Cyclodextrin-Functionalized Polypyrrole Particles for the Extraction of Aromatics from Water.

We describe the preparation of oil-in-water (o/w) colloidal particles with a polypyrrole (pPy) shell in which cyclodextrin has been incorporated at the oil-water interface via either physical adsorption or reaction with the pPy shell. The utility of these particles was assessed by the extraction of organic dyes from water. In all cases, we found that cyclodextrin incorporation significantly improved dye uptake, giving up to 78 ± 11% dye extraction in the case of a 100 ppm solution of 4-nitroaniline with a covalently incorporated cyclodextrin. We demonstrated the ability of our colloidal particles to extract nicotine-derived nitrosamine ketone (NNK), a potent carcinogen, from aqueous solution. By treating the solution containing 100 ppm NNK with our particles over 24 and 48 h, we found that NNK removal reached 65 ± 2 and 83 ± 1%, respectively. The uptake could be improved by re-treating a solution with additional freshly prepared particles, to achieve 95 ± 1% NNK extraction with a covalently incorporated cyclodextrin.

Complex Liquid Crystal Emulsions for Biosensing.

Herein we describe a highly responsive optical biosensor based on dynamic complex liquid crystal (LC) emulsions. These emulsions are simple to prepare and consist of immiscible chiral nematic liquid crystals (N*) and fluorocarbon oils. In this work, we exploit the N* selective reflection to build a new sensing paradigm. Our detection strategy is based on changes in the LC/water interfacial activity of boronic acid polymeric surfactants caused by reversible interactions with IgG antibodies at the LC interface. Such biomolecular recognition events can vary the pitch length of the N* organization due to the presence of binaphthyl units in the polymeric structure, which are known to be powerful chiral dopants. We demonstrate that these interface-triggered reflection changes can be used as an effective optical read-out for the detection of the foodborne pathogen Salmonella.

Excess Polymer in Single-Walled Carbon Nanotube Thin-Film Transistors: Its Removal Prior to Fabrication Is Unnecessary.

Ultrapure semiconducting single-walled carbon nanotube (sc-SWNT) dispersions produced through conjugated polymer sorting are ideal candidates for the fabrication of solution-processed organic electronic devices on a commercial scale. Protocols for sorting and dispersing ultrapure sc-SWNTs with conjugated polymers for thin-film transistor (TFT) applications have been well refined. Conventional wisdom dictates that removal of excess unbound polymer through filtration or centrifugation is necessary to produce high-performance TFTs. However, this is time-consuming, wasteful, and resource-intensive. In this report, we challenge this paradigm and demonstrate that excess unbound polymer during semiconductor film fabrication is not necessarily detrimental to device performance. Over 1200 TFT devices were fabricated from 30 unique polymer-sorted SWNT dispersions, prepared using two different alternating copolymers. Detailed Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) studies of the random-network semiconductor films demonstrated that a simple solvent rinse during TFT fabrication was sufficient to remove unbound polymer from the sc-SWNT films, thus eliminating laborious polymer removal before TFT fabrication. Furthermore, below a threshold polymer concentration, the presence of excess polymer during fabrication did not significantly impede TFT performance. Preeminent performance was achieved for devices prepared from native polymer-sorted SWNT dispersions containing the "original" amount of excess unbound polymer (immediately following enrichment). Lastly, we developed an open-source Machine Learning algorithm to quantitatively analyze AFM images of SWNT films for surface coverage, number of tubes, and tube alignment.

Trace Detection of Hydrogen Peroxide via Dynamic Double Emulsions.

Hydrogen peroxide is a dynamic signaling molecule in biological systems. We report herein a versatile double emulsion sensor that can detect femtomolar quantities of aqueous hydrogen peroxide. The mechanism responsible for this sensitivity is a peroxide induced change in double emulsion structure, which results in a modified directional emission from dyes dissolved in the high index organic phase. The morphology (structure) of the double emulsion is controlled via interfacial tensions and a methyltrioxorhenium catalyzed sulfide oxidation results in an enhancement of the surfactant effectiveness. The incipient polar sulfoxide induced decrease of the interfacial tension at the organic-water (O-W) interface results in an increased interfacial area between the organic phase and water and a diminished emission perpendicular to the supporting substrate. The modularity of our sensory system is demonstrated through cascade catalysis between methyltrioxorhenium and oxidase enzymes, with the latter producing hydrogen peroxide as a byproduct to enable for the selective and sensitive detection of molecular and ionic enzymatic substrates.

A Survey of Strain-Promoted Azide-Alkyne Cycloaddition in Polymer Chemistry.

Highly efficient reactions that enable the assembly of molecules into complex structures have driven extensive progress in synthetic chemistry. In particular, reactions that occur under mild conditions and in benign solvents, while producing no by-products and rapidly reach completion are attracting significant attention. Amongst these, the strain-promoted azide-alkyne cycloaddition, involving various cyclooctyne derivatives reacting with azide-bearing molecules, has gained extensive popularity in organic synthesis and bioorthogonal chemistry. This reaction has also recently gained momentum in polymer chemistry, where it has been used to decorate, link, crosslink, and even prepare polymer chains. This survey highlights key achievements in the use of this reaction to produce a variety of polymeric constructs for disparate applications.

Trace Ethylene Sensing via Wacker Oxidation.

Ethylene is a dynamic plant hormone, and its temporal monitoring can be used to glean insight into plant health and status. However, the real-time distributed detection of ethylene at trace levels under ambient conditions remains a challenge. We report a single-walled carbon nanotube-based chemiresistor catalyst combination that can detect ppb levels of ethylene in air. Cycling between Pd(II) and Pd(0) via Wacker oxidation with a nitrite cocatalyst imparts response discrimination driven by the chemoselectivity of the chemical transformation. Sensitivity is controlled by a combination of the chemical reaction efficiency and the n-doping strength of the Pd(0) species generated in situ. The covalent functionalization of the carbon nanotube sidewall with pyridyl ligands drastically improves the device sensitivity via enhanced n-doping. The utility of this ethylene sensor is demonstrated in the monitoring of senescence in red carnations and purple lisianthus flowers.

Pillar[5]arene-Decorated Single-Walled Carbon Nanotubes.

Control of single-walled carbon nanotube dispersion properties is of substantial interest to the scientific community. In this work, we sought to investigate the effect of a macrocycle, pillar[5]arene, on the dispersion properties of a polymer-nanotube complex. Pillar[5]arenes are a class of electron-rich macrocyclic hosts capable of forming inclusion complexes with electron-poor guests, such as alkyl nitriles. A hydroxyl-functionalized pillar[5]arene derivative was coupled to the alkyl bromide side chains of a polyfluorene, which was then used to coat the surface of single-walled carbon nanotubes. Noncovalent functionalization of carbon nanotubes with the macrocycle-containing conjugated polymer significantly enhanced nanotube solubility, resulting in dark and concentrated nanotube dispersions (600 µg mL-1), as evidenced by UV-vis-NIR spectroscopy and thermogravimetric analysis. Differentiation of semiconducting and metallic single-walled carbon nanotube species was analyzed by a combination of UV-vis-NIR, Raman, and fluorescence spectroscopy. Raman spectroscopy confirmed that the concentrated nanotube dispersion produced by the macrocycle-containing polymer was due to well-exfoliated nanotubes, rather than bundle formation. The polymer-nanotube dispersion was investigated using 1H NMR spectroscopy, and it was found that host-guest chemistry between pillar[5]arene and 1,6-dicyanohexane occurred in the presence of the polymer-nanotube complex. Utilizing the host-guest capability of pillar[5]arene, the polymer-nanotube complex was incorporated into a supramolecular organogel.

Enrichment of Metallic Carbon Nanotubes Using a Two-Polymer Extraction Method.

The large-scale enrichment of metallic carbon nanotubes is a challenging goal that has proven elusive. Selective dispersion of carbon nanotubes by specifically designed conjugated polymers is effective for isolating semiconducting species, but a comparable system does not exist for isolating metallic species. Here, we report a two-polymer system where semiconducting species are extracted from the raw HiPCO or plasma-torch nanotube starting material using an electron-rich poly(fluorene-co-carbazole) derivative, followed by isolation of the metallic species remaining in the residue using an electron-poor methylated poly(fluorene-co-pyridine) polymer. Characterization of the electronic nature of extracted samples was carried out via a combination of absorption, Raman, and fluorescence spectroscopy, as well as electrical conductivity measurements. Using this methodology, the metallic species in the sample were enriched 2-fold in comparison to the raw starting material. These results indicate that the use of electron-poor polymers is an effective strategy for the enrichment of metallic species.

Recent developments in the selective dispersion of single-walled carbon nanotubes using conjugated polymers.

A significant barrier that impedes the commercialization of single-walled carbon nanotube-related applications is that all known synthetic methods produce a complicated mixture of semiconducting and metallic species. For device applications, pure semiconducting or pure metallic samples are desirable. Thus far, the purification methods that have been identified are capable of separating individual carbon nanotube species on a microgram scale, but purification on a large scale has remained elusive. The use of conjugated polymers to selectively disperse specific nanotube species is a promising approach to resolve the scalability issue, but a comprehensive understanding of the selectivity mechanism has not yet been achieved. Here, several of the trends reported in the literature are outlined to further the rational design of conjugated polymers for nanotube sorting. Numerous variables influence dispersion selectivity, including polymer structure and molecular weight, nanotube type used, sonication temperature, amount of polymer relative to nanotube, and solvent. We have organized these seemingly disparate parameters into two simple categories: conjugated polymer structure, and dispersion preparation conditions. Most importantly, we consider the mechanistic arguments that have been proposed, and provide additional insights based on the observations in the literature.

Influence of Polymer Electronics on Selective Dispersion of Single-Walled Carbon Nanotubes.

The separation and isolation of semiconducting and metallic single-walled carbon nanotubes (SWNTs) on a large scale remains a barrier to many commercial applications. Selective extraction of semiconducting SWNTs by wrapping and dispersion with conjugated polymers has been demonstrated to be effective, but the structural parameters of conjugated polymers that dictate selectivity are poorly understood. Here, we report nanotube dispersions with a poly(fluorene-co-pyridine) copolymer and its cationic methylated derivative, and show that electron-deficient conjugated π-systems bias the dispersion selectivity toward metallic SWNTs. Differentiation of semiconducting and metallic SWNT populations was carried out by a combination of UV/Vis-NIR absorption spectroscopy, Raman spectroscopy, fluorescence spectroscopy, and electrical conductivity measurements. These results provide new insight into the rational design of conjugated polymers for the selective dispersion of metallic SWNTs.