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High molecular weight (HMW) poly(butyl acrylate)s (PBAs) and diblock copolymers consisting of PBA blocks were synthesized by ab initio emulsion polymerization using water-soluble organotellurium ch...

In this paper, a poly(methyl methacrylate)-block-poly(ethylene glycol methacrylate) [PMMA-b-P(PEGMA)] copolymer is synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerizat...

Fluorescent drug delivery systems have received increasing attention in cancer therapy because they combine drug delivery and bioimaging into a single platform. For example, polymers with aggregation-induced emission (AIE) fluorophores, such as tetraphenylethylene (TPE), have emerged as an elegant choice for drug delivery/bioimaging applications. In this work, we report one-pot sequential organocatalytic ring-opening polymerization of e-caprolactone (CL) and ethylene oxide (EO) using TPE-(OH)2 as a difunctional initiator, in the presence of a t-BuP2/TEB Lewis pair (catalyst), in THF at room temperature. Two well-defined triblock copolymers with inverse block sequences, TPE-(PCL-b-PEO)2 and TPE-(PEO-b-PCL)2, were synthesized by altering the sequential addition of CL and EO. The physicochemical properties, including hydrodynamic diameter, morphology, and AIE properties of the synthesized amphiphilic triblock copolymers were investigated in aqueous media. The block copolymer micelles were loaded with anticancer drugs doxorubicin and curcumin to serve as drug delivery vehicles. In vitro studies revealed the accelerated drug release at lower pH (5.5), which mimics the tumor microenvironment, different from the physiological pH (7.4). In vitro cytotoxicity studies demonstrated that the neat block copolymer micelles are biocompatible, while drug-loaded micelles exhibited a significant cytotoxic effect in cancer cells. Cellular uptake, examined by confocal laser scanning microscopy, showed that the block copolymer micelles were rapidly internalized by the cells with simultaneous emission of TPE fluorophore. These results suggest that these triblock copolymers can be utilized for intracellular bioimaging.

We report the synthesis of a bottlebrush statistical copolymer (BSCP) architecture and its role in directing molecular packing in the bulk state. Copolymers with a statistical distribution of two c...

High-temperature thermal gradient interaction chromatography (HT-TGIC) can be used to measure the chemical composition distribution of ethylene/α-olefin copolymers using a column packed with porous...

In this study, we synthesized and characterized two nickel complexes featuring conformationally rigid bisphosphine mono-oxide ligands, where one has an o-methoxyphenyl (Ni2) and the other has an o-(2-methoxyethoxy)phenyl (Ni3) substituent on the P═O moiety. We performed metal binding studies using Ni3 and found that its reaction with Li+ and Na+ most likely produced 1:1 and 1:1/2:1 nickel:alkali species in solution, respectively. The nickel complexes were competent catalysts for ethylene homopolymerization and copolymerization, with activities up to 3.8 × 103 and 8.1 × 10 kg mol-1 h-1, respectively. In reactions of ethylene with methyl acrylate (1.0 M), the addition of Li+ to Ni3 led to a 5.4-fold enhancement in catalyst activity and a 1.9-fold increase in polar monomer incorporation in comparison to those by Ni3 alone under optimized conditions. A comparison with other nickel catalysts reported for ethylene and methyl acrylate copolymerization revealed that our nickel-alkali catalysts are competitive with some of the most efficient Ni-based systems developed thus far.

Structural evolution of impact-resistant polypropylene copolymers (IPCs), having different compositions of segmental ethylene–propylene (sEP) copolymers, under tensile deformation was investigated ...

Poly(N-vinylcaprolactam) (PVCap) and related copolymers have been used as kinetic hydrate inhibitors (KHIs) to combat gas hydrate formation in oil and gas field production flow lines. It is known that the addition of certain solvents to the KHI polymer can enhance its ability to hinder gas hydrate formation. In an earlier study, a wide range of alcohols, glycol ethers, and ketones were investigated as synergetic solvents with PVCap. In that study, an outstanding synergetic effect was achieved by 4-methyl-1-pentanol (iHexOl). This report builds on that study by investigating iHexOl in more detail as well as some newly synthesized solvents predicted by the first study to have good synergism. Both slow constant cooling (SCC) and isothermal KHI experiments were conducted in high-pressure steel rocking cells using a structure II-forming natural gas mixture. The KHI polymer concentration, solvent concentration, and mixed solvent systems were investigated. The solvent synergist water solubility, also in brines, and partitioning to the liquid hydrocarbon phase are shown to be important factors to consider for optimizing KHI performance. Further, it was observed that the optimal molecular weight distribution for the KHI polymer when used with a solvent synergist is not the same as the optimum distribution when using the polymer alone.

Heteronuclear complexes are highly active catalysts in alternating ring opening copolymerizations (ROCOP) of cyclohexene oxide (CHO)/carbon dioxide or CHO/phthalic anhydride (PA). In this contribution, a series of new trinuclear complexes is investigated through a structure activity study that reveals the influences of ligand electronic properties and metal selection over the catalytic activity and linkage selectivity. The fastest catalyst shows high activity for CHO/CO2ROCOP at low pressure (1 bar CO2pressure) and features the ligand coordinated to two Zn(II) centers and with inexpensive and abundant Na(I) (TOF = 1084 h–1, catalyst/CHO 1:4000, 1 bar, 100 °C). High CHO/PA copolymerization activity is achieved with the combination of two Mg(II) and one Na(I) center (TOF = 142 h–1, catalyst/PA/CHO 1:200:4000, 100 °C); further the catalyst undergoes “switchable” epoxide/anhydride ROCOP and epoxide ring opening polymerization (ROP), allowing for controlled polyether block formation. Polymerization kinetic investigations reveal the influences of the ligand electronics, complex stability and metal–metal separation, and their influences over the retention of high activity throughout the catalysis. The findings should help in guiding future polymerization catalyst design, facilitate block polymer production, and inspire other CO2utilization processes.

Herein, we report on an advanced design for polymer electrolytes (PEs) based on our previously reported microphase-separated poly(vinyl benzyl methoxy poly(ethylene oxide) ether)-block-polystyrene block copolymers (PVBmPEO-b-PS). Usually, such block copolymers are characterized by a high mechanical stability provided by the PS domain, while the PEO-based domain features decent ionic conductivities, however, mostly only at higher temperatures. To enable suitable ionic conductivities at lower temperatures, we selectively implemented two ionic liquids (ILs) as a model plasticizer for the PEO domain. Since those ILs are nonmiscible with PS, the latter domain is unaffected, thus still providing a great mechanical stability. To maintain the necessary self-standing film forming ability, we adjusted the size of the PS domain to match with the conducting PEO-based domain. For this, a series of four block copolymers with different PS:PVBmPEO block ratios were synthesized, thus enabling the study of the influence of different amounts of IL. Further, all derived polymer electrolytes were thoroughly characterized by thermal, rheological, morphological, and electrochemical analyses. We could prove the microphase-separated morphology with long-range order and a good thermal and mechanical stability as well as the selective mixing of the ILs within the conducting domain. Consequently, electrochemical impedance spectroscopy revealed a significant increase in ionic conductivity up to 2 orders of magnitude and a reduced interfacial resistance in comparison to a nonplasticized reference sample. Moreover, exhaustive studies of the lithium-ion transference number showed not only the importance of such detailed analysis for IL-containing PEs but also the true increase of the effective lithium-ion conductivity. Finally, we conducted a full cycling in Li||LiFePO4 (LFP) cells to clearly demonstrate the applicability of our approach.

We present material substitutions and optical characterization of block copolymer (BCP)-templated gyroid structures that are obtained from a volume-asymmetric polystyrene

The financial support of the National Natural Science Foundation of China (52022031, 21734004, 21971075) and the Fund of Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates (2019B030301003) is acknowledged.

We report the rational design of aldehyde-functional sterically stabilized diblock copolymer nano-objects in aqueous solution via polymerization-induced self-assembly. More specifically, reversible addition-fragmentation chain transfer aqueous dispersion polymerization of 2-hydroxypropyl methacrylate is conducted using a water-soluble precursor block in which every methacrylic repeat unit contains a pendent oligo(ethylene glycol) side chain capped with a cis-diol unit. Systematic variation of the reaction conditions enables the construction of a pseudo-phase diagram, which ensures the reproducible targeting of pure spheres, worms, or vesicles. Selective oxidation of the pendent cis-diol groups using aqueous sodium periodate under mild conditions introduces geminal diols (i.e., the hydrated form of an aldehyde obtained in the presence of water) into the steric stabilizer chains without loss of colloidal stability. In the case of diblock copolymer vesicles, such derivatization leads to the formation of a worm population, indicating partial loss of the original morphology. However, this problem can be circumvented by cross-linking the membrane-forming block prior to periodate oxidation. Moreover, such covalently stabilized aldehyde-functionalized vesicles can be subsequently reacted with either glycine or histidine in aqueous solution, followed by reductive amination to prevent hydrolysis of the labile imine bond. ζ potential measurements confirm that this derivatization significantly affects the electrophoretic behavior of these vesicles. Similarly, the membrane-crosslinked aldehyde-functionalized vesicles can be reacted with a model globular protein, bovine serum albumin, to produce "stealthy" protein-decorated vesicles.

We present the design, synthesis, and characterization of triple hydrogen-bond-forming precursors and their supramolecular triblock copolymers. Thymine end-functionalized polystyrene-b-polyisoprene...

Until now, solar thermal energy storage within phase-change materials (PCMs) depends on π–π and van der Waals interactions to improve their miscibility, which often brings about finite enhancement ...

Achieving controls on the self-assembly of cationic and block copolymer micelles has significant implications for advancing novel material systems for energy, environmental, and biological applicat...

We use umbrella sampling to compute the free energy trajectory of a single chain undergoing expulsion from an isolated diblock copolymer micelle. This approach elucidates the experimentally unobservable transition state, identifies the spatial position of the maximum free energy, and reveals the chain conformation of a single chain as it undergoes expulsion. Combining umbrella sampling with dissipative particle dynamics simulations of A

Small-molecule acceptor (SMA)-based organic solar cells (OSCs) have achieved high power conversion efficiencies (PCEs), while their long-term stabilities remain to be improved to meet the requirements for real applications. Herein, we demonstrate the use of donor-acceptor alternating copolymer-type compatibilizers (DACCs) in high-performance SMA-based OSCs, enhancing their PCE, thermal stability, and mechanical robustness simultaneously. Detailed experimental and computational studies reveal that the addition of DACCs to polymer donor (

An electrochemically controlled synthesis of multiblock copolymers by alternating the redox states of (salfan)Zr(OtBu)2 (salfan = 1,1'-di(2-tert-butyl-6-N-methylmethylenephenoxy)ferrocene) is reported. Aided by electrochemistry with a glassy carbon working electrode, an in situ potential switch alters the catalyst's oxidation state and its subsequent monomer (l-lactide, β-butyrolactone, or cyclohexene oxide) selectivity in one pot. Various multiblock copolymers were prepared, including an ABAB tetrablock copolymer, poly(cyclohexene oxide-b-lactide-b-cyclohexene oxide-b-lactide), and an ABC triblock copolymer, poly(hydroxybutyrate-b-cyclohexene oxide-b-lactide). The polymers produced using this technique are similar to those produced via a chemical redox reagent method, displaying moderately narrow dispersities (1.1-1.5) and molecular weights ranging from 7 to 26 kDa.

Freezing-induced damage to proteins, through osmotic stress and ice recrystallization, during protein processing and long-term storage is a serious concern and may lead to loss of protein activity owing to denaturation. In this study, graft copolymers composed of a cryoprotective polymer (capable of preventing osmotic stress) and poly(vinyl alcohol) (PVA; known for its high ice recrystallization inhibition (IRI) property) were developed. The polymers had high IRI activity, albeit slightly lower than that of PVA alone, but substantially higher than that of succinylated ε-poly-l-lysine (PLLSA) alone. The graft polymers showed an efficiency higher than that of PVA or PLLSA alone in protecting proteins from multiple freeze-thaw cycles, as well as during prolonged freezing, indicating a synergy between PVA and PLLSA. The PLLSA-based graft polymer is a promising material for use in protein biopharmaceutics for the long-term storage of proteins under freezing conditions.

A rigid-and-flexible interphase was established by a starlike copolymer (Pc-PGMA/Pc) consisting of one tetraaminophthalocyanine (TAPc) core with four TAPc-difunctionalized poly(glycidyl methacrylate) (PGMA) arms through the surface modification of carbon fibers (CFs) and compared with various interphases constructed by TAPc and TAPc-connected PGMA (Pc-PGMA). The increase in the content of N-C═O showed that PGMA/Pc branches were successfully attached onto the CF-(Pc-PGMA/Pc) surface, exhibiting concavo-convex microstructures with the highest roughness. Through adhesive force spectroscopy by atomic force microscopy (AFM) with peak force quantitative nanomechanical mapping (PF-QNM) mode and visualization of the relative distribution of TAPc/PGMA via a Raman spectrometer, a rigid interphase with highly cross-linked TAPc and a flexible layer from PGMA arms as the soft segment were separately detected in CF-TAPc/EP and CF-(Pc-PGMA)/EP composites. The rigid-and-flexible interphase in the CF-(Pc-PGMA/Pc)/EP composite provided excellent stress-transfer capability by the rigid inner modulus intermediate layer and energy absorption efficiency from the flexible outer layer, which contributed to 64.6 and 61.8% increment of transverse fiber bundle test (TFBT) strength, and 33.8 and 40.6% enhancement in interfacial shear strength (IFSS) in comparison with those of CF-TAPc/EP and CF-(Pc-PGMA)/EP composites. Accordingly, schematic models of the interphase reinforcing mechanism were proposed. The interfacial failures in CF-TAPc/EP and CF-(Pc-PGMA)/EP composites were derived from the rigid interphase without effective relaxation of interfacial stress and soft interphase with excessive fiber-matrix interface slippage, respectively. The cohesive failure in the CF-(Pc-PGMA/Pc)/EP composite was attributed to the crack deflection through the balance of the modulus and deformability from the twin-stage gradient intermediate layer.

This contribution describes the design and synthesis of multifunctional micelles based on amphiphilic brush block copolymers (BBCPs) for imaging and selective drug delivery of natural anticancer compounds. Well-defined BBCPs were synthesized via one-pot multi-step sequential grafting-through ring-opening metathesis polymerization (ROMP) of norbornene-based macroinitiators. The norbornenes employed contain a poly(ethylene glycol) methyl ether chain, an alkyl bromide chain, and/or a near-infrared (NIR) fluorescent cyanine dye. After block copolymerization, post-polymerization transformations using bromide-azide substitution, followed by the strain-promoted azide-alkyne cycloaddition (SPAAC) allowed for the functionalization of the BBCPs with the piplartine (PPT) moiety, a natural product with well-documented cytotoxicity against cancer cell lines, via an ester linker between the drug and the polymer side chain. The amphiphilic BBCPs self-assembled in aqueous media into nano-sized spherical micelles with neutral surface charges, as confirmed by dynamic light scattering analysis and transmission electron microscopy. During self-assembly, paclitaxel (PTX) could be effectively encapsulated into the hydrophobic core to form stable PTX-loaded micelles with high loading capacities and encapsulation efficiencies. The NIR fluorescent dye-containing micelles exhibited remarkable photophysical properties, excellent colloidal stability under physiological conditions, and a pH-induced disassembly under slightly acidic conditions, allowing for the release of the drug in a controlled manner. The in vitro studies demonstrated that the micelles without the drug (blank micelles) are biocompatible at concentrations of up to 1 mg mL-1 and present a high cellular internalization capacity toward MCF-7 cancer cells. The drug-functionalized micelles showed in vitro cytotoxicity comparable to free PPT and PTX against MCF-7 and PC3 cancer cells, confirming efficient drug release into the tumor environment upon cellular internalization. Furthermore, the drug-functionalized micelles exhibited higher selectivity than the pristine drugs and preferential cellular uptake in human cancer cell lines (MCF-7 and PC3) when compared to the normal breast cell line (MCF10A). This study provides an efficient strategy for the development of versatile polymeric nanosystems for drug delivery and image-guided diagnostics. Notably, the easy functionalization of BBCP side chains via SPAAC opens up the possibility for the preparation of a library of multifunctional systems containing other drugs or functionalities, such as target groups for recognition.

The determination of the block sequence of triblock copolymers is difficult without information on the synthetic conditions, such as starting materials and reagents used or analysis using tandem ma...

The purpose of this work was to investigate the effects of polystyrene-based acidic copolymers and ionomers on the dispersion of asphaltenes in heavy oil. In the first part of the work, we studied ...

Polyhydroxyalkanoates are attractive alternatives to traditional plastics. However, although polyhydroxybutyrate (PHB) is produced in large quantities by Cupriavidus necator H16, its properties are far from ideal for the manufacture of plastic products. These properties may be improved through its coproduction with 3-hydroxypropionate (3HP), which leads to the formation of the copolymer poly(3-hydroxybutyrate-co-3-hydroxypropionate) (poly(3HB-co-3HP). To achieve this, a pathway was designed to enable C. necator H16 to convert β-alanine to 3HP. The initial low levels of incorporation of 3HP into the copolymer were overcome by the overproduction of the native propionyl-CoA transferase together with PHA synthase from Chromobacterium sp. USM2. Following optimization of 3HP incorporation into the copolymer, the molar fraction of 3HP could be controlled by cultivation in medium containing different concentrations of β-alanine. Between 0 and 80 mol % 3HP could be achieved. Further supplementation with 2 mM cysteine increased the maximum 3HP molar fraction to 89%. Additionally, the effect of deletions of the phaA and phaB1 genes of the phaCAB operon on 3HP molar fraction were investigated. A phaAB1 double knockout resulted in a copolymer containing 91 mol % 3HP without the need for cysteine supplementation.

Ethylene–vinyl alcohol copolymers (EVOHs) are important materials available in a variety of compositions and valued in countless applications. In spite of their great adaptability offered by the ad...

A class of heteroatom polymers through anionic chain growth copolymerization of epoxides and isothiocyanates has been successfully obtained under mild conditions via initiation by a simple salt of ...

Monodisperse polymers composed of a discrete number of repeating units have attracted considerable interest as model systems to investigate the behavior of polymers having chemical structures witho...

Although various drug nanocarriers have been developed for treating solid tumors, their clinical transformation is greatly limited by the difficulties in quantity production and unpredictable in vivo toxic effects. Herein, a facile "confined-gelation" strategy is developed to quantity-produce intelligent pluronic organosilica micelles (designated as IPOMs) with an undetectable critical micelle concentration (CMC), which features the self-assembly induced core confinement by block copolymers, the inner hydrolysis-condensation of silane to the oligomer skeleton, and oxidative cross-linking of disulfide skeleton to core gelation. The docetaxel-loaded IPOMs (DTX@IPOMs) with precise glutathione (GSH) responsiveness not only display an ultrahigh tolerated dose (360 mg/kg) in healthy Kunming mice model but also exhibit a remarkable tumor inhibition efficacy in both subcutaneous and orthotopic mice tumor models upon an extraordinarily large dosage (50 mg/kg). The present confined-gelation strategy provides a novel pathway to design and quantity-produce low-toxic and high-efficacy organic-inorganic hybrid nanodrugs in future clinical transformations.

This report presents the effect of insertion of four different π bridges, furan, thienothiophene, thiophene, and thiazole, into a random benzodithiophene (BDT)-fluorinated-thienothiophene (TT-F) based donor. Starting from a structure of synthesized donor (D)-acceptor (A) random copolymer with 3:1 ratio, we have designed four D-π-A systems with four different π bridges. Structural, optoelectronic, and charge transport/transfer properties of these donors and donor/NDI (NDI = poly[N,N'-bis(2-hexyldecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)) blends are investigated using DFT and TD-DFT methodologies. Our results show that the thiazole based TzP1 oligomer has the deepest HOMO value resulting in the highest open circuit voltage among all systems. The maximum absorption wavelengths of π-linked systems are red-shifted compared to the parent molecule. Rates of charge transfer and charge recombination are the highest and smallest in case of the thiazole/NDI blend system. In addition, hole mobilities in thiophene, thienothiophene, and thiazole based systems are larger than in the parent system. The results indicate that the thiazole unit among the four π bridge units is the most suitable for active layer construction.

Trimesic acid (TMA) and ethyelene diamine (ED) were reacted in various molar proportions to yield several branched/hyperbranched copolymers which formed polymersome-like structures, and they were used for encapsulation and release of a model drug, α-tocopherol succinate (TOS). The branched topology of the copolymers was established from spectroscopy, viscometry, and rheological measurements. Hydrodynamic size and transmission electron microscopy revealed the self-aggregated polymersome-like features of the copolymers with a dense core. Zeta potential studies unveiled pH-sensitive features of the aggregates. Both hydrodynamic size and viscosity were found to decrease with more branching, whereas the encapsulation efficiency displayed a drastic increase from 68 to 89.5% from the least branched (30%) to mostly branched grade (68%). The hydrophobic drug was primarily accommodated within the macromolecular voids inside the core and was released slowly following the diffusion mechanism. An indigenous model was established to explain the release kinetics from such a pH-sensitive and highly branched core-shell matrix which yielded a unique parameter called effective diffusivity or ED that took account of those parameters affecting the release rate. The copolymers were found to be biologically viable through a series of in vitro tests, thus inviting

We present a scaling theory describing the equilibrium properties of spherical micelles formed by a diblock copolymer with bottlebrush blocks in a selective solvent. The theory predicts a number of new thermodynamic regimes inherent for copolymers with relatively short main chains (long side chains) in the bottlebrush blocks. These regimes with a novel set of scaling exponents for the micelle properties are characterized by limiting extension of the main chains of the core or/and corona-forming blocks and do not exist for micelles of conventional linear block copolymers. The theoretical predictions are confronted to experiments.

Magnetic core–shell nanoparticle (NP)-polymer-based composite materials, in which the stimuli-responsive polymer acts as a suitable shell, become more advantageous as nanocarriers. Here, nanocompos...

A polymer-antibiotic conjugate with thermoresponsive properties near body temperature is presented. The backbone polymer is a copolymer of 2-n-propyl-2-oxazine (PropOzi) and methoxycarbonylethyl-2-oxazoline (C2MestOx) which is conjugated with the broad-spectrum antibiotic, cefazolin, via modification of the methyl ester group of C2MestOx. The resulting polymer-antibiotic conjugate has a cloud point temperature near body temperature, meaning that it can form a homogenous solution if cooled, but when injected into a skin-mimic at 37 °C, it forms a drug depot precipitate. Cleavage of the ester linker leads to quantitative release of the pristine cefazolin (with some antibiotic degradation observed) and redissolution of the polymer. When Escherichia coli were treated with polymer-antibiotic conjugate total clearance is observed within 12 h. The power of this approach is the potential for localized antibiotic delivery, for example, at a specific tissue site or into infected phagocytic cells.

Surface pressure versus mean molecular area isotherms of Langmuir films of a hybrid diblock copolymer of poly(ethylene glycol) (PEG) and poly(methacrylo polyhedral oligomeric silsesquioxane) P(MA-POSS) together with Brewster angle microscopy reveal details of the phase transitions. The formation of a periodic wrinkling pattern in collapsed films is observed by epifluorescence microscopy after applying several compression-expansion cycles above the surface pressure of ≈18 mN/m. The wrinkle formation is reversible upon compression and expansion of the Langmuir films. Two distinct orientations of POSS molecules are assumed in Langmuir films upon compression, vertically for chains close to the water surface and horizontally orientated upper layers with significant amounts of PEG in between them. Thus, the wrinkling forms mainly in the top stiffer MA-POSS blocks above a certain compressional stress. The wrinkles disappear during the Langmuir-Blodgett (LB) transfer. Nevertheless, atomic force microscopy and grazing incidence wide-angle X-ray scattering experiments reveal the formation of highly ordered POSS molecules in LB films.

The synthesis of ethylene/myrcene copolymers was performed using half-titanocene catalysts in the presence of a methylaluminoxane (MAO) cocatalyst. Cyclopentadienyl-phenoxide catalysts, Cp*TiCl2(O-...

High-performance piezoelectric polymers are promising for a broad range of practical applications, such as sensors, actuators, and energy generators in medical devices, wearable electronics, and so...

Porous carbon films, attributed to their superior thermal and chemical robustness, are attractive for a number of applications. In the context of molecular separation, a major focus has been on films where the effective pore diameter is lower than 1 nm, e.g., carbon molecular sieves. Only a handful of reports are available on carbon films hosting 2-3 nm size pore channels where gas transport mainly takes place by Knudsen diffusion in contrast to activated transport. Recently, we reported nanoporous carbon (NPC) films, by the pyrolysis of phase-separated blockcopolymer/turanose films, as a gas-permeable mechanical reinforcement for crack-free synthesis of single-layer graphene membranes. However, a dedicated study on the nanostructure and transport properties of the standalone NPC film has been missing. Herein, we show that the NPC film has a perforated lamellar (PL) nanostructure where molecular transport is limited by an interlamellar spacing of similar to 2 nm. The unique PL nanostructure of the NPC film originates from its precursor, i.e., a block-copolymer stabilized by hydrogen bonding with a carbohydrate additive, where the latter also acts as the main carbon-forming agent. This nanostructure is highly sensitive to the carbohydrate/block-copolymer ratio and gives way to a lacey structure below a ratio of 2:1. The transport of gases through the interlamellar spacing takes place predominantly in the Knudsen regime, determined by their molecular mass. Attributed to a thickness of 100 nm, the film yields extremely rapid gas transport with a H-2 permeance over two million gas permeation units (GPU) and H-2/CO2 selectivity over 4.5 in a temperature range of 25-300 degrees C. These properties make the NPC film a promising membrane support and a good choice for the mechanical reinforcement for high-permeance twodimensional membranes for gas separation.

We report results from Monte Carlo field-theoretic simulations (MC-FTS) of a compositionally asymmetric diblock copolymer melt (fA = 0.2) at an invariant degree of polymerization of N = 104 for bo...

Block copolymer (BCP) self-assembly produces chemically and topographically patterned surfaces which are used to guide the formation of Cu nanostructures by exploiting differences in the mobility of vapor-deposited species on each microdomain. Cu metal films a few nm thick were deposited on three different BCP surfaces self-assembled from poly(styrene-b-methyl methacrylate) (PS-b-PMMA) and polystyrene-b-poly(2-vinylpyridine) (PS-b-P2VP). For PS-b-PMMA, the effects of chemical heterogeneity dominate over the effects of the 2 nm peak-to-valley topography, and sputtered Cu preferentially wets the PS block. PS-b-P2VP has greater chemical and topographical contrast and shows a wider process window for selective deposition. Cu grown by evaporation has less surface mobility, and shadowing effects are believed to dominate pattern formation. The hierarchical self-assembly process of thin metal films on BCP surfaces provides a route to fabricating heterogeneous metallic nanostructures.