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Zwitterions have been shown experimentally to enhance the dielectric constant of ionic media, owing to their large molecular dipole. Many studies since explored the enhancement of ionic conductivity with zwitterion additives as well as bulk behavior of zwitterions. Here, we examine the capacitance behavior of zwitterions between charged parallel plates using a mean-field theory. Employing only chain connectivity of a cation and anion with neutral monomers in between with mean-field electrostatics, we show that our model captures the high-dielectric behavior of zwitterions. We also predict an optimum in the capacitance of zwitterionic media as a function of chain length. To address the issue of zwitterion screening near charged surfaces, we demonstrate that zwitterions simultaneously partially screen charged walls and act as a pure dielectric that propagates the electric field far from the surface. Moreover, we show that salt solutions with zwitterionic additives outperform the energy density of both salt-only and zwitterion-only capacitors. We find that salt-only capacitors perform better at low applied potential, whereas salt capacitors with zwitterionic additives perform better at high applied potential. [ABSTRACT FROM AUTHOR]

We present a theoretical framework to investigate thermoreversible phase transitions within polyzwitterion systems, encompassing macrophase separations (MPS) and gelation. In addition, we explore concentration fluctuations near critical points associated with MPS, as well as tricritical and bicritical points at the intersection of MPS and gelation. By utilizing mean-field percolation theory and field theory formalism, we derive the Landau free energy in terms of polyzwitterion concentration with fixed dipole strengths and other experimental variables, such as temperatures and salt concentrations. As the temperature decreases, the dipoles can form cross-links, resulting in polyzwitterion associations. The associations can grow to a gel network and enhance the propensity for MPS, including liquid–liquid, liquid–gel, and gel–gel phase separations. Remarkably, the associations also impact critical behaviors. Using the renormalization group technique, we find that the critical exponents of the polyzwitterion concentration correlation functions significantly deviate from those in the Ising universality class due to the presence of polyzwitterion associations, leading to crossover critical behaviors. [ABSTRACT FROM AUTHOR]

Postoperative adhesion (PA) caused by the combination of proteins, inflammatory response and bacterial infection poses substantial challenges for polypropylene meshes (PPMs) based hernioplasty. Herein, inspired by the peritoneum, a Janus PPMs with side-specific functions was developed via a surface-initiated photoiniferter-mediated polymerization technology. A physical barrier composed of zwitterionic polymer brushes (PS) was firstly constructed on the one side of the PPMs, while the polymethacrylic acid (PMAA) brushes acting as the linker for bioactive nanoparticles (HAP) were precisely situated on the opposite surface subsequently. Our findings reveal that the mesh surface modified with PS demonstrated significant antifouling property that more than 99% of protein adhesion could be inhibited even after the co-incubation for 72 h in the crucial test. Meanwhile, on the other surface of the PPMs modified with HAP achieved satisfactory ROS-scavenging, inflammation-inhibiting and cell adhesion-promoting properties as well as good bactericidal performance (killing rate > 99.9%). Furthermore, the Janus PPMs could maintain comparable mechanical property with pristine meshes. Equipped with the above multiple merits and asymmetric property, the constructed Janus PPMs demonstrated effective treatment for abdominal hernia defects in vivo without any PA formation. Overall, this study duplicates the unique characteristics of peritoneum onto PPMs to successfully address postoperative complications of the hernioplasty and also offers a versatile and innovative idea to construct asymmetrical functions on the one implant. The implantation of surgical meshes in the hernia defect provides additional firm support to reinforce the abdomen fascia in tension-free way. However, multiple post-surgery complications induced tissue adhesions is of great challenges for commercial mesh-based hernioplasty. Although material designing and surface modification might circumvent these limitations partly, the construction of side-specific biofunctions on the commercial mesh surfaces is very challenging because of its porous structure. Herein, we demonstrate a feasible and promising approach to construct asymmetric biofunctions on the opposite sides of network structured polypropylene mesh, which is rarely achieved previously. The fabricated Janus PPMs maintains the inherent long-term mechanical support; meanwhile, the opposite sides of PPMs could perform multiple biofunctions independently. [Display omitted] [ABSTRACT FROM AUTHOR]

Liver biobanking is a promising approach that saves the lives of patients with end-stage liver disease. Cryopreservation based on vitrification enables semi-permanent organ preservation, contributing to overcome the shortage of donors for liver transplants. A technical challenge in cryopreservation of transplantable organs lies in thawing methodology, and conventional convective warming cannot maintain the glassy state during thawing because of the large temperature gradient between the inner and outer parts of the organs, leading to ice formation and damage of cells in the organ. Nanowarming, in which magnetic nanoparticles are dispersed in a vitrification solution and heated by exposure of alternating magnetic field, can achieve uniform and rapid heating of organs. Herein, we report that amphiphilic phospholipid polymers composed of 2-methacryloyloxyethyl phosphorylcholine and n -butyl methacrylate can function as a cryoprotectant for nanowarming. The amphiphilic phospholipid polymers enhanced the viability of primary rat hepatocytes after vitrification. Moreover, the polymers enhanced the dispersion stability of magnetic nanoparticles in vitrification solution, and the perfusion of the vitrification solution with magnetic nanoparticles into rat livers through portal vein provided uniform distribution of the nanoparticles in the liver. After perfusion, the vitrified liver was successfully thawed rapidly and uniformly by nanowarming, which maintained tissue integrity and cell viability. [ABSTRACT FROM AUTHOR]

Deep eutectic solvent (DES)‐based eutectogels show significant promise for flexible sensors due to their high ionic conductivity, non‐volatility, biocompatibility, and cost‐effectiveness. However, achieving tough and stretchable eutectogels is challenging, as the highly polar DES tends to screen noncovalent bonds, such as hydrogen and ionic bonds, between polymer chains, limiting their mechanical strength. In this work, this issue is addressed by leveraging the limited solubility of zwitterionic polymers in a specific DES to induce phase separation, promoting dipole–dipole interactions between polymer chains. These interactions improve energy dissipation under mechanical stress, allowing the creation of tough and stretchable P(MAA‐co‐VIPS)/TBAC‐EG eutectogels through a copolymerization‐induced phase separation approach. Methacrylic acid (MAA) and sulfobetaine vinylimidazole (VIPS) are copolymerized within a tetrabutylammonium chloride‐ethylene glycol (TBAC‐EG) DES, resulting in a bicontinuous network. The bicontinuous structure consists of a PVIPS‐rich phase that enhances toughness via dipole–dipole interactions, and a PMAA solvent‐rich phase that enables high stretchability. The resulting eutectogel demonstrates excellent mechanical properties, including a strength of 1.76 MPa, toughness of 16.61 MJ m⁻3, and remarkable stretchability of 1293%, along with self‐recovery, self‐healing, and shape‐memory capabilities. The zwitterionic polymer‐specific DES design opens up broad application potential for these eutectogels in diverse fields. [ABSTRACT FROM AUTHOR]

The Hofmeister effect not only affects the stability and solubility of protein colloids but also has specific effects on the polymer molecules. Here, the impact of the Hofmeister effect on the electrochemical properties of polyelectrolyte hydrogels at room temperature and subzero temperature studied for the first time. Polyelectrolyte hydrogels exhibit an anti‐polyelectrolyte effect in low concentrations of ammonium salt, while they exhibit an obvious Hofmeister effect in high concentrations of ammonium salt. Kosmotropic ions demonstrate strong interaction with water molecules or polymer chains, resulting in the reduction of conductivity of polyelectrolyte hydrogels. However, chaotropic ions exhibit weak interactions with water molecules or molecular chains, leading to an increase in conductivity. The Hofmeister effect has a more significant effect on the polyzwitterion electrolyte. The conductivity of polyzwitterion hydrogel soaked in chaotropic ion is up to 6.2 mS cm‐1 at −40 °C. The supercapacitor assembled by polyzwitterion electrolytes maintains a capacitance retention rate of 85% and ≈100% coulomb efficiency after 15 000 cycles at −40 °C. This study elucidates the influence of the Hofmeister effect on conductivity in polyelectrolytes and expands the regulatory approach for improving the performance of energy storage devices. [ABSTRACT FROM AUTHOR]

Zwitterionic polymers are an important class of polymers with far‐ranging applications. In the widely studied poly(meth)acrylate and poly(meth) acrylamide‐based zwitterions, properties can be tuned by changing the nature of substituents attached to ammonium ions. However, these changes influenced salt tolerance of zwitterionic polymers only to a limited extent. Upon adding salt these polymers expanded in solution initially. Further increase in salt concentration caused the polymer chains to shrink similar to the common water soluble, uncharged polymers thereby deteriorating the viscosity of aqueous solutions. In contrast to the conventional poly(meth)acrylate and poly(meth)acrylamide‐based zwitterions, zwitterionic copolymaleimides showed substituent dependent salt‐tolerant nature. In the absence of any substituent on the polymer backbone such as zwitterionic poly(ethylene‐alt‐maleimide) (ZI‐PEMA) the viscosity of salt solutions increased both with the increasing salt concentration as well as the concentration of polymer. This is likely due to the continuous expansion of polymer coil in salt solutions with increasing salt concentration caused primarily by the rigidity of the polymer backbone. ZI‐PEMA also enhanced the saturation limit of mono‐ and divalent salts like sodium chloride and hydrated calcium bromide in water. This property is useful for various applications like fish curing, for making high‐density fluids, refrigeration, etc. across various industrial sectors. [ABSTRACT FROM AUTHOR]

Polymer electrolytes are of interest in high‐energy‐density batteries. However, how the intrinsic electron‐donating capability of polymer segments involved in coordination affects lithium‐ion dissociation/transmission and rationally guides the design and fabrication of electrolytes is a highly exploratory topic. This study proposes a workable method that integrates machine learning with density functional theory to predict donor numbers (DN) for polymer building units. Using this approach, polymer chains with optimized DN are designed, effectively modulating the solvation structure of lithium‐ion. Molecular dynamics simulations confirm the positive impact of polymer chains on rapid transport of lithium ions. Experimental validation of the proposed zwitterionic polymer electrolyte (ZPE) showcases satisfactory parameters: ion conductivity (0.59 mS cm−1), ion migration numbers (0.82), and activation energy (0.016 eV). Electrochemical analysis on Li|ZPE|Li symmetric batteries demonstrate sustained plating/stripping performance exceeding 3000 hours at a current density of 0.2 mA cm−2. Assembled NCM|ZPE|Li batteries exhibit stable cycling over 1400 cycles at 4.3 V, with a capacity retention ratio of 92.3 %. Moreover, even under ultra‐high voltages of 4.5 V and 4.7 V, NCM|ZPE|Li batteries display stable cycling performances. This approach offers a paradigmatic strategy for polymer molecule design, advancing sustainable battery technologies. [ABSTRACT FROM AUTHOR]

Inspired by the antifouling process observed in fluorescent corals, this study introduces a novel functional antifouling film consisting of Ag-Cu 2 O nanocomposites, zwitterionic polymers, and a phosphor substrate. Zwitterionic polymers serve as a dispersive medium for Ag-Cu 2 O nanocomposites, enabling a uniform coating and optimal structural through spin-coating. During daylight hours, visible light irradiation excites Ag-Cu 2 O nanocomposites to produce reactive oxygen species (ROS), which cooperates with the hydration layer, exhibit a high-level antifouling effect. Notably, the unique structural coating can emit a weak coral-like fluorescence at night, sustaining ROS release and further enhancing antifouling performance. The assembly structure of the composite film was studied by scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and water contact angle (WCA), while its antifouling performance was evaluated through antibacterial tests and a 30-day light-dark cycle anti-algae attachment experiment. The distinct nighttime antifouling capability contributes to 97.30 % anti-algae settled rate over a 30-day diurnal cycle. Moreover, we also investigated the effect of phosphor color on the composite film's antifouling properties. The blue phosphor group exhibited greater antifouling performance than the green or transparent phosphor group. The composite film created with multiple synergistic mechanisms exhibited auspicious antifouling performance. Further improvement and development of this composite film could unlock even greater potential for its antifouling properties. [ABSTRACT FROM AUTHOR]

Marine oil exploration is important yet greatly increases the risk of oil leakage, which will result in severe environment pollution and economic losses. It is an urgent need to develop effective underoil adhesives. However, realizing underoil adhesion is even harder than those underwater, due to the stubborn attachment of a highly viscous oil layer on target surface. Here, inspired by endocytosis, a tough gel tape composed of zwitterionic polymer network and zwitterionic surfactants is developed. The amphiphilic surfactants can form micelle to capture the oil droplets and transport them from the interface to gel via electrostatic attraction of polymer backbone, mimicking the endocytosis and achieving robust underoil adhesion. Benefiting from the oil‐resistance of polymer backbone, the gel further realizes a combination of i) long‐term adhesion with high durability, ii) repeated adhesion in oil, and iii) renewable adhesion efficiency after exhausted use. The tape exhibits an ultra‐high adhesive toughness of 2446.86 J m−2 to stainless steel in silicone oil after 30 days' oil‐exposure; such value of adhesive toughness surpasses many of those achieved in underwater adhesion and is greater than underoil adhesion performance of commercial tape. The strategy illustrated here will motivate the design of sustainable and efficient adhesives for wet environments. [ABSTRACT FROM AUTHOR]

Catheter-associated urinary tract infections (CAUTIs) present significant health risks in medical settings, necessitating innovative solutions to prevent bacterial colonization on catheter surfaces. This study introduces a novel polymeric coating with dual antifouling and light-activated bactericidal properties to enhance the bactericidal efficacy of urinary catheters. The coatings were synthesized using a one-step process involving pyrogallol chemistry to deposit a copolymer composed of zwitterionic sulfobetaine for antifouling and sodium copper chlorophyllin, a photosensitizer that generates reactive oxygen species under light exposure to effectively kill bacteria. We evaluated the antifouling properties, cytocompatibility, and bactericidal performance of the coatings under various light conditions. The results showed significant reductions in bacterial adhesion, with light activation further endowing the catheter with bactericidal effects. Additionally, light could be delivered through an optical fiber within the catheter lumen to target and kill bacteria. The innovative coating using light-activated bactericidal action offers a promising approach to preventing CAUTIs, representing a potential breakthrough in developing safer and more effective urinary catheters. [ABSTRACT FROM AUTHOR]

Organic polymer coatings have been commonly used in biomedical field, which play an important role in achieving biological antifouling, drug delivery, and bacteriostasis. With the continuous development of polymer science, organic polymer coatings can be designed with complex and advanced functions, which is conducive to the construction of biomedical materials with different performances. According to different physical and chemical properties of materials, biomedical organic polymer coating materials are classified into zwitterionic polymers, non-ionic polymers, and biomacromolecules. The strategies of combining coatings with substrates include physical adsorption, chemical grafting, and self-adhesion. Though the coating materials and construction methods are different, many biomedical polymer coatings have been developed to achieve excellent performances, i.e., enhanced lubrication, anti-inflammation, antifouling, antibacterial, drug release, anti-encrustation, anti-thrombosis, etc. Consequently, a large number of biomedical polymer coatings have been used in artificial lungs, ureteral stent, vascular flow diverter, and artificial joints. In this review, we summarize different types, properties, construction methods, biological functions, and clinical applications of biomedical organic polymer coatings, and prospect future direction for development of organic polymer coatings in biomedical field. It is anticipated that this review can be useful for the design and synthesis of functional organic polymer coatings with various biomedical purposes. [ABSTRACT FROM AUTHOR]

A model zwitterionic polysulfobetaine, poly(3-(acrylamidopropyl-dimethyl-ammonium) propyl-1-sulfonate) (pAPAPS), phase separates upon cooling and exhibits an upper critical solution temperature (UCST) behavior with no added salt in deuterium oxide solutions. Dynamic light scattering measurements indicate the presence of distinct fast and slow diffusive modes, where the fast mode is interpreted as a collective diffusion coefficient and the slow mode is attributed to the diffusion of multi-chain dynamic clusters. The relative population of fast and slow modes varies systematically with temperature and concentration. A clustering temperature (T*) was assigned when the slow mode first appeared upon cooling. The slow mode then increases in relative scattering amplitude as the phase boundary is approached. The fast mode exhibits a concentration dependence above T* consistent with the virial expansion in the collective diffusion. The sign of the virial coefficient (kd) is negative, even in the good solvent region above the expected Flory temperature (Θ ≈ 39 °C), a behavior distinct from synthetic neutral polymers in organic solvents. The onset of multi-chain clustering at T < T* coincides with the poor solvent regime (T < Θ). Attractive dipolar interactions due to the zwitterionic sulfobetaine groups in pAPAPS are suggested as the origin of the multi-chain clusters with no salt. Upon the addition of 100 mM NaCl, the slow mode is suppressed, and the hydrodynamic radius is consistent with polyzwitterion chain dimensions in a dilute solution. We find that concentration dependent diffusion is highly linked to the theta temperature and the emergence of dynamic clusters as the polymer goes from good to poor solvent on approach to the UCST. The slow mode in the semidilute regime is reported along with preliminary small-angle neutron scattering data that show salt reduces clustering and leads to predominantly chain scattering. [ABSTRACT FROM AUTHOR]

(a) Preparation of PLD nanomotor: The zwitterionic polymer nanocarrier PSBMA NPs (P NPs) were obtained by free radical polymerization with the polymerization monomer SBMA and the crosslinker BAC, and the active component l -arginine and the anticancer drug DOX were supported under electrostatic interaction, and the drug-loaded nanomotor PSBMA/ l -Arg/DOX (PLD) was constructed; (b) Schematic diagram of treatment in an animal model of peritoneal metastases. The loaded active component l -Arg could be catalyzed to produce NO and enable the loaded drug nanomotor to exhibit chemotactic behavior towards high concentrations of ROS/iNOS, thereby achieving deep penetration into tumor tissue. The introduction of S S bonds could enable the drug-loaded nanomotor to respond to the high expression of glutathione (GSH) in the tumor microenvironment and undergo degradation, releasing a large amount of DOX. [Display omitted] Innovative treatments for peritoneal metastatic cancer have attracted widespread attention from researchers. Here, we propose a drug-loaded nanomotor (PSBMA/ l -Arg/DOX, PLD) based on zwitterionic materials for the treatment of peritoneal metastatic cancer through intraperitoneal injection. Zwitterionic polymer nanocarriers (PSBMA NPs) are obtained by radical polymerization with zwitterionic SBMA as the polymerization monomer and N,N'-Bis(acryloyl)cystamine (BAC) as the cross-linking agent. The zwitterionic substrate of this nanomotor has the ability to resist non-specific protein adsorption in ascites. The loaded l -arginine enables the nanomotor to have the ability to chemotaxis towards high concentrations of ROS/iNOS in tumors and be catalyzed to produce NO, achieving deep penetration into tumor tissue. Furthermore, the disulfide bond (S S) carried by the crosslinking agent used in the preparation of the nanomotor can respond to the high expression of reducing glutathione in the tumor microenvironment and undergo degradation, releasing a large amount of loaded drug DOX. Cell and animal disease model experiments confirme the good therapeutic effect of this drug-loaded nanomotor, providing new therapeutic concepts and strategies for the treatment of peritoneal metastatic cancer. [ABSTRACT FROM AUTHOR]

Living cell‐mediated polymerization offers promising applications in biomaterials, yet its further biological utilization is hindered by the need for metal ions or radical initiators with available methods. In this study, we introduce a living cell‐mediated polymerization that leverages the intrinsic metabolic activities of living cells to initiate and sustain free radical polymerization of zwitterionic methacrylates. The polymerization proceeded in the absence of transition metal catalysts, radical initiators, or light sources. The conversion of zwitterionic methacrylate strongly correlated with cellular activities and achieved a maximum conversion of 98 % within 48 hours. Living cells efflux redox power across membranes through metabolism and that terminal electron fluxes are captured by zwitterionic methacrylates pre‐assembled on the living cell surface to initiate radical polymerization reactions. The polymerization caused significant changes to the cell membrane surface and synthesized hydrogels with tailored mechanical properties. The polymer hydrogel obtained via probiotic E. coli Nissle 1917 was able to release the in situ encapsulated molecules, which demonstrated living cell‐mediated polymer hydrogel as a vehicle for the delivery of both cellular and molecular therapeutic agents. This research offered a green and efficient method for synthesizing bioactive materials and advancing the field of cellular therapeutics and drug delivery. [ABSTRACT FROM AUTHOR]

Background: Acrylamide polymers with zwitterionic carboxybetaine (CB) side groups have attracted attention as stealth polymers that do not induce antibodies when conjugated to proteins. However, they induce antibodies when modified onto liposomes. We hypothesized that antibodies are produced against polymer backbones rather than CB side groups. Objectives: In this study, we designed and synthesized a polymer employing CB in its main chain, poly(N-acetic acid-N-methyl-propyleneimine) (PAMPI), and evaluated the blood retention of PAMPI-modified liposomes in mice. Results: The non-fouling nature of PAMPI-modified liposomes estimated from serum protein adsorption was found to be not inferior to PCB- and PEG-modified liposomes. However, to our surprise, the PAMPI-modified liposomes showed an instantaneous clearance less than 1 h post-injection, comparable to the naked liposomes. Conclusions: The extent of the blood retention of polymer-modified liposomes cannot be predicted by their susceptibility to serum protein adsorption and semi-flexible conformation. [ABSTRACT FROM AUTHOR]

Cationic porous organic polymers have a unique advantage in removing radioactive iodine from the aqueous phase because iodine molecules exist mainly in the form of iodine-containing anions. However, halogen anions will inevitably be released into water during the ion-exchange process. Herein, we reported a novel and easy-to-construct zwitterionic hypercrosslinked polymer (7AIn-PiP)-containing cationic pyridinium-type group, uncharged pyridine-type group, pyrrole-type group, and even an electron-rich phenyl group, which in synergy effectively removed 94.2% (456 nm) of I2 from saturated I2 aqueous solution within 30 min, surpassing many reported iodine adsorbents. Moreover, an I2 adsorption efficiency of ~95% can still be achieved after three cyclic evaluations, indicating a good recycling performance. More importantly, a unique dual 1,3-dipole was obtained and characterized by 1H/13C NMR, HRMS, and FTIR, correlating with the structure of 7AIn-PiP. In addition, the analysis of adsorption kinetics and the characterization of I2@7AIn-PiP indicate that the multiple binding sites simultaneously contribute to the high affinity towards iodine species by both physisorption and chemisorption. Furthermore, an interesting phenomenon of inducing the formation of HIO2 in unsaturated I2 aqueous solution was discovered and explained. Overall, this work is of great significance for both material and radiation protection science. [ABSTRACT FROM AUTHOR]

Cryopreservation is a common way for long‐term storage of therapeutical proteins, erythrocytes, and mammalian cells. For cryoprotection of these biosamples to keep their structural integrity and biological activities, it is essential to incorporate highly efficient cryoprotectants. Currently, permeable small molecular cryoprotectants such as glycerol and dimethyl sulfoxide dominate in cryostorage applications, but they are harmful to cells and human health. As acting in the extracellular space, membrane‐impermeable macromolecular cryoprotectants, which exert remarkable membrane stabilization against cryo‐injury and are easily removed post‐thaw, are promising candidates with biocompatibility and feasibility. Water‐soluble hydroxyl‐containing polymers such as poly(vinyl alcohol) and polyol‐based polymers are potent ice recrystallization inhibitors, while polyampholytes, polyzwitterions, and bio‐inspired (glyco)polypeptides can significantly increase post‐thaw recovery with reduced membrane damages. In this review, the synthetic macromolecular cryoprotectants are systematically summarized based on their synthesis routes, practical utilities, and cryoprotective mechanisms. It provides a valuable insight in development of highly efficient macromolecular cryoprotectants with valid ice recrystallization inhibition activity for highly efficient and safe cryopreservation of cells. [ABSTRACT FROM AUTHOR]

Amino‐acid‐derived polyzwitterions and polybetaines (PBs) are two promising alternatives to non‐ionic polymers, for example, to increase tumor permeability. In this study, amino‐acid‐derived polyzwitterions are synthesized and a strategy to quarternize the amine in the side chain functional group is developed to combine the advantages of both types. The functional monomer is polymerized via reversible addition−fragmentation chain‐transfer polymerization for which a kinetic study is performed. Further, the impact of the permanent positive charge on amino‐acid‐derived polyzwitterions is studied based on two zwitterionic polymers obtained via post‐polymerization modification (PPM) of Poly(N‐acryloxysuccinimide) to allow good comparison between methylated and non‐methylated polymers. Circular dichroism shows that the stereocenter remains intact during PPM. pH titration and ζ‐potential measurements show that the methylated polymer has a negative ζ‐potential over the measured pH range and, therefore, the polymer remains zwitterionic over a broader pH range than its non‐methylated equivalent. Both polymers are well tolerated by mammalian cells up to concentrations of 1 mg mL−1. The study introduces a path to a new polymer class that combines the advantages of both PBs and amino‐acid‐derived polyzwitterions and highlights the impact a permanent charge has on the physiochemical properties. [ABSTRACT FROM AUTHOR]

The repair and regeneration of cartilage is a challenge for scientists and clinical surgery. Achieving cell adhesion and regeneration, anti‐inflammatory, lubrication, targeted drug delivery and controlled release simultaneously in cartilage treatment are the goals of researchers. Polymer composites and hybrids have the potential to realize above functions in cartilage tissue engineering. This review refers to cartilage injuries, current clinical techniques, and their benefits and limitations, focusing on the most relevant and state of art of advanced polymers for cartilage tissue engineering. The frontier applications of multifunctional polymer composites and hybrids in cartilage tissue engineering are discussed in depth, including polymer scaffold, polymer bio‐lubricant, and zwitterionic polymer for drug delivery and sustained drug release. A summary of comprehensive properties of polymers such as processability, mechanical properties, biocompatibility, biodegradability, hydrophilicity, cytotoxicity, etc., and their mechanisms are analyzed. Furthermore, some key challenges and outstanding concerns on polymer‐based materials for cartilage tissue engineering are presented followed by future perspectives. Highlights: The state of art of advanced polymers for cartilage tissue engineering.The advanced bionic property and mechanism of polymer composites and hybrids.Polymers for scaffold, biolubricant, drug delivery, sustained drug release.Future perspectives on polymer composites, hybrids‐based cartilage materials. [ABSTRACT FROM AUTHOR]

Silicon is considered as a promising candidate for anode materials due to its ultrahigh theoretical capacity and natural abundance. However, the commercialization is severely hampered by the large strain and short cycle life. Herein, we have synthesized a reversible polyelectrolyte/polyzwitterion coacervate framework to achieve high‐performance silicon anodes with high initial Coulombic efficiency (ICE) and stable cyclability. Such coacervate framework is formed via in‐situ free radical polymerization of zwitterionic 2‐methacryloyloxy ethyl phosphorylcholine (MPC) with polyacrylic acid (pAA) during heating the slurry. The resulting pAA/pMPC coacervate framework presents excellent adhesion, thermal stability, and negligible swelling in the electrolyte. Comparing with pAA, pAA/pMPC0.1 coacervate framework binder exhibits superior performance during charge/discharge. The ICE is improved from 84.41 %, to 87.61 %. After 250 cycles, the specific capacity of pAA/pMPC0.1 silicon anode is 1678 mAh g−1 with a retention of 78 % while the pAA silicon anode completely failed after less than 200 cycles. Such improvement is ascribed to the structural integrity of the electrode endowed by the self‐healing ability of pAA/pMPC coacervate framework. This work not only offers a feasible method to in‐situ construct coacervate framework with self‐healing capability to achieve high‐performance silicon anodes but also a compatible electrode preparation process for other high‐capacity materials. [ABSTRACT FROM AUTHOR]

Polyethylene oxide (PEO)‐based solid‐state batteries hold great promise as the next‐generation batteries with high energy density and high safety. However, PEO‐based electrolytes encounter certain limitations, including inferior ionic conductivity, low Li+ transference number, and poor mechanical strength. Herein, we aim to simultaneously address these issues by utilizing one‐dimensional zwitterionic cellulose nanofiber (ZCNF) as fillers for PEO‐based electrolytes using a simple aqueous solution casting method. Multiple characterizations and theoretical calculations demonstrate that the unique zwitterionic structure imparts ZCNF with various functions, such as disrupting PEO crystallization, dissociating lithium salts, anchoring anions through cationic groups, accelerating Li+ migration by anionic groups, as well as its inherent reinforcement effect. As a result, the prepared PL‐ZCNF electrolyte exhibits remarkable ionic conductivity (5.37×10−4 S cm−1) and Li+ transference number (0.62) at 60 °C without sacrificing mechanical strength (9.2 MPa), together with high critical current density of 1.1 mA cm−2. Attributed to these merits of PL‐ZCNF, the LiFePO4|PL‐ZCNF|Li solid‐state full‐cell delivers exceptional rate capability and cycling performance (900 cycles at 5 C). Notably, the assembled pouch‐cell can maintain steady operation over 1000 cycles with an impressive 93.7 % capacity retention at 0.5 C and 60 °C, highlighting the great potential of PL‐ZCNF for practical applications. [ABSTRACT FROM AUTHOR]

Triple negative breast cancer (TNBC) has the characteristics of low immune cell infiltration, high expression of tumor programmed death ligand 1 (PD-L1), and abundant cancer stem cells. Systemic toxicity of traditional chemotherapy drugs due to poor drug selectivity, and chemotherapy failure due to tumor drug resistance and other problems, so it is particularly important to find new cancer treatment strategies for TNBC with limited treatment options. Both the anti-tumor natural drugs curcumin and ginsenoside Rg3 can exert anti-tumor effects by inducing immunogenic cell death (ICD) of tumor cells, reducing PD-L1 expression, and reducing cancer stem cells. However, they have the disadvantages of poor water solubility, low bioavailability, and weak anti-tumor effect of single agents. We used vinyl ether bonds to link curcumin (Cur) with N-O type zwitterionic polymers and at the same time encapsulated ginsenoside Rg3 to obtain hyperbranched zwitterionic drug-loaded micelles OPDEA-PGED-5HA@Cur@Rg3 (PPH@CR) with pH response. In vitro cell experiments and in vivo animal experiments have proved that PPH@CR could not only promote the maturation of dendritic cells (DCs) and increase the CD4+ T cells and CD8+ T cells by inducing ICD in tumor cells but also reduce the expression of PD-L1 in tumor tissues, and reduce cancer stem cells and showed better anti-tumor effects and good biological safety compared with free double drugs, which is a promising cancer treatment strategy. [ABSTRACT FROM AUTHOR]

A novel zwitterionic polymer grafted silica stationary phase, Sil‐PZIC, was prepared by bonding poly(ethylene maleic anhydride) molecules on the surface of silica via multiple binding sites, followed by ammonolysis of maleic anhydride through a nucleophilic substitution reaction with ethylenediamine. The stationary phase was characterized by solid‐state 13C nuclear magnetic resonance, zeta potential, and elemental analysis and the results show the successful encapsulation of zwitterionic polymer on the surface of silica. The chromatographic performance of Sil‐PZIC was investigated by using nucleosides and nucleic bases as test analytes The variation of retention and separation performance of these model compounds were investigated by varying the chromatographic conditions such as the components of mobile phase, salt concentration, and pH. The results show that the retention of the Sil‐PZIC phase was dominated by a hydrophilic partitioning mechanism accompanied by secondary interactions such as electrostatic and hydrogen bonding. In addition, saccharides and Amadori compounds were also well separated on the Sil‐PZIC, indicating that the Sil‐PZIC column has potential application for separation of the polar compound. [ABSTRACT FROM AUTHOR]

Biofouling is a great challenge for engineering material in medical-, marine-, and pharmaceutical-related applications. In this study, a novel trimethylamine N-oxide (TMAO)–analog monomer, 3-(2-methylacrylamido)-N,N-dimethylpropylamine N-oxide (MADMPAO), was synthesized and applied for the grafting of poly(MADMPAO) (pMPAO) brushes on quartz crystal microbalance (QCM) chips by the combination of bio-inspired poly-dopamine (pDA) and surface-initiated atom transfer radical polymerization technology. The result of ion adsorption exhibited that a sequential pDA and pMPAO arrangement from the chip surface had different characteristics from a simple pDA layer. Ion adsorption on pMPAO-grafted chips was greatly inhibited at low salt concentrations of 1 and 10 mmol/L due to strong surface hydration in the presence of charged N+ and O− of zwitterionic pMPAO brushes on the outer layer on the chip surface, well known as the "anti-polyelectrolyte" effect. During BSA adsorption, pMPAO grafting also led to a marked decrease in frequency shift, indicating great inhibition of protein adsorption. It was attributed to weaker BSA-pMPAO interaction. In this study, the Au@pDA-4-pMPAO chip with the highest coating concentration of DA kept stable dissipation in BSA adsorption, signifying that the chip had a good antifouling property. The research provided a novel monomer for zwitterionic polymer and demonstrated the potential of pMPAO brushes in the development and modification of antifouling materials. [ABSTRACT FROM AUTHOR]

Electrophysiological signals are commonly used to assess health performance, providing valuable information on body status. However, stable signal acquisition by commercial Ag/AgCl gel or metal electrodes is susceptible to electrode/skin interface interferences due to perspiration and motion during exercise. To address this challenge, herein a sweat absorbing skin electrode (SAE) is designed, which can not only become softer and more adhesive but also enhance conductivity after sweat during exercise. The resulting stable interface between SAE/skin after sweat enables accurate and continuous electrophysiological measurement during exercise. SAE is demonstrated by assembly of MXene (Ti3C2TX) aerogel and zwitterionic polymer, where Ti3C2TX aerogel works as conductive skeleton and zwitterionic polymer endows skin conformability as well as expediting interfacial charge transfer by the inherent ions. SAE can monitor a variety of electrophysiological signals during exercise. As an example, electromyogram (EMG) signals are acquired to assess muscle fatigue, which is impossible by commercial gel electrodes. Via machine learning, the correlation between EMG and physiological markers (body fat percentage (BF) and body mass index (BMI)) are constructed. The research shows that sweat‐absorbing SAEs can reliably monitor electrophysiological signals during exercise, such as muscle status, leading to evidence‐based scientific guidelines for sports and rehabilitation training. [ABSTRACT FROM AUTHOR]

Zwitterionic polymers possess equal total positive and negative charges in the repeating units, making them electrically neutral overall. This unique property results in superhydrophilicity, which makes the zwitterionic polymers highly effective in resisting protein adsorption, thus endowing the drug carriers with long blood circulation time, inhibiting thrombus formation on biomedical devices in contact with blood, and ensuring the good sensitivity of sensors in biomedical application. Moreover, zwitterionic polymers have tumor-targeting ability and pH-responsiveness, rendering them ideal candidates for antitumor drug delivery. Additionally, the high ionic conductivity of zwitterionic polymers makes them an important raw material for ionic skin. Zwitterionic polymers exhibit remarkable resistance to bacterial adsorption and growth, proving their suitability in a wide range of biomedical applications such as ophthalmic applications, and wound dressings. In this paper, we provide an in-depth analysis of the different structures and characteristics of zwitterionic polymers and highlight their unique qualities and suitability for biomedical applications. Furthermore, we discuss the limitations and challenges that must be overcome to realize the full potential of zwitterionic polymers and present an optimistic perspective for zwitterionic polymers in the biomedical fields. Zwitterionic polymers have a series of excellent properties such as super hydrophilicity, anti-protein adsorption, antibacterial ability and good ionic conductivity. However, biomedical applications of multifunctional zwitterionic polymers are still a major field to be explored. This review focuses on the design and application of zwitterionic polymers-based nanosystems for targeted and responsive delivery of antitumor drugs and cancer diagnostic agents. Moreover, the use of zwitterionic polymers in various biomedical applications such as biomedical devices in contact with blood, biosensors, ionic skin, ophthalmic applications and wound dressings is comprehensively described. We discuss current results and future challenges for a better understanding of multifunctional zwitterionic polymers for biomedical applications. [Display omitted] [ABSTRACT FROM AUTHOR]

The behavior of polyzwitterions, constituted by dipole-like zwitterionic monomers, is significantly different from that of uniformly charged polyelectrolytes. The origin of this difference lies in the intrinsic capacity of polyzwitterions to self-associate intramolecularly and associate with interpenetrating chains driven by dominant dipolar interactions. Earlier attempts to treat polyzwitterions implicitly assume that the dipoles of zwitterion monomers are randomly oriented. At ambient temperatures, the dipolar zwitterion monomers can readily align with each other generating quadrupoles and other multipoles and thus generating heterogeneous structures even in homogeneous solutions. Towards an attempt to understand the role of such dipolar associations, we present a mean field theory of solutions of polyzwitterions. Generally, we delineate a high-temperature regime where the zwitterion dipoles are randomly oriented from a low-temperature regime where quadrupole formation is significantly prevalent. We present closed-form formulas for: (1) Coil-globule transition in the low-temperature regime, the anti-polyelectrolyte effect of chain expansion upon addition of low molar mass salt, and chain relaxation times in dilute solutions. (2) Spontaneous formation of a mesomorphic state at the borderline between the high-temperature and low-temperature regimes and its characteristics. A universal law is presented for the radius of gyration of the microgel, as a proportionality to one-sixth power of the polymer concentration. (3) Swelling equilibrium of chemically cross-linked polyzwitterion gels in both the high temperature and low-temperature regimes. Addressing the hierarchical internal dynamics of polyzwitterion gels, we present a general stretched exponential law for the time-correlation function of gel displacement vector, that can be measured in dynamic light scattering experiments. The present theory is of direct experimental relevance and additional theoretical developments to all polyzwitterion systems, and generally to biological macromolecular systems such as intrinsically disordered proteins. [ABSTRACT FROM AUTHOR]

Thermoresponsive sol–gel transition polymers are of significant interest because of their fascinating biomedical applications, including as drug reservoirs for drug delivery systems and scaffolds for tissue engineering. Although extensive research has been conducted on lower critical solution temperature (LCST)-type sol–gel transition polymers, there have been few reports on upper critical solution temperature (UCST)-type sol–gel transition polymers. In this study, we designed an ABA-type triblock copolymer composed of a poly(ethylene glycol) (PEG) block and zwitterionic polymer blocks that exhibit UCST-type thermoresponsive phase transitions. A sulfobetaine (SB) monomer with both ammonium and sulfonate (–SO3) groups in its side chain or a sulfabetaine (SaB) monomer with both ammonium and sulfate (–OSO3) groups in its side chain was polymerized from both ends of the PEG block via reversible addition–fragmentation chain-transfer (RAFT) polymerization to obtain PSB-PEG-PSB and PSaB-PEG-PSaB triblock copolymers, respectively. Although an aqueous solution containing the PSB-PEG-PSB triblock copolymer showed an increase in viscosity upon cooling, it did not undergo a sol-to-gel transition. In contrast, a sol-to-gel transition was observed when a phosphate-buffered saline containing PSaB-PEG-PSaB was cooled from 80 °C to 25 °C. The PSaB blocks with –OSO3 groups exhibited a stronger dipole–dipole interaction than conventional SB with –SO3 groups, leading to intermolecular association and the formation of a gel network composed of PSaB assemblies bridged with PEG. The fascinating UCST-type thermoresponsive sol–gel transition properties of the PSaB-PEG-PSaB triblock copolymer suggest that it can provide a useful platform for designing smart biomaterials, such as drug delivery reservoirs and cell culture scaffolds. [ABSTRACT FROM AUTHOR]

Zwitterionic polymers have garnered significant attention for their distinctive properties, such as biocompatibility, antifouling capabilities, and resistance to protein adsorption, making them promising candidates for a wide range of applications, including drug delivery, oil production inhibitors, and water purification membranes. This study reports the synthesis and characterization of zwitterionic monomers and polymers through the modification of linear, vinyl, and aromatic heterocyclic functional groups via reaction with 1,3-propanesultone. Four zwitterionic polymers with varying molecular structures—ranging from linear to five and six membered ring systems—were synthesized: poly(sulfobetaine methacrylamide) (pSBMAm), poly(sulfobetaine-1-vinylimidazole) (pSB1VI), poly(sulfobetaine-2-vinylpyridine) (pSB2VP), and poly(sulfobetaine-4-vinylpyridine) (pSB4VP). Their molecular weights, thermal behavior, and self-assembly properties were analyzed using gel permeation chromatography (GPC), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and zeta potential measurements. The glass transition temperatures (Tg) ranged from 276.52 °C for pSBMAm to 313.69 °C for pSB4VP, while decomposition temperatures exhibited a similar trend, with pSBMAm degrading at 301.03 °C and pSB4VP at 387.14 °C. The polymers’ self-assembly behavior was strongly dependent on pH and their surface charge, particularly under varying pH conditions: spherical micelles were observed at neutral pH, while fractal aggregates formed at basic pH. These results demonstrate that precise modifications of the chemical structure, specifically in the linear, imidazole, and pyridine moieties, enable fine control over the thermal properties and self-assembly behavior of polyzwitterions. Such insights are essential for tailoring polymer properties for targeted applications in filtration membranes, drug delivery systems, and solid polymer electrolytes, where thermal stability and self-assembly play crucial roles.

Responsive polyzwitterionic materials have become important for a range of applications such as environmental remediation and targeted drug delivery. Much is known about the macroscopic phase-behaviors of such materials, but how the smaller scale single-chain structures of polyzwitterions respond to external stimuli is not well understood, especially at temperatures close to their phase boundaries. Such chain conformation responses are important in directing larger-scale associative properties. Here, we study the temperature dependent single-chain structure of a model polysulfobetaine, poly[3-(acrylamidopropyl-dimethyl-ammonium) propyl-1-sulfonate], using small angle neutron scattering. In the absence of salt, we find that temperature has a large effect on solvent quality with a decreasing trend from good solvent conditions at 50 °C to poor solvent at 10 °C (a temperature just above the cloud point of 7.6 °C) and an estimated theta temperature of 39 °C. When 100 mM NaCl is present, the solvent quality is good with weak temperature dependence. Without salt present, the polymer chain appears to have a nearly Gaussian coil conformation and the backbone becomes slightly more rigid as the temperature is lowered to the cloud point as determined by the Debye-local rod model on a Kratky plot. The addition of salt has a notable effect on the intra-chain correlations where an increase in chain dimensions to a swollen coil conformation and an increase in chain rigidity is observed at 100 mM NaCl in D2O, however, with a negligible temperature dependence. [ABSTRACT FROM AUTHOR]

Bio-inspired transistor synapses use solid electrolytes to achieve low-power operation and rich synaptic behaviors via ion diffusion and trapping. While these neuromorphic devices hold great promise, they still suffer from challenges such as high leakage currents and power consumption, electrolysis risk, and irreversible conductance changes due to long-range ion migrations and permanent ion trapping. In addition, their response to light is generally limited because of "exciton-polaron quenching", which restricts their potential in in-sensor neuromorphic visions. To address these issues, we propose replacing solid electrolytes with polyzwitterions, where the cation and anion are covalently concatenated via a flexible alkyl chain, thus preventing long-range ion migrations while inducing good photoresponses to the transistors via interfacial charge trapping. Our detailed studies reveal that polyzwitterion-based transistors exhibit optoelectronic synaptic behavior with ultralow-power consumption (~250 aJ per spike) and enable high-performance in-sensor reservoir computing, achieving 95.56% accuracy in perceiving the trajectory of moving basketballs. [ABSTRACT FROM AUTHOR]

Marine biofouling–the adhesion of marine organisms onto a ship hull–causes increased fuel consumption, leading to massive carbon dioxide emissions. Many attempts are made to address this issue, and antifouling polymer coatings are extensively investigated owing to their environmental friendliness. Zwitterionic polymers, polysaccharides, and polyethylene glycol are frequently used as surface coatings, demonstrating excellent marine antifouling performance. However, these hydrophilic polymer coatings have a major drawback: when exposed to sediment, various minerals are easily adsorbed by the coatings, causing them to lose their inherent antifouling properties. Amphiphilic polymer coatings have therefore been proposed as alternatives to hydrophilic polymer coatings. In this study, the synthesis of amphiphilic copolymers composed of carboxybetaine methacrylamide and trifluoroethyl methacrylate and the immobilization of these copolymers onto solid surfaces are reported. This method utilizes material‐independent surface‐coating properties and the metal complex‐forming ability of polydopamine to immobilize amphiphilic copolymers onto solid surfaces. The resulting surfaces exhibit good antifouling performance against both diatom adhesion and silt adsorption. As this is a facile and substrate‐independent method for immobilizing polymers, an expectation exists for it to be an effective platform for the coating of new marine antifouling polymers. [ABSTRACT FROM AUTHOR]

Dry eye disease (DED) is associated with ocular hyperosmolarity and inflammation. The marketed topical eye drops for DED treatment often lack bioavailability and precorneal residence time. In this study, we investigated catechol-functionalized polyzwitterion p(MPC-co-DMA), composed of 2-methacryloyloxyethyl phosphorylcholine (MPC) and dopamine methacrylamide (DMA) monomers, as potential topical nanotherapeutics for DED. The copolymers were synthesized via random free-radical copolymerization, producing different proportions of catecholic functionalization. All as-prepared polymer compositions displayed good ocular biocompatibility. At a feeding ratio of 1:1, p(MPC1-co-DMA1) can facilitate a robust mucoadhesion via Michael addition and/or Schiff base reaction, thus prolonging ocular residence time after 4 days of topical instillation. The hydration lubrication of MPC and radical-scavenging DMA endow the nano-agent to ease tear-film hyperosmolarity and corneal inflammation. A single dose of p(MPC1-co-DMA1) (1 mg/mL) after 4 days post-instillation can protect the cornea against reactive oxygen species, inhibiting cell apoptosis and the over-expression of pro-inflammatory factors (IL-6 and TNF-α). In clinical assessment, DED-induced rabbit eyes receiving p(MPC1-co-DMA1) could increase lacrimal fluid secretion by 5-fold higher than cyclosporine A. The catechol-functionalized polyzwitterion with enhanced lubricity, mucoadhesion, and anti-oxidation/anti-inflammation properties has shown high promise as a bioactive eye drop formulation for treating DED. [ABSTRACT FROM AUTHOR]

Current hydrophilic modification strategies improve the antifouling ability of membranes but fail to completely eliminate the fouling of emulsified oil droplets with a wide size distribution. Constructing membranes with superior anti‐oil‐fouling ability to resist various oil droplets especially at high permeation fluxes is challenging. Here, the fabrication of a zero‐oil‐fouling membrane by grafting considerably high coverage of zwitterionic polymer and building defect‐free hydration defense barrier on the surface is reported. A uniform layer of protocatechuic acid with COOH as abundant as existing in every molecule is stably deposited on the membrane so as to provide sufficient reactive sites and achieve dense grafting of the zwitterionic polymer. The coverage of zwitterionic polymer on the membrane plays a crucial role in promoting the antifouling ability to emulsified oil droplets. The poly(vinylidene fluoride) membrane with 93% coverage of the zwitterionic polymer exhibits zero oil fouling when separating multitudinous oil‐in‐water emulsions with ≈0% flux decline, ≈100% flux recovery, and a high water flux of ≈800 L m−2 h−1 bar−1. This membrane outperforms almost all of the reported membranes in terms of the comprehensive antifouling performance. This work provides a feasible route for manufacturing super‐antifouling membranes toward oil/water separation application. [ABSTRACT FROM AUTHOR]

High-performance catheters are essential for interventional surgeries, requiring reliable anti-adhesive and lubricated surfaces. This article develops a strategy for constructing high-density sulfobetaine zwitterionic polymer brushes on the surface of catheters, utilizing dopamine and sodium alginate as the primary intermediate layers, where dopamine provides mussel-protein-like adhesion to anchor the polymer brushes to the catheter surface. Hydroxyl-rich sodium alginate increases the number of grafting sites and improves the grafting mass by more than 4 times. The developed high-density zwitterionic polymer brushes achieve long-lasting and effective lubricity (μ<0.0078) and are implanted in rabbits for four hours without bio-adhesion and thrombosis in the absence of anticoagulants such as heparin. Experiments and molecular dynamics simulations demonstrate that graft mass plays a decisive role in the lubricity and anti-adhesion of polymer brushes, and it is proposed to predict the anti-adhesion of polymer brushes by their lubricity to avoid costly and time-consuming bioassays during the development of amphoteric polymer brushes. A quantitative influence of hydration in the anti-adhesion properties of amphiphilic polymer brushes is also revealed. Thus, this study provides a new approach to safe, long-lasting lubrication and anticoagulant surface modification for medical devices in contact with blood. High friction and bioadhesion on medical device surfaces can pose a significant risk to patients. In response, we have developed a safer, simpler, and more application-specific surface modification strategy that addresses both the lubrication and anti-bioadhesion needs of medical device surfaces. We used dopamine and sodium alginate as intermediate layers to drastically increase the grafting density of the zwitterionic brushes and enabled the modified surfaces to have an extremely low coefficient of friction (μ = 0.0078) and to remain non-bioadhesive for 4 hours in vivo. Furthermore, we used molecular dynamics simulations to gain insight into the mechanisms behind the superior anti-adhesion properties of the high-density polymer brushes. Our work contributes to the development and application of surface-modified coatings. [Display omitted] [ABSTRACT FROM AUTHOR]

Recent advancements in bioengineering and medical devices have been greatly influenced and dominated by synthetic polymers, particularly polyurethanes (PUs). PUs offer customizable mechanical properties and long‐term stability, but their inherent hydrophobic nature poses challenges in practically biological application processes, such as interface high friction, strong protein adsorption, and thrombosis. To address these issues, surface modifications of PUs for generating functionally hydrophilic layers have received widespread attention, but the durability of generated surface functionality is poor due to irreversible mechanical wear or biodegradation. As a result, numerous researchers have investigated bulk modification techniques to incorporate zwitterionic polymers or groups onto the main or side chains of PUs, thereby improving their hydrophilicity and biocompatibility. This comprehensive review presents an extensive overview of notable zwitterionic PUs (ZPUs), including those based on phosphorylcholine, sulfobetaine, and carboxybetaine. The review explores their wide range of biomedical applications, from blood‐contacting devices to antibacterial coatings, fouling‐resistant marine coatings, separation membranes, lubricated surfaces, and shape memory and self‐healing materials. Lastly, the review summarizes the challenges and future prospects of ZPUs in biological applications. [ABSTRACT FROM AUTHOR]

The fouling of separation membranes has consistently been a primary factor contributing to the decline in membrane performance. Enhancing the surface hydrophilicity of the membrane proves to be an effective strategy in mitigating membrane fouling in water treatment processes. Zwitterionic polymers (containing an equimolar number of homogeneously distributed anionic and cationic groups on the polymer chains) have been used extensively as one of the best antifouling materials for surface modification. The conventional application of zwitterionic compounds as surface modifiers is intricate and inefficient, adding complexity and length to the membrane preparation process, particularly on an industrial scale. To overcome these limitations, zwitterionic polymer, directly used as a main material, is an effective method. In this work, a novel zwitterionic polymer (TB)—zwitterionic Tröger's base (ZTB)—was synthesized by quaternizing Tröger's base (TB) with 1,3-propane sultone. The obtained ZTB is blended with TB to fabricate microfiltration (MF) membranes via the vapor-induced phase separation (VIPS) process, offering a strategic solution for separating emulsified oily wastewater. Atomic force microscopy (AFM), scanning electron microscopy (SEM), water contact angle, and zeta potential measurements were employed to characterize the surface of ZTB/TB blended membranes, assessing surface morphology, charge, and hydrophilic/hydrophobic properties. The impact of varying ZTB levels on membrane surface morphology, hydrophilicity, water flux, and rejection were investigated. The results showed that an increase in ZTB content improved hydrophilicity and surface roughness, consequently enhancing water permeability. Due to the attraction of water vapor, the enrichment of zwitterionic segments was enriched, and a stable hydration layer was formed on the membrane surface. The hydration layer formed by zwitterions endowed the membrane with good antifouling properties. The proposed mechanism elucidates the membrane's proficiency in demulsification and the reduction in irreversible fouling through the synergistic regulation of surface charge and hydrophilicity, facilitated by electrostatic repulsion and the formation of a hydration layer. The ZTB/TB blended membranes demonstrated superior efficiency in oil–water separation, achieving a maximum flux of 1897.63 LMH bar−1 and an oil rejection rate as high as 99% in the oil–water emulsion separation process. This study reveals the migration behavior of the zwitterionic polymer in the membrane during the VIPS process. It enhances our comprehension of the antifouling mechanism of zwitterionic membranes and provides guidance for designing novel materials for antifouling membranes. [ABSTRACT FROM AUTHOR]

Hybrid materials based on calcium phosphates and synthetic polymers can potentially be used for caries protection due to their similarity to hard tissues in terms of composition, structure and a number of properties. This study is focused on the biomimetic synthesis of hybrid materials consisting of hydroxiapatite and the zwitterionic polymers polysulfobetaine (PSB) and polycarboxybetaine (PCB) using controlled media conditions with a constant pH of 8.0–8.2 and Ca/P = 1.67. The results show that pH control is a dominant factor in the crystal phase formation, so nano-crystalline hydroxyapatite with a Ca/P ratio of 1.63–1.71 was observed as the mineral phase in all the materials prepared. The final polymer content measured for the synthesized hybrid materials was 48–52%. The polymer type affects the final microstructure, and the mineral particle size is thinner and smaller in the synthesis performed using PCB than using PSB. The final intermolecular interaction of the nano-crystallized hydroxyapatite was demonstrated to be stronger with PCB than with PSB as shown by our IR and Raman spectroscopy analyses. The higher remineralization potential of the PCB-containing synthesized material was demonstrated by in vitro testing using artificial saliva. [ABSTRACT FROM AUTHOR]

Blood-contacting medical devices, such as vascular stents, intravascular catheters, and artificial heart valves, frequently encounter complications in clinical practice, including thrombosis, inflammatory reactions, and infections. These challenges pose significant obstacles in the effective application of blood-contacting medical devices. Given that protein adhesion serves as the primary trigger for detrimental events upon contact with blood, this review focuses on various anti-fouling coating strategies aimed at inhibiting protein adsorption. Currently, surface modification of blood-contacting medical devices primarily involves the construction of active or passive anti-fouling coatings. This review explores the implementation of active and passive anti-fouling coating strategies utilizing chemistry, physics, and biotechnology. Examples of anti-fouling coatings discussed include hydrophilic polymer coatings, zwitterionic polymer coatings, superhydrophobic coatings, and composite coatings. Furthermore, we propose implementation approaches for these coatings to address inflammation and infection challenges associated with blood-contacting devices. The review concludes with a brief overview of current surface modification technologies employed in commercial anti-fouling coatings and offers insights into the future of anti-fouling coating technologies for blood-contacting material surfaces. These advancements are essential for the advancement of design, development, and application of blood-contacting materials. [ABSTRACT FROM AUTHOR]

Surface fouling poses a significant challenge that restricts the analytical performance of electrochemical sensors in both in vitro and in vivo applications. Biofouling resistance is paramount to guarantee the reliable operation of electrochemical sensors in complex biofluids (e.g., blood, serum, and urine). Seeking efficient strategies for surface fouling and establishing highly sensitive sensing platforms for applications in complex media have received increasing attention in the past. In this review, we provide a comprehensive overview of recent research efforts focused on antifouling electrochemical sensors. Initially, we present a detailed illustration of the concept about biofouling along with an exploration of four key antifouling mechanisms. Subsequently, we delve into the commonly employed antifouling strategies in the fabrication of electrochemical sensors. These encompass physical surface topography (micro/nanostructure coatings and filtration membranes) and chemical surface modifications (PEG and its derivatives, zwitterionic polymers, peptides, proteins, and various other antifouling materials). The progress in antifouling electrochemical sensors is proposed concerning the antifouling mechanisms as well as sensing capability assessments (e.g., sensitivity, stability, and practical application ability). Finally, we summarize the evolving trends in the field and highlight some key remaining limitations. [ABSTRACT FROM AUTHOR]

Membrane separation technique has been widely used in recent years for oily wastewater treatment because of the advantages of simplicity of operation, lack of residual contamination and high separation efficiency. However, membrane fouling and pore plugging can cause serious problems, such as short membrane life and decreased flux. Therefore, in this paper, a self-cleaning polyacrylonitrile (PAN) composite membrane with excellent oil–water emulsion separation properties was prepared. The PAN membrane modified with AgI/UiO-66-NH2 was first prepared using electrospinning. The zwitterionic poly(sulfobetaine methacrylate) (pSBMA) was then modified onto the prefabricated electrospinning membrane by atom transfer radical polymerization (ATRP) to prepare hydrophilic polymer brush grafted PAN/AgI/UiO-66-NH2 composite membranes after 2-bromoisobutyryl bromide (BiBB) was introduced to the composite membrane. The membrane possesses a self-cleaning capacity because AgI/UiO-66-NH2 has the ability of visible light driven catalytic degradation. The powerful hydration ability of the pSBMA and the surrounding water molecules enhance the wettability of the composite membrane. The existence of a photocatalyst and hydration of a zwitterionic polymer brush greatly improve the resistance of the membrane towards contamination. The as prepared membrane was used to treat oil/water emulsions and the results revealed that the membrane has high permeability to four kinds of different oil/water emulsions when driven by gravity. The mentioned membrane might have potential application prospects in oily water treatment. [ABSTRACT FROM AUTHOR]

Thread-based microfluidic colorimetric sensors have been deemed a potential tool that may be incorporated into textiles for non-invasive sweat analysis. Nevertheless, their poor performance significantly limits their practical uses in sweat glucose detection down to 20 μM. Herein, a microfluidic glucose sensing device containing a salt-responsive thread is developed for the highly sensitive detection of glucose in human sweat. By grafting a zwitterionic polymer brush—which could react to ionic strength by changing the conformation of the polymer chains from the collapsing state to the stretching state—onto the cotton thread, the salt-responsive thread was created. Compared to the pristine cotton thread, the modified thread has better ion-capture capabilities, a more noticeable swelling effect, and a higher ability to absorb water. These enable a significant enrichment of glucose when the saline solution passes through it. The salt-responsive thread was employed to construct a thread/paper-based microfluidic sensing device for the monitoring of glucose in artificial sweat, exhibiting a sensitivity of −0.255 μM−1 and a detection limit of 14.7 μM. In comparison to the pristine cotton thread-based device, the performance is significantly superior. Using a hydrophobic fabric and salt-responsive threads, a glucose-sensing headband was prepared for on-body sweat glucose monitoring. With the use of a smartphone-based image analysis system, the headband can detect the concentration of glucose in a volunteer's perspiration. Using the thread-based salt-responsive zwitterionic polymer brush might offer a novel approach to creating wearable sweat sensors with extremely high sensitivity. [ABSTRACT FROM AUTHOR]

The resistance of zwitterionic polymer coatings against the adsorption of proteins and the attachment of pathogenic bacteria is influenced by the precise molecular architecture of the polymers. Two until now rarely studied molecular variables in this context are side chain spacer groups separating the zwitterionic moieties from the polymer backbone and spacer groups separating the cationic and anionic groups within the zwitterionic moiety. Therefore, a set of six poly(sulfobetaine)s and poly(sulfabetaine)s is prepared, in which these spacer groups are systematically varied, incorporating ethylene, propylene, and undecylene side chain spacers, as well as ethylene, propylene, and butylene inter‐charge spacers, and their effects on the antifouling behavior are explored. Hence, the corresponding zwitterionic methacrylates are copolymerized with a photo‐reactive methacrylate bearing a benzophenone moiety. All zwitterionic coatings reveal hydrophilic properties when immersed in water and those with relatively short spacers show effective suppression of non‐specific protein adsorption. Polysulfobetaines outperform the polysulfabetaine ones in terms of resistance against adhesion of bacteria. The overall best fouling protection is observed for the polysulfobetaine bearing a propylene side chain spacer, which coincides with their relatively highest water solubility. The results corroborate previous findings that even apparently minor molecular changes of polyzwitterions can strongly affect their antifouling performance. [ABSTRACT FROM AUTHOR]

Nanoscale drug delivery systems (nDDS) have been employed widely in enhancing the therapeutic efficacy of drugs against diseases with reduced side effects. Although several nDDS have been successfully approved for clinical use up to now, biological barriers between the administration site and the target site hinder the wider clinical adoption of nDDS in disease treatment. Polyethylene glycol (PEG)-modification (or PEGylation) has been regarded as the gold standard for stabilising nDDS in complex biological environment. However, the accelerated blood clearance (ABC) of PEGylated nDDS after repeated injections becomes great challenges for their clinical applications. Zwitterionic polymer, a novel family of anti-fouling materials, have evolved as an alternative to PEG due to their super-hydrophilicity and biocompatibility. Zwitterionic nDDS could avoid the generation of ABC phenomenon and exhibit longer blood circulation time than the PEGylated analogues. More impressively, zwitterionic nDDS have recently been shown to overcome multiple biological barriers such as nonspecific organ distribution, pressure gradients, impermeable cell membranes and lysosomal degradation without the need of any complex chemical modifications. The realization of overcoming multiple biological barriers by zwitterionic nDDS may simplify the current overly complex design of nDDS, which could facilitate their better clinical translation. Herein, we summarise the recent progress of zwitterionic nDDS at overcoming various biological barriers and analyse their underlying mechanisms. Finally, prospects and challenges are introduced to guide the rational design of zwitterionic nDDS for disease treatment. [ABSTRACT FROM AUTHOR]

[Display omitted] • Viscoelastic measurements of nanometer-thickness polymer brush films were achieved. • Gap dependence of viscoelasticity was investigated to elucidate the film's lubricity. • Correlation between friction and viscoelasticity was revealed. A hydrated 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer brush exhibits exceptional lubricity. This lubrication mechanism has traditionally been attributed to either the inherent fluidity of the brush or the water film that forms owing to its hydrophilic nature. Given previous findings that the frictional properties of the MPC polymer brush film show load dependence, we hypothesize that the lubrication mechanism can be elucidated by examining the shear gap (varies owing to the load) dependence of the brush's viscoelastic response. MPC polymer brush films with different thicknesses were prepared. Their viscoelastic responses were evaluated across different shear gap widths, and the frictional properties were subsequently compared across states with distinct viscoelastic behaviors. The observed shear viscoelasticity demonstrated a clear gap dependence that correlated with frictional attributes. Our data suggests that the lubrication mechanism shifts based on the shear gap. Specifically, two states exhibited low coefficients of friction: one where the osmotic pressure supports the load while allowing flexible deformation of the brush film, and the other where the brush film undergoes compression and transitions to a fully elastic state. [ABSTRACT FROM AUTHOR]

The lubrication modification of biomedical devices significantly enhances the functionality of implanted interventional medical devices, thereby providing additional benefits for patients. Polymer brush coating provides a convenient and efficient method for surface modification while ensuring the preservation of the substrate's original properties. The current research has focused on a "trial and error" method to finding polymer brushes with superior lubricity qualities, which is time-consuming and expensive, as obtaining effective and long-lasting lubricity properties for polymer brushes is difficult. This review summarizes recent research advances in the biomedical field in the design, material selection, preparation, and characterization of lubricating and antifouling polymer brushes, which follow the polymer brush development process. This review begins by examining various approaches to polymer brush design, including molecular dynamics simulation and machine learning, from the fundamentals of polymer brush lubrication. Recent advancements in polymer brush design are then synthesized and potential avenues for future research are explored. Emphasis is placed on the burgeoning field of zwitterionic polymer brushes, and highlighting the broad prospects of supramolecular polymer brushes based on host-guest interactions in the field of self-repairing polymer brush applications. The review culminates by providing a summary of methodologies for characterizing the structural and functional attributes of polymer brushes. It is believed that a development approach for polymer brushes based on "design-material selection-preparation-characterization" can be created, easing the challenge of creating polymer brushes with high-performance lubricating qualities and enabling the on-demand creation of coatings. Biomedical devices have severe lubrication modification needs, and surface lubrication modification by polymer brush coating is currently the most promising means. However, the design and preparation of polymer brushes often involves "iterative testing" to find polymer brushes with excellent lubrication properties, which is both time-consuming and expensive. This review proposes a polymer brush development process based on the "design-material selection-preparation-characterization" strategy and summarizes recent research advances and trends in the design, material selection, preparation, and characterization of polymer brushes. This review will help polymer brush researchers by alleviating the challenges of creating polymer brushes with high-performance lubricity and promises to enable the on-demand construction of polymer brush lubrication coatings. [Display omitted] [ABSTRACT FROM AUTHOR]

All‐solid‐state stretchable supercapacitors (SSSCs) have attracted widespread attention in the wearable and medical fields because of their nontoxic, safe, and environmentally friendly characteristics. In this paper, a dual network hydrogel polymer was synthesized by a one‐pot method, which was constructed from sodium alginate (SA) and zwitterion copolymer of acrylamide (AM) and sulfobetaine methacrylate (SBMA). The dual network hydrogel polymerSAm/P(AM‐co‐SBMA (SASm for short) were immersed in 1 M H2SO4 electrolyte to obtain gel polymer electrolytes (GPEs). Stretchable electrodes were synthesized on the matrix of SASm gels. Non‐integrated all‐solid‐state stretchable supercapacitors (non‐integrated SSSCs), integrated all‐solid‐state supercapacitors (SSCs) and integrated SSSCs were all assembled into the 'sandwich' structure. The elongation of the integrated SSSC is the best and reaches 280 %, and its areal capacitance is 1.96 mF/cm2 under a current destiny of 50 μA/cm2, and the capacitance still remains 95 % of the initial value after 10000 charge and discharge cycles, and its energy density is 5.8×10−2 μWh/cm2 at a power density of 2.9×10−2 mW/cm2. This integrated SSSC has excellent cycling stability while maintaining good tensile properties. [ABSTRACT FROM AUTHOR]

High-density zwitterionic groups functionalized graphene oxides (PSBMA@GO) were incorporated into sulfonated poly(ether ether ketone) (SPEEK) membranes to create continuous channels for efficient proton/vanadium ion selective conduction. The incorporation of zwitterionic polymers, specifically poly(sulfobetaine methacrylate) (PSBMA) combined with graphene oxide (GO) sheets, enhanced the compatibility of additives with the SPEEK matrix. Furthermore, the impact of PSBMA@GO content on the properties of S/PSBMA@GO hybrid membranes for vanadium redox flow battery (VRFB) application was investigated. S/PSBMA@GO-1 hybrid membrane exhibits ultrahigh ion selectivity 55.3×103 S min cm-3, and the cell with this membrane shows excellent coulombic efficiencies (98.2-99.1%), energy efficiencies (83.6-74.5%) at 100-180 mA cm-2, long cycle life and high capacity retention (35.8% after 100 cycles at 100 mA cm-2). This study demonstrates that PSBMA@GO have great application potential to solve the trade-off effect between proton conductivity and vanadium ion permeability of PEM. [Display omitted] • The PSBMA@GO with high-density zwitterionic groups is prepared. • Efficient ion selective conduction channels are formed in S/PSBMA@GO membrane. • The S/PSBMA@GO membrane shows ultrahigh ion selectivity. • The S/PSBMA@GO membrane exhibits high cell efficiency and good stability. [ABSTRACT FROM AUTHOR]