Phosphorylcholine Groups Research Articles

An antifouling membrane-fusogenic liposome for effective intracellular delivery in vivo

The membrane-fusion-based internalization without lysosomal entrapment is advantageous for intracellular delivery over endocytosis. However, protein corona formed on the membrane-fusogenic liposome surface converts its membrane-fusion performance to lysosome-dependent endocytosis, causing poorer delivery efficiency in biological conditions. Herein, we develop an antifouling membrane-fusogenic liposome for effective intracellular delivery in vivo. Leveraging specific lipid composition at an optimized ratio, such antifouling membrane-fusogenic liposome facilitates fusion capacity even in protein-rich conditions, attributed to the copious zwitterionic phosphorylcholine groups for protein-adsorption resistance. Consequently, the antifouling membrane-fusogenic liposome demonstrates robust membrane-fusion-mediated delivery in the medium with up to 38% fetal bovine serum, outclassing two traditional membrane-fusogenic liposomes effective at 4% and 6% concentrations. When injected into mice, antifouling membrane-fusogenic liposomes can keep their membrane-fusion-transportation behaviors, thereby achieving efficient luciferase transfection and enhancing gene-editing-mediated viral inhibition. This study provides a promising tool for effective intracellular delivery under complex physiological environments, enlightening future nanomedicine design.

Supramolecular self‐assembled nanoparticles for targeted therapy of myocardial infarction by enhancing cardiomyocyte mitophagy

AbstractMyocardial infarction accompanied by diabetes mellitus is accepted as the most serious type of coronary heart disease, and among the current treatment strategies, the precise delivery of protective drugs for inhibiting cardiomyocyte apoptosis is still a challenge. In this study, we developed a biodegradable nanoparticles‐based delivery system with excellent macrophage escape, cardiac targeting, and drug release properties to achieve targeted therapy of myocardial infarction. Specifically, a copolymer of p(DMA–MPC–CD) combining self‐adhesion, hydration lubrication, and targeting peptide binding site was successfully prepared by free radical copolymerization, and it was self‐assembled on the surface of melatonin‐loaded dendritic mesoporous silica nanoparticles (bMSNs) following the integration of adamantane‐modified cardiac homing peptide (CHP) based on supramolecular host–guest interaction. Importantly, a hydration layer formed around the zwitterionic phosphorylcholine groups of the multifunctional nanoparticles, which was confirmed by the enhancement in hydration lubrication and reduction in coefficient of friction, prevented the nanoparticles from phagocytosis by the macrophages. The in vivo bioluminescence imaging test indicated that the nanoparticles were endowed with satisfied cardiac targeting capability, and the in vivo mice study demonstrated that the intravenous injection of drug‐loaded nanoparticles (namely bMSNs–Mel@PDMC–CHP) effectively reduced cardiomyocyte apoptosis, alleviated myocardial interstitial fibrosis, and enhanced cardiac function.

Enzyme stability in polymer hydrogel-enzyme hybrid nanocarrier containing phosphorylcholine group.

Enzymes are biological catalysts with good biocompatibility and high efficiency and have been widely used in many fields, such as wastewater treatment, biosensors, and the medical industry. However, their inherently low stability under conditions of practical use limits further applications. Zwitterionic polymers possessing a pair of oppositely charged groups in their repeating units can increase protein stability because of their good biocompatibility and high water content. In this study, zwitterionic copolymer nanogels comprising poly(2-methacryloyloxyethyl phosphorylcholine (MPC)-co-methacrylic acid-N-hydroxy succinimide ester (MNHS)) (PMS) were synthesized via reversible addition-fragmentation chain-transfer polymerization (RAFT). β-Galactosidase (β-gal) was post-modified within zwitterionic polymer nanogels with a covalently-bound spacer and the activity was compared with that of directly immobilized β-gal and free β-gal. Compared with direct immobilization, covalent immobilization with a spacer could reduce the structural change of β-gal, as confirmed by the circular dichroism spectra. Although the activity of β-gal decreased after immobilization, the hybrids of the β-gal immobilized nanogels, termed hybrid nanogel-enzymes, demonstrated superior stability compared to the free enzymes. The hybrid nanogel-enzymes maintained their function against inactivation by organic solvents and proteinases owing to their high water content, anti-biofouling properties, and limited mass transfer. They can also withstand protein aggregation at high temperatures and maintain their activity. Compared to direct immobilization, immobilization with a spacer resulted in a dramatic increase in the enzyme activity and a slight decrease in the stability. These results indicate that polymer nanogels containing phosphorylcholine units are promising materials for enzyme immobilization, expanding the scope of enzyme applications.

Unraveling the Adhesion Behavior of Different Cell Lines on Biomimetic PEDOT Interfaces: The Role of Surface Morphology and Antifouling Properties.

The poly(3,4-ethylenedioxythiophene) (PEDOT) interface, renowned for its biocompatibility and intrinsic conductivity, holds substantial potential in biosensing and cellular modulation. Through strategic functionalization, PEDOT derivatives can be adaptable for multifaceted applications. Notably, integrating phosphorylcholine (PC) groups into PEDOT, mimicking the hydrophilic headgroups from cell membranes, confers exceptional antifouling properties on the coating. This study systematically investigated biomolecule interactions with distinct forms of PEDOT, incorporating variations in surface modifications and structure. Zwitterionic PEDOT-PC was electropolymerized on smooth and nanostructured surfaces using various feeding ratios in electrolytes to finely control the antifouling properties of the interface. Precise electropolymerization conditions governed the attainment of smooth and nanostructured filamentous surfaces. The study employed a quartz crystal microbalance with dissipation (QCM-D) to assess protein binding behavior. Bovine serum albumin (BSA), lysozyme (LYZ), cytochrome c (cyt c), and fibronectin (FN) were used to evaluate their binding affinities for PEDOT films. FN, a pivotal extracellular matrix component, was included for connecting to cell adhesion behavior. Furthermore, the cellular adhesion behaviors on PEDOT interfaces were evaluated. Three cell lines─MG-63 osteosarcoma, HeLa cervical cancer, and fibroblast NIH/3T3 were examined. The presence of PC moieties significantly altered the adhesive response, including the number of attached cells, their morphologies, and nucleus shrinkage. MG-63 cells exhibited the highest tolerance for PC moieties. A feeding ratio of PEDOT-PC exceeding 70% resulted in cell apoptosis. This study contributes to understanding biomolecule adsorption on PEDOT surfaces of diverse morphologies and degrees of the antifouling moiety. Meanwhile, it also sheds light on the responses of various cell types.

A-364 The Utility of the Highly Sensitive Detection System for Immunochromatographic Assay by Addition of MPC polymer

Abstract Background Immunochromatographic assay (ICA) is frequently used as a point-of-care testing (POCT) in the field of infectious diseases, but it has a problem of low detection sensitivity. Many interfering substances in ICA test materials have been reported to case a decrease in detection sensitivity. For the purpose of increasing the sensitivity of ICA, bovine serum albumin or a polymer with phosphorylcholine groups (MPC polymer) has been used as an additive to a sample diluent. In this study, we evaluated the usability of the sensitizing effect for the addition of MPC polymer with a serum-based HBs antigen test kit. Methods A 2-fold dilution series of a commercially available control serum (Infectrol D, SeraCare Life Sciences, Inc. manufacturer's reference value 108.674 IU/mL) containing 0.05%, 0.10%, 0.5% of several MPC polymers (Biolipidure® from NOF Corporation) as final concentration were prepared with HBs antigen negative serum. The optimal type of MPC polymer and the concentrations added to the sera were determined by comparing the color intensity of their test lines in the evaluation of each test sample with a commercially available test kit (Quick Chaser® from MIZUHO MEDY Co., Ltd.). The color intensities of the test lines were quantified with an immunochromatographic reader. In addition, the correlation of two different test kits (ESPLINE® from FUJIREBIO and Quick Chaser® from MIZUHO MEDY Co., Ltd.) was evaluated with sera obtained from HBs antigen-positive patients regarding the three types of MPC polymer which were improved the detection sensitivity in the evaluation with the control serum. The measurements were performed in triplicate after 0.5% of MPC polymer as final concentration was added to each diluted serum. Results Antigen amount for diluted sera with MPC polymer were determined by CLEIA method, and no difference in the antigen amount was observed regardless of the addition or the types of MPC polymer. In addition, the color intensity in each dilution series was compared to the cutoff value, which is average value of the color intensity of negative control serum without MPC polymer. In the evaluation with control serum, the test line in the case without MPC polymer enabled to detect up to 2-fold diluted control serum while the test line in the case with MPC polymer enabled to detect up to 32-fold diluted control serum. The addition of MPC polymer in the evaluation with sera obtained from HBs antigen-positive patients was also confirmed that the detection sensitivity enhanced up to 8-fold higher in ESPLINE® and up to 4-fold higher in Quick Chaser®. Conclusion The color intensity of the test line enhanced by the addition of MPC polymer. In particular, when the highly hydrophilic and anionic MPC polymer was added, the test line was detected narrower and darker, and we believe that the increased color intensity resulted in improved sensitivity. By considering the influence of interfering substances in clinical materials and the physical properties of the MPC polymer (hydrophobicity, molecular size, etc.), it is expected that the sensitivity of the ICA will be increased to be more suitable for clinical materials.

A Study of the Phosphorylcholine Polymer Coating of a Polymethylpentene Hollow Fiber Membrane.

A phosphorylcholine polymer (poly(MPC-co-BMA-co-TSMA), PMBT) was prepared by free radical polymerization and coated on the surface of the polymethylpentene hollow fiber membrane (PMP-HFM). ATR-FTIR and SEM analyses showed that the PMBT polymer containing phosphorylcholine groups was uniformly coated on the surface of the PMP-HFM. Thermogravimetric analysis showed that the PMBT had the best stability when the molar percentage of MPC monomer in the polymer was 35%. The swelling test and static contact angle test indicated that the coating had excellent hydrophilic properties. The fluorescence test results showed that the coating could resist dissolution with 90% (v/v%) ethanol solution and 1% (w/v%) SDS solution. The PMBT coating was shown to be able to decrease platelet adherence to the surface of the hollow fiber membrane, and lower the risk of blood clotting; it had good blood compatibility in tests of whole blood contact and platelet adhesion. These results show that the PMBT polymer may be coated on the surface of the PMP-HFM, and is helpful for improving the blood compatibility of membrane oxygenation.

Preparation of Water-Soluble Polyion Complex (PIC) Micelles with Random Copolymers Containing Pendant Quaternary Ammonium and Sulfonate Groups.

Cationic random copolymers (PCm) consisting of 2-(methacryloyloxy)ethyl phosphorylcholine (MPC; P) with methacroylcholine chloride (MCC; C) and anionic random copolymers (PSn) consisting of MPC and potassium 3-(methacryloyloxy)propanesulfonate (MPS; S) were prepared via a reversible addition-fragmentation chain transfer method. "m" and "n" represent the compositions (mol %) of the MCC and MPS units in the copolymers, respectively. The degrees of polymerization for the copolymers were 93-99. Water-soluble MPC unit contains a pendant zwitterionic phosphorylcholine group whose charges are neutralized in pendant groups. MCC and MPS units contain the cationic quaternary ammonium and anionic sulfonate groups, respectively. The stoichiometrically charge-neutralized mixture of a matched pair of PCm and PSn aqueous solutions resulted in the spontaneous formation of water-soluble PCm/PSn polyion complex (PIC) micelles. These PIC micelles have the MPC-rich surface and MCC/MPS core. These PIC micelles were characterized using 1H NMR, dynamic and static light scattering, and transmission electron microscopic measurements. The hydrodynamic radius of these PIC micelles depends on the mixing ratio of the oppositely charged random copolymers. The charge-neutralized mixture formed maximum-size PIC micelles.

Bioinspired Polycation Functionalization of the Polyurethane Surface for Enhanced Lubrication, Antibacterial Property, and Anticoagulation

Endowing the implanted biomaterial with a wide range of functions, such as lubrication and antibacterial and anticoagulation properties, is essential for their safe clinical use. In the present study, based on the superlubrication mechanism of articular cartilage, a branched polyelectrolyte polymer (PEI-PMPC) was successfully synthesized based on tert-butyl hydroperoxide-initiated grafting polymerization and then applied to the biocompatible polyurethane (PU) surface. Specifically, the PU sheet was pretreated by polydopamine (PDA), and the PEI-PMPC polymer was grafted onto the PDA-modified PU surface by Schiff base reaction to generate a solid PDA/PEI-PMPC coating. The unmodified and modified surfaces were characterized by Fourier transform infrared spectroscopy, water contact angle, X-ray photoelectron spectroscopy, and surface zeta potential. To compare the lubrication, antibacterial behavior, and hemocompatibility, the relevant properties of the modified surfaces were evaluated by the tribological test, plate count method, surface morphology, hemolysis rate, activated partial thromboplastin time, and thrombin time. The experimental results demonstrated that the adhesion of bovine serum albumin, Escherichia coli, Staphylococcus aureus, platelets, and red blood cells was significantly decreased on the PEI-PMPC-modified PU surface compared with that of the unmodified PU surface. The multi-functional properties of the coating were attributed to the hydration layer formed by zwitterionic phosphorylcholine groups, and additionally, the cationic PEI served to kill the bacteria adhering to the surface. In summary, the bioinspired coating proposed in this study could potentially be used as a promising surface functionalization strategy for biomedical implants.

AGGREGATION BEHAVIORS OF PENDANT PHOSPHORYLCHOLINE GROUPS AND THEIR INFLUENCE ON POLYISOPRENE PROPERTIES

ABSTRACT Terminal phospholipid groups contribute considerably to the excellent comprehensive properties of NR, but their aggregation behaviors and influence on polyisoprene properties during storage and use have not yet been revealed at the molecular level. To begin to address these phenomena, two sequentially different polyisoprene copolymers were suspended with phosphorylcholine groups to disclose their influence on phase separation, network dynamics, mechanical properties, and crystallization differences. Phosphorylcholine groups attached to polymer chains can form aggregates that increase the storage modulus of rubbers, and this process is accelerated at elevated temperatures due to faster chain movement. In addition, phosphorylcholine groups act as crosslinking points in unvulcanized and vulcanized rubbers and increase mechanical properties by promoting strain-induced crystallization (SIC). By contrast, the polymers with pendant hydroxyl groups present sequence-dependent SIC properties that are ascribed to their non-aggregation nature.

Effects of Smart Drugs on Cholinergic System and Non-Neuronal Acetylcholine in the Mouse Hippocampus: Histopathological Approach.

In recent years, people in the United States and other countries have been using smart drugs, called nootropic or cognitive enhancers, to improve concentration and memory learning skills. However, these drugs were originally prescribed for attention-deficit hyperactivity disorder and dementia, and their efficacy in healthy people has not yet been established. We focused on acetylcholine in the hippocampus, which is responsible for memory learning, and elucidate the long-term effects of smart drugs on the neural circuits. Smart drugs were administered orally in normal young mice for seven weeks. The hippocampus was sectioned and compared histologically by hematoxylin and eosin (HE) staining, immunohistochemistry for acetylcholine, and immunoelectron microscopy. There were no significant changes in acetylcholinesterase staining. However, in HE, we found perivascular edema, and choline acetyltransferase staining showed increased staining throughout the hippocampus and new signal induction in the perivascular area in the CA3, especially in the aniracetam and α-glyceryl phosphoryl choline group. Additionally, new muscarinic acetylcholine receptor signals were observed in the CA1 due to smart drug intake, suggesting that vasodilation might cause neuronal activation by increasing the influx of nutrients and oxygen. Moreover, these results suggest a possible new mechanism of acetylcholine-mediated neural circuit activation by smart drug intake.

Preparation of Biocompatible Poly(2-(methacryloyloxy)ethyl phosphorylcholine) Hollow Particles Using Silica Particles as a Template.

Hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) shows biocompatibility because the pendant phosphorylcholine group has the same chemical structure as the hydrophilic part of phospholipids that form cell membranes. Hollow particles can be used in various fields, such as a carrier in drug delivery systems because they can encapsulate hydrophilic drugs. In this study, vinyl group-decorated silica particles with a radius of 150 nm were covered with cross-linked PMPC based on the graft-through method. The radius of PMPC-coated silica particles increased compared to that of the original silica particles. The PMPC-coated silica particles were immersed in a hydrogen fluoride aqueous solution to remove template silica particles to prepare the hollow particles. The PMPC hollow particles were characterized by dynamic light scattering, infrared spectroscopy, thermogravimetric analysis, and transmission electron microscopy observations. The thickness of the hollow particle shell can be controlled by the polymerization solvent quality. When a poor solvent for PMPC was used for the polymerization, PMPC hollow particles with thick shells can be obtained. The PMPC hollow particles can encapsulate hydrophilic guest molecules by immersing the hollow particles in a high-concentration guest molecule solution. The biocompatible PMPC hollow particles can be used in a drug carrier.

Surface characterization of a new contact lens water gradient using fluorescent staining

Purpose: A fluorescently labelled C-reactive protein (CRP) was used to characterize a new contact lens material (lehfilcon A) with a water gradient surface containing embedded phosphoryl choline (PC) groups. The uniformity and functionality of these groups were verified before and after on-eye wear.

Separated Micelles Formation of pH-Responsive Random and Block Copolymers Containing Phosphorylcholine Groups.

The self-assembly of pH-responsive random and block copolymers composed of 2-(N,N-diisopropylamino)ethyl methacrylate and 2-methacryloyloxyethyl phosphorylcholine was investigated in aqueous media. Their pH-responsive behaviors were investigated in aqueous media by dynamic light scattering (DLS) and fluorescence measurements using a pyrene hydrophobic fluorescence probe. In an acidic environment, these copolymers existed as single polymer chains that did not interact with each other. In contrast, upon increasing the pH of the solution above the critical value of ~8, separated micelles were formed in the mixture, which was indicated by bimodal distribution in DLS results with radius of 4.5 and 10.4 nm, corresponding to the random and block copolymer micelles, respectively. Fluorescence resonance energy transfer efficiencies were near to zero in the mixture of the donor labeled block and acceptor labeled random copolymers under both acidic and basic pH. These results demonstrated the coexistence of two distinct micelles.

Mini Review: Structure and Function of Nematode Phosphorylcholine-Containing Glycoconjugates

An unusual aspect of the biology of nematodes is the covalent attachment of phosphorylcholine (PC) to carbohydrate in glycoconjugates. Investigation of the structure of these molecules by ever-increasingly sophisticated analytical procedures has revealed that PC is generally in phosphodiester linkage with C6 ofN-acetylglucosamine (GlcNAc) in bothN-type glycans and glycosphingolipids. Up to five PC groups have been detected in the former, being located on both antenna and core GlcNAc. The PC donor for transfer to carbohydrate appears to be phosphatidylcholine but the enzyme responsible for transfer remains to be identified. Work primarily involving the PC-containingAcanthocheilonema viteaesecreted product ES-62, has shown that the PC attached to nematodeN-glycans possesses a range of immunomodulatory properties, subverting for example, pro-inflammatory signalling in various immune system cell-types including lymphocytes, mast cells, dendritic cells and macrophages. This has led to the generation of PC-based ES-62 small molecule analogues (SMAs), which mirror the parent molecule in preventing the initiation or progression of disease in mouse models of a number of human conditions associated with aberrant inflammatory responses. These include rheumatoid arthritis, systemic lupus erythematosus and lung and skin allergy such that the SMAs are considered to have widespread therapeutic potential.

Preparation of Magnetic Hydrogel Microparticles with Cationic Surfaces and Their Cell-Assembling Performance.

Cationic magnetic hydrogel microparticles with high retention on cell surfaces were prepared using a two-step procedure. Using these magnetic hydrogel microparticles, cells were clustered with each other, and cell aggregates were prepared effectively. Cross-linked poly(vinyl alcohol) (PVA) hydrogel microparticles containing iron oxide nanoparticles were prepared. The diameter of the microparticles was in the range of 200-500 nm. Water-soluble cationic polymers containing both trimethyl ammonium (TMA) groups and phenylboronic acid (PBA) groups were synthesized for the surface modification of the microparticles. To regulate the composition, electrically neutral phosphorylcholine groups were introduced into the polymer. Covalent bonds were formed between the hydroxy groups of PVA microparticles and PBA groups in the polymer. The surface zeta potential of the microparticles reflected the composition of the TMA groups. The particles responded to an external magnetic field and clustered rapidly. Microparticles were adsorbed on the floating cell surface and induced cell aggregation quickly when a magnetic field was applied. Under the most effective conditions, the diameter of the cell aggregates increased to approximately 1 mm after 30 min. Denser cell aggregates were formed by the synergistic effects of the magnetic field and the properties of the microparticles. The formed cell aggregates continued to grow for more than 4 days under an applied magnetic field, indicating that the ability of the cells in the aggregate to proliferate was well maintained.

Facile preparation of water-soluble multiwalled carbon nanotubes bearing phosphorylcholine groups for heat generation under near-infrared irradiation

In the present study, water-soluble molecular complexes between carboxylic acid-functionalized multiwalled carbon nanotubes (MWCNTs) and biocompatible poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) were prepared by hand grinding. MWCNTs could be solubilized in phosphate-buffered saline using this simple method. The suspended concentration of MWCNTs was found to increase with increasing polymer concentration and pH of the solution. Heat generation from the complexes was studied upon irradiation with near-infrared (NIR) radiation at a wavelength of 808 nm. The results demonstrated that MWCNTs absorbed light and generated heat when the molecular complex was irradiated by NIR. The solution temperature increased with increasing MWCNT concentration and irradiation time. This study presents a facile method for preparation of water-soluble molecular complexes between carboxylic acid-functionalized multiwalled carbon nanotube and poly(2-methacryloyloxyethyl phosphorylcholine) (MWCNTs/PMPC) by hand grinding. MWCNTs could be solubilized in aqueous environment with higher suspended concentrations when increasing polymer concentration and pH of the solution. MWCNTs/PMPC adsorbed light and induced heat generation to reach the temperature required for photothermal therapy (PTT) when the complexes were irradiated by near-infrared (NIR) at a wavelength of 808 nm. The water-soluble MWCNT complex covered by biocompatible PMPC is a promising candidate for PTT application.

The evaluation of anchoring processes and chemical stability of zwitterionic molecules via local reactivity indexes

Exposure of materials to blood can result in numerous interactions such as plasma protein adsorption, blood cell activation, platelet adhesion, and thrombotic reactions. Although strategies to minimize the blood-immune response with the coating surface of these biomaterials are being developed, many of the specific factors that trigger this immune response are still unknown. Among the approaches to overcome this situation, the surface modification by zwitterionic molecules is promising due to their recognized biocompatibility and anti-fouling properties. Here we present a computational study on the structural, electronic, and reactivity properties of a series of anti-fouling zwitterionic molecules containing sulfobetaine, carboxybetaine and phosphorylcholine groups with distinct anchoring segments. Details on the adsorption and anchoring of these molecules on SiO2 model systems as well as their interaction with water molecules were investigated. The results indicate that the evaluation of local softness matching can bring valuable information regarding the anchoring processes and stability of zwitterionic molecules. In addition, it is shown that the analysis of the frontier levels of the compound's components defines an effective and cheap approach for the proposition and identification of new/improved systems.

Control of Cell-Substrate Binding Related to Cell Proliferation Cycle Status Using a Cytocompatible Phospholipid Polymer Bearing Phenylboronic Acid Groups.

To provide high-quality cellular raw materials for cell engineering and pharmaceutical engineering, a polymer substrate is prepared for cell separation focusing on the cell proliferation cycle. There are many types of sugar chains on cell membranes, which function as signaling molecules to control interactions with the exterior of the cell; their abundance changes during the cell-proliferation cycle. In this study, a phenylboronic acid group, which has affinity for sugar chains, is introduced into a polymer containing a phosphorylcholine group that does not induce cell activation. On the surface of this polymer, human promyelocytic leukemia cells can adhere. The adhesion rate is increased by pretreating the substrate with an alkaline solution. Moreover, cell adhesion is dependent on the sugar additive in the culture medium. Therefore, cell adhesion is governed by reactions between the sugar chain on the cell membrane and the phenylboronic acid groups on the substrate. It is revealed that the adhesion rate changes depending on the expression level of sugar chains related to the cell-proliferation cycle. Based on this, it may be proposed a cell proliferation cycle-specific separation process using the polymer substrate based on cell adhesion depending on sugar chain density.

Thermo-Responsive Behavior of Mixed Aqueous Solution of Hydrophilic Polymer with Pendant Phosphorylcholine Group and Poly(Acrylic Acid).

A mixed aqueous solution of hydrophilic poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) and poly(acrylic acid) (PAAc) becomes cloudy under acidic conditions at room temperature. The pendant carboxylic acid groups in PAAc form hydrogen bonds with the ester and phosphate groups in PMPC. While the polymers aggregate under acidic conditions, neither one associate under basic conditions because of the deprotonation of the pendant carboxy groups in PAAc. We observed that the interpolymer complex formed from PMPC, and PAAc was dissociated in aqueous solutions with increasing temperature, which is an upper critical solution temperature behavior. With increasing temperature, the molecular motion increased to dissociate the interpolymer complex. The phase transition temperature increased with increasing polymer and salt concentrations, and with decreasing pH.

Direct photoreactive immobilization of water-soluble phospholipid polymers on substrates in an aqueous environment

The purpose of this study is to achieve a simpler and safer surface modification of substrates using a photoreactive polymer in an aqueous environment. We synthesized water-soluble photoreactive polymers with both phenylazide groups and phosphorylcholine groups, poly(2-methacryloyloxyethyl phosphorylcholine-co-4-methacryl tetra(ethylene glycol)oxycarbonyl-4-phenylazide) (PMEPAz), via reversible addition fragmentation chain transfer polymerization. PMEPAz with different polymerization degrees were synthesized with a well-defined structure. To immobilize PMEPAz on the substrate surface by photoreaction, it is necessary to adsorb the polymer on the substrate surface in an aqueous solution because the phenylazide groups chemically bind to the substrate via a hydrogen abstract reaction. The relationship between the polymer solubilization state in the aqueous solution and the adsorption behavior at the surface was investigated. PMEPAz began to form unstable molecular aggregates at a concentration of 10−2 mg/mL and formed stable aggregates at 100 mg/mL. At a concentration of 10−1 mg/mL, unstable molecular aggregates of PMEPAz were formed in the aqueous solution, resulting in the maximization of the amount of adsorbed polymer and effective photoreaction with the substrate. The thickness of the reacted polymer layer on the substrate increased with an increase in the polymerization degree, a uniform polymer layer with a thickness of 3.4 nm was formed when the polymerization degree was 400. After surface modification, the hydrophobic surfaces of the original substrates became hydrophilic. Additionally, fibrinogen adsorption and platelet adhesion were effectively suppressed based on the characteristics of the phosphorylcholine unit.