Electrochemical determination of the procyanidins in peanut skin using a carbon nanotube electrode.

We demonstrated the electrochemical detection of procyanidins in peanut skin, which is often a waste product of the food industry, using a carbon nanotube electrode. Procyanidins, the main ingredients of peanut skin, are oligomers of catechin or epicatechin; therefore, they have various forms such as dimers, trimers, and a different number of linkages between monomers. Quantification using traditional high-performance liquid chromatography-mass spectroscopy (HPLC-MS) is tedious, because many peaks can be traced. The use of CNT electrodes for procyanidin sensing is promising, because CNT's properties, such as high conductivity, catalytic ability, and special geometry (high ratio of surface area to volume), enable common and specific profiles of the cyclic voltammograms (CVs) of procyanidins. Furthermore, the intensity of the anodic peaks (+ 0.32 V) due to the oxidation of catechol groups is proportional to the concentration of procyanidin (linear rang: 2.8-88 mg L-1, sensitivity: 1.4 mA mg-1 L cm-2), and does not depend on the type of procyanidin. The amount of procyanidins in the peanut skin estimated by CV was similar to that estimated by HPLC-MS. This study may contribute to accelerating the utilization of peanut skin for animal food, drugs, and supplementation.

Electrochemical Analysis of Coffee Extractions at Different Roasting Levels Using a Carbon Nanotube Electrode.

This study reports on the electrochemical analysis of coffee extractions at different roasting levels by using a carbon nanotube (CNT) electrode. The roasting levels, ranging from 1 (low) to 6 (high), were determined according to the roasting time after fixing the roasting temperature. Level 1 roasting resulted in light roasted beans and level 6 in dark roasted ones. Based on the roasting level, the concentration of chlorogenic acids, including 3-caffeoylquinic (3CQ), 4-caffeoylquinic (4CQ), and 5-caffeoylquinic (5CQ) acid, can be determined. Cyclic voltammetry (CV) experiments revealed that the reduction current at +0.27 V was proportional to the concentration of chlorogenic acids. High-performance liquid chromatography (HPLC) revealed an inverse correlation between the roasting level and chlorogenic acid amount. The total amounts of chlorogenic acids in coffee extractions determined by HPLC were in agreement with those obtained by CV using the CNT electrode at roasting levels 1 - 5. At level 6, the amount of chlorogenic acids determined by the current peak was larger than that detected by HPLC. As a result, the chlorogenic acid amount was overestimated in the CV experiment at +0.27 V, indicating that electrochemically active materials were generated at level 6. The CV profile showed that the reduction peak at +0.10 V increased with an increase in roasting level. Thus, the peak intensity at +0.10 V can be used to evaluate the roasting level even if the concentration or dilution conditions are provided.

Electrochemical Detection of Curcumin in Food with a Carbon Nanotube-Carboxymethylcellulose Electrode.

Herein, an electrochemical method is presented for the detection of curcumin in food using a carbon nanotube (CNT)-carboxymethylcellulose (CMC) electrode. The CNT-CMC electrode exhibited ideal characteristics for curcumin detection, namely, a high response current and adequate peak separation toward curcumin oxidation. Cyclic voltammetry revealed two oxidation peaks. In the first scan, only the irreversible peak (Peak I) was observed at a higher potential. In the second scan, the reversible redox peak pairs (Peaks II and II') appeared at lower potentials, and the potential of Peak I was decreased. Peak I corresponded to oxidation of the hydroxyl groups of the benzene ring to the catechol group via a phenoxy radical, while Peaks II and II' indicated the redox loop system of the generated catechol group. The current at Peak II was used to quantify the concentration of curcumin in the linear range of 1 - 48 µM and detection limit of 0.084 µM. The concentrations of curcumin determined by the CNT-CMC electrode in real food samples were consistent with those determined by high-performance liquid chromatography.

Electrochemical determination of uric acid in urine and serum with uricase/carbon nanotube /carboxymethylcellulose electrode.

The detection of uric acid in blood and urine is clinically important in terms of suitable diagnosis and self-healthcare. An amperometric thin film biosensor composed of carbon nanotube and uricase enzyme is presented. The CNT is successfully dispersed in aqueous solution with carboxymethylcellulose surfactant. This enables thin film formation by a simple drop-casting layer-by-layer process. The uricase/carboxymethylcellulose dispersed carbon nanotube/gold thin film biosensor shows the best sensing performance compared to that with sodium cholate surfactant in terms of higher current and lower detection potential. The presented procedure shows good performance with neither electron transfer mediator nor complicated process. Cyclic voltammetry exhibited a sensitivity of 233 µA mM-1 cm-2 at +0.35 V, a linear range of 0.02-2.7 mM, and a detection limit of 2.8 µM. We quantify and graph uric acid data in actual physiological samples (serum and urine) for the first time and detection values showed good agreement with those obtained by a conventional analytical method (enzymatic colorimetry kit).

Erratum: Yoshimi, Y., et al. Size of Heparin-Imprinted Nanoparticles Reflects the Matched Interactions with the Target Molecule. Sensors 2019, 19, 2415.

The authors wish to make the following erratum to this paper [...].

Electrochemical determination with a long-length carbon nanotube electrode of quercetin glucosides in onion, apple peel, and tartary buckwheat.

Since the intake of quercetin glucosides has healthy benefits, the analysis of quercetin glucosides in food is useful. The electrochemical determination of individual quercetin glucosides (quercetin-3-glucoside (Q3G), quercetin-4'-glucoside (Q4'G), and quercetin-3,4'-diglucoside (Q34'G)) in food is carried out. For the detection of quercetin glucosides, a long-length carbon nanotube electrode offers attractive properties such as well-defined current peaks, high sensitivity, and high reproducibility. Cyclic voltammetry (CV) demonstrates distinct and specific peak currents: the oxidation peaks at +0.37, +0.45, and +0.78 V are assigned to the catechol group in the B-ring of Q3G, the 3-hydroxy group in the C-ring of Q4'G, and the resorcinol group in the A-ring of both Q4'G and Q34'G, respectively. Currents, which are determined by CV, of individual quercetin glucosides at the peak potential are proportional to the concentrations of onion, apple peel, and tartary buckwheat, which show good agreement with those obtained by high-performance liquid chromatography.

Size of Heparin-Imprinted Nanoparticles Reflects the Matched Interactions with the Target Molecule.

It has been shown that the faradic current at an electrode grafted with molecularly imprinted polymer (MIP) is sensitive to the specific target molecule used as the template. This phenomenon is applicable to sensors with very high selectivity, but the sensing mechanism is still a black box. We investigated the size sensitivity of nanoparticles of molecularly imprinted polymers (MIP-NPs) to a specific interaction for determination of the mechanism of the gate effect and its feasibility for new applications. Nanoparticles of poly(methacryloxy ethyl trimethylammonium chloride-co-acrylamide-co-methylenebisacrylamide) imprinted with heparin immobilized on glass beads were synthesized. The diameter of the MIP-NPs of heparin was increased by the presence of the heparin template but was insensitive to chondroitin sulfate C (CSC), the analogue of heparin. The high selectivity of the MIP-NPs was consistent with the selectivity of electrodes grafted with a heparin-imprinted polymer in our previous studies. The quartz crystal microbalance probes immobilizing heparin or CSC were sensitive to MIP-NPs, which indicates that the binding ability of MIP-NP does not discriminate between the template and other glycosaminoglycans. These results indicate that the size of the MIP-NP is sensitive to the matched binding with the template through the imprinted cavity.

Polyphenol Analysis in Black Tea with a Carbon Nanotube Electrode.

An electrochemical analysis of polyphenols (theaflavin (TF1), theaflavin-3-gallate (TF2A), theaflavin-3'-gallate (TF2B), theaflavin-3,3'-digallate (TF3), and epigallocatechingallate (EGCG)) in a black tea infusion is demonstrated. The characterization of each polyphenol in a solution containing only a single type of polyphenol for a redox reaction at the CNT electrode with cyclic voltammetry (CV) was conducted. The oxidation peak at around +0.30 V for TF1 is assigned to catechol group in a benzotropolone ring. The oxidation peak at around +0.35 V for TF2A, TF2B, and TF3 is assigned to both of the catechol groups in the benzotropolone ring and the pyrogallol group in the gallate ring. The oxidation peak at around +0.35 V for EGCG is assigned to a pyrogallol group in the gallate ring. Current changes of those individual polyphenols at the peak potential are proportional to their concentrations (linear range 0.28 - 94 µM; detection limit 0.11 µM). The CV curve for real black tea, which is mainly composed of a mixture of the mentioned five compounds, is produced by the sum of those. The current change of the mixture solution of polyphenols is also proportional to the mass concentration of the total polyphenols and the sensitivity defined as the slope of current vs. concentration plot is independent of the ratio of the individual polyphenols. This indicates that the peak current at around +0.35 V can quantify the total amount of polyphenols in a black tea. Additionally, the shape of the CV curve can roughly estimate the ratio of [catechins]/[theaflavins]. The values for real samples determined from CVs show good agreement with that obtained by high-performance liquid chromatography.

Separationless and Adsorptionless Quantification of Individual Catechins in Green Tea with a Carbon Nanotube-Carboxymethylcellulose Electrode.

We demonstrate the electrochemical quantification of individual catechins (epicatechin, EC; epigallocatechin, EGC; epicatechingallate, ECG; and epigallocatechingallate, EGCG) in a green tea infusion without a separation process nor any adsorption complication. In the detection of catechins, long-length carbon nanotube (CNT)-carboxymethylcellulose (CMC) thin-film electrodes have attractive properties, such as well-defined current peaks, high reproducibility from sample to sample, high repeatability, and low background current. Cyclic voltammograms (CVs) for real green tea, which is mainly composed of a mixture of the four catechins, are produced by the sum of those catechins. A set of three specific peaks in the CVs of the real green tea samples, as catechin-mixture solutions, was used for quantification of the individual catechins. The CVs of the real samples are similar to the CVs of intentionally prepared mixture solutions with the catechin-component ratios determined by high-performance liquid chromatography (HPLC). The values for the real samples determined from the CVs show good agreement with those obtained by HPLC. The novelty of the work is the demonstration of the usefulness of the CNT-CMC electrode and the separationless quantification of individual catechins in green tea for the first time.

Comparison of Direct and Mediated Electron Transfer in Electrodes with Novel Fungal Flavin Adenine Dinucleotide Glucose Dehydrogenase.

Direct and mediated electron transfer (DET and MET) in enzyme electrodes with a novel flavin adenine dinucleotide-dependent glucose dehydrogenase (FAD-GDH) from fungi are compared for the first time. DET is achieved by placing a single-walled carbon nanotube (CNT) between GDH and a flat gold electrode where the CNT is close to FAD within the distance for DET. MET is induced by using a free electron transfer mediator, potassium hexacyanoferrate, and shuttles electrons from FAD to the gold electrode. Cyclic voltammetry shows that the onset potential for glucose response current in DET is smaller than in MET, and that the distinct redox current peak pairs in MET are observed whereas no peaks are found in DET. The chronoamperometry with respect to a glucose biosensor shows that (i) the response in DET is more rapid than in MET; (ii) the current at more than +0.45V in DET is larger than the current at the current-peak potential in MET; (iii) a DET electrode covers the glucose concentration range for clinical requirements and is not susceptible to interfering agents at +0.45 V; and (iv) a DET electrode with the novel fungal FAD-GDH does not affect sensing accuracy in the presence of up to 5 mM xylose, while it often shows a similar response level to glucose with other conventionally used fungus-derived FAD-GDHs. It is concluded that our DET system overcomes the disadvantage of MET.

Heparin molecularly imprinted polymer thin flm on gold electrode by plasma-induced graft polymerization for label-free biosensor.

Heparin, a highly sulfated glycosaminoglycan, is an important biomaterial having biological and therapeutic functionalities such as anticoagulation, regeneration, and protein stabilization. This study addresses a label-free quartz crystal microbalance (QCM) biosensor for heparin detection based on a macromolecularly imprinted polymer (MIP) as an artificial recognition element. We demonstrate the novel strategy for MIP in the form of thin film on a gold (Au) electrode with the plasma-induced graft polymerization (PIP) technique. The procedure of PIP is as follows: (i) Hexamethyldisiloxane plasma-polymerized thin film (PPF) as a pre-coating scaffold of active species for PIP (post-polymerization) is deposited on an Au electrode. (ii) The PPF/Au electrode is soaked in an water solution containing heparin (template), (2-(methacryloxy)-ethyl)trimethylammonium chloride acrylamide (functional monomer), acrylamide, and N,N-methylenebisacrylamide (crosslinker). Double bonds of monomer and crosslinker attacked by residually active species in pre-coating PPF cause radical chain reaction. Consequently, a growing polymer network of 20 nm thickness of PIP-MIP thin film is formed and grafted on the PPF/Au surface. (iii) The PIP-MIP/PPF/Au is washed by sodium chloride solution so as to remove the template. Non-imprinted polymer (NIP) is carried out like the same procedure without a template. The AFM, XPS, and QCM measurements show that the PIP process facilitates macromolecularly surface imprinting of template heparin where the template is easily removed and is rapidly rebound to PIP-MIP without a diffusional barrier. The heparin-PIP-MIP specifically binds to heparin compared with heparin analog chondroitin sulfate C (selective factor: 4.0) and a detectable range of heparin in the presence of CS (0.1 wt%) was 0.001-0.1 wt%. The PIP-NIP does not show selectivity between them. The evaluated binding kinetics are association (ka = 350 ±â€¯100 M-1 s-1), dissociation (kd = (5.0 ±â€¯2.0) × 10-4 s-1), and binding (KD = 1.3 ±â€¯0.6 µM) constants, demonstrating that the PIP-MIP as a synthetic antibody can be applied to analytical chemistry.

Thermophilic Talaromyces emersonii Flavin Adenine Dinucleotide-Dependent Glucose Dehydrogenase Bioanode for Biosensor and Biofuel Cell Applications.

Flavin adenine dinucleotide (FAD)-dependent glucose dehydrogenase (GDH) was identified and cloned from thermophilic filamentous fungi Talaromyces emersonii using the homology cloning method. A direct electron transfer bioanode composed of T. emersonii FAD-GDH and a single-walled carbon nanotube was produced. Enzymes from thermophilic microorganisms generally have low activity at ambient temperature; however, the T. emersonii FAD-GDH bioanode exhibits a large anodic current due to the enzymatic reaction (1 mA cm-2) at ambient temperature. Furthermore, the T. emersonii FAD-GDH bioanode worked at 70 °C for 12 h. This is the first report of a bioanode with a glucose-catalyzing enzyme from a thermophilic microorganism that has potential for biosensor and biofuel cell applications. In addition, we demonstrate how the glycoforms of T. emersonii FAD-GDHs expressed by various hosts influence the electrochemical properties of the bioanode.

Simultaneous Electrochemical Determination of Nicotinamide Adenine Dinucleotide and Ascorbic Acid at Carbon Nanotube Electrode.

Simultaneous electrochemical determination of nicotinamide adenine dinucleotide (NADH) and ascorbic acid (AA) at a carbon nanotube electrode is presented. The discrimination of NADH and AA is conducted with the difference of peak potential by differential pulse voltammetry. Two well-distinguished anodic peaks, +0.56 and +0.26 V, due to NADH and AA are observed. The characteristics of those peaks were independent from each other. The attained characteristics for simultaneous determination of NADH and AA are (i) NADH measurement at the concentration range of 0.030 - 2.0 mM in the presence of 1.2 mM AA, and (ii) AA measurement at the concentration range of 0.030 - 2.0 mM in the presence of 2.0 mM NADH.

Electronically type-sorted carbon nanotube-based electrochemical biosensors with glucose oxidase and dehydrogenase.

An electrochemical enzyme biosensor with electronically type-sorted (metallic and semiconducting) single-walled carbon nanotubes (SWNTs) for use in aqueous media is presented. This research investigates how the electronic types of SWNTs influence the amperometric response of enzyme biosensors. To conduct a clear evaluation, a simple layer-by-layer process based on a plasma-polymerized nano thin film (PPF) was adopted because a PPF is an inactive matrix that can form a well-defined nanostructure composed of SWNTs and enzyme. For a biosensor with the glucose oxidase (GOx) enzyme in the presence of oxygen, the response of a metallic SWNT-GOx electrode was 2 times larger than that of a semiconducting SWNT-GOx electrode. In contrast, in the absence of oxygen, the response of the semiconducting SWNT-GOx electrode was retained, whereas that of the metallic SWNT-GOx electrode was significantly reduced. This indicates that direct electron transfer occurred with the semiconducting SWNT-GOx electrode, whereas the metallic SWNT-GOx electrode was dominated by a hydrogen peroxide pathway caused by an enzymatic reaction. For a biosensor with the glucose dehydrogenase (GDH; oxygen-independent catalysis) enzyme, the response of the semiconducting SWNT-GDH electrode was 4 times larger than that of the metallic SWNT-GDH electrode. Electrochemical impedance spectroscopy was used to show that the semiconducting SWNT network has less resistance for electron transfer than the metallic SWNT network. Therefore, it was concluded that semiconducting SWNTs are more suitable than metallic SWNTs for electrochemical enzyme biosensors in terms of direct electron transfer as a detection mechanism. This study makes a valuable contribution toward the development of electrochemical biosensors that employ sorted SWNTs and various enzymes.

Amperometric biosensor based on multilayer containing carbon nanotube, plasma-polymerized film, electron transfer mediator phenothiazine, and glucose dehydrogenase.

We report on a novel fabrication approach of amperometric biosensor based on multilayer films containing carbon nanotubes (CNT), a nano-thin plasma-polymerized film (PPF), electron transfer mediator phenothiazine (PT), and enzyme glucose dehydrogenase (GDH). The configuration of the electrochemical electrode is sequentially composed of sputtered gold, acetonitrile PPF, PT, GDH, and acetonitrile PPF (denoted as PPF/GDH/PT/CNT/PPF/Au). First PPF deposited on Au acts as a permselective membrane and as a scaffold for CNT layer formation. Second PPF directly deposited on GDH acts as a matrix for enzyme immobilization. To facilitate the electrochemical communication between the CNT layer and GDH, CNT was treated with nitrogen plasma. The electron transfer mediator PT plays a role as the mediator in which the electron caused by enzymatic reaction transports to the electrode. The synergy between the mediator and CNT provides benefits in terms of lowering the operational potential and enhancing the sensitivity (current). The optimized glucose biosensor revealed a sensitivity of 5.1 ± 0.9 µA mM(-1) cm(-2) at + 0.2V vs. Ag/AgCl, linear dynamic range of 4.9-19 mM, and a response time of 5 ± 1 s. Unlike conventional wet-chemical processes that are incompatible with mass production techniques, this dry-chemistry procedure has great potential for enabling high-throughput production of bioelectronic devices. Furthermore, those devices can be applied and expands for the cell biological functional field as a useful, helpful, or indispensable tool.

Enzyme biosensor based on plasma-polymerized film-covered carbon nanotube layer grown directly on a flat substrate.

We report a novel approach to fabrication of an amperometric biosensor with an enzyme, a plasma-polymerized film (PPF), and carbon nanotubes (CNTs). The CNTs were grown directly on an island-patterned Co/Ti/Cr layer on a glass substrate by microwave plasma enhanced chemical vapor deposition. The as-grown CNTs were subsequently treated by nitrogen plasma, which changed the surface from hydrophobic to hydrophilic in order to obtain an electrochemical contact between the CNTs and enzymes. A glucose oxidase (GOx) enzyme was then adsorbed onto the CNT surface and directly treated with acetonitrile plasma to overcoat the GOx layer with a PPF. This fabrication process provides a robust design of CNT-based enzyme biosensor, because of all processes are dry except the procedure for enzyme immobilization. The main novelty of the present methodology lies in the PPF and/or plasma processes. The optimized glucose biosensor revealed a high sensitivity of 38 µA mM(-1) cm(-2), a broad linear dynamic range of 0.25-19 mM (correlation coefficient of 0.994), selectivity toward an interferent (ascorbic acid), and a fast response time of 7 s. The background current was much smaller in magnitude than the current due to 10 mM glucose response. The low limit of detection was 34 µM (S/N = 3). All results strongly suggest that a plasma-polymerized process can provide a new platform for CNT-based biosensor design.

Amperometric biosensor based on glucose dehydrogenase and plasma-polymerized thin films.

A novel design is described for an amperometric biosensor based on NAD(P)-dependent glucose dehydrogenase (GDH) combined with a plasma-polymerized thin film (PPF). The GDH is sandwiched between several nanometer thick acetonitrile PPFs on a sputtered gold electrode (PPF/GDH/PPF/Au). The lower PPF layer plays the role as an interface between enzyme and electrode because it is extremely thin, adheres well to the substrate (electrode), has a flat surface and a highly-crosslinked network structure, and is hydrophilic in nature. The upper PPF layer (overcoating) was directly deposited on immobilized GDH. The optimized amperometric biosensor characteristics covered 2.5-26 mM glucose concentration at +0.6 V of applied potential; the least-squares slope was 320 nA mM(-1) cm(-2) and the correlation coefficient was 0.990. Unlike conventional wet-chemical processes that are incompatible with mass production techniques, this dry-chemistry procedure has great potential for enabling high-throughput production of bioelectronic devices.

An amperometric biosensor based on a composite of single-walled carbon nanotubes, plasma-polymerized thin film, and an enzyme.

We report on an amperometric biosensor that is based on a nanocomposite of carbon nanotubes (CNT), a nano-thin plasma-polymerized film (PPF), and glucose oxidase (GOx) as an enzyme model. A mixture of the GOx and a CNT film is sandwiched with 10-nm-thick acetonitrile PPFs. Under PPF layer was deposited onto a sputtered gold electrode. To facilitate the electrochemical communication between the CNT layer and GOx, CNT was treated with nitrogen or oxygen plasma. The resulting device showed that the oxidizing current response due to enzymatic reaction was 4-16-fold larger than that with only CNT or PPF, showing that the PPF and/or plasma process is an enzyme-friendly platform for designing electrochemical communication from the reaction center of GOx to the electrode via CNTs. The optimized glucose biosensor showed high sensitivity (sensitivity of 42 microA mM(-1)cm(-2), correlation coefficient of 0.992, linear response range of 0.025-2.2 mM, and a detection limit of 6 microM at signal/noise ratio of 3, +0.8 V versus Ag/AgCl), high selectivity (almost no interference by 0.5 mM ascorbic acid) for glucose quantification, and rapid response (<4 s to reach 95% of maximum response). Additionally, the devices showed a small and stable background current (0.35+/-0.013 microA) compared with the glucose response (ca. 10 microA at 10mM glucose) and suitable reproducibility from sample-to-sample (<3%, n=4).

Adsorption of glucose oxidase onto plasma-polymerized film characterized by atomic force microscopy, quartz crystal microbalance, and electrochemical measurement.

Adsorption of glucose oxidase (GOD) onto plasma-polymerized thin films (PPF) with nanoscale thickness was characterized by atomic force microscopy (AFM), quartz crystal microbalance (QCM), and electrochemical measurements. The PPF surface is very flat (less than 1-nm roughness), and its properties (charge and wettability) can be easily changed while retaining the backbone structure. We focused on three types of surfaces: (1) the pristine surface of hexamethyldisiloxane (HMDS) PPF (hydrophobic and neutral surface), (2) an HMDS PPF surface with nitrogen-plasma treatment (hydrophilic and positive-charged surface), and (3) an HMDS PPF surface treated with oxygen plasma (hydrophilic and negative-charged surface). The AFM image showed that the GOD molecules were densely adsorbed onto surface 2 and that individual GOD molecules could be observed. The longer axis of GOD ellipsoid molecules were aligned parallel to the surface, called the "lying position", because of electrostatic association. On surface 1, clusters of GOD molecules did not completely cover the original PPF surface (surface coverage was ca. 60%). The 10-nm-size step height between the GOD clusters and the PPF surface suggests that the longer axes of individual GOD molecules were aligned perpendicular to the surface, called the "standing position". On surface 3, only a few of the GOD molecules were adsorbed because of electrostatic repulsion. These results indicate that the plasma polymerization process can facilitate enhancement or reduction of protein adsorption. The AFM images show a corresponding tendency with the QCM profiles. The QCM data indicate that the adsorption behavior obeys the Langmuir isotherm equation. The amperometric biosensor characteristics of the GOD-adsorbed PPF on a platinum electrode showed an increment in the current because of enzymatic reaction with glucose addition, indicating that enzyme activity was mostly retained in spite of irreversible adsorption.

Conformational polymorphism and thermochemical analysis of 5,5' ''-bis[(2,2,5,5-tetramethyl-1-aza-2,5-disila-1-cyclopentyl)ethyl]-2,2':5',2' ':5' ',2' ''-quaterthiophene.

The titled compound exists as two polymorphic solid phases (denoted form-I and form-II). Form-I obtained by as-synthesized material is a more stable phase. Form-II is a less stable phase. Spontaneous solid-solid transformation from form-II to form-I is observed in the temperature range between room temperature and the melting point of form-I (Tm = 156.5 degrees C), and its activation energy is estimated to be 96 kJ mol-1 by Arrhenius plot. The solid-solute-solid transformation (recrystallization from solution) from form-II to form-I is also observed. In contrast, form-II is obtained only by a solid-melt-solid transformation from form-I. Therefore, the system of two polymorphs is monotropic. The solid-state NMR measurement shows that form-I has the molecular conformation of complete S-syn-anti-syn in the oligothiophene backbone, whereas form-II has that of S-all-anti. With the solution NMR data, the polymorphism could not be observed. Therefore, the polymorphs originate from the different molecular packing involving the conformational change of the molecule. This unique property is attributed to the extra bulky terminal groups of the compounds. However, despite the extra bulky terminal groups, the mentioned polymorphism is not observed in the titled compound analogue which has S-all-anti conformation (like form-II).