Polymer Chemistry最新文献

{"title":"Gelation-free synthesis of high-molecular-weight hyperbranched aromatic polymers containing silicon by Suzuki–Miyaura polycondensation of tri- or tetra(bromoaryl)silane with arylenediboronate†","authors":"Ryusuke Shimada ,&nbsp;Masato Kubota ,&nbsp;Yoshihiro Ohta ,&nbsp;Tsutomu Yokozawa","doi":"10.1039/d4py01024h","DOIUrl":"10.1039/d4py01024h","url":null,"abstract":"<div><div>Suzuki–Miyaura polycondensation of tri- or tetra(bromoarylsilane) with arylenediboronic acid (ester) in the presence of ^<em>t</em>Bu₃PPd precatalyst was investigated for the synthesis of silicon-containing hyperbranched aromatic polymers by means of simple A₂ + B_<em>x</em> (<em>x</em> = 3, 4) polycondensation without gelation. The key reaction in this polycondensation, successive substitution of with through intramolecular Pd catalyst transfer on the silyl group and π-face of , was investigated by means of model reactions of with a variety of arylboronates in the presence of at room temperature. The Suzuki–Miyaura reaction of tri(bromophenyl)silane , tri(bromofluorenyl)silane , and tetra(bromophenyl)silane with phenylboronic acid and carbazoleboronate yielded exclusively tri- and tetra-substituted products, even though the bromine sites in were present in excess relative to the boronic acid (ester) sites in . The polycondensation of with phenylenediboronate , fluorenylenediboronate , thienylenediboronate , and carbazolylenediboronate afforded high-molecular-weight silicon-containing aromatic hyperbranched polymers without gelation. The use of instead of resulted in the formation of some polymers with low solubility, but the polycondensations of with phenylenediboronic acid having a branched side chain and with yielded the corresponding high-molecular-weight polymers. In the polycondensation of with , afforded a moderate-molecular-weight polymer (<em>M</em>_n = 7610), whereas yielded polymers with <em>M</em>_n = 64 700–80 700. The UV-vis absorption and emission spectra in solution of the silicon-containing hyperbranched polyphenylenes, obtained by the polycondensation of or with , were similar to those of hyperbranched polyphenylene with no silicon (<strong>HBPP</strong>), whereas the fluorescence quantum yields were considerably higher (50–53%) than that of <strong>HBPP</strong> (16%).</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 3","pages":"Pages 368-373"},"PeriodicalIF":4.1,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Symmetric star poly(substituted glycolide) homopolymers and their surface properties†","authors":"Yonca Çolak ,&nbsp;Sema Nur Belen ,&nbsp;Duygu Çetin ,&nbsp;Ugur Cengiz ,&nbsp;Olcay Mert","doi":"10.1039/d4py01229a","DOIUrl":"10.1039/d4py01229a","url":null,"abstract":"<div><div>Well-defined star poly(substituted glycolide) (s-PSG) homopolymers with predetermined lengths and numbers of arms, which are alternatives to polylactides and polyglycolides, may offer great opportunity for the modulation of their physical properties, such as glass transition temperature (<em>T</em>_g), crystallinity, hydrophobicity, and surface characteristics due to their geometric and structural differences. Herein, we report the synthesis of s-PSG homopolymers, including a four-armed symmetrical poly(<span>l</span>-diisopropyl glycolide) (4s-PLDIPG) and poly(<span>l</span>-diisobutyl glycolide) (4s-PLDIBG) from the ring opening polymerization (ROP) of their monomers in the presence of tin(<span>ii</span>) 2-ethylhexanoate [Sn(Oct)₂] as a catalyst and pentaerythritol as an initiator <em>via</em> a core-first approach under melt conditions. 4s-PLDIPG exhibits lower <em>T</em>_g, melting temperature (<em>T</em>_m) and crystallinity % than 4s-PLDIPG (<em>T</em>_g: 33.7 °C <em>vs</em>. 35.9 °C; <em>T</em>_m: 143.9 °C <em>vs</em>. 183.4 °C; <em>X</em>_c: 16.7% <em>vs</em>. 19.1%) due to its lower <em>M</em>_n per arm. 4s-PLDIPG also has a dramatically lower <em>T</em>_m and crystallinity % than its linear counterpart PLDIPG (<em>T</em>_m: 143.9 °C <em>vs</em>. 190.6 °C; <em>X</em>_c: 16.7% <em>vs</em>. 26.7%) due to its short arm length. As the side chain length of s-PSG homopolymers increased, there was a corresponding increase in the water contact angles and surface roughness values of the thin films, while the surface free energy decreased. This correlation between side chain length and surface properties was further validated by SEM and AFM profiles, which confirmed the impact of extended side chains on the polymer's surface characteristics.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 3","pages":"Pages 317-330"},"PeriodicalIF":4.1,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142797569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure–property relationships to direct the dynamic properties of acylsemicarbazide-based materials†","authors":"Stefan J. D. Maessen ,&nbsp;Siebe Lekanne Deprez ,&nbsp;Pascal Vermeeren ,&nbsp;Bart W. L. van den Bersselaar ,&nbsp;Martin Lutz ,&nbsp;Johan P. A. Heuts ,&nbsp;Célia Fonseca Guerra ,&nbsp;Anja R. A. Palmans","doi":"10.1039/d4py01296h","DOIUrl":"10.1039/d4py01296h","url":null,"abstract":"<div><div>Secondary interactions, such as hydrogen bonding or phase separation, can enhance the stability of dynamic covalent materials without compromising on desired dynamic properties. Here, we investigate the combination of multiple secondary interactions in dynamic covalent materials based on acylsemicarbazides (ASCs), with the aim of achieving tunable material properties. The effects of different ASC substituents on the dynamic covalent and hydrogen bonding capabilities were investigated in a small molecule study using a combined experimental and theoretical approach, and revealed the presence of cooperative hydrogen-bonding interactions in 2 directions in one of the derivatives. The different motifs were subsequently incorporated into polymeric materials. Combining ASC motifs capable of strong, multiple hydrogen bonding with a polydimethylsiloxane backbone introduces structure-dependent, ordered nanophase separation in polymeric materials. The thermo-mechanical properties of the materials reveal a strong dependance on the hydrogen-bonding structure and exact nature of the ASC bond. The dynamic behavior in bulk shows that bond exchange depends on the dissociation rate obtained from ASC model compounds, as well as the strength of the secondary interactions in these materials. Differences in hydrogen-bonding structures of the ASC motifs also cause differences in creep resistance of the materials. Interestingly, the materials with strong, ordered and cooperative hydrogen-bonded clusters show the highest creep resistance. Our results demonstrate that tuning both the dissociation rate and the secondary interactions by molecular design in dynamic covalent materials is important for controlling their thermal stability and creep resistance.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 3","pages":"Pages 290-300"},"PeriodicalIF":4.1,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01296h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Glycidyl ethers from acyclic terpenes: a versatile toolbox for multifunctional poly(ethylene glycol)s with modification opportunities†","authors":"Sandra Schüttner ,&nbsp;Gregor M. Linden ,&nbsp;Elena C. Hoffmann ,&nbsp;Philipp Holzmüller ,&nbsp;Holger Frey","doi":"10.1039/d4py01201a","DOIUrl":"10.1039/d4py01201a","url":null,"abstract":"<div><div>Multifunctional poly(ethylene glycol) copolymers (mfPEGs) are accessible <em>via</em> the anionic copolymerization of functional epoxides with ethylene oxide (EO). Glycidyl ethers are conveniently synthesized from bio-renewable alcohols and epichlorohydrin (ECH). Herein, we present the synthesis of a series of acyclic terpenyl glycidyl ethers (TGEs) and their subsequent copolymerization with ethylene oxide (EO) <em>via</em> anionic ring-opening polymerization (AROP). The resulting library of copolymers with varied side chain length and comonomer composition comprises molar masses in the range of 4800 to 8300 g mol⁻¹ and narrow molar mass distributions (<em>Đ</em> = 1.06–1.13). For the copolymerization of the TGEs with EO, detailed ¹H NMR <em>in situ</em> kinetic studies revealed a change from ideally random to slight gradient copolyether microstructures with increasing chain length and hydrophobicity of the respective TGE. The living nature of AROP provides control of molar masses, and optimized reaction conditions, such as low reaction temperatures and a weakly bound cesium counterion, suppress the well-known proton abstraction of monosubstituted epoxides. Since the incorporation of the terpenyl side chains impedes crystallization, thermal properties of the copolyethers can be tailored by the monomer feed ratio. Subsequently, hydrogenation and thiol–ene click reactions at the side chain double bonds were carried out as post-polymerization modifications. The application of potassium azodicarboxylate (PADA) in the diimide reduction of the polymers was demonstrated to possess vast potential for the full hydrogenation of the novel copolymers, offering facile purification options. Overall, the copolymerization of EO and TGEs gives access to biobased, tailormade polyethers with various options for post-functionalization.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 3","pages":"Pages 374-385"},"PeriodicalIF":4.1,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01201a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142782961","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"AlEt3-catalyzed synthesis of circularly polarized luminescence active aggregation-induced emission helical polyisocyanides†","authors":"He Li ,&nbsp;Beiming Yu ,&nbsp;Yufan Li ,&nbsp;Jiaojiao Li ,&nbsp;Jie Zheng ,&nbsp;Junge Zhi ,&nbsp;Xiaofang Li","doi":"10.1039/d4py01037j","DOIUrl":"10.1039/d4py01037j","url":null,"abstract":"<div><div>The facile construction of circularly polarized luminescence (CPL) materials through the clever combination of chirality and fluorescence is of great significance. Herein, we provide a simple and efficient synthesis of CPL-active aggregation-induced emission (AIE) helical polyisocyanides through asymmetric polymerization of commonly used chiral aryl isocyanide monomers featuring a <span>d</span>- or <span>l</span>-methyl-ester pendant group (<span>d</span>/<span>l</span>-IMCIs) catalyzed by a novel AlEt₃/[Ph₃C][B(C₆F₅)₄] binary catalytic system. The typical fluorophore-free chiral <span>d</span>/<span>l</span>-IMCI monomers, silent in circular dichroism (CD), exhibit intriguing AIE properties. After undergoing asymmetric-induced polymerization with remarkable efficiency, the synthesized poly(<span>d</span>/<span>l</span>-IMCI)s have chiral helical structures, manifesting both CD and AIE characteristics. Based on the “matching rule” of the fluorescent moieties and chiral helical polyisocyanides, these poly(<span>d</span>/<span>l</span>-IMCI)s show distinct CPL signals in both the aggregated state and the film state, mirroring each other across the 400–600 nm range in THF, with luminescence dissymmetry factor (|<em>g</em>_lum|) values around 7.6–7.8 × 10⁻⁴ in THF. Moreover, the incorporation of different proportions of an achiral aryl isocyanide bearing an azobenzene pendant (IPPD) into the poly(<span>d</span>/<span>l</span>-IMCI)s through helix-sense-selective copolymerization allows for precise control over the chiroptical properties of the synthesized AIE helical poly(<span>d</span>/<span>l</span>-IMCI-<em>ran</em>-IPPD)s. The nonlinear relationship between the intensity of CD or CPL signals and the <span>d</span>/<span>l</span>-IMCI contents of the synthetic poly(<span>d</span>/<span>l</span>-IMCI-<em>ran</em>-IPPD)s clearly describes strong chiral amplification effects, achieving a maximum |<em>g</em>_lum| value exceeding 1.0 × 10⁻³ in THF, which is superior to those of poly(<span>d</span>/<span>l</span>-IMCI)s. These results demonstrate that the helical (co)polyisocyanide's chirality confers a chiral environment, which in turn effectively induces chirality within both the excited and ground states. This strategy provides new perspectives for the straightforward and simple construction of novel CPL-active AIE polymers through asymmetric polymerization of commonly used functional monomers.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 3","pages":"Pages 308-316"},"PeriodicalIF":4.1,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777078","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multifunctionalization of polybutadiene by RAFT/MADIX technology†","authors":"Congze He ,&nbsp;Jin Dong ,&nbsp;Chaoran Xu ,&nbsp;Zhujun Huang ,&nbsp;Samir Z. Zard ,&nbsp;Xiangcheng Pan","doi":"10.1039/d4py00935e","DOIUrl":"10.1039/d4py00935e","url":null,"abstract":"<div><div>Polybutadiene, a widely used synthetic rubber containing unsaturated bonds, has traditionally undergone functionalization processes such as thiol–ene radical addition, hydrogenation, and epoxidation. In this study, we present a new approach for multi-functionalizing polybutadiene through the reversible addition–fragmentation chain transfer polymerization/macromolecular design by interchange of xanthates (RAFT/MADIX) technology. The addition of xanthates onto polybutadiene was accomplished by thermal initiation, photoinitiation, or oxygen-mediated processes. Leveraging the sustained reactivity of dithiocarbonate on functionalized polymer, we further realized dexanthylation and transformation of dithiocarbonate. Finally, xanthate crosslinkers were synthesized for the simultaneous functionalization and cross-linking of polybutadiene.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 3","pages":"Pages 331-336"},"PeriodicalIF":4.1,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793581","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Towards the synthesis of polythiazolines: a post-polymerization approach†","authors":"Aikaterini Mathianaki ,&nbsp;Aysha Kinjo Demeler ,&nbsp;Adrian Dömling ,&nbsp;Federico Ferrari ,&nbsp;Frieda Clara M. Scheelje ,&nbsp;Hilke Bahmann ,&nbsp;Guillaume Delaittre","doi":"10.1039/d4py00930d","DOIUrl":"10.1039/d4py00930d","url":null,"abstract":"<div><div>The synthesis of novel tertiary polythioamide copolymers, analogues of poly(2-ethyl-2-oxazoline) (PEtOx), is reported. Firstly, the direct synthesis of poly(2-methyl-2-thiazoline) was attempted <em>via</em> the cationic ring-opening polymerization of 2-methyl-2-thiazoline, in analogy to the well-known 2-alkyl-2-oxazoline monomers. Since no conversion was monitored under several conditions – which was investigated in parallel by density functional theory calculations – the post-polymerization modification of PEtOx using Lawesson's reagent was successfully achieved, yielding poly(2-ethyl-2-thiazoline)-<em>co</em>-(2-ethyl-2-oxazoline) copolymers with up to 95 mol% of the thioamide unit. The newly synthesized copolymers exhibited significantly lower water solubility and thermal stability than the pristine PEtOx, as demonstrated during cloud point temperature determination and thermal gravimetric analysis, respectively. Moreover, the glass transition temperature of the copolymers increases linearly with increasing oxygen–sulfur exchange.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 3","pages":"Pages 301-307"},"PeriodicalIF":4.1,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py00930d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142777077","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Insights into the bulk kinetics of a 2K radical polymerization system based on the copper catalyzed cleavage of diboranes and its perspectives†","authors":"F. Pieringer ,&nbsp;Y. Catel ,&nbsp;R. Liska ,&nbsp;P. Knaack","doi":"10.1039/d4py01102c","DOIUrl":"10.1039/d4py01102c","url":null,"abstract":"<div><div>Many applications of polymer materials, such as adhesives, require a polymerization process at room temperature and ambient atmosphere. In those cases, two-component (2K) systems based on redox initiation truly stand out due to their reliable performance. Herein, we present a deep insight into the polymerization kinetics of a newly developed initiation system based on the copper catalyzed cleavage of diborane compounds, followed by rheology coupled with NIR. The analysis of different diboranes led us to further investigate the diborane concentration dependency and the effects on gel time that can be observed. Furthermore, it is shown that the diborane/Cu system yields polymers with high molecular weight at high double bond conversions. In addition, the perspectives of diborane/Cu initiation for radical polymerization are presented, as various different monomer classes showed excellent reactivity towards polymerization, enabling the great potential of this initiation system for various applications in polymer chemistry.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 3","pages":"Pages 337-344"},"PeriodicalIF":4.1,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01102c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142815627","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"3D printable biopolymers as pelvic floor scaffolds†","authors":"Lindsay B. Chambers ,&nbsp;Yuxiang Zhu ,&nbsp;Churan Yu ,&nbsp;Natalie Crutchfield ,&nbsp;Jixin Hou ,&nbsp;Liang Liang ,&nbsp;Xianqiao Wang ,&nbsp;Yang Liu ,&nbsp;M. Taylor Sobczak ,&nbsp;Taylor Theobald ,&nbsp;Xiao Sun ,&nbsp;Carly R. Stoll ,&nbsp;Tiffany V. Pulido ,&nbsp;Johnny Yi ,&nbsp;Jeffrey L. Cornella ,&nbsp;Heather McIlwee ,&nbsp;Hitesh Handa ,&nbsp;Elizabeth J. Brisbois ,&nbsp;Jessica N. Lancaster ,&nbsp;Kenan Song","doi":"10.1039/d4py01103a","DOIUrl":"10.1039/d4py01103a","url":null,"abstract":"<div><div>Pelvic floor disorders (PFD) are common among women, causing dysfunction, incontinence, and discomfort. Surgeries to repair the descended tissues can result in complications due to implant material design, particularly from the hardness and mechanical mismatch to native tissue. A more flexible implant could reduce complications, such as exposure and tissue erosion. This work seeks to characterize a 3D-printed double-crosslinked hydrogel tissue scaffold consisting primarily of polyvinyl alcohol (PVA). It also compares its static/dynamic/thermal/biological properties to existing commercial products used in PFD therapies, showing our pelvic mesh's biodegradability/robustness advantages over the commercial ones. Tensile tests revealed that the hydrogel scaffold was more compliant than the commercial alternatives. Dynamic mechanical testing has shown that these polymers are durable enough to support organs with specific weight above the pelvic floor. <em>In vivo</em> mouse studies demonstrated low inflammation and good biocompatibility over a 28-day period. The development of this scaffold offers a promising alternative for more effective, long-lasting PFD treatments with fewer post-operative complications, advancing personalized medicine.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 3","pages":"Pages 345-355"},"PeriodicalIF":4.1,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01103a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142759904","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tailoring reactive handles on the surface of nanoparticles for covalent conjugation of biomolecules†","authors":"Francesca Mazzotta ,&nbsp;Sharafudheen Pottanam Chali ,&nbsp;Ingo Lieberwirth ,&nbsp;Calum T. J. Ferguson ,&nbsp;Katharina Landfester","doi":"10.1039/d4py01119h","DOIUrl":"10.1039/d4py01119h","url":null,"abstract":"<div><div>Surface modification of nanoparticles involves numerous types of active molecules such as DNA, antibodies, enzymes, or carbohydrates. These modifications usually require reactive handles like amines, carboxylic acids, azides, <em>etc</em>. on the nanoparticles. In this work, utilizing poly-benzyl methacrylate based nanoparticles as a model nanoparticle system, the number of functional groups was tuned with functional comonomers, amino ethyl methacrylate for the amino groups or methyl methacrylate for the carboxylic groups. Herein a systematic study is presented where the functional groups in the nanoparticles are differentiated between total, visible and accessible functional groups. The concentration of each type of functional group is compared using various methods. Polymers synthesized using free radical polymerization were analyzed using ¹H-NMR spectroscopy to obtain the total number of functional groups. <em>Via</em> a miniemulsion–solvent evaporation technique, these polymers were used to synthesize the nanoparticles. Zeta potential, pH value and particle charge detection measurements were used to determine the number of visible functional groups. The number of accessible functional groups was quantified by conjugating small dyes and fluorescence measurements were directly executed on the system under investigation, hence eliminating errors associated with indirect measurements and detecting very low concentrations (<em>e.g.</em> 80 nM). Lastly, human serum albumin was conjugated to investigate the effect of a bulky molecule on the accessibility of these reactive handles.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 4","pages":"Pages 433-440"},"PeriodicalIF":4.1,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01119h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142718445","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}