Diblock Copolymer Poly Research Articles

A Comparative Study of Structural Contribution to Biocidability via Immobilization of Fluorinated and Nonfluorinated Quaternary Ammonium Salts on Top Surfaces.

Higher biocidability of fluorinated quaternary ammonium salt (QAS) is usually contributed to its preferential segregation to the surface to better contact with and kill bacteria. However, whether its structure also elicits better performance is still unclear. Herein, the same amount of a fluorinated QAS and its nonfluorinated counterpart are both immobilized on the top surface to eliminate the effect of concentration distribution to only study their structure-biocidability relationship. Briefly, the fluorinated and nonfluorinated QASs were synthesized by quaternization of N,N-dimethylethanolamine with 2-(perfluorooctyl)ethyl bromide that was prepared by bromination of 2-(perfluorooctyl)ethanol and 1-bromodecane, respectively. Polystyrene (PS) and diblock copolymer poly(styrene)-b-poly(tert-butyl acrylate) (PS-PtBA) were successively spin coated on SiO2 wafers at different concentrations to form bilayer structures that have a PS base layer and a PtBA top layer. The tert-butyl acrylate groups of the PtBA layer of 0.9 nm were converted to carboxylic acid groups with trifluoroacetic acid for respective esterification with the two hydroxy-containing QASs. It was observed that the fluorinated and nonfluorinated surfaces fabricated at the maximum comparable esterification yield of 63.5% fully eradicated ∼104 CFU of Staphylococcus aureus and Escherichia coli in 120 and 150 min, respectively, indicating that the fluorocarbon chain is more biocidal through better interpenetration into bacterial membranes. Immobilization of a functionality on top surface provides a universal strategy to study its structural contribution to activity without interference of the concentration distribution.

Diblock Copolymers of Poly(ethylene oxide)-b-poly(propylene oxide) Stabilize a Blood-Brain Barrier Model under Oxidative Stress.

The blood-brain barrier (BBB) is a highly restrictive barrier at the interface between the brain and the vascular system. Even under BBB dysfunction, it is extremely difficult to deliver therapies across the barrier, limiting the options for treatment of neurological injuries and disorders. To circumvent these challenges, there is interest in developing therapies that directly engage with the damaged BBB to restore its function. Previous studies revealed that poloxamer 188 (P188), a water-soluble triblock copolymer of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), partially mitigated BBB dysfunction in vivo. In the context of stabilization of the damaged BBB, the mechanism of action of PEO-PPO block copolymers is unknown, and there has been minimal exploration of polymers beyond P188. In this study, a human-based in vitro BBB model under oxidative stress was used to investigate polymer-BBB interactions since oxidative stress is closely linked with BBB dysfunction in many neurological injuries and disorders. PEO-PPO block copolymers of varied numbers of chemically distinct blocks, PEO block length, and functionality of the end group of the PPO block were assessed for their efficacy in improving key physiological readouts associated with BBB dysfunction. While treatment with P188 did not mitigate damage in the in vitro BBB model, treatment with three diblock copolymers improved barrier integrity under oxidative stress to a similar extent. Of the considered variations in the block copolymer design, the reduction in the number of chemically distinct blocks had the strongest influence on therapeutic function. The demonstrated efficacy of three alternative PEO-PPO diblock copolymers in this work reveals the potential of these polymers as a class of therapeutics that directly treat the damaged BBB, expanding the options for treatment of neurological injuries and disorders.

Morphology and Emulsification of Poly(N-2-(methacryloyloxy) ethyl pyrrolidone)-b-poly(benzyl methacrylate) Assemblies by Polymerization-Induced Self-Assembly.

In this work, a series of amphiphilic diblock copolymers poly(N-2-(methacryloyloxy) ethyl pyrrolidone)-b-poly(benzyl methacrylate) (PNMP m -b-PBzMA n ) were developed by the dispersion polymerization method in ethanol. The polymerization-induced self-assembly (PISA) behaviors were studied systematically, and a comprehensive structure-property relationship was also established. Two distinct PISA tendencies were observed, which was mainly depended on the polymerization degree m of PNMP segment. When m is small such as 39 and 55, morphological transitions from spherical to vesicle-like assemblies via wormlike ones upon increasing n commonly happen regardless of the solid content. Alternatively, spherical assemblies became the sole morphology for PNMP64-b-PBzMA n block copolymers because of the excellent solvophilicity of the PNMP64 segment. Attributing to the amphiphilicity of PNMP m -b-PBzMA n block copolymers, PNMP m -b-PBzMA n assemblies by PISA are a type of excellent Pickering emulsifiers. These assemblies prefer to stabilize O/W Pickering emulsions as confirmed by the confocal laser scanning microscopy method, and the effects of polymerization degree of PBzMA segment or morphologies of PNMP m -b-PBzMA n assemblies are finite.

Association of Thermoresponsive Diblock Copolymer PDEGMA-b-PDIPAEMA in Aqueous Solutions: The Influence of Terminal Groups.

Aqueous solutions of a thermoresponsive diblock copolymer poly(di-[ethylene glycol] methyl ether methacrylate)-b-poly(2-[diisopropylamino] ethyl methacrylate) (PDEGMA-b-PDIPAEMA) were studied by static, dynamic and electrophoretic light scattering, small-angle X-ray scattering and differential scanning calorimetry. Thermoresponsive behavior of PDEGMA-b-PDIPAEMA was investigated at two pH values, pH = 2, at which the terminal carboxylic group of the PDEGMA chain and the PDIPAEMA block are protonated, and pH = 7, where the carboxyl terminal group is ionized while the PDIPAEMA block is partially deprotonated and more hydrophobic. Both at pH = 2 and 7, PDEGMA-b-PDIPAEMA copolymer underwent extensive association (the size of the aggregates was between 100 and 300 nm), indicating strong interchain interactions. While the measurements confirmed thermoresponsive behavior of PDEGMA-b-PDIPAEMA at pH = 7, no changes in the association with temperature were observed at pH 2 as the thermoresponsivity of PDEGMA was suppressed by hydrogen bonding between carboxylic groups and PDEGMA segments, as well as due to the increased hydrophilicity of the PDIPAEMA block. Fluorescence measurements with pyrene as a fluorescent probe showed that both at pH = 2 and pH = 7 the associates were able to solubilize hydrophobic substances.

Surface Coating of NCM523 Cathode Electrodes by the Difunctional Block Copolymer/Lithium Salt Composites.

Nickel-rich layered oxide cathodes, such as LiNi0.5Co0.2Mn0.3O2 (NCM523), are prevalent in high-power batteries owing to their high energy density. However, these cathodes suffer from undesirable side reactions occurring at the cathode/liquid electrolyte interface, leading to inferior interface stability and poor cycle life. To address these issues, herein, an amphiphilic diblock copolymer poly(dimethylsiloxane)-block-poly(acrylic acid) (PDMS-b-PAA) along with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) is utilized for modifying the electrode surface. This modification causes a thin and stable cathode-electrolyte interface (CEI) on the surface of NCM523 particles, as evidenced by XPS, TEM, and EIS analysis. The introduction of this modified interface successfully suppresses the capacity fading of NCM523. After 200 cycles at a rate of 1.0 C, the capacity of the modified NCM523 cathode is 108.7 mAh g-1, with a capacity retention of 82.8%, while the control samples without the polymer modification display a capacity retention of 72.7%. These results outline the distinct advantage of electrode surface modification with diblock copolymers/LiTFSI for the stabilization of Ni-rich layered oxide cathodes.

Construction of mesoporous silica-implanted tungsten oxides for selective acetone gas sensing

As a key biomarker for noninvasive diagnosis of diabetes, the selective detection of trace acetone in exhaled gas using a portable and low-cost device remains a great challenge. Semiconductor metal oxide (SMO) based gas sensors have drawn signification attention due to their potential in miniaturization, user-friendliness, high cost-effectiveness and selective real-time detection for noninvasive clinical diagnosis. Herein, we propose a one-pot solvent evaporation induced tricomponent co-assembly strategy to design a novel ordered mesoporous SMO of silica-implanted WO3 (SiO2/WO3) as sensing materials for trace acetone detection. The controlled co-assembly of silicon and tungsten precursors and amphiphilic diblock copolymer poly(ethylene oxide)-block-polystyrene (PEO-b-PS), and the subsequent thermal treatment enable the local lattice disorder of WO3 induced by the amorphous silica and the formation of ordered mesoporous SiO2/WO3 hybrid walls with a unique metastable ε-phase WO3 framework. The obtained mesoporous SiO2/WO3 composites possess highly crystalline framework with large uniform pore size (12.0–13.3 nm), high surface area (99–113 m2/g) and pore volume (0.17–0.23 cm3/g). Typically, the as-fabricated gas sensor based on mesoporous 2.5 %SiO2/WO3 exhibits rapid response/recovery rate (5/17 s), superior sensitivity (Rair/Rgas = 105 for 50 ppm acetone), as well as high selectivity towards acetone. The limit of detection is as low as 0.25 ppm, which is considerably lower than the thresh value of acetone concentration (>1.1 ppm) in the exhaled breath of diabetic patients, demonstrating its great prospect in real-time monitoring in diabetes diagnosis. Moreover, the mesoporous 2.5 %SiO2/WO3 sensor is integrated into a wireless sensing module connected to a smart phone, providing a convenient real-time detection of acetone.

Advancing Bone-Targeted Drug Delivery: Leveraging Biological Factors and Nanoparticle Designs to Improve Therapeutic Efficacy.

Designing targeted drug delivery systems to effectively treat bone diseases ranging from osteoporosis to nonunion bone defects remains a significant challenge. Previously, nanoparticles (NPs) self-assembled from diblock copolymers of poly(styrene-alt-maleic anhydride)-b-poly(styrene) (PSMA-b-PS) delivering a Wnt agonist were shown to effectively target bone and improve healing via the introduction of a peptide with high affinity to tartrate-resistant acid phosphatase (TRAP), an enzyme deposited by the osteoclasts during bone remodeling. Despite these promising results, the underlying biological factors governing targeting and subsequent drug delivery system (DDS) design parameters have not been examined to enable the rational design to improve bone selectivity. Therefore, this work investigated the effect of target ligand density, the treatment window after injury, specificity of TRAP binding peptide (TBP), the extent of TRAP deposition, and underlying genetic factors (e.g., mouse strain differences) on TBP-NP targeting. Data based on in vitro binding studies and in vivo biodistribution analyses using a murine femoral fracture model suggest that TBP-NP-TRAP interactions and TBP-NP bone accumulation were ligand-density-dependent; in vitro, TRAP affinity was correlated with ligand density up to the maximum of 200,000 TBP ligands/NP, while NPs with 80,000 TBP ligands showed 2-fold increase in fracture accumulation at day 21 post injury compared with that of untargeted or scrambled controls. While fracture accumulation exhibited similar trends when injected at day 3 compared to that at day 21 postfracture, there were no significant differences observed between TBP-functionalized and control NPs, possibly due to saturation of TRAP by NPs at day 3. Leveraging a calcium-depletion diet, TRAP deposition and TBP-NP bone accumulation were positively correlated, confirming that TRAP-TBP binding leads to TBP-NP bone accumulation in vivo. Furthermore, TBP-NP exhibited similar bone accumulation in both C57BL/6 and BALB/c mouse strains versus control NPs, suggesting the broad applicability of TBP-NP regardless of the underlying genetic differences. These studies provide insight into TBP-NP design, mechanism, and therapeutic windows, which inform NP design and treatment strategies for fractures and other bone-associated diseases that leverage TRAP, such as marrow-related hematologic diseases.

A visualizable strategy to real-time monitor chiral block copolypeptide assembly by AIE fluorescent probes

Aggregation-induced emission (AIE) luminogens show great potential in many applications. In this study, we have synthesized diblock copolymers poly (ethylene glycol) -b-poly (9-anthrylmethyl-L-lysine) (PEG-b-PLLys-An) and poly (ethylene glycol) -b-poly (9-anthrylmethyl-D-lysine) PEG-b-PDLys-An with opposite handedness by ring-opening polymerization and post-modification. Both diblock copolymers can self-assemble into spherical micelles or planar connected disc-like aggregates at different water fractions. In addition, the copolymers present a typical AIE process concomitant with the self-assembly process. To facilitate the study of chain exchange kinetics, we develope a novel visualizable strategy based on fluorescence variation. This strategy allows us to monitor the real-time chain exchange process by mixing equimolar solutions of PEG44-b-PDLys20-An and PEG44-b-PLLys20-An with varying water volume fractions. We indicate that chain exchange predominantly occurs at low water fractions through a single-molecule extraction and redistribution mechanism rather than micellar fission and fusion. In contrast, the micelles appear to be "kinetically frozen" at high water fractions, suggesting suppressed chain exchange under these conditions. Importantly, our approach offers a visually observable method for probing the dynamics of micellar chain exchange in real time.

Controlled Dissociation of Polymeric Micelles in Response to Oxidative Stress.

Nanoparticle-based drug carriers that can respond to oxidative stress in tumor tissue have attracted attention for site-specific drug release. Taking advantage of the characteristic microenvironment in tumors, one of the attractive directions in drug delivery research is to design drug carriers that release drugs upon oxidation. A strategy to incorporate oxidation-sensitive thioether motifs such as thiomorpholine acrylamide (TMAM) to drug carriers has been often used to achieve oxidation-induced dissociation, thereby targeted drug release. However, those delivery systems often suffer from a slow dissociation rate due to the intrinsic hydrophobicity of the thioether structures. In this study, we aimed to enhance the dissociation rate of TMAM-based micelles upon oxidation. The random copolymers of N-isopropylacrylamide and TMAM (P(NIPAM/TMAM)) were designed as an oxidation-sensitive segment that showed a fast response to oxidative stress. We first synthesized P(NIPAM/TMAM) copolymers with different NIPAM:TMAM molar ratios. Those copolymers exhibited low critical solution temperatures (LCSTs) below 32 °C, which shifted to higher temperatures after oxidation. The changes in LCSTs depend on the NIPAM:TMAM molar ratios. At the NIPAM:TMAM molar ratio of 82:18, the LCSTs before and after oxidation were 17 and 54 °C, respectively. We then prepared micelles from the diblock copolymers of poly(N-acryloyl morpholine) (PAM) and P(NIPAM/TMAM). The micelles showed an accelerated dissociation rate upon oxidation compared to the micelles without NIPAM units. Furthermore, the doxorubicin (Dox)-loaded micelles showed enhanced relative toxicity in human colorectal cancer (HT29) cells over human umbilical vein endothelial cells (HUVECs). Our novel strategy to design an oxidation-sensitive micellar core comprising a P(NIPAM/TMAM) segment can be used as a chemotherapeutic delivery system that responds to an oxidative tumor microenvironment in an appropriate time scale.

Enhancing the tumor penetration of multiarm polymers by collagenase modification.

Tumor penetration is a critical determinant of the therapy efficacy of nanomedicines. However, the dense extracellular matrix (ECM) in tumors significantly hampers the deep penetration of nanomedicines, resulting in large drug-untouchable areas and unsatisfactory therapy efficacy. Herein, we synthesized a third-generation PAMAM-cored multiarm copolymer and modified the polymer with collagenase to enhance its tumor penetration. Each arm of the copolymer was a diblock copolymer of poly(glutamic acid)-b-poly(carboxybetaine), in which the polyglutamic acid block with abundant side groups was used to link the anticancer agent doxorubicin through the pH-sensitive acylhydrazone linkage, and the zwitterionic poly(carboxybetaine) block provided desired water solubility and anti-biofouling capability. The collagenase was conjugated to the ends of the arms via the thiol-maleimide reaction. We demonstrated that the polymer-bound collagenase could effectively catalyze the degradation of the collagen in the tumor ECM, and consequently augmented the tumor penetration and antitumor efficacy of the drug-loaded polymers.

Effects of subphase pH and temperature on the interfacial behavior of double hydrophilic diblock copolymer PDEGMA‐b‐PDIPAEMA

AbstractThe aggregation behavior of two pH‐ and temperature‐responsive diblock copolymers of poly[di‐(ethylene glycol) methyl ether methacrylate]‐block‐poly[2‐(diisopropylamino) ethyl methacrylate] (PDEGMA‐b‐PDIPAEMA) at the air/water interface and the structures of their Langmuir–Blodgett (LB) films were studied by the Langmuir monolayer technique and atomic force microscopy, respectively. At the air/water interface, PDEGMA‐b‐PDIPAEMA tends to form the core‐shell‐corona micellar structure composed of a PDIPAEMA main chain core, an amino ethyl ester shell, and a PDEGMA corona. Under acidic, neutral, and alkaline conditions, PDIPAEMA blocks are completely protonated, partially protonated, and completely non‐protonated, respectively, and the protonated amino ethyl ester groups are immersed in water before monolayer compression, whereas PDEGMA coronas are adsorbed at the interface. At pH 3, 7, and 10, the limiting areas (A0) for PDEGMA42%‐PDIPAEMA58% (weight percents) and PDEGMA55%‐PDIPAEMA45% are 8.2/10.2/14.0 and 6.7/8.3/8.4 nm2, respectively. The A0 values of the former copolymer are larger than those of the latter. This is because the shells in the former copolymer are denser due to the higher polymerization degree of PDIPAEMA blocks, providing greater steric hindrance for PDEGMA coronas and making the latter more extended at the interface. In contrast to other copolymer systems, the effect of temperature on the isotherms of PDEGMA‐b‐PDIPAEMA is less obvious.

Self-assembly of PEG-PPS polymers and LL-37 peptide nanomicelles improves the oxidative microenvironment and promotes angiogenesis to facilitate chronic wound healing.

Refractory diabetic wounds are associated with high incidence, mortality, and recurrence rates and are a devastating and rapidly growing clinical problem. However, treating these wounds is difficult owing to uncontrolled inflammatory microenvironments and defective angiogenesis in the affected areas, with no established effective treatment to the best of our knowledge. Herein, we optimized a dual functional therapeutic agent based on the assembly of LL-37 peptides and diblock copolymer poly(ethylene glycol)-poly(propylene sulfide) (PEG-PPS). The incorporation of PEG-PPS enabled responsive or controlled LL-37 peptide release in the presence of reactive oxygen species (ROS). LL-37@PEG-PPS nanomicelles not only scavenged excessive ROS to improve the microenvironment for angiogenesis but also released LL-37 peptides and protected them from degradation, thereby robustly increasing angiogenesis. Diabetic wounds treated with LL-37@PEG-PPS exhibited accelerated and high-quality wound healing in vivo. This study shows that LL-37@PEG-PPS can restore beneficial angiogenesis in the wound microenvironment by continuously providing angiogenesis-promoting signals. Thus, it may be a promising drug for improving chronic refractory wound healing.

Magnetically Recyclable Nanoscale Zero-Valent Iron-Mediated PhotoRDRP in Ionic Liquid toward Smart, Functional Polymers.

A facile method based on recyclable nanoscale zero-valent iron (nZVI)-mediated photoinduced reversible deactivation radical polymerization in ionic liquid (IL) leads to the synthesis of narrow disperse poly(tert-butyl methacrylate) (PTBMA), amphiphilic PTBMA-block-poly(poly(ethylene glycol)methacrylate) diblock copolymer and double hydrophilic poly(methacrylic acid)-block-poly(poly(ethylene glycol)methacrylate) (PMAA-b-PPEGMA) diblock copolymers thereof. Stimuli response of the synthesized PMAA-b-PPEGMA diblock copolymer against variation in pH and temperature is assessed. Recyclability of the nZVI (catalyst) and IL (solvent) is established. Polymerization may be switched ON or OFF, simply by turning the UVA light irradiation ON or OFF, offering temporal control. The diblock copolymer self-aggregates into spherical nanoaggregates which are employed for encapsulation of coumarin 102 (C102, a typical hydrophobic dye), describing their potential application in drug delivery applications. The facile synthesis strategy may open up new avenues for the preparation of intelligent functional polymers for engineering and biomedical applications.

Citric acid-modified pH-sensitive bone-targeted delivery of estrogen for the treatment of postmenopausal osteoporosis.

Bone targeted delivery of estrogen offers great promise for the clinical application of estrogen in the treatment of postmenopausal osteoporosis (PMOP). However, the current bone-targeted drug delivery system still has several issues that need to be solved, such as the side effects of bone-targeted modifier molecules and the failure of the delivery system to release rapidly in the bone tissue. It is important to aggressively search for new bone-targeted modifier molecules and bone microenvironment-responsive delivery vehicles. Inspired by the distribution of citric acid (CA) mainly in bone tissue and the acidic bone resorption microenvironment, we constructed a CA-modified diblock copolymer poly(2-ethyl-2-oxazoline)-poly(ε-caprolactone) (CA-PEOz) drug delivery system. In our study, we found that the CA modification significantly increased the bone targeting of this drug delivery system, and the delivery system was able to achieve rapid drug release under bone acidic conditions. The delivery system significantly reduced bone loss in postmenopausal osteoporotic mice with a significant reduction in estrogenic side effects on the uterus. In summary, our study shows that CA can act as an effective bone targeting modifier molecule and provides a new option for bone targeting modifications. Our study also provides a new approach for bone-targeted delivery of estrogen for the treatment of PMOP.

Toluene‐Mediated Morphology Tuning of Diblock Copolymer‐Templated Porous Si/Ge/K/C Thin Films for Li‐Ion Batteries

Amphiphilic diblock copolymer poly(styrene‐b‐ethylene oxide) templating in combination with sol–gel chemistry is utilized to synthesize porous mixed silicon/germanium/potassium/carbon (Si/Ge/K/C) thin films. As a Si/Ge source, the dissolvable Zintl phase K12Si12Ge5 is used. The toluene‐mediated morphological changes in the porous mixed Si/Ge/K/C thin films are studied with scanning electron microscopy and grazing incidence small/wide‐angle X‐Ray scattering. A dichloromethane solvent vapor annealing step is applied to study the additional morphological transformation inside the films. Since Ge and Si are promising anode materials in Li‐ion batteries, CR2032 half‐cells are manufactured with the porous mixed Si/Ge/K/C thin films and characterized by cyclic voltammograms, cycling, and impedance spectroscopy.

Ligand-installed polymeric nanocarriers for combination chemotherapy of EGFR-positive ovarian cancer

Combination chemotherapeutic drugs administered via a single nanocarrier for cancer treatment provides benefits in reducing dose-limiting toxicities, improving the pharmacokinetic properties of the cargo and achieving spatial-temporal synchronization of drug exposure for maximized synergistic therapeutic effects. In an attempt to develop such a multi-drug carrier, our work focuses on functional multimodal polypeptide-based polymeric nanogels (NGs). Diblock copolymers poly (ethylene glycol)-b-poly (glutamic acid) (PEG-b-PGlu) modified with phenylalanine (Phe) were successfully synthesized and characterized. Self-assembly behavior of the resulting polymers was utilized for the synthesis of NGs with hydrophobic domains in cross-linked polyion cores coated with inert PEG chains. The resulting NGs were small (ca. 70 nm in diameter) and were able to encapsulate the combination of drugs with different physicochemical properties such as cisplatin and neratinib. Drug combination-loaded NGs exerted a selective synergistic cytotoxicity towards EGFR overexpressing ovarian cancer cells. Moreover, we developed ligand-installed EGFR-targeted NGs and tested them as an EGFR-overexpressing tumor-specific delivery system. Both in vitro and in vivo, ligand-installed NGs displayed preferential associations with EGFR (+) tumor cells. Ligand-installed NGs carrying cisplatin and neratinib significantly improved the treatment response of ovarian cancer xenografts. We also confirmed the importance of simultaneous administration of the dual drug combination via a single NG system which provides more therapeutic benefit than individual drug-loaded NGs administered at equivalent doses. This work illustrates the potential of our carrier system to mediate efficient delivery of a drug combination to treat EGFR overexpressing cancers.

Diblock copolymers poly(3-hexylthiophene)-block-poly(2-(dimethylamino)ethyl methacrylate-random-1-pyrenylmethyl methacrylate), controlled synthesis and optical properties

Diblock copolymers poly(3-hexylthiophene)-block-poly(2-(dimethylamino)ethyl methacrylate-random-1-pyrenylmethyl methacrylate), controlled synthesis and optical properties

Smart Anisotropic Colloidal Composites: A Suitable Platform for Modifying the Phase Transition of Diblock Copolymers by Gold Nanoparticles

Surface modification of metallic nanoparticles (NPs) by stimuli-responsive polymers is a benign method to prepare smart colloidal composites which tune the characteristic properties of individual systems. The temperature-dependent transition of diblock copolymer poly(N-isopropylacrylamide)-block-poly(N-vinylcaprolactam) (PNIPMA-b-PVCL) synthesized using reversible addition-fragmentation chain transfer polymerization was studied by incorporating anisotropic gold NPs (AGPs) such as spheres (AuNSs), rods (AuNRs), cubes (AuNCs), and rhombic dodecahedrals (AuRDs). Shape-dependent physiochemical properties of nanostructures alter the lower critical solution temperature (LCST) of the chemical inhomogeneous diblock copolymer. Heterogeneous nucleation of AuNPs was facilitated by seed-mediated synthesis for incorporating uniformity. In the mixed system, the presence of PNIPAM-b-PVCL modifies the surface of AGPs through physisorption which is supported by transmission electron microscopy and field emission scanning electron microscopy showing the NPs embedding in the polymeric matrix. Furthermore, steady state fluorescence spectroscopy and Fourier transform infrared spectroscopy were performed to examine the phase transition behavior of PNIPAM-b-PVCL in AGPs. The formation of a smart polymer nanocomposite alters the physiochemical properties of the diblock copolymer as demonstrated from the variation of LCST in the dynamic light scattering measurement. Henceforth, functionalizing the surfaces of AGPs with a thermoresponsive diblock copolymer provides combinatorial benefits in the properties of smart polymeric colloidal systems with potential applications in bioimaging and drug delivery.

Self-Aggregation in Aqueous Media of Amphiphilic Diblock and Random Block Copolymers Composed of Monomers with Long Side Chains.

Amphiphilic diblock copolymers and hydrophobically modified random block copolymers can self-assemble into different structures in a selective solvent. The formed structures depend on the copolymer properties, such as the ratio between the hydrophilic and the hydrophobic segments and their nature. In this work, we characterize by cryogenic transmission electron microscopy (cryo-TEM) and dynamic light scattering (DLS) the amphiphilic copolymers poly(2-dimethylamino ethyl methacrylate)-b-poly(lauryl methacrylate) (PDMAEMA-b-PLMA) and their quaternized derivatives QPDMAEMA-b-PLMA at different ratios between the hydrophilic and the hydrophobic segments. We present the various structures formed by these copolymers, including spherical and cylindrical micelles, as well as unilamellar and multilamellar vesicles. We also examined by these methods the random diblock copolymers poly(2-(dimethylamino) ethyl methacrylate)-b-poly(oligo(ethylene glycol) methyl ether methacrylate) (P(DMAEMA-co-Q6/12DMAEMA)-b-POEGMA), which are partially hydrophobically modified by iodohexane (Q6) or iodododecane (Q12). The polymers with a small POEGMA block did not form any specific nanostructure, while a polymer with a larger POEGMA block formed spherical and cylindrical micelles. This nanostructural characterization could lead to the efficient design and use of these polymers as carriers of hydrophobic or hydrophilic compounds for biomedical applications.

A multifunctional polymeric coating with self-adsorbed, antifouling and in situ remineralization properties for caries management.

Dental caries is a biofilm-induced bacterial infectious oral disease, where the early attachment of proteins and pathogenic bacteria to tooth surfaces has been known as the main cause of biofilm formation. Typically, dental caries is commonly accompanied by mineral depletion of enamels, thus causing dental demineralization. Multifunctional materials are highly attractive candidates for treating dental caries. Herein, we successfully synthesized diblock copolymers poly(ethylene glycol)-b-poly(aspartic acid) (PEG-PAsp) and modified them with alendronate sodium (ALN) to serve as bioactive bifunctional coatings (PEG-PAsp-ALN) on teeth. The PEG segments are employed for inhibiting proteins and bacterial adhesion. In addition, due to the presence of both PAsp and ALN, a synergistically strong binding capacity could be achieved with the tooth surface, thus promoting rapid and thorough remineralization in situ, while maintaining excellent safety. The combination treatment can significantly suppress the biofilm formation, which is beneficial for alleviating the demineralization of enamels caused by bacteria, and further, facilitate remineralization in situ. This approach thus demonstrates the potential of the copolymer PEG-PAsp-ALN coating as a multifunctional protecting layer on the tooth surface for high-efficiency prevention and treatment of dental caries.