomer polymerization. Macromolecules 54(13): 6101-6108.

Rodríguez-Contreras, A., Calafell-Monfort, M. & Marqués-Calvo, M.S. 2012. Enzymatic degradation of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) by commercial lipases. Polymer Degradation and Stability 97(4): 597-604.

Rosato, A., Romano, A., Totaro, G., Celli, A., Fava, F., Zanaroli, G. & Sisti, L. 2022. Enzymatic degradation of the most common aliphatic bio-polyesters and evaluation of the mechanisms involved: An extended study. Polymers 14(9): 1850.

Santoro, O. & Izzo, L. 2024. Antimicrobial polymer surfaces containing Quaternary Ammonium Centers (QACs): Synthesis and mechanism of action. International Journal of Molecular Sciences 25(14): 7587.

Slor, G., Olea, A.R., Pujals, S., Tigrine, A., De La Rosa, V.R., Hoogenboom, R., Albertazzi, L. & Amir, R.J. 2021. Judging enzyme-responsive micelles by their covers: Direct comparison of dendritic amphiphiles with different hydrophilic blocks. Biomacromolecules 22(3): 1197-1210.

Soykan, C. & Tüfekçi, B. 2025. Antibacterial amphiphilic composites of poly(diethylaminoethyl methacrylate-co-ethyl methacrylate)/polyindole controlling biofilm adhesion for antifouling investigations. El-Cezeri Journal of Science and Engineering 12(2): 167-175.

Stawski, D. 2023. Poly(N,N-dimethylaminoethyl methacrylate) as a bioactive polyelectrolyte - production and properties. Royal Society Open Science 10(9): 230188.

Tarmizi, Z.I.A., Ali, R.R., Nasef, M.M., Radzi, A.M.M., Akim, A.M., Eshak, Z., Noor, S.M., Shafie, N.F.A. & Faizo, S.M. 2023. Thermal and degradation analysis of electrospun polyurethane prepared using radiation induced grafting. Journal of Advanced Research in Fluid Mechanics and Thermal Sciences 108(2): 110-121.

Wei, X.F., Capezza, A.J., Cui, Y., Li, L., Hakonen, A., Liu, B. & Hedenqvist, M.S. 2022. Millions of microplastics released from a biodegradable polymer during biodegradation/enzymatic hydrolysis. Water Research 211: 118068.

Zografos, A., Lynd, N.A., Bates, F.S. & Hillmyer, M.A. 2021. Impact of macromonomer molar mass and feed composition on branch distributions in model graft copolymerizations. ACS Macro Letters 10(12): 1622-1628.

 

 *Corresponding author; email: rusli.daik@ukm.edu.my

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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