Block copolymer (BCP) self-assembly is an effective and versatile approach for the production of complex nanopatterned interfaces. Monolayers of BCP films can be harnessed to produce a variety of different patterns, including lines, with specific spacings and order. In this work, bilayers of cylinder-forming polystyrene-block-polydimethylsiloxane block copolymer (PS-b-PDMS) were transformed into arrays of silica lines with half the pitch normally attained for conventional monolayers, with the PDMS acting as the source for the SiOx. The primary hurdle was ensuring the bilayer silica lines were distinctly separate; to attain the control necessary to prevent overlap, a number of variables related to the materials and self-assembly process were investigated in detail. Developing a detailed understanding of BCP film swelling during solvent annealing, blending of the PS-b-PDMS with PS homopolymer, utilization of a surface brush layer, and adjustment of the plasma exposure conditions, distinct and separate silica lines were prepared. On the microscale, the sample coverage of PS-b-PDMS bilayers was investigated and maximized to attain >95% bilayers under defined conditions. The bilayer BCP structures were also amenable to graphoepitaxy, and thus, dense and highly ordered arrays of silica line patterns with tightly controlled width and pitch were fabricated and distributed uniformly across a Si surface.
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http://dx.doi.org/10.1021/nn401968t | DOI Listing |
Drug Deliv Transl Res
January 2025
Drug Research Program, Division of Pharmaceutical Chemistry and Technology, Faculty of Pharmacy, University of Helsinki, Helsinki, FI-00014, Finland.
Functionalization of polymer nanoparticles (NPs) with targeting peptides is of interest for drug delivery applications to enhance tumor accumulation and penetration. Herein, we evaluated the feasibility of two different methods for the attachment of a tumor-penetrating peptide LinTT1 (AKRGARSTA) to poly(ethylene glycol)-block-poly(ε-caprolactone) (PCL-PEG) NPs: (1) "post-conjugation" onto pre-formed nanoparticles, and (2) "pre-conjugation", the synthesis and purification of peptide-polymer conjugates and subsequent nanoprecipitation of the conjugates diluted with non-functionalized polymers. Conjugation of the labelled peptide via maleimide-thiol chemistry was verified by gel permeation chromatography (GPC) and fluorescence measurements.
View Article and Find Full Text PDFAnal Chem
January 2025
Aix Marseille Univ, CNRS, ICR, Marseille 13013, France.
Size exclusion chromatography-gradient (SEC-Gradient) is a powerful technique to separate polymers by their chemical composition. The stationary phase is first conditioned with a gradient from adsorli to desorli, and polymer samples are injected after the gradient in SEC conditions. Since its first description in 2011 by Schollenberger and Radke, it has never been applied to block copolymers.
View Article and Find Full Text PDFACS Nano
January 2025
Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang 37673, Republic of Korea.
We present a strategy for enhancing Li conduction in block copolymer electrolytes by introducing trace amounts of Li salts into polystyrene--poly(ethylene oxide) (PS--PEO), wherein Li ions preferentially coordinate with the -OH end groups of the PEO chains, resulting in the formation of double primitive cubic (3̅) structures. Compared with TFSI anions in Li salts, smaller anions (PF and BF) could facilitate ion localization more effectively, expanding the salt concentration range for developing stable 3̅ structures. The 3̅ structures formed in PS--PEOs doped with LiBF at = 0.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Tianjin Key Laboratory of Brine Chemical Engineering and Resource Eco-utilization, College of Chemical Engineering and Materials Science, Tianjin University of Science & Technology, Tianjin 300457, P. R. China.
Polymer nanoparticles with low curvature, especially two-dimensional (2D) soft materials, are rich in functions and outstanding properties and have received extensive attention. Crystallization-driven self-assembly (CDSA) of linear semicrystalline block copolymers is currently a common method of constructing 2D platelets of uniform size. Although accompanied by high controllability, this CDSA method usually and inevitably requires a longer aging time and lower assembly concentration, limiting the large-scale preparation of nanoaggregates.
View Article and Find Full Text PDFLangmuir
January 2025
Department of Applied Chemistry, Graduate School of Engineering, University of Hyogo, Shosha, Himeji, Hyogo 671-2201, Japan.
To prepare amphiphilic diblock copolymers (MP), a controlled radical polymerization approach was employed, incorporating hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) with hydrophobic poly(3-methoxypropyl acrylate) (PMPA). The synthesized diblock copolymers feature a PMPC block with a degree of polymerization (DP) of 100 and a PMPA block with DP (=) values of 171 and 552. The hydrophilic PMPC block exhibits biocompatibility, such as inhibition of platelet and protein adsorption, because of its hydrophilic pendant zwitterionic phosphorylcholine groups that have the same chemical structure as cell membrane surfaces.
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