Characteristics and performance of electroactive paper actuator made with cellulose/polyurethane semi‐interpenetrating polymer networks

This article introduces a cellulose/polyurethane (PU) semi‐IPN‐based electroactive paper (EAPap) actuator. The fabrication process, bending actuation test, and its characteristics are explained. For the fabrication of cellulose/PU semi‐IPN EAPap actuator, cotton cellulose was dissolved into N,N‐dimethylacetamide (DMAc) and lithium chloride (LiCl) solvent system. PU prepolymer prepared by poly[di(ethylene glycol) adipate] and hexamethylene diisocyanate (HDI) was mixed with DMAc cellulose solution by stirring. The mixed solution was spin‐coated on a wafer and cured to form cellulose/PU semi‐IPN films using 1,1,1‐tris(hudroxymethyl)propane as the crosslinker. The characteristics of the cellulose/PU semi‐IPN film were investigated by FTIR, scanning electron microscopy (SEM), X‐ray diffraction pattern (XRD), and tensile test. The bending actuation performance of the actuator was evaluated in terms of free bending displacement with respect to the actuation frequencies, voltages, and humidity levels. It shows a good bending actuation at room humidity condition. The actuation principle of the actuator is also discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of electrolytes of Li salts,EMIMBF4, and mixed phases on electrochemical and physical properties of Nafion membrane

Electrolyte‐soaked Nafion is commonly used as an ionic polymer in soft actuators. Here, a multitechnique investigation was applied to correlate the electrochemical behavior of Nafion membranes with their microstructures and nanostructures as a function of electrolyte type. The influence of electrolytes of Li salts with different counteranions on the Nafion membranes was investigated in terms of hydration level, structure (using X‐ray diffraction and small angle X‐ray scattering), stress–strain characteristics, and electrochemical behavior (by cyclic voltammetery and electrochemical impedance spectroscopy). The effects of using ionic liquid (IL), as the electrolyte, addition of different supporting solvent and the addition of Li⁺ ions to water‐free IL‐soaked membranes on the structural and electrochemical properties of Nafion were examined. The nano‐ and microstructure of the Nafion changed considerably as a function of the identity of the electrolyte solution. The electrochemical behavior of the IL‐soaked samples was compared with that of the water‐soaked Li⁺‐exchanged Nafion. It was seen that the ionic conductivity of the Nafion membranes was reduced significantly when water was replaced by pure IL. Using the supporting solvents increased the conductivity of IL‐soaked Nafion membranes dramatically. The presence of a small amount of Li⁺ ions together with the IL ions caused a significant decrease in charge transfer resistance and increases in double layer capacitance and in ionic conductivity over that of the water‐free sample and also over water‐soaked Li⁺‐exchanged Nafion. These findings can be useful to improve the knowledge on Nafion's microstructure and also to improve the electromechanical behavior of Nafion‐based ionic polymer–metal composites actuators. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45239.     

Structural changes of regenerated cellulose dissolved in FeTNa,NaOH/thiourea,and NMMO systems

Regenerated cellulose was prepared from microcrystalline cellulose (MCC) via dissolution in three well‐known nonderivatizing systems: ferric chloride/sodium tartarate/sodium hydroxide (FeTNa), sodium hydroxide/thiourea (NaOH/thiourea), and N‐methylmorpholine‐N‐oxide (NMMO) systems. The effect of regeneration using the different systems on the supramolecular structure of the regenerated celluloses was studied using X‐ray diffraction and Fourier transform infrared (FTIR). The effect of regeneration on supermolecular structure, morphology, and thermal stability of regenerated celluloses were studied using scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The effect of regeneration systems used on the chemical reactivity of cellulose toward carboxymethylation, acetylation, and cyanoethylation reactions was briefly studied. The results showed dependence of all the aforementioned properties on the dissolution reagent used in spite of that all studied reagents cause the same change in cellulose crystalline structure (from cellulose I to cellulose II). The degree of polymerization, crystallinity, and thermal stability of the regenerated cellulose (RC) samples were in the following order: NaOH/thiourea RC > FeTNa RC > NMMO RC. SEM micrograph showed unique surface for the NMMO RC sample. The reactivity of the different regenerated cellulose samples toward carboxymethylation, cyanoethylation, and acetylation depended mainly on the reaction system and conditions used rather than on crystallinity of regenerated cellulose. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Anomalous rheological behavior of poly(1‐vinyl‐2‐pyrrolidone) and CuCl2 in solution and their interactions in solid composites

BACKGROUND: The aggregation structure of polymers in solution is an important aspect of their behavior. The interactions between metal ions and water‐soluble polymers have a significant influence on the conformation behavior of biological macromolecules, and on the ionic selectivity of cells, etc. RESULTS: The rheological behavior of poly(1‐vinyl‐2‐pyrrolidone) (PVP) and CuCl₂ dispersed in N,N‐dimethylformamide was investigated using rheological techniques. Concentrated solutions containing CuCl₂ exhibited a rheological behavior different from those containing other metal chlorides (LiCl, CaCl₂ and CoCl₂). This indicated that the variation in the aggregation state of the PVP chains with concentration of CuCl₂ was different from those of PVP solutions containing Li⁺, Ca²⁺ or Co²⁺ ions. CONCLUSION: The interactions between PVP and CuCl₂ inhibit the crystallization of CuCl₂ and induce the formation of microphase separation in the system. Copyright © 2009 Society of Chemical Industry     

Study on the synthesis,characterization, and sorption of some metal ions on gelatin‐ and acrylamide‐based hydrogels

Graft copolymers and networks of gelatin were synthesized with three acrylamides (acrylamide, 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid, and N‐iso‐propylacrylamide) by using a redox initiator system consisting of ammonium peroxysulfate–ferrous ammonium sulfate in either the absence or the presence of a crosslinker (N,N‐methylene bisacrylamide) at two temperatures. Characterization of synthesized polymers was studied by FTIR and thermal studies to investigate evidence of grafting or interpenetrating network formation and to investigate the effect of reaction conditions and crosslinker concentration on the properties of synthesized polymers. Detailed investigation into water‐uptake properties of these hydrogels was carried out as a function of time, temperature, and pH. The inherent properties of the monomer incorporated onto gelatin collectively act as determinant of the water‐absorption behavior of the hydrogels. Sorption of Fe⁺², Cr⁺⁶, and Cu⁺² ions from their aqueous solutions was also studied on select hydrogels, where it was observed that metal ions are sorbed by effective partitioning between hydrogels and solution phase and apart from the nature of metal ions, and structural aspects of hydrogels also determine the quantum of metal ion uptake. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3856–3871, 2003     

Preparation and properties of chemical cellulose from ascidian tunic and their regenerated cellulose fibers

Chemical cellulose (dissolving pulp) was prepared from ascidian tunic by modified paper‐pulp process (prehydrolysis with acidic aqueous solution of H₂SO₄, digestion with alkali aqueous solution of NaOH/Na₂S, bleaching with aqueous NaOCl solution, and washing with acetone/water). The α‐ cellulose content and the degree of polymerization (DPw) of the chemical cellulose was about 98 wt % and 918, respectively. The Japanese Industrial Standard (JIS) whiteness of the chemical cellulose was about 98%. From the X‐ray diffraction patterns and ¹³C‐NMR spectrum, it was found that the chemical cellulose obtained here has cellulose Iβ crystal structure. A new regenerated cellulose fiber was prepared from the chemical cellulose by dry–wet spinning using N‐methylmorpholine‐ N‐oxide (NMMO)/water (87/13 wt %) as solvent. The new regenerated cellulose fiber prepared in this study has a higher ratio of wet‐to‐dry strength (<0.97) than commercially regenerated cellulose fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1634–1643, 2002.     

Effects of Additives on the Activity and Enantioselectivity of Candida rugosa Lipase in a Biphasic Medium

The effects of Li⁺, Na⁺, K⁺, Mg²⁺ and Zn²⁺ ions on the activity and enantioselectivity of Candida rugosa lipase (CRL) were investigated in a biphasic medium composed of phosphate buffer solution (containing a metal ion within a 50–500 mM concentration range) and isooctane. The hydrolytic activities of CRL towards p‐nitrophenyl acetate were measured after incubation of the enzyme in the presence of metal ions for 24 h, and they were compared to that obtained after incubation in the absence of any metal ion. The CRL activity was stimulated by the chloride salts of Li⁺, K⁺ and Mg²⁺ for all concentrations considered and the highest enhancement was achieved by Li⁺ with a 1.24–1.75 fold increase observed. The effects of metal ions on the enantioselectivity of CRL were investigated by performing the hydrolysis of racemic Naproxen methyl ester in the same biphasic medium containing Li⁺, Na⁺, K⁺, Mg²⁺ and Zn²⁺ ions. The addition of metal ions increased the hydrolysis rate by ca. 1.31–1.45 fold relative to the control, whereas the enantiomeric excess of product increased slightly in the presence of the metal ions. The effect of Triton X‐100 on the activity and enantioselectivity of the CRL was also investigated by employing 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5 mM concentrations of it in phosphate buffer solution of the biphasic medium. High concentrations of Triton X‐100 stimulated the enzyme activity up to 1.66 fold after 24 h incubation. Triton X‐100 increased the hydrolysis rate almost independently of the concentration.     

Effect of the chain‐transfer‐agent content on the emulsion polymerization process and adhesive properties of poly(n‐butyl acrylate‐co‐acrylic acid) latexes

The effect of water on regenerated silkworm silk fibers has been studied and compared with that of water on natural silkworm silk fibers. Regenerated fibers are spun from an N‐methylmorpholine‐N‐oxide (NMMO) fibroin solution through a wet‐spinning process, leading to fibers with two distinct tensile behaviors, labeled as brittle and ductile, respectively. Regenerated fibers show a significant contraction when immersed in water. Contraction increases further after drying. In contrast, natural silkworm silk fibers show a negligible contraction when submerged in water. Regenerated fibers tested in water are considerably more compliant than samples tested in air, though their stiffness and tensile strength are significantly reduced. It has been shown that the tensile properties of brittle regenerated fibers can be modified by a wet‐stretching process, which consists of deforming the fiber while immersed in water. Regenerated wet‐stretched fibers always show a ductile behavior independent from their initial tensile behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dual action bactericides: Quaternary ammonium/N‐halamine‐functionalized cellulose fiber

Bi‐functional antibacterial material was prepared by co‐grafting N‐halamine and quaternary ammonium salt monomers from cellulose fiber. The grafted fiber was characterized by Fourier transform infrared spectra, and X‐ray photoelectron spectra. The N‐halamine derived from the precursor 4‐[(acryloxy)methyl]‐4‐ethyl‐2‐oxazolidinone via chlorination treatment and the oxidative chlorine (Cl⁺) leaching behavior were investigated. The antibacterial activities of singly (only QAs‐functionalized or only Cl⁺‐releasing) and dual (QAs‐functionalized and Cl⁺‐releasing) functional cellulose fibers were tested against Gram‐negative Escherichia coli and Gram‐positive Staphylococcus aureus. Compared to singly functionalized formulations, the bi‐functional cellulose fiber exhibited excellent and rapid bactericidal performance against both E. coli and S. aureus. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40070.     

Synthesis,characterization and actuation behavior of polyaniline‐coated electroactive paper actuators

This investigation deals with the synthesis, characterization and actuation behavior of conductive polyaniline‐coated electroactive paper actuators. The actuator is made by electrochemical deposition of conductive polyaniline on a cellulose paper. The aim of the investigation was to improve the bending displacement of electroactive paper actuators. The displacement outputs of the actuators show that a trilayer is better than a bilayer configuration. The nature of the dopant ion used in the electro‐generation affects the performance. A change in humidity plays a vital role in actuation performance of the actuators. Comparing the performance of electroactive paper actuators with and without a conductive polyaniline coating, the coating improves the displacement output threefold. Finally, the actuation principle mechanism is addressed. Copyright © 2007 Society of Chemical Industry     

Metal‐solvating and self‐association of amphiphilic polyamides containing poly(oxyethylene) blocks

An amphiphilic poly(ether amide) consisting of hydrophilic poly(oxyethylene) amide blocks was prepared from the copolymerization of sebacic acid and two poly(oxyalkylene) diamines including a poly(oxyethylene) diamine (POE‐amine at 2000 M_w) and a poly(oxypropylene) diamine (POP‐amine at 230 M_w). The copolymer was estimated to have an average molecular weight of 15,000 M_w (GPC) or approximately three hydrophilic POE segments per strain. The presence of POE segments rendered polymer hydrophilicity and complexing ability for Li⁺, K⁺, Ca⁺², Ni⁺², Pd⁺², and Cu⁺² salts. In particular, lithium perchlorate affected the copolymer to the greatest extent in enhancing electrostatic dissipation or reducing surface resistivity as low as 10^5.0 Ω/sq (cross‐sectional area) at 1/180 Li⁺/EO from 10^7.2 Ω/sq (without metal ion). In such a metal complexation, the copolymer showed a new POE segmental crystalline phase at a melting temperature between ?10.4 and ?14°C, accompanied with the metal‐free original phase of ?31°C. In static toluene/water, the metal ions had no effect on the copolymer surfactancy in lowering the interfacial tension, reaching 4.4 dyn/cm at a critical micelle concentration (cmc) of 0.01 wt %. When mixing toluene and water, the lithium or nickel ions were found to be detrimental to the emulsifying process. Without the metal ion, fine droplets at average sizes of 4.5–5.0 μm were observed in the copolymer/ toluene/water emulsification. These amphiphilic behaviors of the POE‐segmented polyamide with or without metal ions were explained by the competing noncovalent bonding interactions among POE/metal ion/water. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 612–621, 2002     

Electroactive Paper Actuator Made with Chitosan‐Cellulose Films: Effect of Acetic Acid

This paper introduces an electroactive paper (EAPap) prepared with cellulose and chitosan films. The fabrication process, performance test, and the effect of acetic acid dosage of the EAPap were investigated. For the fabrication of cellulose EAPap, cellulose fibers were dissolved into a solution using N,N‐dimethylacetamide and lithium chloride. The solution was cast and immersed in water to form a cellulose film, followed by casting chitosan/acetic acid and glycerol aqueous solutions on the cellulose film. A bending EAPap actuator was made by depositing thin gold electrodes on both sides of the cellulose film. The bending displacement of the EAPap actuators was evaluated with respect to voltage, frequency, humidity, and acetic acid dosage. An optimum mole ratio of the acetic acid and chitosan structure unit was found. Also, the effects of chitosan and acetic acid on the actuation behavior of the cellulose‐chitosan laminated films were investigated.

     

Pervaporation separation of dimethyl carbonate/methanol mixtures with regenerated perfluoro‐ion‐exchange membranes in chlor‐alkali industry

The waste perfluoro‐ion‐exchange membranes (PFIEMs) in chlor‐alkali industry were regenerated and used to the separation of dimethyl carbonate (DMC)/methanol (MeOH) mixtures by pervaporation process. The energy‐dispersive spectrum (EDS) demonstrates that the impurities on the surfaces of waste PFIEMs can be effectively cleared by the regeneration process. The degree of swelling, sorption, and pervaporation properties of the regenerated PFIEMs with different counter ions were investigated. The results indicate that the counter ions of PFIEMs conspicuously influence the degree of swelling, sorption, and pervaporation properties for DMC/MeOH mixtures. The degree of swelling and solubility selectivity both decreases with the alkali metal counter ions in the sequence: Li⁺ > Na⁺ > K⁺ > Cs⁺. The degree of swelling increases with MeOH concentration increasing in feed liquid. The pervaporation measurements illustrate that the permeation flux decreases and the separation factor increases with the rising in ion radius of counter ions. The increase of feed concentration (MeOH) and feed temperature is advantageous to improve permeation flux while at the cost of separation factor decreasing. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Use of novel hydrogels based on modified cellulosics and methacrylamide for separation of metal ions from water systems

Interpenetrating networks (IPNs) based on extracted cellulose and its derivatives such as hydroxypropyl cellulose (HPC), cyanoethylcellulose, hydroxyethylcellulose, hydrazinodeoxycellulose, cellulosephosphate with methacrylamide (MAAm), and N,N‐methylene bisacrylamide were synthesized at reaction conditions evaluated for optimum network yield as a function of irradiation dose, concentrations of monomer and crosslinker, and amount of water. These networks were used in sorption of Fe²⁺, Cu²⁺, and Cr⁶⁺ ions. The networks were further functionlized by means of partial hydrolysis with 0.5N NaOH and metal ion sorption studies were carried out. Appreciable amount of all the three ions was sorbed and partial functionalization of the hydrogels results in selectivity in ion sorption with enhanced affinity for Fe²⁺ ions and total rejection of Cr⁶⁺ ions. These results are of interest for the development of low‐cost technologies based on smart hydrogels. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 667–671, 2002     

ToF‐SIMS investigation of epoxy resin curing reaction at different resin to hardener ratios

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and principal components analysis (PCA) were used to analyze diglycidyl ether of bisphenol A (DGEBA) and diglycidyl ether of bisphenol F (DGEBF) epoxy resin blend cured with isophorone diamine (IPD) hardener at different resin to hardener ratios. The aim was to establish correlations between the hardener concentration and the nature and progress of the crosslinking reaction. Insights into the cured resin structure revealed using ToF‐SIMS are discussed. Three sets of significant secondary ions have been identified by PCA. Secondary ions such as C₁₄H₇O⁺, CHO⁺, CH₃O⁺, and C₂₁H₂₄O₄⁺ showed variance related to the completion of the curing reaction. Relative intensities of C_xH_yN_z⁺ ions in the cured resin samples are indicative of the un‐reacted and partially reacted hardener molecules, and are found to be proportional to the resin to hardener mixing ratio. The relative ion intensities of the aliphatic hydrocarbon ions are shown to relate to the cured resin crosslinking density. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface‐initiated atom transfer radical polymerization of regenerated cellulose membranes with thermo‐responsive properties

Using atom transfer radical polymerization (ATRP), thermo‐responsive regenerated cellulose membranes were synthesized. Regenerated cellulose membranes were firstly modified by reacting the hydroxyl groups on the surface with 2‐bromoisobutyryl bromide, followed by grafting with poly(N‐isopropylacrylamide). The membranes had obvious thermally modulated permeability properties. Analysis was carried out by means of X‐ray photoelectron spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The results showed that N‐isopropylacrylamide had been grafted successfully on the surface of the regenerated cellulose membranes. The thermally modulated permeability properties of the grafted membranes were studied using water flux measurements. It was found that the thermally modulated permeability properties of a cellulose surface can be tailored by the use of the ATRP method. Copyright © 2010 Society of Chemical Industry     

Synergistic interplay between D2EHPA and TBP towards the extraction of lithium using hollow fiber supported liquid membrane

Extraction of lithium (Li⁺) from synthetically prepared sea bittern using di-2-ethyl hexyl phosphoric acid (D2EHPA) and tri-n-butyl phosphate (TBP) as organic extractants has been studied. The equilibrium studies conducted show synergistic effect between D2EHPA and TBP. The equilibrium constant values for Li⁺, Na⁺ and K⁺ ions were found to be 95.4 × 10^?5 m³/kmol, 4.6 × 10^?5 m³/kmol and 3.69 × 10^?5 m³/kmol, respectively. Hollow fiber supported liquid membrane (SLM) experiments with low concentrations of Li⁺, Na⁺ and K⁺ ions in feed phase showed high flux for Li⁺ ions. However, at significantly high concentrations of Na⁺ and K⁺ in the feed phase, the flux of Li⁺ ions reduced. The model predictions were found to be in good agreement with the experimental data.     

Pervaporation separation of water–ethanol mixtures using metal‐ion‐exchanged poly(vinyl alcohol) (PVA)/sulfosuccinic acid (SSA) membranes

Poly(vinyl alcohol)/sulfosuccinic acid (PVA/SSA) membranes in the hydrogen form were converted to monovalent metal ion forms Li⁺, Na⁺, and K⁺. The effect of exchange with metal ions was investigated by measuring the swelling of water–ethanol (10/90) mixtures at 30 °C and by the pervaporative dehydration performance test for aqueous ethanol solutions with various ethanol concentrations at 30, 40, and 50 °C. In addition, electron spectroscopy for chemical analysis (ESCA) analysis was carried out to study the quantity of metal ions in membranes. From the ESCA analysis, the lithium ion quantity in the resulting membranes is greater than that of any other metal ions in question because of the easy diffusion of a smaller metal ion into the membrane matrix. The swelling ratio was in the following order: PVA/SSA‐Li⁺ > PVA/SSA‐Na⁺ > PVA/SSA‐K⁺ membranes. For pervaporation, the PVA/SSA‐Na⁺ membrane showed the lowest flux and highest separation factor for all aqueous ethanol solutions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1867–1873, 2002     

Interactions of Some Hofmeister Cations with Sodium Dodecyl Sulfate in Aqueous Solution

In this work, we have investigated the influence of some alkali metal ions on the Krafft temperature (T_K) and critical micelle concentration (CMC) of a classical ionic surfactant, sodium dodecyl sulfate (SDS), over a wide range of temperature. The alkali metal cations such as Li⁺, Na⁺, Cs⁺, and K⁺ are found to affect the solubility and hence the T_K of the surfactant. It was observed that kosmotropic Li⁺ lowers the T_K of the surfactant. Due to the common ion effect, the solubility of SDS decreases in the presence of Na⁺, resulting in an increase in the T_K. On the other hand, chaotropic K⁺ and Cs⁺, capable of forming contact ion pairs with the chaotropic dodecyl sulfate ion, lower the solubility and hence elevate the T_K. In terms of decreasing the T_K, the ions follow the trend: Li⁺ > Na⁺ > Cs⁺ > K⁺ except for 0.0025 M CsCl. The added cations screen the charge of the micelle surface and facilitate closer packing of the surfactant with a consequent decrease in the CMC. In terms of the effectiveness in lowering the CMC, the ions follow the order: Cs⁺ > K⁺ > Na⁺ > Li⁺. In the presence of added electrolytes, the γ_CMC values are found to be lower than the corresponding values in pure water. The thermodynamic parameters (Gibbs free energy, enthalpy, and entropy changes) of micellization were calculated to gain insights into the mechanism of the process.     

Neglected Aspects of Anthracenide (Anthracenidyl) Chemistry — Reactions with two N‐Benzoylaziridines

Reaction of anthracenide A ^·‐ with N‐benzoylaziridines 1a,b forms charged radicals 3a,b by single electron transfer and homolytic ring opening. Reactions follow that are known or expected as e.g. coupling with position 9 of A ^·‐ forming dihydroanthracene anions 9a,b that yield amidoethylated dihydroanthracenes 10a,b , or react with 1a,b giving finally 9,10‐bis‐amidoethylated dihydroanthracenes 11a,b . Results depend on experimental conditions and on the counter ions Na⁺ or Li⁺. Coupling is not regiospecific: contributions by positions 2 and 1 reach 29% or 4%, respectively, of total coupling with the primary radical 3a ; much higher contributions are possible with Li. Product 21s (probably 3,3′‐disubstituted tetrahydrobianthryl) may arise by hydrogen detachment from the first intermediate ( 29 ) of coupling with position 2 and dimerization of the formed 2‐substituted A ^·‐ ( 30 ). Coupling products may be fully aromatized or may be hydroxylated in one of the benzylic positions. With counter ion Li⁺ a non‐SET reaction of 1a with the dimer of A ^·‐ is indicated by the isolation of 9‐benzoyl‐dihydroanthracene 15 and by 19% yield of 16a (aromatized 10a ). Reaction of 3b with anthracene is indicated by 10,10′‐disubstituted tetrahydrobianthryl 37 .