Propargyl Methacrylate Research Articles

Surface Grafting of Magnetic Carbon Nanotubes and Their Vertical Alignment in PVDF Asymmetric Ultrafiltration Membranes for Fast Nanochannel Construction

The application of carbon nanotubes (CNTs) in water treatment membranes can increase the permeability and selectivity of the membranes. However, traditional CNTs are usually affected by van der Waals forces, which makes them prone to agglomerate in polymer membranes, and their non-directional arrangement in the membranes limits their transport efficiency as water channels in the membranes. In this paper, a reversible addition-fragmentation chain transfer (RAFT) polymerization method was used to synthesize propargyl methacrylate - random copolymerization - poly (ethylene glycol) methacrylate - block - polymethyl methacrylate [P(PgMA-r-PEGMA) -b-PMMA]. The P(PgMA-r-PEGMA)-b-PMMA grafting rate was 60.4% on the surface of magnetic sulfhydryl functionalized carbon nanotubes (mCNTs-SH) by click-reaction grafting. Poly (vinylidene fluoride) (PVDF)/CNTs composite ultrafiltration membranes were prepared using vapor-induced phase separation (VIPS) combined with magnetic field arraying. When the mCNTs-g-P(PgMA-r-PEGMA)-b-PMMA were vertically aligned in the PVDF membrane through a magnetic field, the effective construction of the vertical nanochannels was realized, and an increased purified water flux from 25.6 LMH to 35.8 LMH, with the composite ultrafiltration membranes was obtained. In addition, the membranes also showed excellent hydrophilicity, mechanical properties, and polyethylene glycol 1200 (PEG1200) rejection. The water contact angle was reduced from 105° to 79°, the rejection of PEG1200 was increased from 44% to 91% of the 0.5 g/L PEG aqueous solutions, and excellent mechanical properties (tensile strengthes up to 9.3 MPa) were achieved. By designing the interface structure of the CNTs and studying the orientation of the CNTs in PVDF membranes, this work provides a new research idea for the field of water treatment ultrafiltration membranes.

Preparation of Protein A Membranes Using Propargyl Methacrylate-Based Copolymers and Copper-Catalyzed Alkyne-Azide Click Chemistry.

The development of convective technologies for antibody purification is of interest to the bioprocessing industries. This study developed a Protein A membrane using a combination of graft polymerization and copper(I)-catalyzed alkyne-azide click chemistry. Regenerated cellulose supports were functionalized via surface-initiated copolymerization of propargyl methacrylate (PgMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA300), followed by a reaction with azide-functionalized Protein A ligand. The polymer-modified membranes were characterized using attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR), gravimetric analysis, and permeability measurements. Copolymer composition was determined using the Mayo-Lewis equation. Membranes clicked with azide-conjugated Protein A were evaluated by measuring static and dynamic binding (DBC10) capacities for human immunoglobulin G (hIgG). Copolymer composition and degree of grafting were found to affect maximum static binding capacities, with values ranging from 5 to 16 mg/mL. DBC10 values did not vary with flow rate, as expected of membrane adsorbers.

Fluorescent poly[N‐(2‐hydroxypropyl) methacrylamide] nanogel by dispersion polymerization as a contrast agent for live‐cell imaging

AbstractHere, we report a novel dispersion polymerization for the preparation of cross‐linked poly[N‐(2‐hydroxypropyl) methacrylamide] (PHPMA)‐based nanogels in water/2‐methoxyethanol mixture (H2O/MetCel), initiated with potassium persulfate (KPS), and stabilized with poly(vinyl alcohol) 25/140 (PVA) and sodium dodecyl sulfate (SDS). Obtained nanogels were characterized using transmission (TEM) and cryogenic transmission electron microscopy (cryo‐TEM), dynamic light scattering (DLS), asymmetric flow field‐flow fractionation (A4F), nuclear magnetic resonance spectroscopy (NMR), and Raman spectroscopy methods in terms of size, particle size distribution, morphology, and structure. N‐(2‐hydroxypropyl) methacrylamide (HPMA) was copolymerized with 20 wt% ethylene dimethacrylate (EDMA) resulting in 138 nm poly[N‐(2‐hydroxypropyl) methacrylamide‐co‐ethylene dimethacrylate] (PHPMA‐EDMA) nanogel dispersion with irregular shape and core‐shell type structure. Next, we copolymerized HPMA with 20 wt% EDMA and 10 wt% propargyl methacrylate (PMA) to incorporate reactive functionality into the final core‐shell type 120 nm poly[N‐(2‐hydroxypropyl) methacrylamide‐co‐ethylene dimethacrylate‐co‐propargyl methacrylate] (PHPMA‐EDMA‐PMA) nanogel dispersion. Then, the biocompatibility of PHPMA‐EDMA‐PMA nanogel was proved using rat mesenchymal stem cells (rMSC), and human foreskin fibroblasts (BJ). PHPMA‐EDMA‐PMA nanogel was fluorescently labeled with sulfo‐cyanine3 azide resulting in 131 nm nanogel. We performed in vitro uptake studies with fluorescently labeled PHPMA‐EDMA‐PMA nanogel using rMSC showing that the fluorescently labeled PHPMA‐EDMA‐PMA nanogel was well‐distributed in the cytosol and taken up into lysosomes.

Synthesis of Multifunctional Protein-Polymer Conjugates via Oxygen-tolerant, Aqueous Copper-Mediated Polymerization, and Bioorthogonal Click Chemistry.

Oxygen-tolerant, aqueous copper-mediated polymerization approaches are combined with click chemistry in either a sequential or a simultaneous manner, to enable the synthesis of multifunctional protein-polymer conjugates. Propargyl acrylate (PgA) and propargyl methacrylate (PgMA) grafting from a bovine serum albumin (BSA) macroinitiator is thoroughly optimized to synthesize chemically addressable BSA-poly(propargyl acrylate) and BSA-poly(propargyl methacrylate) respectively. The produced multifunctional bioconjugates bear pendant terminal 1-alkynes which can be readily post-functionalized via both [3+2] Huisgen cycloaddition and thiol-yne click chemistry under mild reaction conditions. Simultaneous oxygen-tolerant, aqueous copper-catalyzed polymerization, and click chemistry mediate the in situ multiple chemical tailoring of biomacromolecules in excellent yields.

Enhanced Thermal Stability of Mesoporous Carbon Microbeads-Based Lithium-Ion Batteries by Propargyl Methacrylate as Electrolyte Additive.

In this current work, propargyl methacrylate (PMA) was successfully adopted to be an efficient electrolyte additive to stabilize the formation of a solid electrolyte interface (SEI) layer on mesoporous carbon microbeads (MCMB) in Li-ion batteries, especially at elevated temperatures. According to a series of material and electrochemical characterizations, the optimized concentration of PMA additive in the electrolyte was found to be 0.5 wt.%. The MCMB electrode cycled with the optimized 0.5 wt.% PMA-containing electrolyte exhibited impressive capacity retention of 90.3% after 50 cycles at 0.1C at elevated temperature, which was remarkably higher than that using the PMA-free electrolyte (83.5%). The improved electrochemical stability at elevated temperature could be ascribed to the rapid formation of stable and thin SEI layer on MCMB surface, which were investigated and suggested to be formed via PMA copolymerization reactions.

Simple and Scalable Chemical Surface Patterning via Direct Deposition from Immobilized Plasma Filaments in a Dielectric Barrier Discharge.

In this work, immobilization of the often unwanted filaments in dielectric barrier discharges (DBD) is achieved and used for one‐step deposition of patterned coatings. By texturing one of the dielectric surfaces, a discharge containing stationary plasma filaments is ignited in a mix of argon and propargyl methacrylate (PMA) in a reactor operating at atmospheric pressure. From PMA, hydrophobic and hydrophilic chemical and topographical contrasts at sub‐millimeter scale are obtained on silicon and glass substrates. Chemical and physical characterizations of the samples are performed by micrometer‐scale X‐ray photoelectron spectroscopy and infrared imaging and by water contact angle and profilometry, respectively. From the latter and additional information from high‐speed imaging of the plasma phase and electrical measurements, it is suggested that filaments, denser in energetic species, lead to higher deposition rate with higher fragmentation of the precursor, while surface discharges igniting outwards the filaments are leading to smoother and slower deposition. This work opens a new route for a one‐step large‐area chemical and morphological patterning of surfaces at sub‐millimeter scales. Moreover, the possibility to separately deposit coatings from filaments and the surrounding plasma phase can be helpful to better understand the processes occurring during plasma polymerization in filamentary DBD.

Cross-linked polymer microparticles with tunable surface properties by the combination of suspension free radical copolymerization and Click chemistry

We propose a general, versatile and broad in scope two-steps approach for the elaboration of cross-linked polymer microparticles (µPs) with tunable functionalities and surface properties. Surface-functionalized cross-linked polymer µPs with diameter in the 80 μm range are prepared by the combination of: 1) suspension free radical copolymerization of styrene, propargyl methacrylate and 1,6-hexanediol dimethacrylate, 2) subsequent covalent tethering of a variety of azide-functionalized moieties (i.e. rhodamine B fluorescent dye or poly(ethylene glycol) (PEG) brush precursor) by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and, 3) optional N-alkylation of the 1,2,3-triazole groups followed by anion exchange reaction to afford covalently-tethered 1,2,3-triazolium ionic liquids with iodide or cresol red counter-anions. The resulting µPs are characterized by laser diffraction, differential scanning calorimetry, as well as by optical, confocal fluorescence, scanning electron and atomic force microscopies. Finally, the rheological properties of concentrated suspensions (volume fractions of 0.40 and 0.44) of the different synthesized µPs dispersed in a 1:1 (vol/vol) mixture of polyalkylene glycol and water are studied. The modification of µPs surface properties contributes not only to change the stability of the suspensions against flocculation, but also to significantly modify their rheological behavior at high shear stresses. This represents a clear experimental evidence of the importance of non-hydrodynamic contact forces in the rheology of non-Brownian suspensions (NBSs).

Synthesis of a Thermal-Responsive Dual-Modal Supramolecular Probe for Magnetic Resonance Imaging and Fluorescence Imaging.

Dual-modal imaging can integrate the advantages of different imaging technologies, which could improve the accuracy and efficiency of clinical diagnosis. Herein, a novel amphiphilic thermal-responsive copolymer obtained from three types of monomers, N-isopropyl acrylamide, 2-(acetoacetoxy) ethyl methacrylate, and propargyl methacrylate, by RAFT copolymerization, is reported. It can be grafted with β-cyclodextrin and aggregation-induced emission (AIE) luminogens tetraphenylethylene by click chemistry and Biginelli reaction. The multifunctional supramolecular polymer (P4) can be constructed by host-guest inclusion between the copolymer and the Gd-based contrast agent (CA) modified by adamantane [Ad-(DOTA-Gd)]. And it can form vesicles with a bilayer structure in aqueous which will enhance the AIE and magnetic resonance imaging effects. As fluorescent thermometer, P4 can enter HeLa cells for intracellular fluorescence imaging (FI) and is sensitive to temperature with detection limit value of 1.5°C. As magnetic resonance CA, P4 exhibits higher relaxation compared to Magnevist, which can prolong the circulation time in vivo. In addition, Gd3+ in the polymer can be quickly released from the body by disassembly that reduced the biological toxicity. This work introduces new synthetic ideas for dual-modal probe, which has great potential for clinical diagnostic applications in bioimaging.

Sequential intraparticle Förster resonance energy transfer for multi-wavelength bioimaging

Core/shell nanoparticles composed of a silica core over which a propargyl methacrylate (PMA) shell was polymerized around were synthesized. To employ the shell coating, the surface of the silica nanoparticles (SiNPs) was modified with an alkene-terminated organometallic silane linker that allowed for the covalent attachment of a poly(propargyl methacrylate) (pPMA) shell. The alkyne groups resulting from the pPMA shell were utilized in copper(I)-catalyzed azide/alkyne cycloaddition (CuAAC) reactions to attach azide-modified Förster resonance energy transfer (FRET) pairs of naphthalimide (azNap), rhodamine B (azRhod), and silicon phthalocyanine (azSiPc) derivatives to the shell surface. The luminescence of the system was manipulated by the covalent attachment of one, two, or three of the fluorophores resulting in no energy transfer, one energy transfer, or two energy transfers, respectively. When all three fluorophores were attached to the core/shell particles, an excitation of azNap with a wavelength of 400 nm resulted in the sequential energy transfer between two FRET pairs and the sole emission of azSiPc at 670 nm. These particles may have applications as bioimaging probes as their luminescence is easily detected using fluorescence microscopy.

Thermal and dielectric investigation of magnetic nanoparticles functionalized with PVC via click chemistry

In the first phase, PVC was modified with sodium azide through a nucleophilic substitution reaction. Then, the propargyl methacrylate was synthesized from propargyl alcohol and methacryloyl chloride. The copolymerization of propargyl methacrylate and vinyltrimethoxysilane was carried out by free-radical polymerization method in tetrahydrofuran (THF) at 70 °C in with AIBN as the initiator. The magnetic nanoparticle was bonded to vinyltrimethoxysilane units of the copolymer. Finally, the copolymer with propargyl end group bearing the magnetic nanoparticle on its side chain was bonded to PVC-N3 by click reaction. FTIR spectroscopy was used for the characterization. The thermal stability of PVC decreased after the azidation reaction and increased by grafting of magnetic nanoparticles to the copolymer. Vibration sample magnetometer (VSM) measurements revealed that the product reached saturation magnetization (Ms) at 33.7 emu/g, while the pure Fe3O4 nanoparticle showed Ms value of 53.2 emu/g. As the applied frequency increased, the dielectric constant (e′) and dielectric loss factor (e″) of the copolymers diminished, while the AC conductivity (σac) increased.

Synthesis and characterization of poly(vinyl chloride-g-methyl methacrylate) graft copolymer by redox polymerization and Cu catalyzed azide-alkyne cycloaddition reaction

The synthesis of poly(vinyl chloride-g-methyl methacrylate) graft copolymer was carried out by use of a Cu catalyzed azide-alkyne cycloaddition reaction to graft terminally propargyl polymethyl methacrylate (PMMA-propargyl) to polyvinyl chloride azido (PVC-N3). For this purpose, PMMA-propargyl was obtained by reaction of methyl methacrylate and propargyl alcohol by redox polymerization. PVC-N3 was synthesized by using polyvinyl chloride and sodium azide. By using PVC-N3 and PMMA-propargyl, the graft copolymer was obtained. Characterizations of the modified homopolymers and the graft copolymer were performed by using FT-IR, 1H-NMR, SEM, TGA and GPC analyses. It has been monitored that both group modifications and coupling reaction have been successfully performed with spectroscopic and thermal analysis methods.

β-Cyclodextrin-based star polymers for membrane surface functionalization: Covalent grafting via “click” chemistry and enhancement of ultrafiltration properties

This work provides the proof-of-concept that surface functionalization of porous membranes with well-defined star-like polymers of varied number of arms and arm length leads to a tunable effective thickness of grafted layers and a specific influence on size-selective sieving through ultrafilter pores. Alkyl-brominated β-cyclodextrine with either 7 or 21 initiator sites per molecule was synthesized and further used for controlled atom transfer radical polymerization of copolymers of 2-dimethylamino(ethyl) methacrylate (DMAEMA) and propargyl methacrylate (PgMA), leading to star polymers with either 7 or 21 arms. Alkyne-containing PgMA segments enable the “click” coupling while DMAEMA segments provide the bulk of the polymer. Star polymers were characterized with respect to chemical structure and molecular weight (M). During ultrafiltration (UF) through cellulose membranes with different molecular weight cut-off, rejection was not simply correlated with star polymer M but was governed by macromolecular architecture, i.e. the smaller colloidal diameter for macromolecules of same M but 21 instead of 7 arms. Azide-functionalized poly(ethylene terephthalate) (PET) track-etched (TE) membranes and cellulose UF membranes were prepared by polymer-analogous surface functionalization so that the alkyne-substituted star polymers could be “click”-grafted. Isoporous PET TE membranes with a nominal pore diameter of 200 nm were used as model system to study the grafting and its effects onto pore size via the reduction of hydraulic permeability. Effective grafted layer thickness in the range of 10–50 nm correlated with macromolecular structure and architecture. For “click”-functionalized cellulose UF membranes, the effective pore size in the barrier layer was influenced by grafted star polymers, and a pronounced additional influence of the architecture and arm length of the grafted star polymer on macromolecular sieving was observed. Of particular interest are results with the more flexible 7-armed star polymers (compared to 21-armed counterparts); their grafting at the UF membrane pores of similar dimension leads to a large increase of test solute rejection at very low reduction of convective water flux, both compared to the unmodified membrane.

Generating Surface-Anchored Zwitterionic Networks and Studying Their Resistance to Bovine Serum Albumin Adsorption

We report a simple method to generate surface-anchored zwitterionic network coatings that exhibit low nonspecific protein adsorption. We first synthesize amphiphilic random copolymers comprising 2-(dimethylamino)ethyl methacrylate (DMAEMA) and propargyl methacrylate (PGMA) units in two different nominal molar ratios (50:50 and 75:25) by free radical copolymerization. The DMAEMA moieties in the copolymers are then betainized with 1,3-propane sultone to obtain zwitterionic macromolecules. We create substrate-anchored network coatings by casting thin copolymer films (∼100 nm) containing 2 wt % of photoactive benzophenone onto a polystyrene substrate and cross-link them by UV-light irradiation at 365 nm (UV dose = 9–10 J/cm2). We investigate the cross-linking reaction with infrared spectroscopy, monitor the change in film thickness, and study the swelling behavior of the coatings as a function of ionic strength and electrolyte using spectroscopic ellipsometry. We demonstrate the performance of such surface-at...

Tailoring the surface of attapulgite by combining redox-initiated RAFT polymerization with alkynyl-thiol click reaction for polycarbonate nanocomposites:Effect of polymer brush chain length on mechanical, thermal and rheological properties

In this work, we proposed the tuning of the interface between attapulgite (ATP) and polycarbonate (PC) by the surface tailoring of ATP via a combination of RAFT polymerization and alkynyl-thiol click reaction. The side alkynyl-functionalized random copolymer poly(MMA-co-PgMA) was synthesized as the immobilization block via redox-initiated room-temperature RAFT copolymerization of MMA and propargyl methacrylate (PgMA). Then, the dispersion block was synthesized by room-temperature RAFT polymerization of MMA using poly(MMA-co-PgMA) as the macro chain transfer agent to afford poly((MMA-co-PgMA)-b-MMA). FTIR, 1H NMR, gel permeation chromatograph (GPC), and kinetic results indicated the successful synthesis of copolymers with well-defined structures. Copolymers with different length of PMMA segment were tethered onto the surface of thiol-functionalized ATP via alkynyl-thiol click reaction to mediate the interfacial interaction between ATP and PC, the successful covalent grafting of copolymers was confirmed by FTIR, TGA, XPS and XRD, and the effects of dispersion blockchain length on nanocomposites were investigated. The functionalized ATP demonstrated an improved dispersity in nanocomposites and enhanced mechanical properties with increasing dispersion blockchain length. The PC nanocomposites with functionalized ATP showed lower Tg and complex viscosity as compared to that of pure PC and nanocomposites with bare ATP, which enhanced the processability of nanocomposites.

Atmospheric Pressure Plasma Deposition of Hydrophilic/Phobic Patterns and Thin Film Laminates on Any Surface

Patterned and layered hydrophilic/phobic coatings were deposited on multiple surfaces using nonfluorinated precursors (AA, acrylic acid; PMA, propargyl methacrylate) with an atmospheric pressure dielectric barrier discharge operating in open air. Water contact angles of the resulting films could be tuned from <5° (superhydrophilic) to >135° (very hydrophobic) by adjusting the AA/PMA feed ratio and/or via postdeposition exposure of films to an Ar/O2 plasma treatment. Coatings could be applied to any surface and were seen to be water stable, due in large part to cross-linking induced from the reactivity of the PMA pendant groups. Hybrid hydrophilic/phobic patterns at submillimeter length scales, and philic/phobic/philic laminates were produced using a shadow mask and sequential deposition, respectively. Chemical heterogeneity of films was assessed using XPS, SIMS, and micro-IR imaging and suggest that localization of COOH and OH groups are primarily responsible for hydrophilicity. Overall, this work demonstrates that atmospheric pressure plasma polymerization is a simple and scalable method for robust and tunable control of wettability of surfaces of all kinds.

Effective and simple one-step strategy for preparation of “clickable” cellulose modules: support to build antibacterial materials

An efficient and simple way to generate “clickable” cellulose modules called alkyne-functionalized cellulose fibers (ACFs) for click reaction was presented. This method is only based on one step reaction: propargyl methacrylate (PMA) with pendant alkynyl groups was grafted onto the surface of cellulose fibers (CFs) using ceric ammonium nitrate as the initiator in aqueous medium. This has been providing a new and versatile platform for the wide utilization of cellulose resources and creation of novel functional materials. The effect of process variables on grafting copolymerization of PMA was investigated and suitable preparation conditions were identified. The clickability of ACFs was evaluated by reacting with two azides. The antibacterial cellulose functional material was achieved through incorporation of a “clickable” handle (alkynyl groups) to cellulose fibers followed by rapid attachment of β-cyclodextrin with an azide tag using copper-catalyzed click reaction and loading with ciprofloxacin hydrochloride (CipHCl). Pure CFs and ACFs showed a little affinity to CipHCl, whereas click products (ACFs@Azide-β-CD) increased the loading amount dramatically because the equilibrium amount was higher than pure CFs and ACFs. Meanwhile, the release process of CipHCl from ACFs@Azide-β-CD was prolonged to reaches the equilibrium. The ACFs@Azide-β-CD loaded with CipHCl showed excellent antibacterial activity against Escherichia coli. The ACFs@Azide-β-CD loading CipHCl have considerably longer bacterial activity against E. coli compared to CFs and ACFs.

Tuning the Thermal Properties of Azopolymers Synthesized by Post‐Functionalization of Poly(propargyl Methacrylate) with Azobenzene Azides: Influence on the Generation of Linear and Circular Birefringences

AbstractA series of side‐chain polymers with a bifunctional repeating unit are prepared by post‐polymerization functionalization of poly(propargyl methacrylate) (PPMA) with several azides derived from bis(hydroxymethyl)propionic acid (bis‐MPA). The azide incorporates one photoresponsive 4‐cyanoazobenzene unit and one photoinert promesogenic moiety at each repeating unit. Both the effect of the photoinert (4‐cyanobipheynyl vs 4‐cyanotolane) and of the linking group (ester vs carbamate) on the liquid crystalline properties and the generation of optical anisotropy, linear or circular birefringences are explored.

Self-Assembly of a Double Hydrophilic Block Glycopolymer and the Investigation of Its Mechanism.

We report the self-assembly of a double hydrophilic block glycopolymer (DHBG) via hydrogen bonding and coordinate bonding. This DHBG, composed of poly(ethylene)glycol (PEG) and glycopolymer, self-assembled into a well-defined structure. The DHBG was prepared through the controlled radical polymerization of trimethylsilyl-protected propargyl methacrylate using a PEG-based reversible addition-fragmentation chain transfer reagent, followed by sugar conjugation using click chemistry. The DHBG self-assembly capability was investigated by transmission electron microscopy and dynamic light scattering. Interestingly, the DHBG self-assembled into a spherical structure in aqueous solution. Hydrogen bonding and coordinate bonding with Ca2+ were identified as the driving forces for self-assembly.

Effect of the polymer architecture on the photoinduction of stable chiral organizations

The paper presents a series of light responsive block copolymers that have been prepared by sequential polymerization of propargyl methacrylate and methyl methacrylate by atom transfer radical polymerization (ATRP). The pendant alkyne groups of the poly (propargyl methacrylate) block have been subsequently modified with azides from 2,2-bis(hydroxymethyl)propanoic acid decorated with two motifs, either two azobenzenes or one azobenzene and one biphenyl. This general and versatile synthetic approach simplifies the rational inclusion of structural modifications onto these polymers and, thus, establishing structure-properties relationships as a way to tailor the final properties of the material. By polymerizing the poly(propargyl methacrylate) firstly and poly(methyl methacrylate) secondly, block copolymers with low mass fractions, i.e. highly diluted contents, of the photoresponsive block have been achieved where the effect of the polymeric architecture on the induction of chirality using circularly polarized light (CPL) and its temporal stability has been evaluated. The relevance of the liquid crystallinity on the photoinduction of chirality in the block copolymers has also been investigated mainly in relation to thick films of good optical quality.

Controlling the lectin recognition of glycopolymers via distance arrangement of sugar blocks.

The arrangement of sugars in glycopolymers contributes to their recognition. The molecular recognition of proteins was controlled by the living radical polymerization of glycopolymers. The glycopolymers were prepared by the copolymerization of propargyl methacrylate (Pr-MA) and triethyleneglycol methacrylate (TEG-MA) via living radical polymerization with a reversible addition-fragmentation glycopolymer chain transfer (RAFT) reagent and by subsequent sugar conjugation by click chemistry. The block copolymers were prepared by the polymerization of Pr-MA and TEG-MA. The molecular recognition of glycopolymers was analyzed using the fluorescence quenching of lectin and found to be dependent on the glycopolymer structures. Two-site binding of glycopolymers to concanavalin A (ConA) was attained by both the glycopolymer with a 105-mer and the tri-block glycopolymer with a 103-mer. Glycopolymers with either a 27- or 54-mer showed much weaker interaction because of one-site binding. The molecular recognition of the glycopolymer was controlled by the arrangement and size of the sugar cluster and not by the sugar density.