In situ metallization of patterned polymer brushes created by molecular transfer print and fill.

A chemical pattern consisting of end-grafted polystyrene brushes (20 nm lines on a 40 nm pitch) on the native oxide of silicon wafers was defined by molecular transfer printing from assembled block co-polymer films. End-grafted hydroxyl-terminated poly(2-vinyl pyridine) brushes were selectively deposited in the interspatial regions. The poly(2-vinyl pyridine) regions selectively sequester acidic HAuCl4 from solution and form arrays of small Au nanoparticles upon exposure to oxygen plasma within the confines of the macromolecular brush layer. This print and fill process to pattern polymer brushes is a generalizable strategy to create functional chemical surface patterns.

Metal nanodot memory by self-assembled block copolymer lift-off.

As information technology demands for larger capability in data storage continue, ultrahigh bit density memory devices have been extensively investigated. To produce an ultrahigh bit density memory device, multilevel cell operations that require several states in one cell have been proposed as one solution, which can also alleviate the scaling issues in the current state-of-the-art complementary metal oxide semiconductor technology. Here, we report the first demonstration of metal nanodot memory using a self-assembled block copolymer lift-off. This metal nanodot memory with simple low temperature processes produced an ultrawide memory window of 15 V at the +/-18 V voltage sweep. Such a large window can be adopted for multilevel cell operations. Scanning electron microscopy and transmission electron microscopy studies showed a periodic metal nanodot array with uniform distribution defined by the block copolymer pattern. Consequently, this metal nanodot memory has high potential to reduce the variability issues that metal nanocrystal memories previously had and multilevel cells with ultrawide memory windows can be fabricated with high reliability and manufacturability.

Preparation of poly(ethylene glycol) protected nanoparticles with variable bioconjugate ligand density.

Maleimide-functional poly(ethylene glycol)-b-poly(epsilon-caprolactone) nanoparticles (NPs) were prepared via the Flash NanoPrecipitation technique. Subsequent reaction with a model ligand, bovine serum albumin (BSA), was conducted using thiol-maleimide conjugation. Reaction of up to 22% of NP surface maleimide-PEG tethers was obtained, with the percent conversion being essentially independent of the ratio of maleimide-PEG to methyl-PEG over the range 30-100%, respectively. At the highest surface coverage, BSA is calculated to essentially cover the NP surface area. Reaction parameters (reaction order and docking constant) describing the extent of ligand conjugation were determined. The reaction order is applicable to the conjugation of ligands presenting free thiol functionalities, while the value of the docking constant is ligand-dependent and accounts for physical and dynamic properties of the ligand-PEG interaction. Jointly, the particle formation process, using block copolymer-directed kinetically controlled assembly and surface functionalization represent a versatile new platform for the preparation of bioconjugated NPs with accurate control of ligand density and minimal processing steps.

Epidemiology Characteristics of Human Coxsackievirus A16 and Enterovirus 71 Circulating in Linyi, China, from 2009 to 2017.

In China, a rapid expansion of hand, foot, and mouth disease (HFMD) outbreaks has occurred since 2004, and HFMD has become an important issue in China. There are more than 20 types of enterovirus causing HFMD, of which coxsackievirus A16 (CA16) and enterovirus 71 (EV71) are the most common. This study aimed to analyze the epidemiological characteristics of HFMD caused by EV71 and CA16 in Linyi, Shandong province, China, from 2009 to 2017. The stool specimens and throat samples of 5,324 patients with HFMD were obtained for nucleic acid detection of enterovirus. A total of 4,040 HFMD cases were caused by viral pathogens. Of these, 1,706 cases were positive for EV71 and 1,266 were positive for CA16. These 2 virus strains appeared alternately in Linyi city. The incidence of EV71-positive and CA16-positive cases was highest in children aged 0-5 years, with male patients being predominant. This outbreak of HMFD caused by EV71 and CA16 mainly occurred between April and July and appeared alternately between the years 2011 and 2017. These results demonstrated that the epidemiological analysis of EV71 and CA16 can provide a scientific basis for the prevention and treatment of the disease.

Self-assembly and chiroptical property of poly(N-acryloyl-L-amino acid) grafted celluloses synthesized by RAFT polymerization.

Three amphiphilic poly(N-acryloyl-L-amino acid) grafted celluloses were prepared by RAFT polymerization of N-acryloyl-L-amino acid, where amino acid is alanine, proline or glutamic acid, onto cellulose backbones. The chemical structure and solution properties of the brush copolymers were characterized with FTIR, NMR and wide angle X-ray diffraction (WAXD). The thermal stability of the brush copolymers was estimated by thermal gravimetric analysis (TGA). Circular dichroism (CD) and specific rotation measurements confirmed that these grafted celluloses had characteristic chiroptical properties. The amphiphilic brush copolymers self-assembled into micelles in the aqueous solution as confirmed by transmission electron microscopy (TEM) and dynamic light scattering (DLS) analyses. The micellar aggregates showed a tunable pH-responsive property and disaggregated to form unimolecular micelles at higher pH in diluted solutions. The brush copolymers have potential applications in controlled drug release and high-performance liquid chromatography, and so forth.

Directed assembly of non-equilibrium ABA triblock copolymer morphologies on nanopatterned substrates.

The majority of past work on directed assembly of block copolymers on chemically nanopatterned surfaces (or chemical patterns) has focused on AB diblock copolymers, and the resulting morphologies have generally corresponded to equilibrium states. Here we report a study on directed assembly of ABA triblock copolymers. Directed assembly of thin films of symmetric poly(methyl methacrylate-b-styrene-b-methyl methacrylate) (PMMA-b-PS-b-PMMA) triblock copolymers is shown to be capable of achieving a high degree of perfection, registration, and accuracy on striped patterns having periods, L(s), commensurate with the bulk period of the copolymer, L(o). When L(s) is incommensurate with L(o), the triblock copolymer domains can reach dimensions up to 55% larger or 13% smaller than L(o). The range over which triblock copolymers tolerate departures from a commensurate L(s) is significantly larger than that accessible with the corresponding diblock copolymer material on analogous directed assembly systems. The assembly kinetics of the triblock copolymer is approximately 3 orders of magnitude slower than observed in the diblock system. Theoretically informed simulations are used to interpret our experimental observations; a thermodynamic analysis reveals that triblocks can form highly ordered, non-equilibrium metastable structures that do not arise in the diblock.

Molecular transfer printing using block copolymers.

Soft lithographic techniques augment or enhance the capabilities of traditional patterning processes and expand the diversity of materials that can be patterned. Realization of robust parallel techniques for creating chemical patterns at the nanoscale has been challenging. Here we present a method for creating and replicating chemical patterns that uses functionalized homopolymer inks that are preferentially segregated into the nanodomains of phase-separated diblock copolymer films. The inks are transferred by reaction to substrates that are brought into contact with block copolymer films, creating chemical patterns on the substrate that mirror the domain structure present at the film surface with high fidelity and resolution. In addition to printing from self-assembled domain structures, we can also direct the assembly of the block copolymer films from which transfer occurs using lithographically defined masters so as to replicate and transfer patterns of inks with controlled and well-defined geometries. The transferred patterns may be at higher resolution than the lithographically defined master, and the process can be repeated to create multiple copies of identical replicas. Transfer of one ink from one block of the copolymer is also possible, and filling the interspatial regions of the pattern with a second ink provides a pathway toward creating patterns with diverse chemical functionalities.

Formation of block copolymer-protected nanoparticles via reactive impingement mixing.

Reactive impingement mixing was employed to produce polymer-protected nanoparticles. Amphiphilic block copolymer was formed in situ by reactive coupling of hydrophobic and hydrophilic blocks. Simultaneously, a hydrophobic compound and the copolymer coprecipitated to form nanoparticles in the range of 100 nm. Specifically, beta-carotene was stabilized by the amphiphilic diblock copolymer, formed from the reaction of an amino-terminated hydrophilic block, poly(ethylene glycol) (PEG-NH2), with an acid chloride-terminated hydrophobic block, either poly(epsilon-caprolactone) (PCL-COCl) or polystyrene (PS-COCl). Spherical particles were observed by scanning and cryogenic transmission electron microscopy. Process conditions, including feed concentration of beta-carotene and feed concentrations of polymeric stabilizers, had little or no effect on average particle sizes over the range studied. Further, for Reynolds numbers greater than 500 the feed flow rates also had no effect. The effect of glass transition temperature (Tg) of the hydrophobic polymer on morphology and particle formation mechanism is discussed.