974 results on '"DIBLOCK COPOLYMER"'
Search Results
2. Organocatalyzed polymerization of diblock copolymer based on poly(3-hexylthiophene) and poly(furfurylmethacrylate)
- Author
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Hai Le Tran, Chau Duc Tran, Cam Hong Thi Nguyen, Thao Phuong Le Nguyen, Le-Thu Thi Nguyen, Thiet-Quoc Nguyen, Mai Ha Hoang, Tam Huu Nguyen, and Ha Tran Nguyen
- Subjects
diblock copolymer ,poly(3-hexylthiophene) ,organic photocatalyst ,biomass-based monomer ,atom transfer radical polymerization ,Chemical technology ,TP1-1185 - Abstract
Abstract A novel conjugated rod–coil diblock copolymer poly(3-hexylthiophene)-block-poly(furfuryl methacrylate) (P3HT-b-PFMA) has been successfully synthesized for the first time using photoinduced organocatalyzed atom transfer radical polymerization (O-ATRP). This process utilized an organic photoredox catalyst of N-aryl phenoxazine, namely 10-(Perylene-3-yl-10H-Phenoxazine, under 365 nm UV irradiation. The diblock copolymer P3HT-b-PFMA was produced efficiently in a controlled manner, resulting in designed average molecular weights and a narrow polydispersity index. Notably, the furfurylmethacrylate (FMA) monomer derived from biomass-based furfuryl compounds was applied for this controlled polymerization, leading to the formation of conjugated diblock copolymers. The synthesized P3HT-b-PFMA was characterized through 1H-NMR, FT-IR, and GPC methods. Furthermore, the optical and hydrophilic-hydrophobic properties of P3HT-b-PFMA were also evaluated through UV-Vis spectroscopy and contact angle measurements.
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- 2024
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3. Copolymer-Coated Au–Pt Nanomotors for Delivery of Disulfiram Prodrug.
- Author
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Kamankesh, Mojtaba, Kargari Aghmiouni, Delaram, and Khoee, Sepideh
- Abstract
Researchers have been exploring the use of nanomotors powered by hydrogen peroxide for cancer treatment through targeted drug delivery. Asymmetric bimetallic nanorods made of platinum and gold have been found to navigate through the H
2 O2 environment quickly and effectively, making them a promising option for the delivery of drugs to specific areas. We developed a delivery system for the hydroxyethyl disulfiram (DSF–OH) anticancer prodrug using a bimetallic Au/Pt nanomotor that moves toward its target in the presence of hydrogen peroxide. A copolymer consisting of poly-(polyethylene glycol methyl ether methacrylate)-co-poly acrylic acid was used to conjugate the drug. The conjugate was then attached to the nanomotor's gold (Au) component using the sulfur moieties present in the DSF. The1 H NMR,13 C NMR, TGA, and FT-IR analyses confirmed the successful synthesis of the copolymer, whereas the SEM, EDX, XRD, and DLS analyses confirmed the production of the bimetallic nanomotor. Hydroxyethyl disulfiram (DSF–OH) was found to have different complex formation capabilities and time-dependent stabilities in comparison to disulfiram (DSF). It is suitable for prolonged drug release evaluations. UV–vis analysis evaluations showed around 34% of the released DSF–OH from the nanomotors. Particle tracking revealed a correlation between H2 O2 concentration and particle motion, indicating that higher H2 O2 concentration results in higher velocity and mean-square displacements (MSDs). MTT assays further validated superior selectivity and toxicity of drug-containing nanomotors toward MCF-7 breast cancer cells compared to L929 fibroblast cells. These findings have implications for drug delivery systems and provide insight into designing more efficient systems. [ABSTRACT FROM AUTHOR]- Published
- 2024
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4. Synthesis of MPEG-b-PLLA Diblock Copolymers and Their Crystallization Performance with PDLA and PLLA Composite Films.
- Author
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Wu, Wenjing, Wu, Weixin, Guo, Mingwei, Wang, Ruizhe, Wang, Xuanxuan, and Gao, Qinwei
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DIBLOCK copolymers , *THERMODYNAMICS , *RING-opening polymerization , *CRYSTALLIZATION kinetics , *CRYSTALLIZATION , *DIFFERENTIAL scanning calorimetry - Abstract
Methoxy poly(ethylene glycol)-block-poly(L-lactide) (MPEG-b-PLLA) has a wide range of applications in pharmaceuticals and biology, and its structure and morphology have been thoroughly studied. In the experiment, we synthesized MPEG-b-PLLA with different block lengths using the principle of ring-opening polymerization by controlling the amount of lactic acid added. The thermodynamic properties of copolymers and the crystallization properties of blends were studied separately. The crystallization kinetics of PDLA/MPEG-b-PLA and PLLA/MPEG-b-PLA composite films were studied using differential scanning calorimetry (DSC). The results indicate that the crystallization kinetics of composite films are closely related to the amount of block addition. The crystallinity of the sample first increases and then decreases with an increase in MPEG-b-PLLA content. These results were also confirmed in polarized optical microscope (POM) and wide-angle X-ray diffraction (WAXD) tests. When 3% MPEG-b-PLLA was added to the PDLA matrix, the blend exhibited the strongest crystallization performance. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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5. Self-assembly behaviour of diblock copolymer-diblock copolymer under oscillating shear field.
- Author
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Guo, Y., He, H., and Fu, X.
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PHASE transitions , *MIXTURES , *DIBLOCK copolymers - Abstract
The self-assembly behaviour of a diblock copolymer-diblock copolymer mixture under an oscillating shear field is investigated via cell dynamics simulation. The results indicate that the macrophase separation of the composite system is accompanied by the corresponding microphase separation induced by the oscillating shear field. With an increase in the shear frequency, the AB phase changes from a tilted layered structure to a parallel layered structure, and finally to a vertical layered structure. The CD phase transforms from the initial concentric ring into a parallel layer in the ring and then into a parallel layered structure; thus, the system finally forms a layered structure of the AB phase (vertical layer) and CD phase (parallel layer) perpendicular to each other. To verify the phase transition, the dynamic evolution of the domain size at different shear frequencies is analysed. The ordered phase transition with an increase in the oscillating shear field varies when the initial composition ratio of the system is changed. This conclusion provides a valuable guidance for the formation and transformation of ordered structures in experiments. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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6. Dynamics of High Molecular Weight Cylindrical and Lamellar Block Copolymers with X‐ray Photon Correlation Spectroscopy.
- Author
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Taleb, Omar, Blatt, Michael Patrick, Signorini, Virginia, Oparaji, Onyekachi, Kim, Kyougmin, Lochner, Eric, Narayanan, Suresh, Zhang, Qingteng, and Hallinan, Daniel
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LIGHT beating spectroscopy , *BLOCK copolymers , *MOLECULAR weights , *SMALL-angle X-ray scattering , *MOLECULAR dynamics , *GLASS transition temperature - Abstract
The structure and dynamics of polystyrene (PS)‐b‐poly(ethylene oxide) block copolymers (BCPs) are studied. The BCPs exhibit microphase‐separated cylindrical and lamellar morphologies. Structural dynamics are measured with X‐ray photon correlation spectroscopy in the small‐angle regime. Morphologies and domain sizes are evaluated using small‐angle X‐ray scattering (SAXS), scanning electron microscopy, and atomic force microscopy. Different solvent processing conditions are investigated. Grain sizes evaluated using SAXS are found to depend on processing only for the rubbery majority BCP. The structural relaxation times are examined as a function of PS volume fraction, temperature, morphology, and structural sizes. Well above the glass transition temperature (Tg) of PS, all samples exhibit stretched autocorrelation decays and diffusive dynamics. Near Tg of PS, the dynamics of all samples are anomalous with compressed autocorrelation decays and hyperdiffusive dynamics. This transition occurs at 153 °C or 1.13 Tg of PS. In the diffusive regime (at high temperature), structural relaxation times are dependent on the processing method. Near PS Tg (at low temperature), structural relaxation times scale with the PS volume fraction. Structural relaxation times do not correlate with grain size, indicating that the out‐of‐equilibrium state of PS dominates the structural dynamics of these strongly phase‐segregated BCPs. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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7. Self-assembly behaviour of diblock copolymer-diblock copolymer under oscillating shear field
- Author
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Y. Guo, H. He, and X. Fu
- Subjects
diblock copolymer ,oscillating shear field ,self-assembly ,Physics ,QC1-999 - Abstract
The self-assembly behaviour of a diblock copolymer-diblock copolymer mixture under an oscillating shear field is investigated via cell dynamics simulation. The results indicate that the macrophase separation of the composite system is accompanied by the corresponding microphase separation induced by the oscillating shear field. With an increase in the shear frequency, the AB phase changes from a tilted layered structure to a parallel layered structure, and finally to a vertical layered structure. The CD phase transforms from the initial concentric ring into a parallel layer in the ring and then into a parallel layered structure; thus, the system finally forms a layered structure of the AB phase (vertical layer) and CD phase (parallel layer) perpendicular to each other. To verify the phase transition, the dynamic evolution of the domain size at different shear frequencies is analysed. The ordered phase transition with an increase in the oscillating shear field varies when the initial composition ratio of the system is changed. This conclusion provides a valuable guidance for the formation and transformation of ordered structures in experiments.
- Published
- 2024
- Full Text
- View/download PDF
8. Semi-automatic fingerprint image restoration algorithm using a partial differential equation
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Chaeyoung Lee, Sangkwon Kim, Soobin Kwak, Youngjin Hwang, Seokjun Ham, Seungyoon Kang, and Junseok Kim
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automatic fingerprint restoration ,diblock copolymer ,the cahn-hilliard (ch) equation ,phase-field model ,Mathematics ,QA1-939 - Abstract
A fingerprint is the unique, complex pattern of ridges and valleys on the surface of an individual's fingertip. Fingerprinting is one of the most popular and widely used biometric authentication methods for personal identification because of its reliability, acceptability, high level of security, and low cost. When using fingerprints as a biometric, restoring poor-quality or damaged fingerprints is an essential process for accurate verification. In this study, we present a semi-automatic fingerprint image restoration method using a partial differential equation to repair damaged fingerprint images. The proposed algorithm is based on the Cahn-Hilliard (CH) equation with a source term, which was developed for simulating pattern formation during the phase separation of diblock copolymers in chemical engineering applications. In previous work, in order to find an optimal model and numerical parameter values in the governing equation, we had to make several trial and error preliminary attempts. To overcome these problems, the proposed novel algorithm minimizes user input and automatically computes the necessary model and numerical parameter values of the governing equation. Computational simulations on various damaged fingerprint samples are presented to demonstrate the superior performance of the proposed method.
- Published
- 2023
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9. Stabilizing undulated lamellae by diblock copolymers confined in alternately adsorbed thin films
- Author
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Pengjie Xie, Minghu Xu, Qingshu Dong, Qingliang Song, and Meijiao Liu
- Subjects
Diblock copolymer ,Self-assembly ,Undulated lamellae ,Self-consistent field theory ,Thin film ,Science (General) ,Q1-390 - Abstract
The self-assembly behavior of AB diblock copolymer confined in staggering alternately adsorbed thin films is studied using the self-consistent field theory (SCFT) and dissipative particle dynamics (DPD), focusing on the emergence and stability of the undulated lamella (UL) phase. Phase diagrams for the volume fraction of blocks, period of the adsorbed pattern and thickness of the confinement are constructed. Our results indicate that the UL phase can be stable in the case with a large period of adsorbed pattern, and is more favorable in the asymmetrical diblock copolymer with volume fraction around f = 0.40, which becomes cylindrical phases (C) with too small f and transforms into tilted lamellae (TL) on the contrary. Furthermore, the number of layers in the UL phases can be regulated by adjusting the period of the adsorbed pattern and the confinement degree of the thin film. In addition, the formation of the UL is verified by DPD simulations. The study demonstrates that the specially confined diblock copolymers provide an efficient route to regulate the stability of the complex UL phases.
- Published
- 2024
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10. Effective delivery and selective insecticidal activity of double‐stranded RNA via complexation with diblock copolymer varies with polymer block composition.
- Author
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Pugsley, Charlotte E., Isaac, R. Elwyn, Warren, Nicholas J., Stacey, Martin, Ferguson, Calum T. J., Cappelle, Kaat, Dominguez‐Espinosa, Rosa, and Cayre, Olivier J.
- Subjects
DIBLOCK copolymers ,DOUBLE-stranded RNA ,BLOCK copolymers ,RNA interference ,POLYMERS ,DROSOPHILA suzukii ,SMALL interfering RNA - Abstract
BACKGROUND: Chemical insecticides are an important tool to control damaging pest infestations. However, lack of species specificity, the rise of resistance and the demand for biological alternatives with improved ecotoxicity profiles means that chemicals with new modes of action are required. RNA interference (RNAi)‐based strategies using double‐stranded RNA (dsRNA) as a species‐specific bio‐insecticide offer an exquisite solution that addresses these issues. Many species, such as the fruit pest Drosophila suzukii, do not exhibit RNAi when dsRNA is orally administered due to degradation by gut nucleases and slow cellular uptake pathways. Thus, delivery vehicles that protect and deliver dsRNA are highly desirable. RESULTS: In this work, we demonstrate the complexation of D. suzukii‐specific dsRNA for degradation of vha26 mRNA with bespoke diblock copolymers. We study the ex vivo protection of dsRNA against enzymatic degradation by gut enzymes, which demonstrates the efficiency of this system. Flow cytometry then investigates the cellular uptake of Cy3‐labelled dsRNA, showing a 10‐fold increase in the mean fluorescence intensity of cells treated with polyplexes. The polymer/dsRNA polyplexes induced a significant 87% decrease in the odds of survival of D. suzukii larvae following oral feeding only when formed with a diblock copolymer containing a long neutral block length (1:2 cationic block/neutral block). However, there was no toxicity when fed to the closely related Drosophila melanogaster. CONCLUSION: We provide evidence that dsRNA complexation with diblock copolymers is a promising strategy for RNAi‐based species‐specific pest control, but optimisation of polymer composition is essential for RNAi success. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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11. Effect of In‐Plane Electric Field on the Microphase Separation in Thin Films of a Symmetric ABA Triblock Copolymer.
- Author
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Kriksin, Yury A. and Kudryavtsev, Yaroslav V.
- Subjects
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ELECTRIC field effects , *THIN films , *SELF-consistent field theory , *ELECTRIC fields , *PHASE diagrams - Abstract
The structure of a thin film of symmetric ABA triblock copolymer melts in an external in‐plane DC or AC electric field is studied theoretically. The situation is considered when the triblock copolymer forms a hexagonal morphology of standing cylinders in bulk in the absence of an external field. Self‐consistent field theory calculations are carried out to determine the most thermodynamically favorable thin film structure among the cylindrical phases perpendicular and parallel to the substrate and the lamellar phase perpendicular to the substrate. The results are presented as phase diagrams with the film thickness and electric field energy on the axes and as distributions of the local composition, which serve as an order parameter in the system. It is confirmed that electric fields only weakly affect the spinodal curves of block copolymers but they can reorient or markedly modify microphase‐separated morphologies in those systems. Such restructuring is consistent with a considerable modulation of the free surface of a copolymer film and it can lead to the coexistence of different phases that appear in the film areas with different local thicknesses. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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12. Hydrophilic Cross-Linked Aliphatic Hydrocarbon Diblock Copolymer as Proton Exchange Membrane for Fuel Cells.
- Author
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Julius, David, Lee, Jim Yang, and Hong, Liang
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ATRP ,PEM ,diblock copolymer ,direct methanol fuel cell ,hydrophilic crosslink ,Chemical Sciences ,Engineering - Abstract
This study proposes a hydrophobic and hydrophilic aliphatic diblock copolymer wherein the hydrophobic block contains glycidyl methacrylate (GMA) units that are distanced by poly(acrylonitrile) (PAN) segments to fabricate a proton exchange membrane (PEM). This diblock copolymer also known as ionomer due to the hydrophilic block comprising 3-sulfopropyl methacrylate potassium salt (SPM) block. The diblock copolymer was synthesized in the one-pot atom transfer radical polymerization (ATRP) synthesis. Subsequently, the membrane was fabricated by means of solution casting in which an organic diamine, e.g., ethylene diamine (EDA), was introduced to crosslink the diblock copolymer chains via the addition of amine to the epoxide group of GMA. As a result, the PEM attained possesses dual continuous phases, in which the hydrophobic domains are either agglomerated or bridged by the EDA-derived crosslinks, whereas the hydrophilic domains constitute the primary proton conducting channels. The in-situ crosslinking hydrophobic block by using a hydrophilic cross-linker represents the merit aspect since it leads to both improved proton conductivity and dimensional stability in alcohol fuel. To characterize the above properties, Nafion® 117 and random copolymer of P(AN-co-GMA-co-SPM) were used as control samples. The PEM with the optimized composition demonstrates slightly better fuel cell performance than Nafion 117. Lastly, this diblock ionomer is nonfluorinated and hence favors lowering down both material and environmental costs.
- Published
- 2021
13. Synthesis of a novel photochemical and thermoresponsive diblock biomaterial with end-functionalized zinc porphyrin
- Author
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Nannan Qiu, Xinyuan Pan, Ruizhang Hu, and Zhenzhen Hui
- Subjects
zinc porphyrin ,diblock copolymer ,fluorescence ,cis/trans isomerization ,photocatalytic activity ,thermosensitive property ,Biotechnology ,TP248.13-248.65 - Abstract
Porphyrin compound-based photochemical molecules and biomaterials have been synthesized for photosensitivity and bioimaging experiments. However, most porphyrin photosensitizers have limited application in biological environments owing to severe aggregation in aqueous solutions. In the present study, we prepared amphipathic and photosensitive copolymers using zinc porphyrin via consecutive atom transfer-free radical polymerizations (ATRPs) comprising photoresponsive and thermosensitive chain segments. Furthermore, we evaluated the photocatalytic activity of the copolymer for methylene blue (MB) in water.Methods: First, we synthesized a photoresponsive ain segment of poly (6-[4-(4-methoxyphenylazo)phenoxy]hexyl methacrylate) (ZnPor-PAzo); then, ZnPor-PAzo was used as a macroinitiator and was polymerized with N-isopropylacrylamide (NIPAM) via ATRPs to obtain a novel photochemical and thermoresponsive diblock biomaterial with end-functionalized zinc porphyrin [(ZnPor-PAzo)–PNIPAMs].Results: The polydispersity index (Mw/Mn) of (ZnPor-PAzo)–PNIPAMs was 1.19–1.32. Furthermore, its photoresponsive and thermosensitive characteristics were comprehensively studied.Discussion: The end-functionalized diblock copolymer (ZnPor-PAzo)–PNIPAM exhibits obvious fluorescence and efficient photocatalytic activity for aqueous MB under visible light.
- Published
- 2023
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14. Numerical Approximations of Diblock Copolymer Model Using a Modified Leapfrog Time-Marching Scheme.
- Author
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Chen, Lizhen, Ma, Ying, Ren, Bo, and Zhang, Guohui
- Subjects
LINEAR algebra ,LINEAR systems - Abstract
An efficient modified leapfrog time-marching scheme for the diblock copolymer model is investigated in this paper. The proposed scheme offers three main advantages. Firstly, it is linear in time, requiring only a linear algebra system to be solved at each time-marching step. This leads to a significant reduction in computational cost compared to other methods. Secondly, the scheme ensures unconditional energy stability, allowing for a large time step to be used without compromising solution stability. Thirdly, the existence and uniqueness of the numerical solution at each time step is rigorously proven, ensuring the reliability and accuracy of the method. A numerical example is also included to demonstrate and validate the proposed algorithm, showing its accuracy and efficiency in practical applications. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
15. Recent Advances in Polymerization‐Induced Self‐Assembly (PISA) Syntheses in Non‐Polar Media.
- Author
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György, Csilla and Armes, Steven P.
- Subjects
- *
SMALL-angle neutron scattering , *SMALL-angle X-ray scattering , *DIBLOCK copolymers , *OPTICAL spectroscopy , *MINERAL oils , *SILICONE rubber , *POLAR solvents - Abstract
It is well‐known that polymerization‐induced self‐assembly (PISA) is a powerful and highly versatile technique for the rational synthesis of colloidal dispersions of diblock copolymer nanoparticles, including spheres, worms or vesicles. PISA can be conducted in water, polar solvents or non‐polar media. In principle, the latter formulations offer a wide range of potential commercial applications. However, there has been just one review focused on PISA syntheses in non‐polar media and this prior article was published in 2016. The purpose of the current review article is to summarize the various advances that have been reported since then. In particular, PISA syntheses conducted using reversible addition‐fragmentation chain‐transfer (RAFT) polymerization in various n‐alkanes, poly(α‐olefins), mineral oil, low‐viscosity silicone oils or supercritical CO2 are discussed in detail. Selected formulations exhibit thermally induced worm‐to‐sphere or vesicle‐to‐worm morphological transitions and the rheological properties of various examples of worm gels in non‐polar media are summarized. Finally, visible absorption spectroscopy and small‐angle X‐ray scattering (SAXS) enable in situ monitoring of nanoparticle formation, while small‐angle neutron scattering (SANS) can be used to examine micelle fusion/fission and chain exchange mechanisms. [ABSTRACT FROM AUTHOR]
- Published
- 2023
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- View/download PDF
16. Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs
- Author
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Sun, Jing, Wang, Zhiwei, Zhu, Chenhui, Wang, Meiyao, Shi, Zhekun, Wei, Yuhan, Fu, Xiaohui, Chen, Xuesi, and Zuckermann, Ronald N
- Subjects
Macromolecular and Materials Chemistry ,Engineering ,Chemical Sciences ,Bioengineering ,self-assembly ,polypeptoid ,diblock copolymer ,crystallization ,solvophobicity - Abstract
Hierarchical nanomaterials have received increasing interest for many applications. Here, we report a facile programmable strategy based on an embedded segmental crystallinity design to prepare unprecedented supramolecular planar nanobrush-like structures composed of two distinct molecular packing motifs, by the self-assembly of one particular diblock copolymer poly(ethylene glycol)-block-poly(N-octylglycine) in a one-pot preparation. We demonstrate that the superstructures result from the temperature-controlled hierarchical self-assembly of preformed spherical micelles by optimizing the crystallization-solvophobicity balance. Particularly remarkable is that these micelles first assemble into linear arrays at elevated temperatures, which, upon cooling, subsequently template further lateral, crystallization-driven assembly in a living manner. Addition of the diblock copolymer chains to the growing nanostructure occurs via a loosely organized micellar intermediate state, which undergoes an unfolding transition to the final crystalline state in the nanobrush. This assembly mechanism is distinct from previous crystallization-driven approaches which occur via unimer addition, and is more akin to protein crystallization. Interestingly, nanobrush formation is conserved over a variety of preparation pathways. The precise control ability over the superstructure, combined with the excellent biocompatibility of polypeptoids, offers great potential for nanomaterials inaccessible previously for a broad range of advanced applications.
- Published
- 2020
17. 原位制备PS-b-P (MMA-co-TBMA) 纳米组装粒子.
- Author
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王 剑 and 王国伟
- Subjects
NUCLEAR magnetic resonance spectroscopy ,BLOCK copolymers ,GEL permeation chromatography ,MOLECULAR weights ,PLASTICS ,METHYL methacrylate - Abstract
Copyright of Plastics Science & Technology / Suliao Ke-Ji is the property of Plastics Science & Technology Editorial Office and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
- Published
- 2023
- Full Text
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18. Numerical investigations of pattern formation in binary systems with inhibitory long-range interaction
- Author
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Frank Baginski and Jiajun Lu
- Subjects
micro phase separation ,diblock copolymer ,pattern formation ,Mathematics ,QA1-939 ,Applied mathematics. Quantitative methods ,T57-57.97 - Abstract
We investigate pattern formation in a two-dimensional manifold using the Otha-Kawasaki model for micro-phase separation of diblock copolymers. In this model, the total energy includes a short-range and a long-range term. The short-range term is a Landau-type free energy that is common in phase separation problems and favors large domains with minimum perimeter. The inhibitory long-range interaction term is the Otha-Kawasaki functional derived from the theory of diblock copolymers and favors small domains. The balance of these terms leads to equilibrium states that exhibit a variety of patterns, including disk-like droplets, droplet assemblies, elongated droplets, dog-bone shaped droplets, stripes, annular rings, wriggled stripes and combinations thereof. For problems where analytical results are known, we compare our numerical results and find good agreement. Where analytical results are not available, our numerical methods allow us to explore the solution space revealing new stable patterns. We focus on the triaxial ellipsoid, but our methods are general and can be applied to higher genus surfaces and surfaces with boundaries.
- Published
- 2022
- Full Text
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19. Effect of Disparity in Self Dispersion Interactions on Phase Behaviors of Molten A-b-B Diblock Copolymers.
- Author
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Zhang, Xinyue, Zhao, Mingge, and Cho, Junhan
- Subjects
- *
DIBLOCK copolymers , *BULK modulus , *EQUATIONS of state , *SELF , *DISPERSION (Chemistry) , *YIELD strength (Engineering) - Abstract
Phase behaviors of molten A-b-B diblock copolymers with disparity in self dispersion interactions are revisited here. A free energy functional is obtained for the corresponding Gaussian copolymers under the influence of effective interactions originating in the localized excess equation of state. The Landau free energy expansion is then formulated as a series in powers of A and B density fluctuations up to 4th order. An alternative and equivalent Landau energy is also provided through the transformation of the order parameters to the fluctuations in block density difference and free volume fraction. The effective Flory χ is elicited from its quadratic term as the sum of the conventional enthalpic χ H and the entropic χ S that is related to energetic asymmetry mediated by copolymer bulk modulus. It is shown that the cubic term is balanced with Gaussian cubic vertex coefficients in corporation with energetics to yield a critical point at a composition rich in a component with stronger self interactions. The full phase diagrams with classical mesophases are given for the copolymers exhibiting ordering upon cooling and also for others revealing ordering reversely upon heating. These contrasting temperature responses, along with the skewness of phase boundaries, are discussed in relation to χ H and χ S . The pressure dependence of their ordering transitions is either barotropic or baroplastic; or anomalously exhibits anomalously both at different stages. These actions are all explained by the opposite responses of χ H and χ S to pressure. [ABSTRACT FROM AUTHOR]
- Published
- 2023
- Full Text
- View/download PDF
20. Numerical Approximations of Diblock Copolymer Model Using a Modified Leapfrog Time-Marching Scheme
- Author
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Lizhen Chen, Ying Ma, Bo Ren, and Guohui Zhang
- Subjects
phase field ,linear scheme ,energy stable ,Diblock copolymer ,Electronic computers. Computer science ,QA75.5-76.95 - Abstract
An efficient modified leapfrog time-marching scheme for the diblock copolymer model is investigated in this paper. The proposed scheme offers three main advantages. Firstly, it is linear in time, requiring only a linear algebra system to be solved at each time-marching step. This leads to a significant reduction in computational cost compared to other methods. Secondly, the scheme ensures unconditional energy stability, allowing for a large time step to be used without compromising solution stability. Thirdly, the existence and uniqueness of the numerical solution at each time step is rigorously proven, ensuring the reliability and accuracy of the method. A numerical example is also included to demonstrate and validate the proposed algorithm, showing its accuracy and efficiency in practical applications.
- Published
- 2023
- Full Text
- View/download PDF
21. Synthesis optimization of PEG diblock copolymer-based nanoemulsion of cypermethrin through central composite design and bioefficacy evaluation against fish ectoparasite Argulus bengalensis.
- Author
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Sarkar, Dhruba Jyoti, Bera, Asit Kumar, Baitha, Raju, and Das, Basanta Kumar
- Abstract
Nanosizing antiparasitic formulation has tremendous potential to control parasite infection by rectifying drawbacks of conventional formulations. The present study investigates synthesis optimization of cypermethrin nanoemulsion using PEG diblock copolymers through a spontaneous emulsification technique. Synthesis parameters of nanoemulsion were optimized using response surface methodology with central composite design to get nanoemulsion (NEC-1) with lowest particle size (179.8 nm) and highest encapsulation efficiency (90.24%). TEM and DLS revealed the spherical morphology and negative zeta potential (− 42.4–57.2 mV) of the developed nanoemulsion formulations. Bioefficacy of the NEC-1 was studied against fish ectoparasite Argulus bengalensis at embryonic and adult stages. It was observed that treatment of nanoemulsion disrupted the natural developmental stage of A. bengalensis egg at a very low concentration (0.001 ppm). The calculated LC
50 against the adult parasite and LC50 for prevention of 50% egg hatching was found to be 0.005 and 0.006 ppm, respectively. In the recent scenario of repetitive antiparasitic resistance, the developed nanoemulsion could come out as a potential solution; however, further study is required for its feasibility for use in actual field conditions. [ABSTRACT FROM AUTHOR]- Published
- 2022
- Full Text
- View/download PDF
22. Production of paclitaxel-loaded PEG-b-PLA micelles using PEG for drug loading and freeze-drying.
- Author
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Rasoulianboroujeni, Morteza, Repp, Lauren, Lee, Hye Jin, and Kwon, Glen S.
- Subjects
- *
MICELLES , *POLYETHYLENE glycol , *MOLECULAR weights , *FREEZE-drying , *ALKALOIDS , *COPOLYMERS , *PACLITAXEL , *CARBOPLATIN - Abstract
A new approach named PEG-assist is introduced for the production of drug-loaded polymeric micelles. The method is based on the use of PEG as the non-selective solvent for PEG- b -PLA in the fabrication procedure. Both hydration temperature and PEG molecular weight are shown to have a significant effect on the encapsulation efficiency of PTX in PEG 4kDa - b -PLA 2kDa micelles. The optimal procedure for fabrication includes the use of PEG 1kDa as the solvent at 60 °C, cooling the mixture to 40 °C, hydration at 40 °C, freezing at −80 °C and freeze-drying at −35 °C, 15 Pa. No significant difference (p > 0.05) in PTX encapsulation, average particle size and polydispersity index is observed between the samples before freeze-drying and after reconstitution of the freeze-dried cake. The prepared PTX formulations are stable at room temperature for at least 8 h. Scaling the batch size to 25× leads to no significant change (p > 0.05) in PTX encapsulation, average particle size and polydispersity index. PEG-assist method is applicable to other drugs such as 17-AAG, and copolymers of varied molecular weights. The use of no organic solvent, simplicity, cost-effectiveness, and efficiency makes PEG-assist a very promising approach for large scale production of drug-loaded polymeric micelles. [Display omitted] • PEG-assist method for fabrication of drug-loaded polymeric micelles is introduced. • The procedure for optimizing the fabrication temperature and PEG molecular weight is presented. • The approach is suggested as being proficient for large-scale production of polymeric micelles. [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
- View/download PDF
23. Numerical investigations of pattern formation in binary systems with inhibitory long-range interaction.
- Author
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Baginski, Frank and Lu, Jiajun
- Subjects
- *
FREE energy (Thermodynamics) , *COPOLYMERS , *NUMERICAL analysis , *PHASE separation , *MANIFOLDS (Mathematics) - Abstract
We investigate pattern formation in a two-dimensional manifold using the Otha-Kawasaki model for micro-phase separation of diblock copolymers. In this model, the total energy includes a short-range and a long-range term. The short-range term is a Landau-type free energy that is common in phase separation problems and favors large domains with minimum perimeter. The inhibitory long-range interaction term is the Otha-Kawasaki functional derived from the theory of diblock copolymers and favors small domains. The balance of these terms leads to equilibrium states that exhibit a variety of patterns, including disk-like droplets, droplet assemblies, elongated droplets, dog-bone shaped droplets, stripes, annular rings, wriggled stripes and combinations thereof. For problems where analytical results are known, we compare our numerical results and find good agreement. Where analytical results are not available, our numerical methods allow us to explore the solution space revealing new stable patterns. We focus on the triaxial ellipsoid, but our methods are general and can be applied to higher genus surfaces and surfaces with boundaries. [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
- View/download PDF
24. Hydroxide‐ion transport and stability of diblock copolymers with a polydiallyldimethyl ammonium hydroxide block
- Author
-
Cotanda, Pepa, Petzetakis, Nikos, Jiang, Xi, Stone, Greg, and Balsara, Nitash P
- Subjects
Engineering ,Materials Engineering ,Chemical Sciences ,base-stable ,base ,block copolymer ,conducting materials ,conductivity ,diallyl dimethyl ammonium chloride ,diblock copolymer ,hydroxide conductivity ,ion exchange ,Macromolecular and Materials Chemistry ,Physical Chemistry (incl. Structural) ,Polymers ,Macromolecular and materials chemistry ,Physical chemistry - Abstract
Base-stable amphiphilic diblock copolymers with a polydiallyl dimethyl ammonium hydroxide block were synthesized and characterized to quantify hydroxide-ion transport in the hydrated state; polystyrene was the hydrophobic block. The challenge of synthesizing a copolymer comprising blocks with very different solubility behaviors was addressed by a combination of reversible addition fragmentation chain transfer polymerization and ion metathesis. Both monomers used in the polymerization are commercially available on industrial scales. Hydroxide-ion conductivities of 0.8 mS/cm were achieved in hot-pressed membranes immersed in water at room temperature despite relatively low water uptake (4.2 water molecules per hydroxide ion). The stability of the polydimethyl ammonium hydroxide chains was investigated in 2 M NaOD at 60 °C. 1H NMR spectroscopy studies showed no detectable degradation after 2000 hours. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2243–2248.
- Published
- 2017
25. Amphiphilic diblock copolymers of polyisobutylene-b-poly(2-ethyl-2-oxazoline) via cationic polymerization.
- Author
-
Wu, Ying-Zi, Gao, Yu-Zhuang, Zhao, Cong-Lei, Wu, Meng-Ying, and Wu, Yi-Xian
- Subjects
- *
SILVER nanoparticles , *ADDITION polymerization , *RING-opening polymerization , *ESCHERICHIA coli , *DIBLOCK copolymers , *PHASE separation , *COPOLYMER micelles - Abstract
A series of amphiphilic polyisobutylene- b -poly (2-ethyl-2-oxazoline) (PIB- b -PEOX) diblock copolymer/Ag nanoparticle composites were successfully in-situ synthesized via cationic ring-opening polymerization of 2-ethyl-2-oxazoline (EOX) with high initiation efficiency by using allyl bromide end functionalized polyisobutylene (PIB-allylBr) as a macroinitiator and AgClO 4 as a coinitiator. The microphase separation formed in the resulting PIB- b -PEOX diblock copolymers due to the thermodynamic imcompability of hydrophilic PEOX segments and hydrophobic PIB segments. The micromorphology of phase separation is dependent on the copolymer composition, in which sea-island micromorphology formed for PIB 118 - b -PEOX 80 and bicontinuous phase micromorphology formed for PIB 118 - b -PEOX 97. The micelles with nano-scale size in the range of 15–80 nm and having high drug loading rate of ca. 48.9 % can be formed by self-assembly of the amphiphilic diblock copolymers in n -hexane. The drug cumulative release rate can be increased with an increase in the proportion of PEOX segments, due to the strong interaction between ibuprofen and the PEOX segments. The hydrophilicity of the PIB- b -PEOX diblock copolymer surfaces can be improved after ethanol vapor induction. The PIB- b -PEOX diblock copolymers behave biocompatibility and good anti-protein adsorption property. The amphiphilic PIB- b -PEOX diblock copolymer/Ag nanoparticle composites exhibit high antibacterial efficiency for Gram-negative bacterium (E. coli) and Gram-positive bacterium (S. aureus). To the best of our knowledge, this is the first example of PIB- b -PEOX diblock copolymer/Ag nanoparticle (6.4 ± 2.6 nm) composites synthesized in-situ with good biocompatibility, anti-protein adsorption, and antibacterial properties, which would have potential applications for drug delivery and anti-protein coating in biomedical areas. [Display omitted] • ✓A series of amphiphilic polyisobutylene- b -poly (2-ethyl-2-oxazoline) (PIB- b -PEOX) diblock copolymer/Ag nanoparticle composites were successfully in-situ synthesized via cationic ring-opening polymerization of 2-ethyl-2-oxazoline (EOX). • The micelles with nano-scale size in the range of 15–80 nm and having high drug loading rate of ca. 48.9 % can be formed by self-assembly of the amphiphilic diblock copolymers in n -hexane. • The PIB- b -PEOX diblock copolymer/Ag nanoparticle (6.4 ± 2.6 nm) composites synthesized in-situ with good biocompatibility, anti-protein adsorption, and antibacterial properties. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
- View/download PDF
26. PVDF membranes modified with diblock copolymer PEO-b-PMMA as additive: Effects of copolymer and barrier pore size on filtration performance and fouling in a membrane bioreactor.
- Author
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Ahsani, Mina, Oghyanous, Farid Alizad, Meyer, Jens, Ulbricht, Mathias, and Yegani, Reza
- Subjects
- *
DIBLOCK copolymers , *FOULING , *AERATION tanks , *SURFACE chemistry , *METHYL methacrylate , *ETHYLENE oxide - Abstract
In the present work, filtration performance and fouling behavior of four poly(vinylidene difluoride) (PVDF) membranes with different composition and molecular weight cut-off (MWCO) were investigated in a lab-scale submerged membrane bioreactor (MBR) system, treating real pharmaceutical wastewater. Poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) diblock copolymer or FeCl 2 or the combination of PEO-b-PMMA and FeCl 2 were used as special additives during membrane formation. A 30-day filtration experiment was performed using four membranes in the same aeration tank simultaneously, and filtration performance of the membranes was investigated over the entire filtration period. Fouling parameters were calculated for all membranes and the TMP-step method was used to determine the critical flux of the membranes. Formed cake layers onto the surface of the membranes at the end of each filtration run were collected and extracellular polymeric substances (EPSs), excitation and emission matrix (EEM) fluorescence spectroscopy, and Fourier transform infrared (FTIR) spectroscopy analyses were performed for the cake layers. Collected cake layers after EPSs extraction were dried and their masses were measured to estimate anti-biofilm formation potential of the membranes. Obtained results revealed that incorporation of the PEO-b-PMMA diblock copolymer into the PVDF membrane accompany with FeCl 2 salt which tailors the MWCO and prevents the increment of the pore size improves membrane performance and reduces its fouling propensity, in a way that membrane with smaller MWCO containing copolymer revealed lower flux decline, higher critical flux, higher flux recovery ratio (FRR) and lower biofilm mass per area. Moreover, EPS and EEM analyses revealed that membrane surface chemistry has considerable effect on the composition of the cake layers. Finally, chemical oxygen demand (COD) removal efficiency proved that MWCO does not have obvious effect on effluents' quality. The present study confirms the importance of the surface chemistry and MWCO on fouling behavior of the membranes in the MBR system and reveals that the addition of the PEO-b-PMMA diblock copolymer to the PVDF membrane improves antifouling property of the membrane considerably. • Four PVDF membranes with different MWCO and surface chemistry were prepared. • FeCl 2 and PEO-b-PMMA diblock copolymer were used as additives. • Fouling behavior of the membranes were investigated in an MBR system. • Membranes with smaller MWCO showed better fouling behavior. • Addition of PEO-b-PMMA copolymer reduces fouling propensity of the membranes. [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
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27. Patch formation on diblock copolymer micelles confined in templates for inducing patch orientation and cyclic colloidal molecules.
- Author
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Jeon, Jonghyuk, Kang, Heejung, Lee, Kyunghyeon, and Sohn, Byeong-Hyeok
- Subjects
- *
COPOLYMER micelles , *DIBLOCK copolymers , *BLOCK copolymers , *MOLECULES , *SCANNING electron microscopy , *MICELLES , *MOLECULAR structure - Abstract
[Display omitted] Chemically or physically distinct patches can be induced on the micelles of amphiphilic block copolymers, which facilitate directional binding for the creation of hierarchical structures. Hence, control over the direction of patches on the micelles is a crucial factor to attain the directionality on the interactions between the micelles, particularly for generating colloidal molecules mimicking the symmetry of molecular structures. We hypothesized that direction and combination of the patches could be controlled by physical confinement of the micelles. We first confined spherical micelles of diblock copolymers in topographic templates fabricated from nanopatterns of block copolymers by adjusting the coating conditions. Then, patch formation was conducted on the confined micelles by exposing them with a core-favorable solvent. Microscopic techniques of SEM, TEM, and AFM were employed to investigate directions of patches and structures of combined micelles in the template. The orientation of the patches on the micelles was guided by the physical confinement of the micelles in linear trenches. In addition, by confining the micelles in a circular hole, we obtained a specific polygon arrangement of the micelles depending on the number of micelles in the hole, which enabled the formation of cyclic colloidal molecules consisting of micelles. [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
- View/download PDF
28. Encapsulation of hemoglobin within mPEG-b-PCL micelle for development of artificial oxygen carrier.
- Author
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Othman, Mislia, Mahmud, Khadijah, Mohammed, Rafeezul, Mohd Noor, Siti Noor Fazliah, Tuan Din, Sharifah Azdiana, and Zabidi, Muhammad Azrul
- Subjects
- *
POLYMERSOMES , *OXYGEN carriers , *HEMOGLOBINS , *CRITICAL micelle concentration , *RING-opening polymerization , *CELL survival , *CELL aggregation - Abstract
The aim of this study is to develop hemoglobin (hb) encapsulated self-assembled polymer for use as artificial oxygen carrier. Methoxy-polyethylene glycol (mPEG45) block and poly (ɛ-caprolactone [ɛ-CL]) (mPEG-b-PCL) that formed diblock copolymer was synthesized via ring-opening polymerization (ROP). Extracted and purified hb was then encapsulated in polymer with critical micelle concentration (CMC) at 1.0–2.0 mg/mL. Average encapsulation efficiency of the human hb-micelle was 45 ± 5% as compared to 66.7 ± 15% of bovine hb-micelle. The derived half-life of hb encapsulated micelle was 112,242 ± 40 min upon atmospheric air exposure as compared to 30 ± 10 min of the experiment control (free hb). Results of oxygen reversibility study also demonstrated the capability of hb-micelle to endure minimum average of six oxygenation and deoxygenation cycles as compared to an average less than one average cycle by the control. Control (free bovine and human hb) and treated cell (bovine and human hb-micelle) were incubated for 48 h and analyzed every 4, 8, 12, 16, 24, and 48 h. Cell viability assay on macrophage cell demonstrated both free hb(s) recorded decreasing cell growths as early as 8 h as compared to the increasing cell viability pattern by the encapsulated hb(s) indicating lesser cytotoxicity. [ABSTRACT FROM AUTHOR]
- Published
- 2022
- Full Text
- View/download PDF
29. Self-assembly of polystyrene-block-polybutadiene diblock copolymers in selective solvents and its crosslinking behavior upon γ-ray irradiation
- Author
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FAN Kai, LI Linfan, and LI Jihao
- Subjects
polystyrene-block-polybutadiene (ps-b-pb) ,diblock copolymer ,self-assembly ,micelles ,γ-ray ,crosslinking behavior ,Nuclear and particle physics. Atomic energy. Radioactivity ,QC770-798 ,Medical physics. Medical radiology. Nuclear medicine ,R895-920 - Abstract
In our approach, using Delsa™ Nano submicron particle size dynamic light scattering analyzer, atomic force microscope, scanning electron microscope, and thermo-gravimetric analyzer, we investigated the self-assembly behavior of block copolymer polystyrene polybutadiene (PS-b-PB) in selective solvent, 2-butanone, as well as the effect of irradiation crosslinking that resulted in the immobilization of micelles. Since the selective solvent, 2-butanone, is the soluble solvent of PS segment and insoluble solvent of polybutadiene (Pb) segment, under suitable conditions, PS-b-PB could form monodisperse "core-shell" nano-micelles microstructure. The experimental results showed that under suitable conditions, PS-b-PB could form monodisperse nano-micelles with different core-shell components in selective solvent, and the size of micelles could be adjusted by controlling the mass fraction of PS-b-PB in the solvent. The micelle solution of 2-butanone/PS-b-PB block polymer system was further irradiated by γ-ray irradiation without oxygen, and the results showed that the micelles had a certain improvement in the micro-morphology and thermodynamic stability. The reason is that the crosslinking reaction of PB chain in the micelles induced by γ-ray irradiation is immobilized, and the cured micelles are no longer affected by ultrasonic vibration, solvent dilution, and volatilization. This study provided a new approach and method for the preparation of polymer nano-micelles.
- Published
- 2021
- Full Text
- View/download PDF
30. Effect of Solvent Vapor Annealing on Diblock Copolymer-Templated Mesoporous Si/Ge/C Thin Films: Implications for Li-Ion Batteries.
- Author
-
Weindl, Christian L., Fajman, Christian E., Giebel, Michael A., Wienhold, Kerstin S., Yin, Shanshan, Tian, Ting, Geiger, Christina, Kreuzer, Lucas P., Schwartzkopf, Matthias, Roth, Stephan V., Fässler, Thomas F., and Müller-Buschbaum, Peter
- Abstract
Although amphiphilic diblock copolymer templating of inorganic materials such as TiO
2 is already well investigated, sol–gel synthesis routines for porous silicon and germanium are relatively rare. Therefore, especially in the field of Li-ion batteries, novel synthesis routines with the possibility to tune the silicon and germanium ratio and the morphology in the nanometer regime are of high interest. Here, we demonstrate a synthesis method that allows a change of morphology and elemental composition with minimal effort. We evidence a morphological transformation in the nanometer regime with real space (scanning electron microscopy) and complementary reciprocal space analysis methods (grazing-incidence small-angle X-ray scattering). Although energy-dispersive X-ray spectroscopy (EDS) reveals a considerable amount of oxygen in the thin film, crystalline Ge in the bulk is detected with powder X-ray diffraction (PXRD) and Raman spectroscopy. Due to the system's simplicity, chemical mass production options such as roll-to-roll or slot-die printing can also be considered high-yield methods compared to standard synthesis routines. [ABSTRACT FROM AUTHOR]- Published
- 2022
- Full Text
- View/download PDF
31. Porous self-supporting film of semi-flexible supracolloidal chains of diblock copolymer micelles.
- Author
-
Lee, Kyunghyeon, Kim, Joon Young, Kim, Kyungtae, Jeon, Jonghyuk, Kang, Heejung, and Sohn, Byeong-Hyeok
- Subjects
- *
DIBLOCK copolymers , *MICELLES , *COPOLYMER micelles - Abstract
[Display omitted] Patchy micelles of diblock copolymers can be polymerized into a linear supracolloidal chain. We measure the persistence and contour lengths of supracolloidal chains coated on a solid substrate to evaluate their flexibility. Based on the analysis, the chain is semi-flexible, and the conformation is suitably explained by the worm-like chain model. In addition, utilizing a spin-coating technique with the semi-flexible nature of the chains, we produce a self-supporting film of supracolloidal chains having nanoscale pores essentially from colloidal constituents that tend to form dense packing if there is no prior organization of them into a semi-flexible chain. [ABSTRACT FROM AUTHOR]
- Published
- 2021
- Full Text
- View/download PDF
32. Loading and Controlled Releasing of Anti-cancer Drug Bortezomib by Glucose-Containing Diblock Copolymer
- Author
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Zhang, Xiao-Ting, Dong, Hai-Liang, Niu, Zhong-Li, Xu, Jia-Ming, Wang, Dan-Yue, Tong, Han, Jiang, Xiao-Ze, Zhu, Mei-Fang, and Han, Yafang, editor
- Published
- 2018
- Full Text
- View/download PDF
33. Propofol-loaded nanomicelle with improved anesthetic, pharmacokinetic, hemocompatibility, safety, and permeation profiles
- Author
-
Hongfei Chen, Long He, Da Li, Feng Jin, and Yanqiu Ai
- Subjects
Propofol ,Diblock copolymer ,Nanomicelle ,Pharmacokinetic ,Hemolytic activity ,Permeation ,Chemistry ,QD1-999 - Abstract
Propofol is known as one of the most potential anesthetics which suffer from limited duration of anesthesia water insolubility. Therefore, in the present study, a formulation of propofol- carboxylic acid-poly [ethylene glycol (COO-PEG)]-b-poly[ D,L lactide (PDLA)]-nanomicelle was developed and its characterization was done by transmission electron microscopy (TEM) and dynamic light scattering analysis (DLS) studies. Afterwards, drug release assay was carried out to determine the efficacy of COO-PEG-PLDA nanomicelle in drug delivery systems. Cytotoxic, hemolytic, pharmacokinetic, and permeation assays were also followed by anesthetic efficacy of propofol- COO-PEG-PLDA nanomicelle in the rat hind paw model. The results indicated that the diameter, hydrodynamic radius and zeta potential of fabricated drug-loaded nanomicelles were 30 nm, 73.24 nm and –23.59 mV, respectively and the nanomicelles were stable for a period of 50 min. Also, COO-PEG-PLDA nanomicelle showed a sustained propofol release at physiological pH. Moreover, it was indicated that COO-PEG-PLDA nanomicelle reduced the cytotoxic and hemolytic effects of propofol and increased the steady-state flux (Jss) by 6.64 times (***P
- Published
- 2021
- Full Text
- View/download PDF
34. Selective Silver Nanocluster Metallization on Conjugated Diblock Copolymer Templates for Sensing and Photovoltaic Applications.
- Author
-
Gensch, Marc, Schwartzkopf, Matthias, Brett, Calvin J., Schaper, Simon J., Kreuzer, Lucas P., Li, Nian, Chen, Wei, Liang, Suzhe, Drewes, Jonas, Polonskyi, Oleksandr, Strunskus, Thomas, Faupel, Franz, Müller-Buschbaum, Peter, and Roth, Stephan V.
- Abstract
Polymer–metal composite films with nanostructured metal and/or polymer interfaces show a significant perspective for optoelectronic applications, for example, as sensors or in organic photovoltaics (OPVs). The polymer components used in these devices are mostly nanostructured conductive polymers with conjugated π-electron systems. Enhanced OPV's power conversion efficiencies or sensor sensitivity can be achieved by selective metal deposition on or into polymer templates. In this study, we exploit time-resolved grazing-incidence X-ray scattering to observe the metal–polymer interface formation and the cluster crystallite size in situ during silver (Ag) sputter deposition on a poly-(3-hexylthiophene-2,5-diyl)-b-poly-(methyl methacrylate) (PMMA-b-P3HT) template. We compare the arising nanoscale morphologies with electronic properties, determine Ag growth regimes, and quantify the selective Ag growth for the diblock copolymer (DBC) template using the corresponding homopolymer thin films (P3HT and PMMA) as a reference. Hence, we are able to describe the influence of the respective polymer blocks and substrate effects on the Ag cluster percolation: the percolation threshold is correlated with the insulator-to-metal transition measured in situ with resistance measurements during the sputter deposition. The Ag cluster percolation on PMMA-b-P3HT starts already on the network of the hexagonal P3HT domain before a complete metal film covers the polymer surface, which is complemented by microscopic measurements. In general, this study demonstrates a possible method for the selective Ag growth as a scaffold for electrode preparation in nanoelectronics and for energy harvesting applications. [ABSTRACT FROM AUTHOR]
- Published
- 2021
- Full Text
- View/download PDF
35. High-Quality Three-Dimensionally Cultured Cells Using Interfaces of Diblock Copolymers Containing Different Ratios of Zwitterionic N -Oxides.
- Author
-
Ogiwara N, Nakano T, Baba K, Noguchi H, Masuda T, and Takai M
- Subjects
- Acrylamides chemistry, Oxides chemistry, Ions chemistry, Methacrylates chemistry, Humans, Animals, Mice, Surface Properties, Chemical Phenomena, Cell Adhesion, Gene Expression, RNA, Messenger genetics, Cells, Cultured, Spheroids, Cellular cytology, Spheroids, Cellular metabolism, Polymers chemistry, Acrylates chemistry, Nylons chemistry, Cell Culture Techniques, Three Dimensional methods
- Abstract
To control three-dimensional (3D) cell spheroid formation, it is well-known the surface physicochemical and mechanical properties of cell culture materials are important; however, the formation and function of 3D cells are still unclear. This study demonstrated the precise control of the formation of 3D cells and 3D cell functions using diblock copolymers containing different ratios of a zwitterionic trimethylamine N -oxide group. The diblock copolymers were composed of poly( n -butyl methacrylate) (PBMA) as the hydrophobic unit for surface coating on a cell culture dish and stabilization in water, and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) as the precursor of N -oxide. The zwitterionic N -oxide converted from 0 to 100% using PDMAEMA. The wettability and surface zeta potential varied with different ratios of N -oxide diblock copolymer-coated surfaces, and the amount of protein adsorbed in the cell culture medium decreased monotonically with increasing N -oxide ratio. 3D cell spheroid formations were observed by seeding human umbilical cord mesenchymal stem cells (hUC-MSCs) in diblock copolymer-coated flat-bottom well plates, and the N -oxide ratio was over 40%. The cells proliferated in two-dimensions (2D) and did not form spheroids when the N -oxide ratio was less than 20%. Interestingly, the expression of undifferentiated markers of hUC-MSCs was higher on surfaces that adsorbed proteins to some extent and formed 50-150 μm spheroids in the range of 40-70% of N -oxide ratio. We revealed that a moderately protein-adsorbed surface allows precise control of spheroid formation and undifferentiated 3D cells and has potential applications for high-quality spheroids in regenerative medicine and drug screening.
- Published
- 2024
- Full Text
- View/download PDF
36. Design of Polymeric Self-Assembling Materials and Nanocomposites in the Semi-dilute Density Regime: Multiscale Modeling
- Author
-
Capone, Barbara, Locatelli, Emanuele, and Coluzza, Ivan, editor
- Published
- 2017
- Full Text
- View/download PDF
37. Nanofabrication by Self-Assembly
- Author
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Cui, Zheng and Cui, Zheng
- Published
- 2017
- Full Text
- View/download PDF
38. Hierarchical supramolecular assembly of a single peptoid polymer into a planar nanobrush with two distinct molecular packing motifs.
- Author
-
Jing Sun, Zhiwei Wang, Chenhui Zhu, Meiyao Wang, Zhekun Shi, Yuhan Wei, Xiaohui Fu, Xuesi Chen, and Zuckermann, Ronald N.
- Subjects
- *
ETHYLENE glycol , *POLYMERS , *HIGH temperature physics , *MICELLES , *NANOSTRUCTURED materials - Abstract
Hierarchical nanomaterials have received increasing interest for many applications. Here, we report a facile programmable strategy based on an embedded segmental crystallinity design to prepare unprecedented supramolecular planar nanobrush-like structures composed of two distinct molecular packing motifs, by the self-assembly of one particular diblock copolymer poly(ethylene glycol)-block-poly(N-octylglycine) in a one-pot preparation. We demonstrate that the superstructures result from the temperature-controlled hierarchical self-assembly of preformed spherical micelles by optimizing the crystallization-solvophobicity balance. Particularly remarkable is that these micelles first assemble into linear arrays at elevated temperatures, which, upon cooling, subsequently template further lateral, crystallization-driven assembly in a living manner. Addition of the diblock copolymer chains to the growing nanostructure occurs via a loosely organized micellar intermediate state, which undergoes an unfolding transition to the final crystalline state in the nanobrush. This assembly mechanism is distinct from previous crystallization-driven approaches which occur via unimer addition, and is more akin to protein crystallization. Interestingly, nanobrush formation is conserved over a variety of preparation pathways. The precise control ability over the superstructure, combined with the excellent biocompatibility of polypeptoids, offers great potential for nanomaterials inaccessible previously for a broad range of advanced applications. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
- View/download PDF
39. Effect of molecular weight on the properties of polyethylene glycol polyurethane-co-polydimethylsiloxane polyurethane.
- Author
-
Jee, Chanhyuk, Kang, Kyung Seok, Bae, Ji-Hong, Min, Jin Gyu, Kim, Byeong Joo, Seo, Chang Min, and Huh, PilHo
- Abstract
A series of thermoplastic polyurethanes (TPUs) composed of polyethylene glycol polyurethane (PEG-PU) and polydimethylsiloxane polyurethane (PDMS-PU) were prepared to examine the effects of the PEG molecular weight (MW) on the surface and physical properties. The adaptive PEG-PU-co-PDMS-PU structures resembled the architectures of a diblock copolymer, which used the MW-fractionated PEG. The sufficient MW dependence was observed within the range 200 < MW < 400, indicating that the increased urethane groups of PEG-PU block limit the surface and physical properties of these samples. The difference in properties according to the degree of the urethane groups was evaluated using a universal test machine (UTM) as well as by measuring the contact angle and water vapor transmission rate (WVTR). [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
- View/download PDF
40. Preparation of Responsive Zwitterionic Diblock Copolymers Containing Phosphate and Phosphonate Groups.
- Author
-
Samav, Yasemin, Akpinar, Bernice, Kocak, Gökhan, and Bütün, Vural
- Abstract
In this study, novel zwitterionic diblock copolymers, namely poly(2-(N-morpholino)ethyl methacrylate))-block-poly(2-(methacryloyloxy)ethyl phosphate) (PMEMA-b-PMOEP) and poly(2-(N-morpholino)ethyl methacrylate))-block-poly ((methacryloyloxy)methyl phosphonic acid) (PMEMA-b-PMOMP), were synthesized via reversible addition-fragmentation chain transfer controlled radical polymerization. Solution properties of these phosphorus-based diblock copolymers were investigated using dynamic light scattering, transmission electron microscopy and proton nuclear magnetic resonance spectroscopy. Since the PMEMA block has both salt- and thermo-responsive properties, PMEMA-b-PMOEP and PMEMA-b-PMOMP diblock copolymers formed core-shell micelles in basic aqueous media as the PMEMA block formed insoluble micelle core with the addition of Na
2 SO4 or an increase in temperature in basic solution. Additionally, PMEMA-b-PMOMP diblock copolymers interacted strongly with calcium cations and yielded reverse micellar structures via complexation of phosphate with metal cation in aqueous media. [ABSTRACT FROM AUTHOR]- Published
- 2020
- Full Text
- View/download PDF
41. Conjugated hydrophobic and hydrophilic blocks through a drug moiety as a leading macromolecular system for sustainable drug delivery.
- Author
-
Kailash, S., Meenarathi, B., Parthasarathy, V., and Anbarasan, R.
- Subjects
- *
DRUG delivery systems , *DIBLOCK copolymers , *MOIETIES (Chemistry) , *RING-opening polymerization , *PENICILLIN G - Abstract
Ring-opening polymerization (ROP) of ε-caprolactone (CL) had been performed at 160 °C in the presence of drug molecules such as penicillin g (Pen), streptavidin (Strep) and terramicin (Ter) as a lone chemical initiator using the catalyst, stannous octoate (SO) under N2 atmosphere. The prepared drug bridged poly (ε-caprolactone) (PCL) was further copolymerized with tetrahydrofuran (THF) and the diblock copolymers were examined using the various analytical tools (FT-IR, DSC, TGA, SEM, FE-SEM, EDX, UV-visible and GPC). The functionalities of the drug bridged diblock copolymers were concluded by FT-IR spectra. The formation of the diblock copolymer was further understood from the increase in Mw. The drug release activity of homo and diblock copolymer had been tested with the drug release model and mechanism. The mechanical properties are also studied. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
- View/download PDF
42. КОМПОЗИЦІЯ α-ТОКОФЕРИЛАЦЕТАТУ З МІЦЕЛЯРНИМИ НАНОНОСІЯМИ ТА МОЖЛИВОСТІ ЇЇ ВИКОРИСТАННЯ ЯК БІОЛОГІЧНОАКТИВНОЇ ДОБАВКИ
- Author
-
ПЕРМЯКОВА, Н. М., ЖЕЛТОНОЖСЬКА, Т. Б., КАРПОВСЬКИЙ, В. І., ПОСТОЙ, Р. В., МАКСІН, В. І., ПАРЦЕВСЬКА, С. В., ГРІЩЕНКО, Л. М., КЛИМЧУК, Д. О., and КЛЕПКО, В. В.
- Subjects
- *
ETHYLENE oxide , *VITAMIN E , *SALINE solutions , *LIGHT scattering , *MICELLAR solutions - Abstract
Based on the asymmetric diblock copolymer (DBC) poly(ethylene oxide)/polyacrylic acid, effective, biocompatible and biodegradable micellar carriers were obtained for the delivery of vitamin E analogue, α-tocopheryl acetate (α-TOCA), in living organisms. The monitoring of the stability of micellar structures of the block copolymer and its composition with α-TOCA over time, in a saline solution and when the pH of the solution changes, was carried out. The stability of DBC micelles over time at pH = 3.5, partial disaggregation of micelles at pH = 9 and an increase in their aggregation in physiological solution were shown. The high stability of the α-TOCA/DBC composition formed in situ in time in the range of pH=3.5-9 and a significant decrease in its solutions of salting out effects in the presence of NaCl were established. The thermodynamic parameters of the process of the micelle formation of the pure α-TOCA in water/ethanol solution (95/5 v/v) as well as the size and morphology of its micellar structures were determined by light scattering and TEM methods. The initial α-TOCA micelles in water/ethanol solution were stable over a wide pH range, but their stability was much lower and the sensitivity to the presence of NaCl was much higher than that of DBC micelles. The dialysis method revealed the gradual release of the drug from the micellar carrier through a semipermeable membrane into the surrounding aqueous and aqueous-saline media. However, the rate and efficiency of α-TOCA release from the DBC micelles in an aqueous medium were significantly lower compared to a similar process of drug release from the pure α-TOCA dispersion. Thus, a possibility of providing of long-term controlled release of α-TOCA in the living organism due to the use of DBC micelles has been proven. Based on in vivo tests of the biological action of the composition on pregnant sows, its high bioavailability, rapid absorption, active participation in metabolic processes and positive effect on the reproductive qualities of sows compared to pure α-TOCA, were displayed, which improves the safety and productivity of newborn piglets. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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- View/download PDF
43. Synthesis, characterization and applications of nano-Ag-tagged poly(ε-caprolactone-block-tetrahydrofuran).
- Author
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Jeyapriya, Muthuramalingam, Meenarathi, Balakrishnan, Tung, Kuo-Lun, and Anbarasan, Ramasamy
- Subjects
- *
EMISSION spectroscopy , *GEL permeation chromatography , *CATALYTIC reduction , *BLOCK copolymers , *FOURIER transform infrared spectroscopy , *ATMOSPHERIC nitrogen , *NICKEL phosphide , *CIRCULAR dichroism - Abstract
A diblock copolymer consists of ε-caprolactone, and tetrahydrofuran was synthesized by using a novel natural amino acids such as penicillamine and tyrosine as a chemical initiator in the presence of stannous octoate as a catalyst through bulk polymerization method under nitrogen atmosphere with mild stirring condition. The synthesized diblock copolymer was treated with AgNO3 to form a nano-Ag-tagged diblock copolymer. The above-synthesized polymer systems were characterized by various analytical tools such as FTIR spectroscopy, NMR spectroscopy, fluorescence emission spectroscopy, circular dichroism, gel permeation chromatography, FESEM, HRTEM, EDX, DSC and TGA. Its applications toward catalytic reduction of p-nitrophenol (NiP), wound healing activity and low-temperature splinting activity were tested. Due to the incorporation of poly(tetrahydrofuran) (PTHF), the % elongation value of the diblock copolymer was increased but the DSC and TGA results showed depressed results. The HRTEM declared the size of Ag nanoparticle as < 50 nm. From the values of UV–visible absorbance, apparent rate constant (kapp) was determined and compared with the literature report. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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44. Efficient and energy stable method for the Cahn-Hilliard phase-field model for diblock copolymers.
- Author
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Zhang, Jun, Chen, Chuanjun, and Yang, Xiaofeng
- Subjects
- *
DIBLOCK copolymers , *BIHARMONIC equations , *LINEAR equations , *TIME management - Abstract
• We propose a novel stabilized SAV approach for solving the phase field model for diblock copolymers. • The proposed schemes are second-order accurate, provably unconditionally energy stable, non-iterative. • The added linear stabilization term is shown to be crucial enhance the stability while keeping the required accuracy. • One only need to solve three decoupled linear equations at each time step. • We further prove the unconditional energy stabilities rigorously and present numerous 2D and 3D simulations. In this paper, we consider numerical approximations to solving the Cahn-Hilliard phase field model for diblock copolymers. We combine the recently developed SAV (scalar auxiliary variable) approach with the stabilization technique to arrive at a novel stabilized-SAV method, where a crucial linear stabilization term is added to enhancing the stability and keeping the required accuracy while using the large time steps. The scheme is very easy-to-implement and fast in the sense that one only needs to solve two decoupled fourth-order biharmonic equations with constant coefficients at each time step. We further prove the unconditional energy stability of the scheme rigorously. Through the comparisons with some other prevalent schemes like the fully-implicit, convex-splitting, and non-stabilized SAV scheme for some benchmark numerical examples in 2D and 3D, we demonstrate the stability and the accuracy of the developed scheme numerically. [ABSTRACT FROM AUTHOR]
- Published
- 2020
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45. Facile synthesis and polymerization of 1,4,5-oxadithiepan-2-one for disulfide-based redox-responsive drug delivery.
- Author
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Chakraborty, Debojit, Sengupta, Anindita, Bhattacharyya, Jayanta, and Jacob, Josemon
- Subjects
- *
DIBLOCK copolymers , *BLOCK copolymers , *FICK'S laws of diffusion , *RING-opening polymerization , *DRUG delivery systems , *METHOXYETHANOL , *PLASMA stability - Abstract
Chemotherapeutic drugs have been shown to be promising for the treatment of tumors, however, they are associated with several disadvantages including low aqueous solubility, non-specificity, and poor plasma stability. Hence, they accumulate in the health organs and create several adverse effects. Drug encapsulated stimuli-responsive nanoparticles bearing redox-responsive disulfide linkages have emerged as promising delivery vehicle to address these limitations. A glutathione (GSH) responsive disulfide-based drug delivery system based on a polyethylene glycol methyl ether (PEGME) and a polydisulfide (PDS) diblock copolymer has been developed. The cyclic lactone containing a disulfide link, 1,4,5-oxadithiepan-2-one, was prepared using a thiol-free method utilizing the reaction of 2-bromoethyl bromoacetate with sodium disulfide. Ring-opening polymerization (ROP) of 1,4,5-oxadithiepan-2-one using 1-butanol in the presence of Sn(oct) 2 generated the homopolymer PDS whereas the diblock copolymer PEGME- b -PDS was obtained when PEGME was used as a macroinitiator. In aqueous solution, PEGME- b -PDS self-assembled into spherical-shaped micelles with a hydrodynamic radius of 146 and 116 nm as measured by Field-emission Scanning Electron Microscopy (FESEM) and Dynamic Light Scattering (DLS), respectively. At pH = 7.4, a Doxorubicin (DOX) loaded PEGME- b -PDS micelle showed a cumulative release of ∼98.2, ∼9.9, and ∼1.9 % in presence of 2 mM, 2 μM DTT and in absence of DTT, respectively clearly demonstrating the redox responsiveness of the PDS block. The best fit of kinetic data using with the Korsmeyer-Peppas model suggests a Fickian diffusion as well as chain-relaxation controlled drug release process. DOX loaded micelles and free DOX displayed similar cytotoxicity towards both 4T1 and MCF-7 cells indicating that the encapsulation inside the micelle did not affect the anticancer efficacy of the drug. The drug loaded micelle showed higher cellular uptake than free DOX in both 4T1 and MCF-7 lines and lower cellular uptake than free DOX in 3T3-L1 cell lines. This polymeric micellar nanoparticle may be further exploited for encapsulation of other hydrophobic drugs. [Display omitted] • A feasible and easy synthesis of 1,4,5-oxadithiepan-2-one from sodium disulfide. • Synthesis of disulfide based homopolymer and block copolymer using ring opening polymerization of 1,4,5-oxadithiepan-2-one. • The cumulative drug release from the micelle was 98.2% and 9.9% after 72 h in presence of 2 mM and 2 μM dithiothreitol, respectively. • The cellular uptake of drug loaded micelle was higher than the free drug in both 4T1 and MCF-7 cell lines and lower than the free drug in 3T3-L1 cells. [ABSTRACT FROM AUTHOR]
- Published
- 2024
- Full Text
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46. Advanced Engineering Approaches in the Development of PLGA-Based Nanomedicines
- Author
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El-Hammadi, Mazen M., Arias, José L., and Aliofkhazraei, Mahmood, editor
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- 2016
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47. Local and global minimality results for an isoperimetric problem with long-range interactions
- Author
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Morini, Massimiliano, Fusco, Nicola, editor, and Pratelli, Aldo, editor
- Published
- 2016
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48. SUSHI: Density Functional Theory Simulator
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Honda, Takashi and Chemical Innovation, Japan Association for, editor
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- 2016
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49. Well-defined PE-b-PTFE diblock copolymers via combination of coordination chain transfer polymerization and condensation reaction: Facile preparation and surface modification of polyethylene film
- Author
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Feng He, Peiyuan Li, Anyang Wu, Tao Xu, Zhisheng Fu, Liang Zhu, and Zhiqiang Fan
- Subjects
polyethylene ,polytetrafluoroethylene ,diblock copolymer ,synthesis ,application ,Polymers and polymer manufacture ,TP1080-1185 - Abstract
In this paper, a series of well-defined polyethylene-b-polytetrafluoroethylene diblock copolymers (PE–b– PTFEs) were prepared by a coupling reaction of hydroxyl-terminated polyethylene (PE–OH) and isocyanateterminated 1H,1H-perfluoro-1-tetradecanol (PFDO–NCO). PE–OH was prepared by the coordination chain transfer polymerization using 2,6-bis[1-(2,6-diisopropylphenyl)imino ethyl] pyridine iron (II) dichloride /dry ethylaluminoxane/ZnEt2 as catalyst and subsequent in situ oxidation with oxygen. PFDO–NCO was synthesized through the condensation reaction of 1H,1H- perfluoro-1-tetradecanol (PFDO) with isophoronediisocyanate (IPDI). Subsequently, the thermal characterization and the application of these diblock copolymers were investigated. The relationship between the molecular structure and the properties was disclosed. The results indicated that the diblock copolymers were effective surface modification agents for linear low density polyethylene (LLDPE). After that the PE–b–PTFE being spin-coated onto the surface of LLDPE film, the film was dramatically turned into a superhydrophobic film with a water contact angle as high as 151.4º. This kind of film is potential to be used as selfcleaning, anti-icing and anticorrosion material.
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- 2017
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50. Hollow Gyroid
- Author
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Salvatore, Stefano and Salvatore, Stefano
- Published
- 2015
- Full Text
- View/download PDF
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