{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T01:20:18Z","timestamp":1760059218494,"version":"build-2065373602"},"reference-count":35,"publisher":"MDPI AG","issue":"11","license":[{"start":{"date-parts":[[2025,6,1]],"date-time":"2025-06-01T00:00:00Z","timestamp":1748736000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"ICAT, Hokkaido University"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>Network polymers with \u03b2-cyclodextrin moieties were prepared by nucleophilic substitution reactions between polyamines, linear polyethyleneimine (LPEI), polyallylamine (PAA), (\u03b5-poly-L-lysine) (EPL), and monochlorotriazinyl-\u03b2-cyclodextrin (MCTCD) in methanol\/water mixed solvent or water. The reactions under conditions of high material concentration (30 wt%) and a feed ratio of [MCT]\/[NH] = 0.5 (mol\/mol) successfully yield porous polymers via reaction-induced phase separation. The molecular structure of the polyamines and reaction conditions strongly affected the morphology of the resulting porous polymers. The porous polymers were composed of connected particles, gathered (slightly connected) particles, and\/or disordered bulky structures, with sizes of 10\u22129 m\u201310\u22128 m. An increase in the molecular weight of LPEI and PAA and the feed molar ratio of [MCT]\/[NH] tended to decrease the particle size. Young\u2019s moduli of the LPEI-MCTCD and PAA-MCTCD porous polymers increased with an increase in bulk density, which was derived from small particle sizes. The wide particle size distribution and disordered structure caused collapse by the compression under 50 N of pressure. An LPEI-MCTCD adsorbed methyl orange, methylene blue, and phenolphthalein through ionic interactions, \u03c0\u2013\u03c0 interaction, and\/or \u03b2-cyclodextrin inclusion.<\/jats:p>","DOI":"10.3390\/ma18112588","type":"journal-article","created":{"date-parts":[[2025,6,2]],"date-time":"2025-06-02T08:34:13Z","timestamp":1748853253000},"page":"2588","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Synthesis of Porous Polymers by Nucleophilic Substitution Reaction of Polyamines and Monochlorotriazinyl-\u03b2-Cyclodextrin and Application to Dye Adsorption"],"prefix":"10.3390","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0695-5011","authenticated-orcid":false,"given":"Naofumi","family":"Naga","sequence":"first","affiliation":[{"name":"College of Engineering, Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo 135-8548, Japan"},{"name":"Graduate School of Science & Engineering, Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo 135-8548, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Risa","family":"Hiura","sequence":"additional","affiliation":[{"name":"Graduate School of Science & Engineering, Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo 135-8548, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7843-4146","authenticated-orcid":false,"given":"Tamaki","family":"Nakano","sequence":"additional","affiliation":[{"name":"Institute for Catalysis and Graduate School of Chemical Sciences and Engineering, Hokkaido University, N 21, W 10, Kita-ku, Sapporo 001-0021, Japan"},{"name":"Integrated Research Consortium on Chemical Sciences, Institute for Catalysis, Hokkaido University, N 21, W 10, Kita-ku, Sapporo 001-0021, Japan"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2025,6,1]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Steuerle, U., and Feuerhake, R. (2006). Aziridines. Ullmann\u2019s Encyclopedia of Industrial Chemistry, Wiley-VCH.","DOI":"10.1002\/14356007.a03_239.pub2"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"586","DOI":"10.3183\/npprj-2000-15-05-p586-597","article-title":"Polyelectrolyte adsorption onto cellulose fibers\u2014A review","volume":"15","author":"Wagberg","year":"2006","journal-title":"Nord. Pulp Pap. Res. J."},{"key":"ref_3","unstructured":"Madkour, T.M. (1999). Polymer Data Handbook, Oxford University Press, Inc."},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Vancha, A.R., Govindaraju, S., Parsa, K.V.L., Jasti, M., Gonzalez-Garcia, M., and Ballestero, R.P. (2004). Use of polyethyleneimine polymer in cell culture as attachment factor and lipofection enhancer. BMC Biotechnol., 4.","DOI":"10.1186\/1472-6750-4-23"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1523","DOI":"10.1016\/j.addr.2006.09.008","article-title":"Molecular hurdles in polyfectin design and mechanistic background to polycation induced cytotoxicity","volume":"58","author":"Hunter","year":"2006","journal-title":"Adv. Drug Deliv. Rev."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"990","DOI":"10.1016\/j.ymthe.2005.02.010","article-title":"A two-stage poly(ethylenimine)-mediated cytotoxicity: Implications for gene transfer\/therapy","volume":"11","author":"Moghimi","year":"2005","journal-title":"Mol. Ther."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"7297","DOI":"10.1073\/pnas.92.16.7297","article-title":"A versatile vector for gene and oligonucleotide transfer into cells in culture and in vivo: Polyethyleneimine","volume":"92","author":"Boussif","year":"1995","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"269","DOI":"10.1002\/1521-2254(200007\/08)2:4<269::AID-JGM112>3.0.CO;2-F","article-title":"In vivo gene delivery to the lung using polyethylenimine and fractured polyamidoamine dendrimers","volume":"2","author":"Rudolph","year":"2000","journal-title":"J. Gene Med."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"657","DOI":"10.1002\/jgm.696","article-title":"Exploring polyethylenimine-mediated DNA transfection and proton sponge hypothesis","volume":"7","author":"Akinc","year":"2004","journal-title":"J. Gene Med."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"3193","DOI":"10.1099\/00221287-143-10-3193","article-title":"Polyethyleneimine is an effective permeabilizer of Gram-negative bacteria","volume":"143","author":"Helander","year":"1997","journal-title":"Microbiology"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"515","DOI":"10.1070\/RC1965v034n07ABEH001499","article-title":"Advances in the Chemistry of Polyethyleneimine (Polyaziridine)","volume":"34","author":"Zhuk","year":"1965","journal-title":"Russ. Chem. Rev."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"714","DOI":"10.1080\/10837450.2022.2107014","article-title":"An overview of polyallylamine applications in gene delivery","volume":"27","author":"Gholami","year":"2022","journal-title":"Pharm. Dev. Tech."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"529","DOI":"10.1021\/acsabm.2c00845","article-title":"Self-Assembled Oleic Acid-Modified Polyallylamines for Improved siRNA Transfection Efficiency and Lower Cytotoxicity","volume":"6","author":"Salvador","year":"2023","journal-title":"ACS Appl. Bio Mater."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"804","DOI":"10.1039\/D0MA00289E","article-title":"Hybrid poly(allylamine hydrochloride)\u2013graphene oxide microcapsules: Preparation, characterization and application in textiles with controlled release behavior","volume":"1","author":"Zhao","year":"2020","journal-title":"Mater. Adv."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Jurko, L., Bra\u010di\u010d, M., Hribernik, S., Makuc, D., Plavec, J., Jerenec, F., \u017dabkar, S., Gubeljak, N., \u0160tern, A., and Kargl, R. (2021). Succinylation of Polyallylamine: Influence on Biological Efficacy and the Formation of Electrospun Fibers. Polymers, 13.","DOI":"10.3390\/polym13172840"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"2041","DOI":"10.1021\/acsapm.3c02836","article-title":"Amine-Acrylate Michael Addition: A Versatile Platform for Fabrication of Polymer Electrolytes with Varied Cross-Linked Networks","volume":"6","author":"Wang","year":"2024","journal-title":"ACS Appl. Polym. Mater."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"2101955","DOI":"10.1002\/adma.202101955","article-title":"Amine-Acrylate Liquid Single Crystal Elastomers Reinforced by Hydrogen Bonding","volume":"33","author":"Zou","year":"2021","journal-title":"Adv. Mater."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"135","DOI":"10.1002\/pi.6102","article-title":"Network formation by aza-Michael addition of primary amines to vinyl end groups of enzymatically synthesized poly(glycerol adipate)","volume":"70","author":"Alaneed","year":"2021","journal-title":"Polym. Int."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"256","DOI":"10.1016\/j.eurpolymj.2016.09.025","article-title":"Sequential curing of amine-acrylate-methacrylate mixtures based on selective aza-Michael addition followed by radical photopolymerization","volume":"84","author":"Konuray","year":"2016","journal-title":"Eur. Polym. J."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"2745","DOI":"10.1007\/s00289-020-03241-0","article-title":"Synthesis of polymer networks by means of addition reactions of tri-amine and poly(ethylene glycol) diacrylate or diglycidyl ether compounds","volume":"78","author":"Naga","year":"2021","journal-title":"Polym. Bull."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"3925","DOI":"10.1002\/anie.201509864","article-title":"Triazine-Based Sequence-Defined Polymers with Side-Chain Diversity and Backbone\u2013Backbone Interaction Motifs","volume":"55","author":"Grate","year":"2016","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"7","DOI":"10.2494\/photopolymer.37.7","article-title":"Synthesis of Semiaromatic Polyguanamines from Tetraazacalix[2]arene[2]-triazine Dichloride with Aliphatic Diamines","volume":"37","author":"Shibasaki","year":"2024","journal-title":"J. Photopolym. Sci. Technol."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"1190","DOI":"10.1021\/acssuschemeng.2c06621","article-title":"Metal-Free Amine-Anchored Triazine-Based Covalent Organic Polymers for Selective CO2 Adsorption and Conversion to Cyclic Carbonates Under Mild Conditions","volume":"11","author":"Ravi","year":"2023","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"136","DOI":"10.1016\/j.polymdegradstab.2018.12.014","article-title":"Cyclodextrin cross-linked polymer monolith for efficient removal of environmental pollutants by flow-through method","volume":"160","author":"Mizuno","year":"2019","journal-title":"Polym. Degrad. Stab."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"29","DOI":"10.1007\/s10965-025-04254-x","article-title":"Synthesis and morphology control of a tetra-functional epoxy\/polyethylenepolyamine monolithic porous polymers aspiring to selective molecular adsorption","volume":"32","author":"Naga","year":"2025","journal-title":"J. Polym. Res."},{"key":"ref_26","doi-asserted-by":"crossref","unstructured":"Naga, N., Miyazaki, Y., and Nakano, T. (2025). Porous Composite Polymers Composed of Polyethyleneimine and Cyclodextrins: Synthesis and Application as Adsorbents for an Organic Compound. Separations, 12.","DOI":"10.3390\/separations12040094"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"3136","DOI":"10.1021\/la047182l","article-title":"Fibrous Crystalline Hydrogels Formed from Polymers Possessing a Linear Poly(ethyleneimine) Backbone","volume":"21","author":"Yuan","year":"2005","journal-title":"Langmuir"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"51234","DOI":"10.1002\/app.51234","article-title":"Tunable fluorescent and antimicrobial properties of poly(vinyl amine) affected by the acidic or basic hydrolysis of poly(N-vinylformamide)","volume":"138","author":"Sutekin","year":"2021","journal-title":"J. Appl. Polym. Sci."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"2102","DOI":"10.1021\/acsomega.8b02534","article-title":"\u03b2-Cyclodextrin-Functionalized Cellulose Nanocrystals and Their Interactions with Surfactants","volume":"4","author":"Zhang","year":"2019","journal-title":"ACS Omega"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"147","DOI":"10.1002\/pen.760140211","article-title":"A method for estimating both the solubility parameters and molar volumes of liquids","volume":"14","author":"Fedors","year":"1974","journal-title":"Polym. Eng. Sci."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"2301","DOI":"10.1002\/pol.20200268","article-title":"Synthesis and properties of \u03c3-\u03c0 conjugated porous polymers obtained with Mizoroki\u2013Heck reaction of tetra vinyl cyclic siloxane with dibromo fluorene","volume":"58","author":"Naga","year":"2020","journal-title":"J. Polym. Sci."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2411","DOI":"10.1007\/s00289-021-03643-8","article-title":"Synthesis of network polymers by photo-initiated thiol-ene reaction between multi-functional thiol and poly(ethylene glycol) diacrylate","volume":"79","author":"Naga","year":"2022","journal-title":"Polym. Bull."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"127409","DOI":"10.1016\/j.matchemphys.2023.127409","article-title":"Quaternary ammonium ionene porous polymers via Menschutkin reaction of methylated polyethyleneimine and dibromoalkanes","volume":"297","author":"Naga","year":"2023","journal-title":"Mater. Chem. Phys."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"10615","DOI":"10.1021\/acsapm.4c01753","article-title":"Preparation of sulfonate-grafted tetraphenylethylene-based hyper-cross-linked polymers for efficient adsorption of organic dyes in aqueous solutions","volume":"6","author":"Luo","year":"2024","journal-title":"ACS Appl. Polym. Mater."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"108427","DOI":"10.1016\/j.cep.2021.108427","article-title":"Highly efficient removal of methyl orange from aqueous media by amine functional cyclotriphosphazene submicrospheres as reusable column packing material","volume":"165","author":"Onder","year":"2021","journal-title":"Chem. Eng. Process. Process Intensif."}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/18\/11\/2588\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T17:45:26Z","timestamp":1760031926000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/18\/11\/2588"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,6,1]]},"references-count":35,"journal-issue":{"issue":"11","published-online":{"date-parts":[[2025,6]]}},"alternative-id":["ma18112588"],"URL":"https:\/\/doi.org\/10.3390\/ma18112588","relation":{},"ISSN":["1996-1944"],"issn-type":[{"type":"electronic","value":"1996-1944"}],"subject":[],"published":{"date-parts":[[2025,6,1]]}}}