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The legalization of hemp cultivation in the United States has caused the price of hemp-derived cannabinoids to decrease 10-fold within 2 years. Cannabidiol (CBD), one of many naturally occurring diols found in hemp, can be purified in high yield for low cost, making it an interesting candidate for polymer feedstock. In this study, two polyesters were synthesized from the condensation of either CBD or cannabigerol (CBG) with adipoyl chloride. Poly(CBD-Adipate) was cast into free-standing films and subjected to thermal, mechanical, and biological characterization. Poly(CBD-Adipate) films exhibited a lack of cytotoxicity toward adipose-derived stem cells while displaying an inherent antioxidant activity compared to poly(lactide) films. Additionally, this material was found to be semi-crystalline and able to be melt-processed into a plastic hemp leaf using a silicone baking mold.

Polymer dielectrics essentially revolutionized the electrical power system, pervasively used in nearly all the key electronic and electrical devices, due mainly to their suitably large bandgaps. However, insufficient attention has been paid to the bandgap in the design of new polymer dielectrics for high temperatures. In this paper, we present a unified principle for the design of flexible, high temperature polymer dielectrics. As exemplified by our recently discovered poly(oxa)norbornenes (POFNB), saturated bicyclics with varying carbonyl and ether groups in the bicyclic repeat units, connected by unconjugated alkenes and freely rotatable single bonds in conjunction with freely rotating fluorinated benzene ring side-groups, can impart flexibility yet retain thermal stability while providing large bandgaps to olefinic polymers. The results indicate that POFNB has stably low conduction current under concurrent high electric field and elevated temperatures beneficial from its large band gap of ∼5 eV and high glass transition temperature of 186 °C.

Flexible large bandgap dielectric materials exhibiting ultra-fast charging-discharging rates are key components for electrification under extremely high electric fields. A polyoxafluoronorbornene (m-POFNB) with fused five-membered rings separated by alkenes and flexible single bonds as the backbone, rather than conjugated aromatic structure typically for conventional high-temperature polymers, is designed to achieve simultaneously high thermal stability and large bandgap. In addition, an asymmetrically fluorinated aromatic pendant group extended from the fused bicyclic structure of the backbone imparts m-POFNB with enhanced dipolar relaxation and thus high dielectric constant without sacrificing the bandgap. m-POFNB thereby exhibits an unprecedentedly high discharged energy density of 7.44 J/cm(3) and high efficiency at 150 °C. This work points to a strategy to break the paradox of mutually exclusive constraints between bandgap, dielectric constant, and thermal stability in the design of all-organic polymer dielectrics for harsh condition electrifications.

Ultrafast infrared vibrational spectroscopy is widely used for the investigation of dynamics in systems from water to model membranes. Because the experimental observation window is limited to a few times the probe's vibrational lifetime, a frequent obstacle for the measurement of a broad time range is short molecular vibrational lifetimes (typically a few to tens of picoseconds). Five new long-lifetime aromatic selenocyanate vibrational probes have been synthesized and their vibrational properties characterized. These probes are compared to commercial phenyl selenocyanate. The vibrational lifetimes range between ∼400 and 500 ps in complex solvents, which are some of the longest room-temperature vibrational lifetimes reported to date. In contrast to vibrations that are long-lived in simple solvents such as CCl4, but become much shorter in complex solvents, the probes discussed here have ∼400 ps lifetimes in complex solvents and even longer in simple solvents. One of them has a remarkable lifetime of 1235 ps in CCl4. These probes have a range of molecular sizes and geometries that can make them useful for placement into different complex materials due to steric reasons, and some of them have functionalities that enable their synthetic incorporation into larger molecules, such as industrial polymers. We investigated the effect of a range of electron-donating and electron-withdrawing para-substituents on the vibrational properties of the CN stretch. The probes have a solvent-independent linear relationship to the Hammett substituent parameter when evaluated with respect to the CN vibrational frequency and the ipso 13C NMR chemical shift.

The dielectric constant (ϵ) is a critical parameter utilized in the design of polymeric dielectrics for energy storage capacitors, microelectronic devices, and high-voltage insulations. However, agile discovery of polymer dielectrics with desirable ϵ remains a challenge, especially for high-energy, high-temperature applications. To aid accelerated polymer dielectrics discovery, we have developed a machine-learning (ML)-based model to instantly and accurately predict the frequency-dependent ϵ of polymers with the frequency range spanning 15 orders of magnitude. Our model is trained using a dataset of 1210 experimentally measured ϵ values at different frequencies, an advanced polymer fingerprinting scheme and the Gaussian process regression algorithm. The developed ML model is utilized to predict the ϵ of synthesizable 11,000 candidate polymers across the frequency range 60–1015 Hz, with the correct inverse ϵ vs. frequency trend recovered throughout. Furthermore, using ϵ and another previously studied key design property (glass transition temperature, Tg) as screening criteria, we propose five representative polymers with desired ϵ and Tg for capacitors and microelectronic applications. This work demonstrates the use of surrogate ML models to successfully and rapidly discover polymers satisfying single or multiple property requirements for specific applications.

Advances in materials can be achieved once we understand their property well. In this study, a series of zinc and cadmium aliphatic polyesters with varying numbers of methylene spacer(s), 1 to 8, are synthesized and characterized to understand their features, which control their dielectric properties. The rational co-design of these materials is adopted by Density Functional Theory (DFT) computations of local structural features, and physical properties as dielectric constant and band gap energies. Synthesized polyesters of zinc and cadmium exhibit high band gap energies, > 5 eV, with the dielectric constant from ca. 4.69-3.61 and ca. 6.61-4.01, respectively; with metal volume fractions ca. 3–12% experimentally, which supports the DFT computations strongly to behave as a good dielectric material. These initial studies give insight into the potential advantages and expansion of the chemical design space for developing new dielectrics and provide valuable validation and feedback to enrich Material Genome Initiative.

In order to interface power sources with any electrical load, energy storage and conversion are important components. The ability to store electrical energy is essential in many applications. Dielectric materials with high electric energy density are essential components in modern power electronics such as pulsed power systems and switched mode power supplies. The current state-of-the-art film capacitor is biaxially oriented polypropylene that has a breakdown strength of >730 MV/m and low dielectric loss of

Flexible dielectrics operable under simultaneous electric and thermal extremes are critical to advanced electronics for ultrahigh densities and/or harsh conditions. However, conventional high-performance polymer dielectrics generally have conjugated aromatic backbones, leading to limited bandgaps and hence high conduction loss and poor energy densities, especially at elevated temperatures. A polyoxafluoronorbornene is reported, which has a key design feature in that it is a polyolefin consisting of repeating units of fairly rigid fused bicyclic structures and alkenes separated by freely rotating single bonds, endowing it with a large bandgap of ≈5 eV and flexibility, while being temperature-invariantly stable over -160 to 160 °C. At 150 °C, the polyoxafluoronorbornene exhibits an electrical conductivity two orders of magnitude lower than the best commercial high-temperature polymers, and features an unprecedented discharged energy density of 5.7 J cm-3 far outperforming the best reported flexible dielectrics. The design strategy uncovered in this work reveals a hitherto unexplored space for the design of scalable and efficient polymer dielectrics for electrical power and electronic systems under concurrent harsh electrical and thermal conditions.

Flexible films having high dielectric constants with low dielectric loss have promising application in the emerging area of high-energy-density materials. Here, for the first time, an organometallic, Sn-polyester-containing hybrid free-standing film in polyimide matrix is reported. Polyimide, pBTDA-HDA, is used with poly(dimethyltin glutarate) and poly(dimethyltin-3,3-dimethyglutarate) (pDMTDMG) for having a processable film with tunable dielectric properties. Hybrid film with 60% pDMTDMG and 40% PI (HB2) is found to have improved dielectric features over previously synthesized organic polyimide and organometallic Sn-polyester homopolymers. These novel organometallic-organic hybrid systems expanded a new area of dielectrics for next-generation electronics with superior overall electrical performance.

The use of the fluorinated alcohol, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as a processing solvent for orthogonal alignment of a DNA–surfactant complex is reported herein. 1-butanol (BuOH) was used as the control. At low frequencies, films of DNA–CTMA cast from HFIP exhibited a higher, more consistent dielectric constant and a lower dissipation factor compared to films cast from BuOH.

Conductive poly(3,4-ethylenedioxythiophene):sulfonated polyimide (PEDOT: SPI) nanoscale thin films were successfully developed by addition of anionic surfactant and poly(vinyl alcohol) (PVA) for potential application in electronic devices. In this work, sodium dodecyl sulfate (SDS) surfactant was introduced into PEDOT:SPI aqueous suspensions to improve the dispersion stability of the particles in water, leading to high transparency and low contact angle of PEDOT:SPI thin films. All of the conducting polymer thin films showed high transparency of more than 85% transmission. Conductivity enhancement and good film-formation properties of PEDOT:SPI were achieved by adding various amounts of PVA to each polymer aqueous suspension because of the resulting conformational changes. The highest conductivity of 0.134 S/cm was achieved at 0.08 wt.% PVA in PEDOT:SPI2/SDS/PVA film, increased by a factor of 3.5 compared with the original material. In addition, PVA also improved the thermal stability of the conductive films, as verified by thermogravimetric analysis (TGA). The interactions between conducting polymers, PVA, and SDS surfactant affecting nano-thin film properties were revealed and investigated. Moreover, the interactions between SDS and SPI were proven to be different from those between SDS and poly(styrenesulfonate) (PSS) in conventional PEDOT:PSS solutions.

In this work, the integration of the useful concepts of polymer blending and doping agent to simultaneously improve various properties of poly(3,4-ethylene dioxy thiophene) poly(styrene sulfonate) (PEDOT:PSS) nano-thin films was shown. According to the polymer-blending concept, insulating poly(vinyl alcohol) (PVA) has a good deal of potential to be utilized as a filler to improve the critical properties of the PEDOT:PSS matrix, especially conductivity, wettability, and thermal and mechanical properties. At the appropriate amount of PVA, 0.08 wt%, it acts as a binder to improve the connection network between PEDOT:PSS chains, leading to a maximum conductivity of 1.18 S/cm, and also providing a good contact angle of 8.8°. The transmission of the films decreased with increasing PVA content; however, all specimens still showed excellent transmittance values of more than 80 %. The thermal stability and the resistance to abrasion of the nano-thin conductive films were improved by strong covalent bonds between PVA and PSS, which were verified by TGA and a scratching test, respectively. In addition, the relationship of PEDOT:PSS properties versus various amounts of insulating PVA for practical usage for specific electronic fields were shown. Use of the doping agent quinoxaline was aimed to particularly enhance the conductivity of PEDOT:PSS. The highest conductivity (2.75 S/cm) was achieved when 0.5 wt% quinoxaline was added into 0.08 wt% PVA/PEDOT:PSS while the other properties were not significantly altered.

The polymer PEDOT + mediates a Nazarov-likecyclization of dienones, in an heterogeneous system and in hydrocarbon solvents.The polymer-mediated reactions show clear differences in productformation when compared to the same reaction with tosic acid, orwhen compared to reports in the literature. Comparable or improvedyields are observed, as well as the ability to give a -Nazarovproduct in cases where treatment with acid fails to give cyclization,or leads to an undesirable rearrangement. In addition, the abilityto recycle the polymer makes this a potentially useful protocolfor an important organic chemical reaction.

Hybrid free standing films of tin-polyester with polyimide are prepared by blending process which exhibit tunable dielectric constants. The maximum achievable dielectric constant for hybrid systems have 60% load of tin-polyester and their dielectric values raging from ca. 5.5-6.2, close to that of the tin homopolymers. These values show improvement over polyimide p(BTDA-HDA) having a dielectric constant of ca. 3.5 with minimum frequency dispersion maintaining low dissipation factor. The hybrid systems of 60% p(DMTDMG) with 40% polyimide stand out by their morphological and electrical properties showing a breakdown strength of 464 MV/m, with a maximum energy density of 5.9 J/cm3, slightly higher than the commercial standard BOPP with improved operational temperature ca. 140 oC. Figure 1

Detection of multiple cancer biomarker proteins in human serum and tissue at point-of-care is a viable approach for early cancer detection, but presents a major challenge to bioanalytical device development. This article reviews recent approaches developed in our laboratories combining nanoparticle decorated electrodes and multilabeled secondary antibody labeled particles to achieve high sensitivity for the detection of cancer biomarker proteins. Two nanomaterial-based sensor platforms were used: (a) upright single wall carbon nanotube forests and (b) layers of densely packed 5 nm gold nanoparticles. Both platforms feature pendant carboxylate groups for easy attachment of enzymes or antibodies by amidization. In quality performance tests, the biocatalytic responses for determination of hydrogen peroxide of AuNP layers with attached horseradish peroxidase (HRP) on electrodes gave somewhat better detection limit and sensitivity than single wall carbon nanotube (SWNT) forest platforms with HRP attached. Evaluation of these sensors as platforms for sandwich immunoassays for cancer biomarker prostate specific antigen (PSA) in serum showed that both approaches gave accurate results for human serum samples from cancer patients. The best detection limit (0.5 pg mL − 1 ) and sensitivity were obtained by combining the AuNP immunosensors with binding of 1 μm diameter magnetic particles decorated with secondary antibodies and 7500 HRP labels.

A general procedure to calculate the maximum contrast from an electrochromic material is presented. The obtained results were tested by spectroelectrochemical studies of two different conducting polymer films: poly-3, 4-ethylenedioxy-thiophene (PEDOT) and poly-3,6-bis(2-(3,4-ethylenedioxy)thienyl)-N-methylcarbazole (PBEDOT-NMCz). The presented methodology constitutes a useful tool for the optimization of electrochromic devices. Keywords: Conducting polymer, Electrochromism, Maximum contrast, Electrochromic device

Electrocardiography (ECG) is an essential technique for analyzing the proper electrical functioning of heart. Traditionally Ag/AgCl electrodes have been used for monitoring ECG signal from the body. However, Ag/AgCl is known to cause skin irritation on prolonged usage and measurements cannot be done in wet conditions. Conjugated polymers, with their mixed ionic and electronic conduction, offer an alternative to Ag/AgCl. This work provides an easy to fabricate ECG sensor from commercially available PEDOT:PSS using screen printing technique onto a commercially sold T-shirt. ECG signals from screen printed PEDOT:PSS electrodes were recorded during motion at a heart rate of up to 180 bpm. Variation of ECG signal amplitude vs impedance of electrodes was studied. In addition, PEDOT:PSS was also demonstrated to work as an organic wire for copper lead replacement used in recording ECG signals. Reusability of the shirt was demonstrated by recording ECG signal under active exercise even after 3 wash cycles and subsequent drying. Figure 1

To date, trial and error strategies guided by intuition have dominated the identification of materials suitable for a specific application. We are entering a data-rich, modelling-driven era where such Edisonian approaches are gradually being replaced by rational strategies, which couple predictions from advanced computational screening with targeted experimental synthesis and validation. Here, consistent with this emerging paradigm, we propose a strategy of hierarchical modelling with successive downselection stages to accelerate the identification of polymer dielectrics that have the potential to surpass ‘standard’ materials for a given application. Successful synthesis and testing of some of the most promising identified polymers and the measured attractive dielectric properties (which are in quantitative agreement with predictions) strongly supports the proposed approach to material selection.

Electrochemical detection combined with nanostructured sensor surfaces offers potentially low-cost, high-throughput solutions for detection of clinically significant proteins. Inkjet printing offers an inexpensive non-contact fabrication method for microelectronics that is easily adapted for incorporating into protein immunosensor devices. Herein we report the first direct fabrication of inkjet-printed gold nanoparticle arrays, and apply them to electrochemical detection of the cancer biomarker interleukin-6 (IL-6) in serum. The gold nanoparticle ink was printed on a flexible, heat resistant polyimide Kapton substrate and subsequently sintered to create eight-electrode arrays costing0.2 euro per array. The inkjet-printed working electrodes had reproducible surface areas with RSD3%. Capture antibodies for IL-6 were linked onto the eight-electrode array, and used in sandwich immunoassays. A biotinylated secondary antibody with 16-18 horseradish peroxidase labels was used, and detection was achieved by hydroquinone-mediated amperometry. The arrays provided a clinically relevant detection limit of 20 pg mL(-1) in calf serum, sensitivity of 11.4 nA pg(-1) cm(-2), and a linear dynamic range of 20-400 pg mL(-1).

Poly(3,4-propylenedioxythiophene)s as a Single Platform for Full Color Realization Tanmoy Dey, Michael A. Invernale, Yujie Ding, Zeki Buyukmumcu, and Gregory A. Sotzing* The Polymer Program, Institute of Materials Science, Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269, United States Department of Chemistry, Faculty of Science, Erciyes University, Kayseri 38039, Turkey

Processability remains a fundamental issue for the implementation of conducting polymer technology. A simple synthetic route towards processable precursors to conducting polymers (main chain and side chain) was developed using commercially available materials. These soluble precursor systems were converted to conjugated polymers electrochemically in aqueous media, offering a cheaper and greener method of processing. Oxidative conversion in aqueous and organic media each produced equivalent electrochromics. The precursor method enhances the yield of the electrochromic polymer obtained over that of electrodeposition, and it relies on a less corruptible electrolyte bath. However, electrochemical conversion of the precursor polymers often relies on organic salts and solvents. The ability to achieve oxidative conversion in brine offers a less costly and a more environmentally friendly processing step. It is also beneficial for biological applications. The electrochromics obtained herein were evaluated for electronic, spectral, and morphological properties.

We have achieved reversible tunability of local surface plasmon resonance in conjugated polymer functionalized gold nanoparticles. This property was facilitated by the preparation of 3,4-ethylenedioxythiophene (EDOT) containing polynorbornene brushes on gold nanoparticles via surface-initiated ring-opening metathesis polymerization. Reversible tuning of the surface plasmon band was achieved by electrochemically switching the EDOT polymer between its reduced and oxidized states.

Solid-state electrochromic windows from 3,4-propylenedioxythiophene (ProDOT) derivatives using dual polymer electrochromic architecture were fabricated and their electro-optical characteristics were recorded. DibenzylProDOT (DiBz-ProDOT) and biphenylmethyloxymethyl ProDOT (BPMOM-ProDOT) were used as cathodically coloring polymers, whereas bis(2-(3,4-ethylenedioxy)thienyl)-N-methyl carbazole (BEDOT-NMCz) was used as their complementary anodically coloring polymer. Straightforward assembly of the devices was designed by means of using a UV photo-curable gel. These devices exhibited response speeds of approximately 1 s with photopic contrasts as high as 52% for the complete device, and were found to exhibit good stability under open circuit conditions. Convenience of reporting photopic values to characterize electrochromic devices compared to reporting contrasts at a single wavelength is remarked., © Elsevier

Correction for ‘Orthogonal alignment of DNA using hexafluoroisopropanol as solvent for film castings’ by Donna Marie D. Mamangun et al., RSC Adv., 2014, 4, 39798–39801.

Poly(3,4-ethylenedioxy)thiophene-poly(styrene sulfonate) (PEDOT-PSS) was used as the conductive component in a matrix of chemically different insulating polymers to form an array of vapor detectors. Such composites produced larger relative differential resistance responses when exposed to polar analytes than did the corresponding carbon black filled polymer composite detectors. However, the PEDOT-PSS composites produced smaller responses than carbon black composites when exposed to nonpolar analytes. The resolving power of a PEDOT-PSS detector array was compared to that of a carbon black composite array for a broadly construed set of organic vapors. The PEDOT-PSS array exhibited better, on average, discrimination between pairs of polar analytes and polar/nonpolar analytes than did the carbon black composite array. The carbon black composite array out-performed the PEDOT-PSS array in discriminating between nonpolar compounds. The addition of PEDOT-PSS composites to an array of carbon black composite detectors therefore can produce improved overall discrimination in a vapor sensor system when used in tasks to differentiate between of a broad set of analyte vapors.

Chemically-sensitive resistors have been developed that allow rapid detection of an important class of compounds, biogenic amines, at levels of 1−10 parts per trillion in ambient air. The materials are composites of a conducting organic polymer, the emeraldine salt of polyaniline, with particles of another conducting phase, carbon black. The resistance response of an EM−DBSA(1:0.5)/CB (80:20) detector exposed to water (a), acetone (b), methanol (c), ethyl acetate (d), and butanol (e) is approximately a factor of a million smaller than that to butylamine (f).

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The dual polymer configuration is commonly used when constructing electrochromic devices (ECDs) due to the expected electrochemical stability and enhanced optical properties. In this configuration, two different polymers are used which are optically complementary. Herein we report the construction and characterization of dual-type ECDs using poly(3, 4-ethylenedioxythiophene) (PEDOT) and poly[3, 6-bis(2-(3, 4-ethylenedioxy)thienyl)-N-methylcarbazole] (PBEDOT-NMCz) as the two complementary electrochromic polymers for the device. A variety of gel electrolyte solutions were prepared and evaluated for these devices. The use of ionic liquids within these gels imparted interesting properties, including long lifetimes, and thermal stability of devices. Switching speeds for the various devices, as well as optical contrasts, were also obtained for the gel electrolytes containing different amounts of ionic liquid as plasticizer.