Efficient Synthesis of 3,4-Ethylenedioxythiophene (EDOT)-Based Functional π-Conjugated Molecules through Direct C–H Bond Arylations

A variety of 3,4-ethylenedioxythiophene (EDOT)-based π-conjugated molecules were efficiently synthesized in good yields through Pd-catalyzed direct C–H bond arylations, wherein a detailed synthetic investigation, including the screening of various kinds of palladium catalysts, ligands, additives, and solvents, was carried out. In addition, the spectroscopic and electrochemical properties of these EDOT-containing molecules were also investigated

A Proton-Doped Calix[4]arene-Based Conducting Polymer

Segmented conducting polymers based upon a calix[4]arene scaffold are reported. The cone conformation creates a zigzag orientation of the polymer segments. Their acid-dependent conductivities are similar to the strong pH conductivity dependence of polyaniline which is said to be acid dopable. On the other hand, they have a segmented structure that imposes greater localization of the carriers. The conductivity of such a system can be considered to result from rapid self-exchange between discrete units. Hence, electron exchange between radical cations and p-diquinone salts produces the high conductivity of these polymers

Hybrid “Kill and Release” Antibacterial Cellulose Papers Obtained via Surface-Initiated Atom Transfer Radical Polymerization

Infectious diseases triggered by bacteria cause a severe risk to human health. To counter this issue, surfaces coated with antibacterial materials have been widely used in daily life to kill these bacteria. The substrates enabled with a hybrid kill and release strategy can be employed not only to kill the bacteria but also to wash them using external stimuli (temperature, pH, etc.). Utilizing this concept, we develop thermoresponsive antibacterial-cellulose papers to exhibit hybrid kill and release properties. Thermoresponsive copolymers [p­(NIPAAm-co-AEMA)] are grafted on cellulose papers using a surface-initiated atom transfer radical polymerization approach for bacterial debris release. Later for antibacterial properties, silver nanoparticles (AgNPs) are immobilized on thermoresponsive copolymer-grafted cellulose papers using electrostatic interactions. We confirm the thermoresponsive copolymer grafting and AgNP coating by attenuated total reflection Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. Thermoresponsiveness and reusability of the modified cellulose papers are confirmed through water contact angle measurements. The interaction potency between AgNPs and modified cellulose is validated by inductively coupled plasma atomic emission spectroscopy analysis. Gram-negative bacteria Escherichia coli (E. coli DH5-α) is used to demonstrate antibacterial hybrid kill and release performance. Agar-diffusion testing demonstrates the antibacterial nature of the modified cellulose papers. The fluorescence micrograph reveals that modified cellulose papers can effectively release almost all the dead bacterial debris from their surfaces after thermal stimulus wash. The modified cellulose paper surfaces are expected to have wide applications in the field of exploring more antibacterial and smart surfaces

DataSheet1_Biguanide- and Oligo(Ethylene Glycol)-Functionalized Poly(3,4-Ethylenedioxythiophene): Electroactive, Antimicrobial, and Antifouling Surface Coatings.pdf

The challenge of infectious diseases remains a critical concern to the global public health. Recently, it is common to encounter touch-screen electronic devices everywhere to access services. The surface of such devices may easily get contaminated by an infected person, which leads to transmission of infectious diseases between individuals. Moreover, the challenge is complicated by surgical infections from implantable biomedical devices. Such problems can be minimized by the use of long-term active antimicrobial surface coatings. We present herein the preparation of novel electroactive antimicrobial surface coatings through the covalent attachment of the biguanide moiety onto 3,4-ethylenedioxythiophene (EDOT). The biguanide-functionalized EDOT (EDOT-BG) was thus electropolymerized on different substrates to give the corresponding poly(EDOT-BG) polymer. The poly(EDOT-BG) polymer showed an excellent bactericidal efficiency (∼92% bacterial death) and excellent biocompatibility with mammalian cells. Furthermore, the antimicrobial EDOT-BG was electro-copolymerized with antifouling tetra ethylene glycol functionalized-EDOT (EDOT-EG4) to give a multifunctional poly(EDOT-EG4-co-EDOT-BG) copolymer. The poly(EDOT-EG4-co-EDOT-BG) copolymer showed excellent resistance to protein adsorption and mammalian/bacterial cell binding without losing its bactericidal efficiency. These novel materials can be applied to domestic and bioelectronic devices to minimize infectious diseases.</p

Dynamic Nuclear Polarization with Biradicals

Dynamic nuclear polarization (DNP) experiments in rotating solids have been performed for the first time using biradicals rather than monomeric paramagnetic centers as polarizing agents. Specifically, two TEMPO radicals were tethered with a poly(ethylene glycol) chain of variable length where the number of glycol units was 2, 3, or 4. NMR experiments show that the signal observed in DNP experiments is approximately inversely proportional to the length of the chain. Thus, the shorter chain with larger electron dipolar couplings yields larger enhancements. The size of the enhancement is a factor of 4 larger than obtained with the identical concentration of monomeric nitroxide radicals achieving a value of ∼175 for the n = 2 chain

<i>S,S</i>-Dimethyl Dithiocarbonate: A Convenient Reagent for the Synthesis of Symmetrical and Unsymmetrical Ureas

S,S-Dimethyl Dithiocarbonate:  A Convenient Reagent for the Synthesis of Symmetrical and Unsymmetrical Urea

Conductivity Shift of Polyethylenedioxythiophenes in Aqueous Solutions from Side-Chain Charge Perturbation

Conductivity Shift of Polyethylenedioxythiophenes in Aqueous Solutions from Side-Chain Charge Perturbatio

Oligoethylene-Glycol-Functionalized Polyoxythiophenes for Cell Engineering: Syntheses, Characterizations, and Cell Compatibilities

A series of methyl- or benzyl-capped oligoethylene glycol functionalized 2,5-dibromo-3-oxythiophenes are synthesized and successfully polymerized by either Grignard metathesis (GRIM) polymerization or reductive coupling polymerization to yield the corresponding polymers in reasonable yields and molecular weights with narrow molecular weight distribution. These synthesized polyoxythiophenes exhibit high electroactivity and stability in aqueous solution when a potential is applied. Polyoxythiophenes from different polymerization approaches display different colors after purification and spectroelectrochemical studies confirm that the difference of color is from the difference of doping state. Little cytotoxicity is observed for the polymers by in vitro cell compatibility assay. NIH3T3 fibroblast cells are well attached and proliferate on spin-coated films. These results indicate that oligoethylene-glycol-functionalized polyoxythiophenes are promising candidates as conducting biomatierals for biomedical and bioengineering applications

Nano-On-Nano: Responsive Nanosubstrate-Mediated Liposome Delivery with High Cellular Uptake Efficiency

Efficiently delivering liposomal content to cells in a relatively uniform dose and patterned fashion, especially bypassing the degradative endocytosis pathway, is an important technology in cell culture and potentially to tissue engineering that still remains challenging. We developed a “nano-on-nano” platform technology that consists of the following three material features: (1) high density silicon nanopillars to create a pseudo-3-dimensional nanoenvironment for cell culturing, (2) thermoresponsive polymer grafted onto silicon nanopillars to form a responsive nanosubstrate, and (3) immobilized liposomes using a biotin-streptavidin-biotin conjugation. The working principle is that the liposomes are detached for cellular uptake upon thermal stimulation and high local liposome concentration between the cells and substrates drives the cellular uptake with nonendocytic pathways. Cryo-EM images confirms that liposomes are attached to form liposome-warped nanopillars. Upon thermal stimulation, an 8 times higher increase in the liposomal fluorescence intensity is observed compared to the conventional solution-phase liposome delivery, indicating that high local concentration drives liposome uptake with greater efficiency. Moreover, preliminary mechanistic studies reveal that these liposomes are taken up by nonendocytic pathways. The ability of our nano-on-nano delivery system that achieves efficient dose-uniform cellular delivery can open a unique era in cell and tissue engineering by controlling cell behaviors with the delivery of bioactive ingredient-loaded liposomes

Polydioxythiophene Nanodots, Nonowires, Nano-Networks, and Tubular Structures: The Effect of Functional Groups and Temperature in Template-Free Electropolymerization

Various nanostructures, including nanofibers, nanodots, nanonetwork, and nano- to microsize tubes of functionalized poly(3,4-ethylenedioxythiophene) (EDOT) and poly(3,4-propylenedioxythiophene) (ProDOT) are created by using a template-free electropolymerization method on indium–tin–oxide substrates. By investigating conducting polymer nanostructures containing various functional groups prepared at different polymerization temperature, we conclude a synergistic effect of functional groups and temperature on the formation of polymer nanostructures when a template-free electropolymerization method is applied. For unfunctionalized EDOT and ProDOT, or EDOT containing alkyl functional groups, nanofibers and nanoporous structures are usually found. Interesting, when polar functional groups are attached, conducting polymers tend to form nanodots at room temperature while grow tubular structures at low temperature. The relationship between surface properties and their nanostructures is evaluated by contact angle measurements. The capacity and electrochemical impedance spectroscopy measurements were conducted to understand the electrical properties of using these materials as electrodes. The results provide the relationship between the functional groups, nanostructures, and electrical properties. We also discuss the potential restriction of using this method to create nanostructures. The copolymerization of different functionalized EDOTs may cause irregular and unexpected nanostructures, which indicates the complex interaction between different functionalized monomers during the electropolymerization