We present a conceptually simple approach to nanolithographic patterning utilizing ex situ fabricated nanoporous masks from block copolymers. The fabricated block copolymer (BC) masks show predictable morphology based on the correlation between BC composition and bulk properties, independent of substrates' surface properties. The masks are prepared by microtoming of prealigned nanoporous polymer monoliths of hexagonal morphology at controlled angles; they appear as 30-60 nm thick films of typical dimensions 100 μm × 200 μm. Masks cut perpendicular to the cylindrical axis show monocrystalline hexagonal packing of 10 nm pores with a principal period of 20 nm. We demonstrate the transfer of the hexagonal pattern onto silicon by means of reactive ion etching through the masks. In addition, patterns of elliptic and slit-like holes on silicon are obtained by utilizing masks cut at 45° relative to the cylinder axis. Finally, we demonstrate the first transfer of moiré patterns from block copolymer masks to substrate. The nanoporous masks prepared ex situ show outstanding long-range order and can be applied directly onto any flat substrate, eliminating the need for topographic and chemical surface modification, which are essential prerequisites for the conventional procedure of block copolymer directed self-assembly. The demonstrated elliptic and moiré pattern transfers prove that the proposed ex situ procedure allows us to realize nanolithographic patterns that are difficult to realize by the conventional approach alone.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.langmuir.5b00482 | 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.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!