Surface-initiated Polymerization Research Articles

Synthesis of Oil-Soluble Polymer-Grafted Carbon Dots with Outstanding Colloidal Stability and Tribological Properties in Polyalphaolefin.

Herein, a series of polylauryl methacrylate-grafted CDs (CDs-PLMA-m, m denotes the reaction time in hours) with core-shell structure were synthesized via surface-initiated atom-transfer radical polymerization (SI-ATRP). Due to the good solubility of PLMA in hydrocarbons, all of the CDs-PLMA-m can be facilely dispersed in polyalphaolefin (PAO) to form pellucid colloidal dispersions. The reciprocating ball-on-plate sliding friction tests proved that the addition of 3.0 wt % CDs-PLMA-1 markedly lessened the wear and friction of PAO by 53.0 and 40.0%, respectively. The tribological performances of the CDs-PLMA-1 (3.0 wt %)/PAO dispersion did not attenuate sharply when the friction duration extended from 20 to 200 min or the applied load increased from 20 to 100 N, revealing the long lifetime and desirable load-carrying effect of CDs-PLMA-1. Based on the friction tests, the antifriction behavior of CDs-PLMA-1 was related to the synergies between the molecular lubrication of PLMA-1 brushes and the nanolubrication of CDs. Furthermore, the wear analyses disclosed the deposition of tribofilm composed of a lot of CDs-PLMA-1 and a spot of iron oxides, which provided oxidation resistance and an antiwear function. This study established a reliable route to the synthesis of oil-soluble polymer-grafted CDs, enabling high-efficiency lubrication of CDs in PAO.

Scattering-Free and Fast Response Polymer Brush-Stabilized Liquid Crystals Beam Steering Using Surface-Initiated Polymerization Technique.

Nonmechanical fast response optical beam steering technology is increasingly essential for telecommunications, imaging systems, optical sensing, displays, and military applications. Polymer network liquid crystal (PNLC) beam steering can achieve submillisecond response times but faces limitations due to scattering issues arising from the refractive index mismatch between the polymer network and the liquid crystals (LCs). In this article, we demonstrate a scattering-free, fast-response LC beam steering by using polymer brushes to stabilize the gradient refractive index. First, the initiator is incorporated into the alignment layer and the monomer is mixed into the LC layer. Surface-initiated polymerization (SIP) is then employed to grow the polymer brushes exclusively on the substrate's surface, thus confining the polymer network's growth to the LC bulk and reducing interfacial scattering. For polymer brush stabilized liquid crystal (PBSLC) beam steering device with a period size of 225 μm and a cell gap of 7.2 μm, the average transmission rate reaches 88% in the visible light spectrum with a haze value of only 6.91. The steering angle is 0.16, and the diffraction efficiency is 80.3%. When a voltage of 35 Vrms is applied, the primary energy can be tuned to the zeroth order, with a response time close to 1 ms. By cascading two PBSLC beam steering devices with opposite steering directions, the primary energy of the beam can be adjusted between zeroth, +1, and -1 order. This method requires only a UV light source, a precision displacement stage, a power supply, and a mask, avoiding the need for expensive equipment and complex electrode fabrication. By adjustment of the phase change period, step width, and number of steps during fabrication, the steering angles and diffraction efficiency of the PBSLC beam steering device can be easily controlled, highlighting its significant potential for industrial production.

A novel molecularly imprinted solid phase based on SiO2-Ag2O double-nucleation doped with graphene oxide for extraction and determination of flavonoids from Acanthaceae ebracteatus via HPLC-MS/MS

(Objectives) A novel method was developed for extracting and determining flavonoids from marine mangrove medicinal plants. This approach utilizes surface molecular imprinting to increase selectivity. Graphene oxide doped with a SiO2–Ag2O dual core structure served as a scaffold for synthesizing multilayer surface-imprinted polymers. The surface of the SiO2-Ag2O@GO composite was modified through self-polymerization. (Methods) Acacetin molecularly imprinted polymers (AMIPs) were created via surface-initiated precipitation polymerization with acacetin as the template. These AMIPs were synthesized and characterized via ultraviolet (UV) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). Recycling experiments demonstrated the stability of the AMIPs. Analysis of the adsorption mechanism via the Langmuir and Freundlich models indicated that the Langmuir model was more suitable for predicting AMIPs. (Results) Scatchard plots showing two different binding sites of AMIPs for acacetin adsorption at various concentrations. The class selectivity of AMIPs for flavonoids was found in Acanthaceae ebracteatus. Compared with other analogs, competitive binding experiments revealed that the polymer had greater selectivity for acacetin. After AMIP solid-phase extraction (AMISPE), the linearity, LOD, LOQ, intraday and interday variabilities, recovery, and repeatability of AMIPs combined with HPLC–MS/MS were validated, confirming the method’s selectivity, precision, accuracy, and reproducibility. The contents of acacetin, apigenin, kaempferol, luteolin, quercetin, and genistein in Acanthaceae ebracteatus were determined. (Conclusions) These results indicate that AMISPE coupled with HPLC–MS/MS is a new, simple, and practical method for extracting, purifying, and enriching flavonoids from complex samples, such as those of herbs and other natural marine plants.

Fe0-MAP Prepared Glycosurfaces for Selective Cell Capture: From Adherent to Suspended Cells.

The specific capture of live cells is crucial for various biomedical applications. Existing methods often are limited by complex production processes. This study introduces Fe0-mediated monomer-adaptation polymerization (Fe0-MAP), a convenient and rapid synthesis approach for selective cell capture using surface-engineered glycopolymer brushes. This method utilizes surface-initiated zerovalent iron-mediated reversible-deactivation radical polymerization (Fe0-SI-RDRP), offering advantages like simplicity, biocompatibility and oxygen-tolerance due to the use of iron sheet as catalysts. We successfully employed Fe0-MAP to selective capture both adherent (HeLa, L929) and suspended cells (Ramos, U937) in mammalian cell cultures. Combining excellent biocompatibility, specific and reusable cell capture capabilities, and applicability to suspended cells, Fe0-MAP establishes itself as a promising strategy for selective cell capture, holding significant potential for diverse biomedical applications.

Synthesis of a perovskite surface-coated polymer brush by photo-induced atom transfer radical polymerization

Lead halide perovskite nanocrystals (PNCs) are expected to be applied in the field of optoelectronics due to their color tunability, high color purity, and near-unity photoluminescence quantum yields. Moreover, the construction of nanocomposite structures with functional polymers has been reported to improve the material stability as well as the ordered structure with high orientation and periodicity. In this study, we demonstrated the synthesis of polymethyl methacrylate (PMMA) on the PNCs by surface-initiated polymerization. We synthesized PMMA polymer brushes by photo-induced atom transfer radical polymerization (p-ATRP) after coordinating the initiator on the PNC surface. We succeeded in obtaining PMMA-PNCs with a degree of polymerization of 21. Moreover, thermal stability tests showed that PMMA-PNCs achieved improved thermal stability compared to pristine-PNCs. This work can provide guidance for developing polymer brush-PNCs via surface-initiated polymerization.

Swelling and Degrafting of Poly(3-sulfopropyl methacrylate) Brushes.

Upon exposure to a good solvent, polymer brushes prepared via surface-initiated polymerization can undergo degrafting via cleavage of bonds that anchor the polymer tethers to the underlying substrate. As polymer brushes are often used in a solvent swollen state, this has implications for the longevity of these polymer coatings. Improving the fundamental understanding of this process is thus also of practical importance. It is believed that degrafting is the consequence of tension amplification at the bonds that anchor the polymer grafts, which is driven by swelling of the polymer brush film. Taking advantage of the sensitivity of the swelling behavior of poly(3-sulfopropyl methacrylate) (PSPMA) brushes toward changes in ionic strength, this study has investigated the degrafting behavior of these brushes in aqueous media at different LiCl and NaCl concentrations. The aim of these experiments was to investigate whether the rate constant of the degrafting process was correlated with the swelling ratio of the PSPMA brushes. The experiments show that in aqueous LiCl solutions, the initial rate constant of the degrafting process is correlated with the swelling ratio of the PSPMA brush. This observation represents a first example of the correlation between these two parameters for hydrophilic polymer brushes in aqueous media and supports the idea that degrafting is a mechanochemical process driven by a swelling-induced tension at the polymer-substrate interface.

Surface-Initiated Reversible Addition-Fragmentation Chain Transfer Polymerization (SI-RAFT) to Produce Molecularly Imprinted Polymers on Graphene Oxide for Electrochemical Sensing of Methylparathion.

A nonenzymatic redox-responsive sensor was put forward for the detection of methylparathion (MP) by designing globular nanostructures of molecularly imprinted polymers on graphene oxide (GO@MIPs) via surface-initiated reversible addition-fragmentation chain transfer polymerization (SI-RAFT). Fourier transform infrared (FTIR) spectroscopy, field emission scanning electron microscopy (FESEM), and small-angle X-ray scattering (SAXS) studies have confirmed the successful formation of receptor layers of MIPs on RAFT agent-functionalized GO sheets. The electrochemical signal with an amplified current response was attained because of the enhanced diffusion rate of ions at the interface provided by widening the pore size of the MIP film. The analytical response of GO@MIPs, validated by recording square-wave anodic stripping voltammetry (SWASV) at varying MP concentrations, followed the linear response between 0.2 and 200 ng/mL. Under optimized conditions, the sensor exhibited a limit of detection of 4.25 ng/mL with high selectivity over other interfering ions or molecules. The anti-interfering ability and good recovery (%) in food samples directed the use of the proposed sensor toward real-time monitoring and also toward future mimicking of surfaces.

Improvement of tribological and anti-corrosive performance of MXene nanosheets by grafting polymer brush

Herein, the anti-corrosive polymer brush functionalized MXene (P-MBTS2MA@MXene) was successfully prepared via surface-initiated polymerization. First, the dopamine initiator (DA-Br) can self-assemble onto MXene nanosheets formation of initiator modified MXene (PDA-Br@MXene) via spontaneous oxidative polymerization, then the corrosion inhibitor MBT derivative MBTS2MA monomer was grafted onto MXene nanosheets through surface-initiated atom transfer radical polymerization (SI-ATRP) to obtain polymer brush P-MBTS2MA functionalized MXene (P-MBTS2MA@MXene). The prepared P-MBTS2MA@MXene served as lubricant additive, manifesting good tribological properties with a low COF of 0.098 % and 94.8 % wear-reduction, which is attributed to the shielding effect and protective film formed by P-MBTS2MA@MXene. Additionally, the grafting P-MBTS2MA endows MXene nanosheets with improved anti-corrosion property, which prevents further corrosion of the metal surface via releasing corrosion resistance molecule MBT.

Imparting semi-permanent demoldability to stainless steel mold using surface-initiated solution polymerization of stearyl methacrylate

The growing market demand for compact and precisely-designed polymeric products has raised challenges during the demolding stage of manufacturing. An increased contact area between the product and the mold increases adhesion, which reduces dimensional stability and aesthetics. Conventional solutions like surface roughness improvement or release agent coatings suffer from reduced productivity and impurity-related issues affecting mechanical properties. To address these challenges, we imparted the semi-permanent demoldability to a stainless steel (SUS) mold by polymerizing stearyl methacrylate monomer on its surface using a surface-initiated solution polymerization technique. The polymerization state was confirmed through Fourier transform infrared spectroscopy and field emission scanning electron microscopy. The demoldablity was investigated using the appropriately-designed lap shear tests to simulate the demolding stage of epoxy resin-filled SUS mold to ensure sufficient performance compared with the neat and commercial release agent (RA) treated molds, and durability of the demoldability was confirmed via repetitive single-lap shear tests simulating the molding and demolding processes. The surfaced polymerized mold exhibited excellent demoldability with 96.5 % improvement over the neat one, and showed excellent durability over 5 repeated molding cycles, while the commercial RA showed significant degradation of demoldability. Furthermore, the mechanism of demoldability enhancement using the proposed surface polymerization was investigated by characterization of the surface dewetting pattern and contact angle measurements of the epoxy resin on the modified mold surface.

Grafting photochromic spiropyran polymer brushes on natural rubber surface via surface-initiated ring-opening metathesis polymerization

The modification of stereoregulated functionalized polymers on the surface of natural rubber (NR) is a challenging task. This work provided a practicable grafting method to design photochromic polymer brushes on the NR surfaces using surface-initiated ring-opening metathesis polymerization (SI-ROMP). The designed photochromic polymer brushes were based on norbornenes with spiropyrin (SP) pendents, and grew from the surface of NR films in the presence of Grubbs 2nd catalyst. The results showed that the grafting rate of polymer brushes with photoisomerization structure reached up to 44.91 %. The modified natural rubber (NR-SP) films exhibited rapid coloring/decolorization property under UV irradiation and visible light. This photochromic property initiated by the light-induced isomerisation of the spiropyran structure and the increased surface energy under light stimuli. NR-SP films exhibited stable photochromic characteristics and outstanding anti-fatigue properties after exposing to over six cycles of consecutive UV/Vis irradiation. A simple and practical strategy for the preparation of highly sensitive photochromic natural rubber materials is proposed and provides a potential application in the fields of information storage and anti-counterfeiting.

Surface-Grafted Biocompatible Polymer Conductors for Stable and Compliant Electrodes for Brain Interfaces.

Durable and conductive interfaces that enable chronic and high-resolution recording of neural activity are essential for understanding and treating neurodegenerative disorders. These chronic implants require long-term stability and small contact areas. Consequently, they are often coated with a blend of conductive polymers and are crosslinked to enhance durability despite the potentially deleterious effect of crosslinking on the mechanical and electrical properties. Here the grafting of the poly(3,4 ethylenedioxythiophene) scaffold, poly(styrenesulfonate)-b-poly(poly(ethylene glycol) methyl ether methacrylate block copolymer brush to gold, in a controlled and tunable manner, by surface-initiated atom-transfer radical polymerization (SI-ATRP) is described. This "block-brush" provides high volumetric capacitance (120 F cm─3), strong adhesion to the metal (4h ultrasonication), improved surface hydrophilicity, and stability against 10000 charge-discharge voltage sweeps on a multiarray neural electrode. In addition, the block-brush film showed 33% improved stability against current pulsing. This approach can open numerous avenues for exploring specialized polymer brushes for bioelectronics research and application.

Ionic conjugated microporous polymer nanofiltration membrane with optimized site for rapid separation of dyes

Nowadays, organic dyes are one of the main sources of water pollution, posing a serious threat to human life and public safety, and the development of materials capable of eliminating dyes from water is challenging due to their high chemical stability that makes them difficult to eliminate. Herein, we report an example of a dense and continuous ionic conjugated microporous polymer (iCMP) membranes constructed by a surface-initiated polymerization strategy, in which the pore size of the iCMP membranes was tuned by exchanging different counter-anions (Cl-, Br-, BF4-) to achieve effective separation of organic dyes in water. Our study shows that the BF4- exchanged iCMP membrane has the smallest pore size, allowing it to effectively separate organic dyes in water without loss of water permeability (water permeability can reach as low as 447.9 L m−2 h−1 MPa−1 and rejection can reach as low as 99.5 % or more), which is far superior to commercially available membranes. This strategy of incorporating size regulation in two-dimensional membrane materials may evolve into a versatile platform for precision separations.

Hydrogen bonds-based flexible regulation of acetaminophen adsorption/desorption behavior in aqueous system: Role of the smart thermoresponsive graphene oxide

Adsorption and regeneration techniques are crucial for the treatment of pharmaceuticals in drinking water. However, adsorbents with strong adsorption binding force and simple regeneration have been a challenging issue in the adsorption area that has not been successfully resolved. In this study, a thermos-responsive smart adsorbent, poly (N-isopropylacrylamide) modified graphene oxide (GO-g-PNIPAM) was successfully synthesized using a “graft from” surface-initiated atom-transfer radical polymerization (Si-ATRP) technology. Acetaminophen (Acet) has an excellent efficient adsorption/desorption behavior (107.40/83.9 mg/g) that is potentially flexible controlled by the modified adsorbent only by adjusting the temperature. This exceptional property is primarily caused by the phenomenon that PNIPAM cooperated with GO to undergo hydrophilic transformation in response to temperature changes, allowing for the free construction and deconstruction of hydrogen bonds between PNIPAM and contaminants. More importantly, as external factors (NaCl and urea) are mediated, the development of hydrogen bonds would be further encouraged to further stabilized the efficiency, and the desorption temperature would continue decrease by 2 and 6 °C, respectively, to promote the regeneration process. This outstanding work provides novel perspectives for subsequent smart sensitive materials to flexibly regulate the treatment efficiency of pollutants.

Durable and dense zwitterionic polymer brushes initiated from surface-segregated cyclic initiator via atom transfer radical polymerization

Immobilization of initiators on a polymer surface for surface-initiated polymerization has primarily been achieved via covalent bonds. However, this approach is subject to limitations, such as the requirement for additional processing steps and different customized methods tailored to the specific characteristics of each polymer. In this study, initiator immobilization was achieved by surface segregation, a phenomenon observed in polymer blends wherein one component spontaneously enriches the surface, thereby enabling the modification of surface properties. Specifically, we designed cyclic oligomers containing an atom transfer radical polymerization (ATRP) initiator. The enhanced performance of surface segregation mediated by the cyclic topology was evaluated, along with the surface-initiated polymerization initiated by the surface-segregated oligomer. The kinetics of the ATRP reaction for the cyclic initiators were investigated, and the zwitterion polymer brush density was also calculated. The robustness of the brushes was evaluated through leaching tests, which revealed no notable alterations before and after the assessments. The antifouling effect of the brushes was confirmed through protein adsorption, platelet adhesion, bacterial attachment, and whole-blood circulation experiments. These antifouling examinations demonstrated reduced substance attachment of zwitterionic polymer brushes. Lastly, experiments on optimizing the ATRP catalyst loading during the surface-initiated ATRP were conducted. The excellent performance of the cyclic initiators is expected to provide new insights and opportunities in the field of surface-initiated polymerization. Moreover, the formation of zwitterion brushes via cyclic initiators holds promise for versatile applications in the field of long-term utilization in biointerfaces, offering a wide range of potential uses.

XPS Depth-Profiling Studies of Chlorophyll Binding to Poly(cysteine methacrylate) Scaffolds in Pigment-Polymer Antenna Complexes Using a Gas Cluster Ion Source.

X-ray photoelectron spectroscopy (XPS) depth-profiling with an argon gas cluster ion source (GCIS) was used to characterize the spatial distribution of chlorophyll a (Chl) within a poly(cysteine methacrylate) (PCysMA) brush grown by surface-initiated atom-transfer radical polymerization (ATRP) from a planar surface. The organization of Chl is controlled by adjusting the brush grafting density and polymerization time. For dense brushes, the C, N, S elemental composition remains constant throughout the 36 nm brush layer until the underlying gold substrate is approached. However, for either reduced density brushes (mean thickness ∼20 nm) or mushrooms grown with reduced grafting densities (mean thickness 6-9 nm), elemental intensities decrease continuously throughout the brush layer, because photoelectrons are less strongly attenuated for such systems. For all brushes, the fraction of positively charged nitrogen atoms (N+/N0) decreases with increasing depth. Chl binding causes a marked reduction in N+/N0 within the brushes and produces a new feature at 398.1 eV in the N1s core-line spectrum assigned to tetrapyrrole ring nitrogen atoms coordinated to Zn2+. For all grafting densities, the N/S atomic ratio remains approximately constant as a function of brush depth, which indicates a uniform distribution of Chl throughout the brush layer. However, a larger fraction of repeat units bound to Chl is observed at lower grafting densities, reflecting a progressive reduction in steric congestion that enables more uniform distribution of the bulky Chl units throughout the brush layer. In summary, XPS depth-profiling using a GCIS is a powerful tool for characterization of these complex materials.

In Situ Preparation of Star-Shaped Protein-"Smart" Polymer Conjugates with pH and Thermo-Dual Responsibility for Bacterial Separation.

To achieve effective separation and enrichment of bacteria, a novel synthetic scheme was developed to synthesize star-style boronate-functionalized copolymers with excellent hydrophilicity and temperature and pH responsiveness. A hydrophilic copolymer brush was synthesized by combining surface-initiated atom-transfer radical polymerization with amide reaction using bovine serum albumin as the core. The copolymer brush was further modified by introducing and immobilizing fluorophenylboronic acids through an amide reaction, resulting in the formation of boronate affinity material BSA@poly(NIPAm-co-AGE)@DFFPBA. The morphology and organic content of BSA@poly(NIPAm-co-AGE)@DFFPBA were systematically characterized. The BSA-derived composites demonstrated a strong binding capacity to both Gram-positive and Gram-negative bacteria. The binding capabilities of the affinity composite to Staphylococcus aureus and Salmonella spp. were 195.8 × 1010 CFU/g and 79.2 × 1010 CFU/g, respectively, which indicates that the novel composite exhibits a high binding capability to bacteria and shows a particularly more significant binding capacity toward Gram-positive bacteria. The bacterial binding of BSA@poly(NIPAm-co-AGE)@DFFPBA can be effectively altered by adjusting the pH and temperature. This study demonstrated that the star-shaped affinity composite had the potential to serve as an affinity material for the rapid separation and enrichment of bacteria in complex samples.

Sealing porous carbon via surface-initiated polymerization achieves low-surface-area Si-C microparticles for Li-ion batteries

Porous Si-carbon composite architecture represents an effective design for lithium-ion batteries (LIBs) anodes. However, the high specific surface area (SSA) greatly negates cell initial Coulombic efficiency (ICE), and the function of porous carbon is challenged by practical conditions such as calendaring and high-mass-loading cycling. Here, we report a crosslinked conductive polymer layer as sealing layer for porous Si-C particles to enable high ICE and stable cycling of densified Si-anodes. A surface-initiated polymerization was adopted to form a conformal polymeric skin that can greatly lower the SSA and improve ICE of porous Si-C particles (94.8 vs. 5.7 m2/g, and 77.3% vs. 84.4%). The “sealed” Si-C particle maintains desirable intraparticle porosity to digest the volume changes during Li insertion, while the polymeric skin is key to shield off electrolyte penetration into the particles interior and to mechanically package the porous secondary particles throughout calendaring and cycling. The Si-C graphite mixtures anode (650 mAh/g) retains 70.8% capacity after 500 cycles. Adopting high-mass-loading NCM622, the full cell with stringent electrode metrics (anode at 1.2 g/cm3, NCM622 at 3.1 g/cm3, 3.4 mAh/cm2) demonstrates 65.9% capacity retention after 100 cycles. This study opens up a pathway to produce low-SSA porous anodes for practical LIBs.

PEG-functionalized aliphatic polycarbonate brushes with self-polishing dynamic antifouling properties

Hydrophilic antifouling polymers provide excellent antifouling effects under usual short-term use conditions, but the long-term accumulation of contaminants causes them to lose their antifouling properties. To overcome this drawback, surface-initiated ring-opening graft polymerization (SI-ROP) was performed on the surface of the material by applying the cyclic carbide monomer 4′-(fluorosulfonyl)benzyl-5-methyl-2-oxo-1,3-dioxane-5-carboxylate (FMC), which contains a sulfonylfluoride group on the side chain, followed by a “sulfur(IV)-fluorine exchange” (SuFEx) post click modification reaction to link the hydrophilic polyethylene glycol (PEG) to the polyFMC (PFMC) brush, and a novel antifouling strategy for self-polishing dynamic antifouling surfaces was developed. The experimental results showed that the antifouling surface could effectively prevent the adsorption of proteins such as bovine serum albumin (BSA, ∼96.4%), fibrinogen (Fg, ∼87.8%) and lysozyme (Lyz ∼69.4%) as well as the adhesion of microorganisms such as the bacteria Staphylococcus aureus (S. aureus) (∼87.5%) and HeLa cells (∼67.2%). Moreover, the enzymatically self-polished surface still has excellent antifouling properties. Therefore, this modification method has potential applications in the field of biosensors and novel antifouling materials.

Surface-Initiated Polymerization with an Initiator Gradient: A Monte Carlo Simulation.

Due to the difficulty of accurately characterizing properties such as the molecular weight (Mn) and grafting density (σ) of gradient brushes (GBs), these properties are traditionally assumed to be uniform in space to simplify analysis. Applying a stochastic reaction model (SRM) developed for heterogeneous polymerizations, we explored surface-initiated polymerizations (SIPs) with initiator gradients in lattice Monte Carlo simulations to examine this assumption. An initial exploration of SIPs with 'homogeneously' distributed initiators revealed that increasing σ slows down the polymerization process, resulting in polymers with lower molecular weight and larger dispersity (Đ) for a given reaction time. In SIPs with an initiator gradient, we observed that the properties of the polymers are position-dependent, with lower Mn and larger Đ in regions of higher σ, indicating the non-uniform properties of polymers in GBs. The results reveal a significant deviation in the scaling behavior of brush height with σ compared to experimental data and theoretical predictions, and this deviation is attributed to the non-uniform Mn and Đ.

Grafting Block Copolymer Nanoparticles to a Surface via Aqueous Photoinduced Polymerization-induced Self-Assembly at Room Temperature.

The creation of well-defined surface nanostructures is important for a diverse set of applications such as cell adhesion, superhydrophobic coating, and lithography. In this study, we describe a robust bottom-up method for surface functionalization that involves surface-initiated reversible deactivation radical polymerization (RDRP) and the grafting of block copolymer nanoparticles to material surfaces via aqueous photoinduced polymerization-induced self-assembly (photo-PISA) at room temperature. Using silica nanoparticles as a model substrate, colloidal mesoscale hybrid assemblies with various morphologies were successfully prepared. The morphologies can be easily tuned by changing the lengths of macromolecular chain transfer agents and parameters of the silica nanoparticles. The surface-initiated photo-PISA approach can also be employed for other large-scale substrates such as silicon wafer. Taking advantage of mild reaction conditions of this method (room temperature, aqueous medium, and visible light), enzymatic deoxygenation was introduced to develop oxygen-tolerant surface-initiated photo-PISA that can fabricate well-defined nanostructures on large-scale substrates under open-to-air conditions.