Molecular Brushes Research Articles

Reconfigurable All-Oil Microfluidic Devices by 3D Printing.

Nanoparticle surfactants have been widely used to construct structured liquids in oil-water systems. Less attention, though, has been given in non-aqueous systems, for example, oil-oil systems, mainly due to the lack of suitable surfactants. Here, by using newly developed molecular brush surfactants (MBSs) that form at the DMSO-silicone oil interface, the construction of all-oil microfluidic devices is reported with advanced functions. Due to the high interfacial activity of MBSs, Plateau-Rayleigh instabilities of liquid jets can be completely suppressed, leading to the production of liquid threads with jammed MBSs at the interface. Taking advantage of the 3D printing technique, all-oil microfluidic devices with complex structures can be constructed, showing promising applications in mass transmission, chemical separation, and material synthesis.

Oligo(ethylene glycol) methacrylate-based molecular bottlebrushes: Correlations between composition and phase transition temperatures in aqueous solutions

Correlations between phase transition temperatures (Tpt) in aqueous solutions and quantitative amphiphilic characteristics of a large array of thermoresponsive molecular bottlebrushes, polymethacrylates containing oligoethylene glycol (OEG), oligopropylene glycol (OPG), higher n-alkyl blocks of different lengths in their side chains, have been systematically studied for the first time. The estimated hydrophilic-lipophilic balance (HLBp) of the polymers calculated from the HLBm of the starting monomers using the Davis group number method was used for the amphiphilic characterization. The adequacy of this approach was confirmed by analyzing experimental data on the distribution of monomers and polymers in hexane-water heterophase system. Depending on the mutual arrangement of OEG-, OPG- and n-alkyl blocks in macromolecules, 107 considered molecular brushes considered were divided into 5 types and specific correlations between Tpt and HLBp values were determined for each type. The correlations found can be used to predict the phase transition temperatures of promising thermoresponsive polymethacrylic molecular brushes containing OEG-, OPG- and higher n-alkyl blocks in the side chains when varying the length of the blocks and their ratio in the macromolecules.

Beyond Traditional Stimuli: Exploring Salt-Responsive Bottlebrush Polymers-Trends, Applications, and Perspectives.

Bottlebrush polymers represent an important class of high-density side-chain-grafted polymers traditionally with high molecular weights, in which one or more polymeric side chains are tethered to each repeating unit of a linear polymer backbone, such that these macromolecules look like "bottlebrushes". The arrangement of molecular brushes is determined by side chains located at a distance considerably smaller than their unperturbed dimensions, leading to substantial monomer congestion and entropically unfavorable extension of both the backbone and the side chains. Traditionally, the conformation and physical properties of polymers are influenced by external stimuli such as solvent, temperature, pH, and light. However, a unique stimulus, salt, has recently gained attention as a means to induce shape changes in these molecular brushes. While the stimulus has been less researched to date, we see that these systems, when stimulated with salts, have the potential to be used in various engineering applications. This potential stems from the unique properties and behaviors these systems show when exposed to different salts, which could lead to new solutions and improvements in engineering processes, thus serving as the primary motivation for this narrative, as we aim to explore and highlight the various ways these systems can be utilized and the benefits they could bring to the field of engineering. This Review aims to introduce the concept of stimuli-responsive bottlebrush polymers, explore the evolutionary trajectory, delve into current trends in salt-responsive bottlebrush polymers, and elucidate how these polymers are addressing a variety of engineering challenges.

Amidoxime‐based Star Polymer Adsorbent with Ultra‐High Uranyl Affinity for Extremely Fast Uranium Extraction from Natural Seawater

AbstractPolymer adsorbents functionalized with amidoxime groups are widely considered to have the most industrial potential for uranium extraction from seawater. However, the entanglement upon the collapse of polymer chain in seawater greatly reduces the utilization ratio of amidoxime ligands. Herein, a novel star‐shaped molecular brush adsorbent (β‐CD‐g‐PAO) is obtained by densely grafting polyamidoxime (PAO) chains from β‐cyclodextrin (β‐CD). Experimental and theoretical results reveal that, in contrast to conventional linear polymer adsorbents, the star polymer adsorbent with a high grafting density of PAO side chains enables strong steric repulsion between the polymer chains, leading to increased persistence length and disentanglement of side chains. As a result, the star polymer adsorbent shows higher accessibility of the adsorption ligands with lower adsorption energy, achieving an adsorption capacity of up to 944.75 mg g−1 in uranium‐spiked seawater, surpassing that of conventional linear PAO by 3.2 times. Remarkably, this star polymer adsorbent demonstrates an extraordinarily adsorption capacity of 10.9 mg−1 g−1 in only 1 day in natural seawater, coupled with excellent affinity for uranyl ions (K = 0.31 pM). The unique topological structure design provides a new approach to solving the problem of low utilization ratio of functional ligands in polymer adsorbents.

Realization of Enhanced Interfacial Lithium-Ion Transfer in Composite Polymer Electrolytes via Grafting Oligo-PEG Molecular Brushes on Silica-Coated Nanofibers for All-Solid-State Lithium Metal Batteries.

Polyether-based polymer electrolytes are attractive but still challenging for high-energy-density solid-state lithium metal batteries due to their limited Li-ion conductivity at room temperature. Herein, an oligomeric polyethylene glycol methyl ether methacrylate (PEGMEM)-modified silica-coated polyimide fibrous scaffold (PINF@PEGMEM-SiO2) was introduced in polyethylene glycol dimethyl ether (PEGDME) to enhance the Li-ion transportation at room temperature. PINF@PEGMEM-SiO2 was developed to build a continuous and interconnected interface for continuous Li-ion transportation in bulk. The carbonyl groups (C═O) of PEGMEM on SiO2 can promote the dissociation of lithium salts and enhance the migration of free Li ions at the interface. The same -C-C-O- unit contained in both PEGMEM and PEGDME ensures the compatibility of PEGMEM at the interface and PEGDME in the bulk. The prepared PEGDME-based polymer electrolyte exhibits a high ionic conductivity of 1.14 × 10-4 S cm-1 at 25 °C and an improved Li-ion transference number of 0.41. Furthermore, LiFePO4/Li and LiNi0.8Co0.1Mn0.1O2/Li cells with excellent cyclability and rate capability at ambient temperature are obtained.

Cellulose nanocrystal thermal smart molecular brushes with upper critical aggregation temperature

Grafting thermo-responsive polymers onto cellulose nanocrystals (CNCs) and achieving critical temperature regulation has drawn significant research interest. The thermal transition behavior of CNCs can be controlled by adjusting the polymer molecular brushes on the CNCs surface. We synthesized poly((2-dimethylamino) ethyl methacrylate) (PDMAEMA) grafted CNCs via surface-initiated reversible addition–fragmentation chain transfer, followed by modifying PDMAEMA brushes into poly-3-dimethyl(methacryloyloxyethyl) ammonium propane sulfonate (PDMAPS) brushes via quaternization. The critical temperature was regulated by modifying and grafting of poly (ethylene glycol) methacrylate. Found the thermal stimulus-responsive type and transition point of CNCs can be controlled by adjusting the surface molecular brushes. Ultraviolet-visible spectroscopy and dynamic light scattering analyses indicated that CNC–PDMAEMA aggregated above 70 °C, whereas CNC–PDMAPS aggregated below 31 °C. The thermo-responsive materials based on CNCs exhibited a conversion from a lower critical aggregation temperature to an upper critical aggregation temperature (UCAT) type. CNC–PDMAPS–mPEG was obtained by modifying and grafting for UCAT to be regulated to approximately 37 °C, which is close to the human body temperature. CNC–PDMAPS and CNC–PDMAPS–mPEG exhibited only microscopic alterations and could encapsulate and release substances. Therefore, they demonstrate considerable potential for biomedical applications.

Selenium Nanoparticles Stabilized by Amphiphilic Molecular Brushes with Varying Degrees of Polymerization of Side Chains: Spectral and Structural-Morphological Characteristics

Selenium Nanoparticles Stabilized by Amphiphilic Molecular Brushes with Varying Degrees of Polymerization of Side Chains: Spectral and Structural-Morphological Characteristics

Icephobic Durability of Molecular Brush-Structured PDMS Soft Coatings.

The accumulation of ice can pose numerous inconveniences and potential hazards, profoundly affecting both human productivity and daily life. To combat the challenges posed by icing, extensive research efforts have been dedicated to the development of low-ice adhesion surfaces. In this study, we harness the power of molecular dynamics simulations to delve into the intricate dynamics of polymer chains and their role in determining the modulus of the material. We present a novel strategy to prepare ultralow-modulus poly(dimethylsiloxane) (PDMS) elastomers with a molecular brush configuration as icephobic materials. The process involves grafting monohydride-terminated PDMS (H-PDMS) as side chains onto backbone chain PDMS with pendant vinyl functional groups to yield a molecular brush structure. The segments of this polymer structure effectively restrict interchain entanglement, thereby rendering a lower modulus compared to traditional linear structures at an equivalent cross-linking density. The developed soft coating exhibits a remarkably ultralow ice adhesion strength of 13.1 ± 1.1 kPa. Even after enduring 50 cycles of icing and deicing, the ice adhesion strength of this coating steadfastly stayed below 16 kPa, showing no notable increase. Importantly, the molecular brush coating applied to glass demonstrated an impressive light transmittance of 92.1% within the visible light spectrum, surpassing the transmittance of bare glass, which was measured at 91.3%. This icephobic coating with exceptional light transmittance offers a wide range of applications and holds significant potential as a practical icephobic material.

Regulating molecular brush structure on cotton textiles for efficient antibacterial properties

The molecular brush structures have been developed on cotton textiles for long-term and efficient broad-spectrum antimicrobial performances through the cooperation of alkyl-chain and quaternary ammonium sites. Results show that efficient antibacterial performances can be achieved by the regulation of the alkyl chain length and quaternary ammonium sites. The antibacterial efficiency of the optimized molecular brush structure of [3-(N,N-Dimethylamino)propyl]trimethoxysilane with cetyl modification on cotton textiles (CT-DM-16) can reach more than 99 % against both E. coli and S. aureus. Alkyl-chain grafting displayed significantly improvement in the antibacterial activity against S. aureus with (N,N-Diethyl-3-aminopropyl)trimethoxysilane modification on cotton textiles (CT-DE) based materials. The positive N sites and alkyl chains played important roles in the antibacterial process. Proteomic analysis reveals that the contributions of cytoskeleton and membrane-enclosed lumen in differentially expressed proteins have been increased for the S. aureus antibacterial process, confirming the promoted puncture capacity with alkyl-chain grafting. Theoretical calculations indicate that the positive charge of N sites can be enhanced through alkyl-chain grafting, and the possible distortion of the brush structure in application can further increase the positive charge of N sites. Uncovering the regulation mechanism is considered to be important guidance to develop novel and practical antibacterial materials.

Structure and Organization of Amphiphilic Mikto-Grafted Molecular Brushes at Liquid/Liquid Planar Interfaces

Structure and Organization of Amphiphilic Mikto-Grafted Molecular Brushes at Liquid/Liquid Planar Interfaces

The impact of architecture on the behavior of siloxane-grafted polymethacrylate

In this paper, we studied for the first time the impact of the molecular weight, Mn, and the topology on the molecular dynamics of a series of grafted poly(poly(dimethylsiloxane methacrylate)) (polyPDMSMA). The behavior of grafted (molecular brushes) polyPDMSMA and their three-armed counterparts of tailor-made properties prepared by Atom Transfer Radical Polymerization (ATRP) was monitored by means of broadband dielectric spectroscopy (BDS), differential scanning calorimetry (DSC) and comprehensive rheology analysis. Surprisingly, the dielectric loss spectra of all studied polyPDMSMA exhibit the presence of two dielectric relaxation processes above their glass transition temperature, Tg. A comparison of dielectric, calorimetric and mechanical data indicated that the faster and slower relaxation processes identified in loss spectra can be related to the segmental and chain dynamics, respectively. Interestingly, we observed that the “local” segmental dynamics of studied polyPDMSMA, involving the mobility of few repeatable units creating a segment, is almost unaffected by neither the length of polymer chain, number of grafts nor its topology. This is also reflected in a weak molecular weight-dependences of Tg of studied polyPDMSMA independently to their topology. On the other hand, the time-scale separation between segmental and the chain modes as well as the amplitude of the latter process increase with growing Mn of all examined polyPDMSMA. Additionally, it should be mentioned that the mechanical data collected for samples characterized by high molecular weight (of Mn > 280 kg/mol) reveal the emergence of additional process (most likely related to the grafts and/or the star arm relaxation) at the intermediate regime, independently to their topology. Interestingly, this mode was observed to be much slower for the star-shaped macromolecules when compared to the grafted polymers, despite their lower Mn. This implies that the observed differences are not a result of different molecular weights, but rather originate from a various molecular mechanism due to the different topology of the studied samples. In this context, one can assume that in the case of high-molecular-weight macromolecules, the backbone architecture has a significant influence on the behavior of polymers, including their molecular dynamics.

Molecular brushes with long polyfluorene backbones and polymethacrylic acid side chains: Luminescent properties and self‐organization in solutions

AbstractA series of molecular brushes with a polyfluorene (PF) backbone and polymethacrylic acid side chains of varying lengths were prepared by atom transfer radical polymerization. The structure and composition of the synthesized compounds were confirmed by 1H NMR and IR spectroscopy. Effect of the length of the backbone on spectral and conformational parameters of the macromolecules in solutions was analyzed. The grafting density of side chains was about 90%. Spectral methods have been used to determine the dependence of side chain grafting on the luminescent properties of polymer solutions, including quantum yields. It was shown that an optimal length of polymethacrylic acid side chains provides solubility of the polymer brushes. Solutions of PF‐graft‐polymethacrylic acid complexes with the model substance curcumin were investigated. It was established that the molecular brushes containing curcumin form monomolecular micelles. Molecular brushes with zinc phthalocyanine, potential systems for photodynamic, and photothermal therapy, were studied.

Searching for the synthetic methods towards siloxane molecular brushes

Searching for the synthetic methods towards siloxane molecular brushes

Copolyimide molecular brushes with poly(methacrylic acid) side chains as additive to polyphthalamide membrane: Organization, physical, and transport properties

AbstractMacromolecules of complex architecture find application as modifiers of commercial polymeric membrane materials. In this work, copolyimide molecular brushes (coPI) composed of polyimide backbone and poly(methacrylic acid) side chains were used to modify poly(m‐phenylene iso‐phthalamide) (PPA). Structure, physical, mechanical, and transport properties of dense nonporous PPA/coPI membranes containing up to 10 wt% coPI were studied. The effect of included coPI on the membrane structure was estimated using atomic force microscopy and mechanical tests. The coPI modifier contributes to the additional formation of free volume elements evenly distributed throughout the membrane. Transport properties of PPA/coPI membranes were investigated via sorption tests and pervaporation separation of methanol (MeOH) and methyl tert‐butyl ether (MTBE) mixtures. The inclusion of coPI modifier in the PPA membrane leads to an increase in the total flux of the membrane. The highest separation factor was found for the PPA/coPI membrane containing 10 wt% coPI; transport properties of the best membrane were compared with the literature data on separation of the azeotropic MeOH–MTBE mixture.

Facile synthesis of asymmetric molecular brushes with triple side chains using a multivalent monomer strategy

Heterografted molecular brushes comprising three different brushes were synthesized based on the Br-acrylate-epoxide multivalent monomer strategy, which enabled the fabrication of 2D platelets and the stabilization of different emulsions.

Asymmetric porous hydrogel encapsulating vulcanized molecular brushes with anti-bacterial adhesion, anti-infection, and pro-healing properties towards infected wound treatment.

Inspired by the hierarchical structure of the skin, asymmetric porous hydrogel encapsulating vulcanized molecular brushes (VMB@APH) as multifunctional wound dressing has been integrally constructed. The as-obtained VMB@APH effectively combines the anti-bacterial adhesion, anti-infection, and pro-healing properties, which is of great significance for accelerating the recovery of infected wounds.

Fabrication of a poly(N-isopropylacrylamide)-grafted alginate composite aerogel for efficient treatment of emulsified oily wastewater

The treatment of emulsion wastewater poses significant challenges. In this study, a novel porous material, namely esterified bagasse/poly(N, N-dimethylacrylamide)/sodium alginate (SBS/PDMAA/Alg) aerogel, was developed for efficient demulsification and oil recovery. By grafting a poly(N-isopropylacrylamide) (PNIPAM) brush onto the SBS/PDMAA/Alg skeleton through free radical polymerization, the resulting aerogel exhibits both surface charge and a molecular brush structure. The aerogel demonstrates remarkable demulsification efficiency for cationic surfactant-stabilized emulsions at various concentrations, achieving a demulsification efficiency of 95.6% even at an oil content of 100 g L−1. Furthermore, the molecular brush structure extends the application range of the aerogel, enabling a demulsification efficiency of 98.3% for anionic and non-ionic surfactant-stabilized emulsions. The interpenetrating polymer network (IPN) structure formed by SBS, PDMAA, and alginate enhances the mechanical stability of the aerogel, enabling a demulsification efficiency of 91.3% even after 20 repeated cycles. The demulsification ability of the composite aerogel is attributed to its surface charge, high interfacial activity, and unique brush-like structure. A demulsification mechanism based on the synergistic effect of surface charge and molecular brush is proposed to elucidate the efficient demulsification process.

Passivation protein-adhesion platform promoting stent reendothelialization using two-electron-assisted oxidation of polyphenols

Superhydrophilic surfaces play an important role in nature. Inspired by this, scientists have designed various superhydrophilic materials that are widely used in the field of biomaterials, such as PEG molecular brushes and zwitterionic materials. However, superhydrophilic coatings with only anti-fouling properties do not satisfy the requirements for rapid reendothelialization of cardiovascular stent surfaces. Herein, a novel polyphenol superhydrophilic surface with passivated protein-adsorption properties was developed using two-electron oxidation of dopamine and polyphenols. This coating has a multiscale effects: 1) macroscopically: anti-fouling properties of superhydrophilic; 2) microscopically: protein adhesion properties of active groups (quinone-, amino-, hydroxyphenyl groups and aromatic ring). Polyphenols not only enhance the ability of coating to passivate protein-adsorption, but also make the coating have polyphenol-related biological functions. Therefore, the polyphenol and passivated protein-adsorption platform together maintain the stability of the scaffold microenvironment. This, in turn, provides favorable conditions for the growth of endothelial cells on the scaffold surface. In vivo implantation of the coated stents into the abdominal aorta resulted in uniform and dense endothelial cells covering the surface of the neointima. Moreover, new endothelial cells secreted large amounts of functional endothelial nitric oxide synthase like healthy endothelial cells. These results indicate that the polyphenol superhydrophilic coating potentially resists intra-stent restenosis and promotes surface reendothelialization. Hence, polyphenol superhydrophilic coatings with passivated protein-adsorption properties constructed by two-electron-assisted oxidation are a highly effective and versatile surface-modification strategy for implantable cardiovascular devices.

Morphologically Tunable Rectangular Platelets Self-Assembled from Diblock Molecular Brushes Containing Azopyridine Pendants.

Two-dimensional (2D) platelet structures are of growing importance as building blocks for the preparation of optical and electrical devices. However, the creation of morphologically tunable rectangular platelets through polymer self-assembly still remains a challenge. Herein, we describe a rational strategy for the fabrication of 2D rectangular platelets by stacking azopyridine-containing diblock molecular brushes in two dimensions in a selective solvent. Amphiphilic PEG-co-(PtBA-g-PAzoPy) DMBs with poly(ethylene glycol) (PEG) block, poly(t-butyl acrylate) (PtBA) backbone, and poly(6-(4-(4-pyridyazo)phenoxy)-hexyl methacrylate) (PAzoPy) brush were synthesized by sequential reversible addition-fragmentation chain transfer polymerization and atom transfer radical polymerization. Various rectangular platelets were obtained via the solution self-assembly of PEG-co-(PtBA-g-PAzoPy) through a heating-cooling-aging process in which the morphology and size of platelets could be controlled by adjusting the composition of DMBs as well as the solvent polarity. In addition, we investigated the metal chelation ability and H-bonding-assisted co-assembly capability of PEG-co-(PtBA-g-PAzoPy). The results displayed that 2D hybrids and flower-like platelets were formed, respectively. Our study presents an efficient method to fabricate rectangular platelets with tunable morphologies.

MXene-based polymer brushes decorated with small-sized Ag nanoparticles enabled high-performance lithium host for stable lithium metal battery

Li metal stands out as a promising anode material for next-generation energy storage devices. Nevertheless, the application of Li metal anode is hampered by some severe issues of uncontrolled dendrite growth and infinite volume expansion during cycling. In this study, a high-performance Li metal host consisting of poly(4-vinylpyridine) grafted Ti3C2 MXene molecular brushes decorated with uniformly distributed small-sized Ag nanoparticles was prepared. Benefiting from the synergetic effect between Ti3C2-g-PV4P sheets and Ag nanoparticles, dendrite-free Li deposition was achieved with a low nucleation overpotential (∼3.2 mV) and high Coulombic efficiencies (>98 % after 200 cycles). The full cells assembled with the Li@host anode and LiFePO4 cathode delivered a high discharge capacity (102.8 mAh g−1 at 5C) and excellent cycling stability (137.8 mAh g−1 after 150 cycles at 1C). This work demonstrates a perspective design and application of Li metal host materials.