Conventional Radical Research Articles

One-step zwitterionization and quaternization of thick PDMAEMA layer grafted through subsurface-initiated ATRP for robust antibiofouling and antibacterial coating on PDMS

In this work, we demonstrate the grafting of thick poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA) layer on PDMS via subsurface-initiated atom transfer radical polymerization (SSI-ATRP). The self-migration of DMAEMA monomers into the subsurface of PDMS is proven to be the dominant factor for the success of SSI-ATRP. The as-prepared thick microscale graft layer on PDMS shows much better abrasion resistance than nanoscale graft layer obtained by conventional surface-initiated atom transfer radical polymerization (SI-ATRP) under identical condition. Taking advantage of the tertiary amines of PDMAEMA, the simultaneous zwitterionization and quaternization of the PDMAEMA thick layer is realized through a facile one-step process. The effect of zwitterionization and quaternization degree on the antibiofouling and antibacterial properties is investigated. The results show that a relatively high zwitterionization degree (75 mol%) and a low quaternization degree (25 mol%) exhibit a good well-balanced effect on both fouling repellence and bactericidal activity. This work may lead to the development of robust bifunctional antibiofouling and antibacterial surfaces via SSI-ATRP strategy.

Ultrasonic synthesis of Mn-Ni-Fe tri-metallic oxide anchored on polymer-grafted conductive carbon for rechargeable zinc-air battery

As a promising electrochemical energy device, a rechargeable zinc-air battery (RZAB) requires cost-effective cathode catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Some earth-abundant transition metal oxides have certain levels of bi-functional ORR/OER catalytic activities yet low electronic conductivities. The addition of high-electronic-conductivity material such as carbon black could result in another problem because there is low compatibility between metal oxide and carbon. In this work, polymer chains are ultrasonically prepared to act as binders to anchor metal-oxide active sites to porous domains of carbon black. The monomer N-isopropyl acrylamide is polymerized under ultrasonication instead of using conventional radical initiators which are dangerous and harmful. Reactive free radicals produced by ultrasonic irradiation can also help to form the Mn-Ni-Fe tri-metallic oxide. Thus, aided by the amide-type polymer as an adhesive, the tri-metallic oxide anchored on polymer-grafted carbon black prepared by ultrasonication possess a large number of metal-oxide active sites and hierarchical pores, contributing substantially to the enhanced ORR/OER electrocatalytic performance in the RZABs. Accordingly, this work provides interesting insight into the effective combination of inherently incompatible components for the fabrication of composite materials from an ultrasonic standpoint.

Three-port approach vs standard laparoscopic radical cystectomy with an ileal conduit: a single-centre retrospective study

BackgroundThis study aimed to evaluate the effect of the three-port approach and conventional five-port laparoscopic radical cystectomy (LRC) with an ileal conduit.MethodsEighty-four patients, who were diagnosed with high-risk non-muscle-invasive and muscle-invasive bladder carcinoma and underwent LRC with an ileal conduit between January 2018 and April 2020, were retrospectively evaluated. Thirty and fifty-four patients respectively underwent the three-port approach and five-port LRC. Clinical characteristics, pathological data, perioperative outcomes, and follow-up data were analysed.ResultsThere were no differences in perioperatively surgical outcome, including pathology type, prostate adenocarcinoma incidence, tumour staging, and postoperative creatinine levels between the two groups. The operative time (271.3 ± 24.03 vs. 279.57 ± 48.47 min, P = 0.299), estimated blood loss (65 vs. 90 mL, P = 0.352), time to passage of flatus (8 vs. 10 days, P = 0.084), and duration of hospitalisation post-surgery (11 vs. 12 days, P = 0.922) were no clear difference between both groups. Compared with the five-port group, the three-port LRC group was related to lower inpatient costs (12 453 vs. 14 134 $, P = 0.021). Our follow-up results indicated that the rate of postoperative complications, 90-day mortality, and the oncological outcome did not show meaningful differences between these two groups.ConclusionsThree-port LRC with an ileal conduit is technically safe and feasible for the treatment of bladder cancer. On comparing the three-port LRC with the five-port LRC, our technique does not increase the rate of short-term and long-term complications and tumour recurrence, but the treatment costs of the former were reduced.

Ubiquitous Nature of Rate Retardation in Reversible Addition-Fragmentation Chain Transfer Polymerization.

Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most powerful reversible deactivation radical polymerization (RDRP) processes. Rate retardation is prevalent in RAFT and occurs when polymerization rates deviate from ideal conventional radical polymerization kinetics. Herein, we explore beyond what was initially thought to be the culprit of rate retardation: dithiobenzoate chain transfer agents (CTA) with more active monomers (MAMs). Remarkably, polymerizations showed that rate retardation occurs in systems encompassing the use of trithiocarbonates and xanthates CTAs with varying monomeric activities. Both the simple slow fragmentation and intermediate radical termination models show that retardation of all these systems can be described by using a single relationship for a variety of monomer reactivity and CTAs, suggesting rate retardation is a universal phenomenon of varying severity, independent of CTA composition and monomeric activity level.

Cross-linking fluorene copolymers via thiol-ene click chemistry

A series of 9,9-bis(allyl)fluorene copolymers (PFAF) with allyl groups on the side chain were synthesized by Suzuki coupling reaction. The cross-linked fluorene copolymers were realized via thiol-ene click reaction between allyl groups and thiol groups from crosslinker under ultraviolet light. Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), UV–Vis absorption spectroscopy and photoluminescence spectroscopy (PL) were used to investigate the crosslinking efficiency of the thiol-ene click reaction and the impacts of crosslinking on the performances of fluorene copolymers. The results showed that allyl fluorene copolymers with high molecular weight and different content of 9,9-bis(allyl) fluorene units were successfully synthesized. Fluorene copolymers containing allyl fluorene structural units can be effectively crosslinked by the thiol-ene click reaction. The crosslinking conditions and the factors which influence the crosslinking were investigated in detail. The fluorene copolymer films which were composed of a fluorene copolymer with 10 mol% allyl fluorene structural units (PF10AF) and 39 wt% pentaerythritol tetra(3-mercaptopropionate) (PETMP) can be crosslinked to 85% crosslinking degree under irradiation of 1.8 mW/cm2 LED UV light at 390 nm for 50 s in air. It was found that the thiol-ene click cross-linking had little effects on the photoluminescence spectra of the fluorene copolymers. The thiol-ene click crosslinking showed a much faster crosslinking rate and higher crosslinking efficiency for fluorene copolymers than those of conventional free radical polymerization crosslinking. The results of this study provide a feasible method for cross-linking conjugated polymers in various applications.

Radical Scavenging Could Answer the Challenge Posed by Electron-Electron Dipolar Interactions in the Cryptochrome Compass Model.

Many birds are endowed with a visual magnetic sense that may exploit magnetosensitive radical recombination processes in the protein cryptochrome. In this widely accepted but unproven model, geomagnetic sensitivity is suggested to arise from variations in the recombination rate of a pair of radicals, whose unpaired electron spins undergo coherent singlet–triplet interconversion in the geomagnetic field by coupling to nuclear spins via hyperfine interactions. However, simulations of this conventional radical pair mechanism (RPM) predicted only tiny magnetosensitivities for realistic conditions because the RPM’s directional sensitivity is strongly suppressed by the intrinsic electron–electron dipolar (EED) interactions, casting doubt on its viability as a magnetic sensor. We show how this RPM-suppression problem is overcome in a three-radical system in which a third “scavenger” radical reacts with one member of the primary pair. We use this finding to predict substantial magnetic field effects that exceed those of the RPM in the presence of EED interactions in animal cryptochromes.

Less invasive and equivalent short-term outcomes with simultaneous en bloc robot-assisted radical cystectomy and laparoscopic nephroureterectomy: Comparison with conventional open radical cystectomy and nephroureterectomy.

To clarify the safety and efficacy of en bloc simultaneous robot-assisted radical cystectomy (RARC) and laparoscopic nephroureterectomy (LNU) for synchronous muscle-invasive bladder carcinoma and upper tract urothelial carcinoma (UTUC) or UTUC of a solitary kidney, we evaluated the perioperative and short-term outcomes of this surgical procedure compared with those of simultaneous open radical cystectomy and nephroureterectomy. We prospectively enrolled consecutive patients receiving en bloc simultaneous RARC and LNU between December 2018 and March 2020 at two institutes. Patients' characteristics, surgical, perioperative, and pathological outcomes and recurrence rate within 6months were compared with a historical control receiving simultaneous open radical cystectomy and nephroureterectomy. Ten patients receiving simultaneous RARC and LNU and 17 receiving simultaneous open radical cystectomy and nephroureterectomy were included in the study. Simultaneous RARC and LNU significantly reduced bleeding volume and blood transfusion (P < .0001, P < .0001, respectively) and significantly prolonged operating time (P=.035). RARC and LNU significantly shortened hospitalization after operation (P=.003) and showed reduced tendency of postoperative complications within 30 days but not significantly (P=.25). Pathological characteristics and recurrence within 6months were not significantly different between the two groups. Our results suggested that en bloc simultaneous RARC and LNU were safer surgical procedures with equivalent short-term oncological outcomes compared to conventional open procedures. It can be a standard minimally invasive surgical method in countries where robot-assisted radical nephroureterectomy is inaccessible.

Emulsion iodine transfer polymerization of nearly uniform submicrometer‐sized polystyrene particles

AbstractEmulsifier‐free emulsion iodine transfer polymerization (emulsion ITP) of styrene was carried out using unpurified and purified poly(methacrylic acid)–iodine (PMAA‐I). PMAA‐I was previously synthesized by solution ITP in dioxane. The solution ITP of methacrylic acid was completed at 40 °C for 24 h. Unexpectedly, 64% of added CHI3 remained in dioxane even after the polymerization. The emulsion ITP was carried out at pH ∼ 9 with unpurified or purified PMAA‐I. The number‐average diameter (dn) of the polymer particles obtained using purified PMAA‐I (148 nm at 93% conversion) was much smaller than that using unpurified PMAA‐I (710 nm at 68% conversion). In both cases, in the early stage of the polymerization, polystyrene (PS) particles stabilized by some PMAA‐b‐PS copolymer chains were formed. This indicates that PMAA‐I worked not only as a macro chain transfer agent but also as a colloidal stabilizer. In the unpurified system, the remaining CHI3 also operated as a chain transfer agent. It resulted in PS‐I homopolymers having controlled molecular weight in the PS particles. On the other hand, many high molecular weight PS homopolymers were formed in the purified system by emulsion conventional radical polymerization in the PS particles. To depress emulsion conventional radical polymerization, the CHI3 was post‐added after 90 min. Nearly uniform submicrometer‐sized (82 nm) PS particles with narrow molecular weight distribution (Mw/Mn = 1.24) were achieved. These polymerization behaviors were reasonably explained from the results obtained by gel permeation chromatography and diffusion ordered spectroscopy 1NMR. © 2021 Society of Industrial Chemistry.

Solution to prevent tumor spillage in minimally invasive radical hysterectomy using the endoscopic stapler for treating early-stage cervical cancer: Surgical technique with video

Gynecologic oncologists had originally preferred minimally invasive surgery (MIS) over laparotomic surgery for patients with early-stage cervical cancer until the Laparoscopic Approach to Cervical Cancer (LACC) trial reported a worse prognosis and more loco-regional recurrence in patients treated with MIS. Although some controversy remains, experts suggested that tumor cell spillage and aggravation may have been caused by intra-corporeal colpotomy, usage of uterine elevators, maintenance of Trendelenburg position, and tumor irritation by capnoperitoneum during surgery. Thus, we introduce a surgical procedure with some steps added to the conventional MIS radical hysterectomy for preventing tumor spillage during the surgery, which is currently being evaluated in terms of safety and efficacy through a prospective, multicenter, single-arm, phase II study, entitled “Safety of laparoscopic or robotic radical surgery using endoscopic stapler for inhibiting tumor spillage of cervical neoplasms (SOLUTION trial: NCT04370496)”.

Effect of oleic purity on the chemical structure, thermal and rheological properties of bio-based polymers derived from high oleic cottonseed oil via RAFT polymerization

Vegetable oils are natural products, and their compositions and quality mainly rely on the plants, seasons, and growing conditions. It seems to be obvious that the fatty acid compositions from vegetable oils can impact on the properties of resulting polymer materials made from them, however, it is rarely discussed. This study reports how the oleic purity influences the chemical, thermal and rheological properties of the corresponding bio-based polymers derived from cottonseed oil. Two cottonseed oil sources including a commercially available cottonseed oil and a high oleic cottonseed oil were chosen to prepare samples with different oleic purity levels using the urea inclusion methodology. The oils with different oleic purity levels were subsequently transformed to the cottonseed oil-based methacrylate reactive monomers with various oleic purity via an esterification reaction at room temperature. The monomers were then polymerized via Reversible Addition Fragmentation chain Transfer, RAFT, polymerization in the presence of a RAFT agent. A pure oleic acid source and the conventional free radical polymerization method were used for comparison. The chemical structures of synthesized bio-based monomers and polymers with different oleic content were confirmed using nuclear magnetic resonance, Fourier transform infrared spectroscopy, and characterized through gel permeation chromatography, thermogravimetric analysis and differential scanning calorimetry. The results demonstrated significant influence of oleic purity, the proportion the saturated palmitic and unsaturated linoleic in the oils on the properties of the corresponding bio-based RAFT polymers. The RAFT polymer derived from commercially available cottonseed oil had a higher glass transition temperature, lower viscosity, and less thermal resistance than that of RAFT polymer derived from high oleic cottonseed oil. The ramie fabric coated by the synthesized bio-based RAFT polymer from high oleic cottonseed oil displayed a hydrophobic surface with a water contact angle of 110°.

Hydrogenation of poly(myrcene) and poly(farnesene) using diimide reduction at ambient pressure

AbstractAmbient pressure chemical hydrogenation using p‐toluene sulfonyl hydrazide (TSH) via thermal diimide formation (N2H2) permitted reduction of double bonds of poly(myrcene) (poly[Myr]) and poly(farnesene) (poly[Far]). Both pendent and backbone double bonds in poly(Myr) (Mn = 56 kg/mol) and poly(Far) (Mn = 62 kg/mol) synthesized by conventional free radical polymerization were hydrogenated to almost completion. Furthermore, TSH semi‐batch addition efficiently hydrogenated double bonds, while avoiding undesired autohydrogenation of diimides that occurred in batch mode. Thermal stability improved for hydrogenated poly(Myr) and poly(Far), where temperature at 10% weight loss (T10%) increased from 188 to 404°C for poly(Myr) and from 310 to 379°C for poly(Far). Tgs of poly(Myr) and poly(Far) also increased by about 10–25°C, indicating increased stiffness after hydrogenation. Finally, viscosities of poly(Myr) and poly(Far) were also increased after hydrogenation, and a greater increase was observed for poly(Myr) (by two orders of magnitude from 102 to 104 Pa s) due to its Mn being much higher than its entanglement molecular weight. Poly(Far) viscosity only increased by 1.5 times after hydrogenation (~104 Pa s), comparable to the poly(Myr) after hydrogenation, suggesting unsaturated poly(Far) was more entangled than unsaturated poly(Myr) because of its longer side chains.

Effects of graphite oxide on thermal and electrical behaviors of coumarin‐based methacrylate copolymers: Its single chain polymer molecule via intramolecular cyclobutane formation

AbstractThe random copolymers of methyl methacrylate (MMA) and 4‐methyl‐2‐oxo‐2H‐chromen‐7‐yl methacrylate (COUMA) [poly (COUMA0.49‐co‐MMA)] (COMCOP1) and [poly(COUMA0.36‐co‐MMA)] (COMCOP2) were prepared via the conventional radical polymerization method. The copolymers were characterized by 1H‐NMR, Fourier‐transform infrared spectroscopy (FT‐IR), UV–visible (UV–vis), thermogravimetric analysis, and differential scanning calorimetry instruments. A kinetic study of the thermal decomposition of COMCOP1 and COMCOP1/GO 16 wt% was investigated using thermogravimetric analyzer with non‐isothermal methods selected for analyzing solid‐state kinetics data. The average activation energy values were calculated via Flynn Wall and Ozawa (FWO) and Kissinger‐Akahira‐Sunose models in a period of α = 0.10–0.70. The average values of activation energy obtained from Kissinger method for COMCOP1 and COMCOP1/GO 16 wt% were 94.5 and 78.4 kJ/mol, respectively, whereas, those of estimated by FWO method were 103.5 and 87.0 kJ/mol. We indicate that well‐defined single chain polymer molecule (SCPM) via intramolecular cyclobutane formation could be obtained by the intrachain photodimerization of coumarin groups during UV irradiation at 365 nm diluted solution of COMCOP1. The photodimerization of coumarin groups in the copolymer was confirmed by UV–vis, FT‐IR, and 1H‐NMR instruments. Dielectric and electrical behaviors of the composites having a semiconductor behavior filled GO were investigated. The activation energy values based on dc conductivity for COMCOP1 loaded GO 10 and 12 wt% were decreased from 0.206 to 0.069 eV. Also, the Ea values estimated for COMCOP2‐loaded GO 12 and 13.6 wt% were 0.0580 and 0.0859 eV, respectively.

Controlled Radical Polymerization: from Oxygen Inhibition and Tolerance to Oxygen Initiation

Molecular oxygen is a radical scavenger in both conventional and controlled radical polymerization (CRP), resulting in many time-consuming methods for physically removing oxygen before the polymerization. Different approaches have been developed to have oxygen tolerance by chemically consuming or converting molecular oxygen into non-initiating species to address this issue. Recently, we propose another approach called oxygen initiation that directly transforms molecular oxygen into the initiating carbon radical in CRP. This Feature Article summarizes our recent developments in this direction. Oxygen-initiated reversible addition-fragmentation transfer (RAFT) polymerization has been successfully conducted using oxygen and trialkylborane as co-initiators under the ambient conditions and atmosphere without any prior degassed procedures. This gas-trigger initiation provides the opportunity for spatiotemporal control of the polymerization by molecular oxygen or air. Rationally synthesized alkylborane compounds could derive the predesigned structure of the initiating alkyl radical to minimize the side reactions and free polymer chains, achieving the synthesis of ultra-high molecular weight polymers. The challenges and perspectives are also discussed at the end.

The Diagnosis of Perineural Invasion: A Crucial Factor in Novel Algorithm of Coexistence of Conventional and Nerve-Sparing Radical Hysterectomy.

Nerve-sparing radical hysterectomy (NSRH) was introduced to mitigate adverse effects associated with conventional radical hysterectomy (CRH) in cervical cancer. However, the introduction of NSRH was compromised by possible existence of perineural invasion (PNI). Additionally, the coexistence of NSRH and CRH is currently the fact. The aim of the study was to review the literature and attempt to construct a novel and preliminary PNI diagnostic algorithm that would establish the coexistence of NSRH and CRH in one system of early-stage cervical cancer (ESCC) surgical treatment. This algorithm takes into account the PNI risk factors and current and future diagnostic methods such as imaging and biopsy.

Exploring the advantages of oxygen-tolerant thiol-ene polymerization over conventional acrylate free radical photopolymerization processes for pressure-sensitive adhesives

Exploring the advantages of oxygen-tolerant thiol-ene polymerization over conventional acrylate free radical photopolymerization processes for pressure-sensitive adhesives

Synthesis of Amino Acid-derived Curing Reagents Containing a Disulfide Bond and Their Application to Anionic UV Curing Materials

Anionic UV curing has been applied for many kinds of industrial resins, because it overcomes technical problems in conventional radical and cationic UV curing. In this study, a cystine-based latent curing reagent was designed, and synthesized from l- and d-cysteine. The reagents showed not only good solubility toward organic media, but also good thermal decomposition behavior in the presence of basic species. Using them with a photo-base generator and an epoxy resin having a disulfide bond, UV-cured films of B-to-3B grade of pencil-hardness were fabricated successfully, after 10 J/cm2 of 365 nm-light irradiation and subsequent heating at 120-160°C for 30 min. Furthermore, two glass substrates were adhered by using this anionic UV curing system, and 1.6-3.7 MPa of shear stress was recorded in the photo-adhesion and re-adhesion experiments.

Long-lasting hydrophilic surface generated on poly(dimethyl siloxane) with photoreactive zwitterionic polymers

Poly(dimethylsiloxane) (PDMS) is known as one of the most established polymers for making elastomers. Therefore, it is commonly used for the fabrication of biomedical devices. Many PDMS surface modification processes have been proposed recently to increase PDMS reliability in medical fields. However, the modified surface's long-term stability is still limited. Hydrophobic recovery of PDMS is widely recognized as a factor that reduces the efficacy of PDMS surface modification. The photoreactive zwitterionic polymer effectively suppresses the hydrophobic recovery of PDMS, according to the current analysis. The photoreactive zwitterionic monomer, 2-[2-(Methacryloyloxy)ethyldimethylanmmonium] ethyl benzophenoxy phosphate (MBPP) was polymerized by conventional radical polymerization and coated on O2-plasma-treated PDMS specimens. The specimens were immersed in an aqueous solution of 2-methacryloyloxyethyl phosphorylcholine (MPC) and exposed under ultraviolet (UV) radiation for 3 h. Instead, of poly(MBPP) (PMBPP), benzophenone (BP) was also used as a conventional photoinitiator. The time-dependent change in the wettability and elemental composition of the specimen surface was monitored for nine weeks after photo-grafting of poly[2-methacryloyloxyethyl phosphorylcholine (MPC)] (PMPC). The advancing and receding contact angles (θA/θR) of the pristine PDMS specimen were 112°/71° and significantly decreased immediately after the grafting of PMPC regardless of types of photoinitiator. However, the hydrophobicity of the surface gradually recovered, and θA was changed from 12° to 81° for nine weeks of storage under air atmosphere when BP was used as a photoinitiator for graft polymerization of MPC. However, surface hydrophilicity (θA ≅ 20°) of the surface grafted with PMPC with PMBPP as an initiator was effectively preserved for nine weeks. This surface also showed excellent lubricity and non-fouling properties regardless of the storage periods. Therefore, zwitterionic photoreactive polymer, PMBPP, is then used as a macrophotoinitiator for the surface modification of PDMS.

P1102 - Retzius-sparing vs. conventional robotic assisted radical prostatectomy in a prospective, randomised trial – early functional outcome and quality of life

P1102 - Retzius-sparing vs. conventional robotic assisted radical prostatectomy in a prospective, randomised trial – early functional outcome and quality of life

Ion transport and relaxation in phosphonium poly(ionic liquid) homo‐ and co‐polymers

AbstractIn the present work, a poly(ionic liquid) (PIL), poly(triphenyl‐4‐vinylbenzylphosphonium chloride) and a series of its random copolymers with nonionic hydrophobic poly(methyl methacrylate) (PMMA) are synthesized by conventional free radical polymerization (CFRP) and reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. The understanding of some fundamental aspects about ion transport and relaxation mechanism in PIL and PIL copolymers are investigated using dielectric spectroscopy via several theoretical models. The influence of copolymer compositions, physical blending of neat PIL and PMMA, size of counter anions (Cl− and TFSI−) and variation of molecular weights on thermal stability, moisture sensitivity, ionic transport and relaxation properties are also studied. An enhancement of thermal stability and ionic transport property of the PIL copolymer is observed compared to those of the physically mixed blend of two homopolymers with same compositions. The incorporation of hydrophobic PMMA segment definitely decreases the moisture content in PIL copolymers than the PIL itself. In all these PIL‐ based systems, the temperature dependence of ionic conductivity, relaxation time and ion diffusivity are well described by Vogel‐Tammann‐Fulcher model. The studies of some fundamental properties of these new PIL copolymers with less moisture sensitivity may help in using them as potential polymer electrolytes in energy storage devices.

Thermoresponsive Glycopolymers Based on Enzymatically Synthesized Oligo-β-Mannosyl Ethyl Methacrylates and N-Isopropylacrylamide.

We present here a series of thermoresponsive glycopolymers in the form of poly(N-isopropylacrylamide)-co-(2-[β-manno[oligo]syloxy] ethyl methacrylate)s. These copolymers were prepared from oligo-β-mannosyl ethyl methacrylates that were synthesized through enzymatic catalysis, and were subsequently investigated with respect to their aggregation and phase behavior in aqueous solution using a combination of 1H NMR spectroscopy, dynamic light scattering, cryogenic transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). The thermoresponsive glycopolymers were prepared by conventional free radical copolymerization of different mixtures of 2-(β-manno[oligo]syloxy)ethyl methacrylates (with either one or two saccharide units) and N-isopropylacrylamide (NIPAm). The results showed that below the lower critical solution temperature (LCST) of poly(NIPAm), the glycopolymers readily aggregate into nanoscale structures, partly due to the presence of the saccharide moieties. Above the LCST of poly(NIPAm), the glycopolymers rearrange into a heterogeneous mixture of fractal and disc/globular aggregates. Cryo-TEM and SAXS data demonstrated that the presence of the pendant β-mannosyl moieties in the glycopolymers induces a gradual conformational change over a wide temperature range. Even though the onset of this transition is not different from the LCST of poly(NIPAm), the gradual conformational change offers a variation of the temperature-dependent properties in comparison to poly(NIPAm), which displays a sharp coil-to-globule transition. Importantly, the compacted form of the glycopolymers shows a larger colloidal stability compared to the unmodified poly(NIPAm). In addition, the thermoresponsiveness can be conveniently tuned by varying the sugar unit-length and the oligo-β-mannosyl ethyl methacrylate content.