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Background and purpose Botulinum toxin (BT) injection into the laryngeal muscles has been a standard treatment for spasmodic dysphonia (SD). However, few high‐quality clinical studies have appeared, and BT is used off‐label in most countries. Methods We performed a multicenter, placebo‐controlled, randomized, double‐blinded, parallel‐group comparison/open‐label clinical trial to obtain approval for BT (Botox) therapy in Japan. Twenty‐four patients (22 with adductor SD and two with abductor SD) were enrolled. The primary end point was the change in the number of aberrant morae (phonemes) at 4 weeks after drug injection. The secondary end points included the change in the number of aberrant morae, GRBAS scale, Voice Handicap Index (VHI), and visual analog scale (VAS) over the entire study period. Results In the adductor SD group, the number of aberrant morae at 4 weeks after injection was reduced by 7.0 ± 2.30 (mean ± SE) in the BT group and 0.2 ± 0.46 in the placebo group (p = 0.0148). The improvement persisted for 12 weeks following BT injections. The strain element in GRBAS scale significantly reduced at 2 weeks after BT treatment. The VHI and VAS scores as subjective parameters also improved. In the abductor SD group, one patient responded to treatment. Adverse events included breathy hoarseness (77.3%) and aspiration when drinking (40.9%) but were mild and resolved in 4 weeks. Conclusions Botulinum toxin injection was safe and efficacious for the treatment of SD. Based on these results, BT injection therapy was approved as an SD treatment in Japan., The number of aberrant morae (phonemes) decreased significantly at 2 to 12 weeks after botulinum toxin injection into the thyroarytenoid muscle in patients with adductor spasmodic dysphonia, whereas the placebo group showed insignificant change. This study showed the significant effectiveness of botulinum toxin therapy for spasmodic dysphonia.

Atypical adenoma of the thyroid is a rare form of tumor, and its accurate diagnosis prior to surgical resection is difficult as the histological and pathological morphologies are very similar to those of anaplastic thyroid carcinoma (ATC), and its anaplastic transformation remains to be elucidated. We reported a case of a 75-year-old female with a thyroid isthmus nodule diagnosed repeatedly by FNAC as anaplastic carcinoma. Both the first and second FNAC specimen slides showed a large number of scattered or aggregated atypical cells consisting of large, pleomorphic nuclei with irregular membranes, chromatin clumps and prominent nucleoli. The morphology of the surgical specimen was similar to that of an anaplastic carcinoma and although it showed signs of transition from a normal follicular epithelium, there was no invasive growth or mitosis. This lesion was diagnosed as an atypical adenoma, and a papillary carcinoma was also present in the right lobe of the thyroid. Here we evaluate the molecular features of atypical adenomas in comparison with 9 ATC samples, and discuss whether or not atypical adenomas represent a form of premalignant lesion. Ki-67 expression was found to be very low in atypical adenomas whereas all ATC samples showed high levels of Ki-67 expression. Epithelial-mesenchymal transition (EMT) marker expression suggested that atypical adenomas maintain their epithelial phenotype to a higher degree than do ATCs. Differential diagnosis between ATC and atypical adenoma is difficult by cytological and histological methods alone, and Ki-67 and EMT marker expression may support the diagnosis.

Type II thyroplasty (TPII) is one of the surgical options offered in the management of adductor spasmodic dysphonia (AdSD); however, there have been no detailed reports of its safety and associated complications during the perioperative period. Our aim was to assess the complications and safety of TPII. TPII was performed for consecutive 15 patients with AdSD from April 2012 through May 2014. We examined retrospectively the perioperative complications, the degree of surgical invasion, and recovery process from surgery. All patients underwent successful surgery under only local anesthesia. Vocal fold erythema was observed in 14 patients and vocal fold edema in 10 patients; however, all of them showed complete resolution within 1 month. No patient experienced severe complications such as acute airway distress or hemorrhage. Fourteen patients were able to have oral from the 1st postoperative morning, with the remaining patient able to have oral intake from the 2nd postoperative day. In addition, no patient experienced aspiration postoperatively. In conclusion, only minor complications were observed in association with TPII in this study. No dysphagia was observed postoperatively, which is an advantage over other treatments. The results of our study suggest that TPII is a safe surgical treatment for AdSD.

Summary Objectives Voice onset time (VOT) for word-initial voiceless consonants in adductor spasmodic dysphonia (ADSD) and abductor spasmodic dysphonia (ABSD) patients were measured to determine (1) which acoustic measures differed from the controls and (2) whether acoustic measures were related to the pause or silence between the test word and the preceding word. Methods Forty-eight patients with ADSD and nine patients with ABSD, as well as 20 matched normal controls read a story in which the word "taiyo" (the sun) was repeated three times, each differentiated by the position of the word in the sentence. The target of measurement was the VOT for the word-initial voiceless consonant /t/. Results When the target syllable appeared in a sentence following a comma, or at the beginning of a sentence following a period, the ABSD patients' VOTs were significantly longer than those of the ADSD patients and controls. Abnormal prolongation of the VOTs was related to the pause or silence between the test word and the preceding word. Conclusions VOTs in spasmodic dysphonia (SD) may vary according to the SD subtype or speaking conditions. VOT measurement was suggested to be a useful method for quantifying voice symptoms in SD.

Background Osteoradionecrosis (ORN) of the hyoid bone sometimes induces severe front neck infection and can cause laryngeal stenosis and carotid rupture. Although ORN of the hyoid bone is known to be a complication of chemoradiotherapy for head and neck cancer, there has been no basis for its evaluation. Our purpose is to present the clinical and MR imaging features of ORN of the hyoid bone. Methods The study group comprised patients with advanced oropharyngeal cancer treated with targeted intra-arterial cisplatin infusion with concomitant radiotherapy. ORN of the hyoid bone was identified on the basis of decreased signal intensity of the bone marrow on T1WI images. Signal intensity on T2WI images was used to distinguish between inflammation and fibrosis. Results A total of 39 pre-treatment MR images and follow-up MR images were reviewed. ORN of the hyoid bone were detected in 30% of patients after treatment, with 23% of them showing inflammation and 7.7% fibrosis. Two patients developed severe neck infection and received antibiotics and underwent surgical intervention by tracheostomy and resection of the hyoid bone. Conclusion Our MR imaging study showed that ORN of the hyoid bone is not particularly rare in patients with oropharyngeal cancer treated with chemoradiotherapy. Clinicians should evaluate images carefully to prevent the development of severe complication due to infection associated with ORN of the hyoid bone.

Summary Objectives The aim of this study was to evaluate speech in patients with adductor spasmodic dysphonia (ADSD) by perceptual evaluations and acoustic measures, and to examine the reliability and validity of these measures. Methods Twenty-four patients with ADSD and 24 healthy volunteers were included in the study. Speech materials consisted of three sentences constructed from serial voiced syllables to elicit abductor voice breaks. Three otolaryngologists rated the degree of voice symptoms using a visual analog scale (VAS). VAS sheets with five 100-mm horizontal lines were given to each rater. The ends of the lines were labeled normal vs severe, and the five lines were labeled as overall severity of each of the four speech symptoms (strangulation, interruption, tremor and strained speech). Nine words were selected for acoustic analysis, and abnormal acoustic events were classified into one of the three categories. To evaluate the intra- and inter-rater and intermeasurer reliabilities of the VAS scores or acoustic measures, Pearson r correlations were calculated. To examine the validity of perceptual evaluations and acoustic measures, the sensitivity and the specificity were calculated. Results Pearson r correlation coefficients for overall severity showed the highest intra- and inter-rater reliabilities. For acoustic events, the intrameasurer reliabilities were r = .645 (frequency shifts), r = .969 (aperiodic segments), and r = 1.0 (phonation breaks), and the intermeasurer reliability ranged from r = .102 to r = 1.0. Perceptual evaluation showed high sensitivity (91.7%) and specificity (100%), whereas acoustic analysis showed low sensitivity (70.8%) and high specificity (100%). Conclusion Both perceptual evaluation and acoustic measures alone were found likely to overlook patients with true ADSD.

Atypical adenoma of the thyroid is a rare form of tumor, and its accurate diagnosis prior to surgical resection is difficult as the histological and pathological morphologies are very similar to those of anaplastic thyroid carcinoma (ATC), and its anaplastic transformation remains to be elucidated. We reported a case of a 75-year-old female with a thyroid isthmus nodule diagnosed repeatedly by FNAC as anaplastic carcinoma. Both the first and second FNAC specimen slides showed a large number of scattered or aggregated atypical cells consisting of large, pleomorphic nuclei with irregular membranes, chromatin clumps and prominent nucleoli. The morphology of the surgical specimen was similar to that of an anaplastic carcinoma and although it showed signs of transition from a normal follicular epithelium, there was no invasive growth or mitosis. This lesion was diagnosed as an atypical adenoma, and a papillary carcinoma was also present in the right lobe of the thyroid. Here we evaluate the molecular features of atypical adenomas in comparison with 9 ATC samples, and discuss whether or not atypical adenomas represent a form of premalignant lesion. Ki-67 expression was found to be very low in atypical adenomas whereas all ATC samples showed high levels of Ki-67 expression. Epithelial-mesenchymal transition (EMT) marker expression suggested that atypical adenomas maintain their epithelial phenotype to a higher degree than do ATCs. Differential diagnosis between ATC and atypical adenoma is difficult by cytological and histological methods alone, and Ki-67 and EMT marker expression may support the diagnosis.

It is difficult to determine the surgical indication of type 2 thyroplasty for spasmodic dysphonia because: 1) there is a great variety of symptoms among patients, 2) there is a high rate of changeability with time, and consequently 3) it is difficult to diagnose. There seems to be no objective criteria for making a diagnosis or for deciding the indication. Based on our surgical experience of over 300 cases, our principal policy for deciding is that the indication should be limited to those with an apparent excessively tight closure of the glottis during phonation; or those with severe anguish resulting from spasmodic dysphonia. While the deprivation of easy communication in itself isn’t an indication of surgery, the strong desire of a patient to get relief from this malady is an indication. If the decision is difficult to make, one should take into account: 1) the period of time of the past suffering, 2) the objective findings such as anterior foaming at the glottis on phonation, 3) the severity of speech distortion, 4) the strong desire of the patient for the operation, and 5) voice recordings under other circumstances such as on the phone. Full information regarding the operation should be made available to the patients.

To search for natural materials that protect human skin from damage caused by ultraviolet-B (UV-B) irradiation, we prepared water extracts of the following four dry berries: lowbush blueberry (LBB) ( Vaccinium angustifolium L.), highbush blueberry (HBB) ( Vaccinium corymbosum L.), cranberry (CB) ( Vaccinium macrocarpon Ait.) and grape ( Vitis vinifera L.). Normal human epidermal keratinocytes (NHEKs) were pretreated with each of the extracts and then subjected to transient UV-B irradiation (15.0 W m -2 ) for 80 s. The results showed that pretreatment of NHEKs with LBB extract significantly attenuated UV-B-induced damage. The concentrations of proanthocyanidins, total flavonoids and total polyphenols in LBB extract were higher than those in the other three berry extracts. Therefore, these compounds might mediate the protection of NHEKs from UV-B-induced damage.

Temperature dependence of the complex dielectric constant at 16.3 GHz has been measured on dry poly(dA)–poly(dT) DNA with Na + counterions under different relative humidity (RH). The rotational motion of sole water dipoles hydrated in PO 2 − is detected at low RH, and the collective motion due to water network in major groove is successfully observed at high RH. From the infrared (IR) spectroscopy in dry DNA introducing metallic ions (M-DNA), the symmetric and antisymmetric stretching bands of PO 2 − distinctly depend on RH and type of metallic ions. The IR spectral change indicates that the monovalent ions (Li and Na) are arranged in PO 2 − though the divalent and trivalent ions connect to the base molecules.

In this work, a ruthenium hexafluorophosphate complex, [Ru(bpy) 3 ](PF 6 ) 2 in poly(methylmethacrylate) (PMMA) was employed to build a single layer light electrochemical cell on indium tin oxide polyester flexible substrate. The electroluminescence spectrum features a relatively broad band peaked near 625 nm, with CIE ( x , y ) color coordinates of (0.61, 0.39). The driving voltage is only 3 V, and for the maximum electrical current of 10 mA the brightness reaches 1 cd/m 2 . Regarding the useful application of the device, its opto-electrical behavior under mechanical strain was studied considering the central curvature. In these situations, both electrical characterization in DC mode and luminance were analyzed.

TEMPO-containing norbornene monomers 1−8 (TEMPO = 2,2,6,6-tetramethylpiperidine-1-oxy) were synthesized and polymerized via ring-opening metathesis using a ruthenium−carbene catalyst. The TEMPO moiety did not inhibit the polymerization, and the monomers gave corresponding polymers in good to high yields. Poly(2) and poly(3) were soluble in common solvents and possessed high molecular weight, while other polymers were insoluble. The resulting polymers were thermally stable up to ca. 240 °C according to TGA measurements in air. In the case of poly(1)−poly(3), the charge/discharge capacities of the polymer-based cells were largely dependent on the spatial arrangement of the two TEMPO moieties on each repeating unit. Quite interestingly, the capacity of the poly(2)-based cell reached its theoretical value (109 A h/kg), and a large capacity (>90 A h/kg) was retained even at high current densities up to 6 A/g, indicating the possibility of very fast charging (within 1 min). The cells utilizing the present polym...

Ethyl cellulose derivatives [EC-T and EC-P] and cellulose acetate derivatives [CA-T and CA-P] carrying TEMPO or PROXY radicals (TEMPO = 2,2,6,6-tetramethyl-1-piperidinyloxy, PROXY = 2,2,5,5-tetramethyl-1-pyrrolidinyloxy) were synthesized with moderate number-average molecular weights of 62 400–126 000 in 84–88% yield by the reaction of 4-carboxy-TEMPO or 3-carboxy-PROXY with residual hydroxyl group of ethyl cellulose or cellulose acetate. All the free radical-containing cellulose derivatives demonstrated reversible charge/discharge processes, whose discharge capacities were 42.8–61.1 A h/kg. In particular, the CA-T-based cell displayed two-stage discharge process, and the first-stage discharge capacity reached 29.5 A h/kg which corresponds to 74% of its theoretical value, and that of the total capacity was 61.1 A h/kg which approaches up to 153% of the theoretical value for one-electron redox reaction.

The 2,2,6,6-tetramethyl-1-piperidinoxy (TEMPO)-containing acetylenic monomers HC[triple bond]CC(6)H(3)-p,m-(CONH-4-TEMPO)(2) (1), HC[triple bond]CC(6)H(3)-p,m-(COO-4-TEMPO)(2) (2), (S,S,S,S)-HC[triple bond]CC(6)H(3)-p,m-[CO-NHCH{COO-(4-TEMPO)}CH(2)COO-(4-TEMPO)](2) (3), (S,S)-HC[triple bond]CC(6)H(4)CO-NHCH{COO-(4-TEMPO)}CH(2)COO-(4-TEMPO) (4), HC[triple bond]CC(6)H(4)-p-OCO-4-TEMPO (5), HC[triple bond]CCH(2)C(CH(3))(CH(2)OCO-4-TEMPO)(2) (6), HC[triple bond]CCH(2)NHCO-4-TEMPO (7), and HC[triple bond]CCH(2)OCO-4-TEMPO (8) were polymerized to afford novel polymers containing the TEMPO radical at high densities. Monomers 1, 3-6, and 8 provided polymers with average molecular weights of 10 000-136 500 in 62-99 % yield in the presence of a rhodium catalyst, whereas monomers 2 and 7 gave insoluble polymers in 100 % yield. The formed polymers were thermally stable up to approximately 274 degrees C according to thermogravimetric analysis (TGA). All the TEMPO-containing polymers demonstrated reversible charge/discharge processes, whose discharge capacities were 21.3-108 A h kg(-1). In particular, the capacity of poly(1)-, poly(4)-, and poly(5)-based cells reached 108, 96.3, and 89.3 A h kg(-1), respectively, which practically coincided with their theoretical values.

β′-(BEDT-TTF)(TCNQ) is a compound of BEDT-TTF (=ET) and TCNQ molecules aligned orthogonally with each other, forming two-dimensional sheets and one-dimensional columns of 1/4-filled π band, respectively. It is known that the metal-insulator transition occurs at 330 K at ambient pressure. We have measured the electronic spin susceptibility by means of the EPR-NMR method at 50 MHz, and the angular dependence of g-factor and line width of EPR both at Q (34 GHz) and W (94 GHz) band. We successfully confirmed that the antiferromagnetic transition occurs in ET sheets and TCNQ columns, independently.

The quarter-filled π band systems, (DMe-DCNQI)2M(M=Li1−xCux(x ≤ 0.14), Ag) were systematically studied with electron paramagnetic resonance (EPR). The intercolumn spin hopping rate D⊥ in Li1−xCux-salt was obtained from the EPR linewidth. The temperature dependence of D⊥ can be understood with the hole soliton model which also explains the DC conductivity. The π − d mixing of the Cu-salt enhances both D⊥ and σ⊥ by103 times more than the Li-salt, which is consistent with the fact that the only Cu-salt has three-dimensional Fermi surface, but that Ag-salt is one-dimensional in spite of the mixing enhancement of D⊥ by 10 times more than the Li-salt.

Electronic states of pristine and metal ion doped salmon DNA’s are studied with EPR and SQUID. Intrinsically no EPR signal is observed in purified salmon DNA, consistent with a semiconducting nature of the pristine DNA, but inconsistent with a metal or a superconductor as reported previously. Although we obtained successfully the divalent metal ion-DNA complexes with one-dimensional array of ions located in between the bases of a base pair, substantial EPR signal except for the case of 3d transition metal ions is not observed. This leads to the conclusion that divalent metal ions counterbalances two phosphate anions instead of Na counter ions in B-DNA, which contradicts the metallic behavior reported previously (A. Rakitin, et al., PRL 86, 3670 (2001)). A comment will also be given on the recent report: “Intrinsic Low Temperature Paramagnetism in B-DNA” (S. Nakamae et al., PRL 94, 248102 (2005)).

The electron spin susceptibility of (BEDT-TTF)(ClMeTCNQ) was measured by ESR under pressure. Analysis of the susceptibility leads to the temperature dependence of the ionic fraction through the neutral-ionic phase transition, revealing that the transition is broad and continuous. It is demonstrated that this transition is crossover-like between the two phases, which can be understood by the unique double-well potential.

X-band electron spin resonance was employed to study the structural anisotropy in several polythiophene derivatives. Because of the dominating homoge- neous width, the obtained absorption spectra were Lorentzian-shaped. Information about the structural anisotropy was obtained from the position and width of the absorption peak. Qualitatively, the anisotropy was in full agreement with earlier results from X-ray diffraction, including a flip in molecular orientation with respect to the film substrate between solution-cast and spin-cast films. With the Monte Carlo technique, the spectra were fitted with a biaxial g tensor, an anisotropy parameter S, and an intrinsic width . The simulations showed that g could be treated as pseudo- uniaxial, with the unique axis along the side chains rather than along the ring normal. Closed-form analytical expressions relating g to the anisotropy were obtained and used for a quantitative assessment of the molecular anisotropy. Because the molecular g tensor for these materials was not known, a known value of S for one of the samples obtained by X-ray diffraction was used for normalization. Fairly consistent values were obtained for both g and S. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3011-3025, 2003

Nanocomposites of conducting polyaniline (PAN) with inorganic Na+−montmorillonite (MMT) clay were synthesized by the emulsion polymerization method. The dodecylbenzenesulfonic acid (DBSA) was used for both dopant and emulsifier. Analyses of X-ray diffraction patterns demonstrated that conducting PAN-DBSA was intercalated between inorganic clay layers at the nanoscale level (

To unveil the electronic states of divalent metal ion incorporated M-DNAs, where M is Mg, Mn, Ni, Co, or Fe, optical absorption spectra have been studied in aqueous solutions of single-stranded (SS) 30mer DNA of poly(dA) (adenine), poly(dG) (guanine), poly(dT) (thymine), poly(dC) (cytosine), salmon-sperm DNA (B-DNA), and M-DNA. The absorption spectrum of the double-stranded (DS) B-DNA can be reproduced with the sum of the four absorption spectra of the SS oligo-DNAs in the ratio corresponding to the composition of B-DNA. This observation suggests that the interactions between complementary strands of DS DNA are negligibly weaker than the bandwidths of the optical spectra. In the metal-incorporated M-DNAs, except for Fe-DNA, the absorption spectra show no significant qualitative change from that of B-DNA. Quantitatively, however, the absorption intensity decreases by $\ensuremath{\approx}$15% uniquely in a DS poly(dA)-poly(dT) solution with adding ${\text{MCl}}_{2}$, while nothing happens quantitatively and qualitatively in any SS oligo-DNA and DS poly(dG)-poly(dC) solutions, suggesting some suppression of the electronic excitation only in the Adenine-M-Thymine complex. In contrast, remarkable differences have been observed in Fe-DNA, prepared with ${\text{FeCl}}_{2}$ and B-DNA. New absorption bands appear in the intragap energy of Fe-DNA, in addition to the suppression of the interband absorption peak of DNA at 4.8 eV. The intragap absorption is attributed to the appearance of Fe${}^{3+}$ species with the same spectral feature as that of ${\text{FeCl}}_{3}$, that is, purely ionic Fe${}^{3+}$ species. This observation suggests that ${\text{FeCl}}_{2}+\mathrm{B}$-DNA forms Fe-DNA with hydrated Fe${}^{3+}$ ions with ionic bonds. Thus, it is concluded that the charge transfer from Fe${}^{2+}$ to DNA has occurred in Fe-DNA and that the transferred charges are expected to be located in the nearby bases.

Electron paramagnetic resonance (EPR) is applied to orthorhombic ${\mathrm{Rb}}_{1}{\mathrm{C}}_{60}$ 1D polymer under hydrostatic pressure. The EPR linewidth is interpreted in terms of Elliott mechanism. EPR signal intensity provides us the antiferromagnetic transition temperature ${T}_{\mathrm{N}}$ where the intensity drops suddenly. Finally, a phase diagram of the electronic states in $o{\ensuremath{-}\mathrm{R}\mathrm{b}}_{1}{\mathrm{C}}_{60}$ is constructed from ${T}_{\mathrm{N}}$ vs pressure diagram, along with the resistivity under pressure, reported by Khazeni et al. [Phys. Rev. B 56, 6627 (1997)]. From this diagram we can definitely conclude that $o{\ensuremath{-}\mathrm{R}\mathrm{b}}_{1}{\mathrm{C}}_{60}$ is not a SDW system typical for 1D electronic band, but a 3D Mott-Hubbard insulator near a border of the transition.

Photoluminescence and electroluminescence of PVK films doped with fac- [ClRe(CO) 3 (bpy)], bpy = 2,2′-bipyridine, are investigated. Photoluminescence spectra of spin-coated PVK films ( λ exc = 290 nm) exhibit a broad band centered at 405 nm. As the concentration of dopant increases, the polymer emission is quenched and a band at 555 nm appears (isosbestic point at 475 nm). In OLEDs with ITO/PEDOT:PSS/PVK/butylPBD/Al architecture doped with fac- [ClRe(CO) 3 (bpy)], the polymer host emission is completely quenched even at the lowest concentration of dopant. The electroluminescence spectra of the devices show that there is an efficient energy transfer from the host to the dopant, which exhibits a very intense emission at 580 nm.

Dye-sensitized solar cells, named by us Dye-Cells, are one of the most promising devices for solar energy conversion due to their reduced production cost and low environmental impact, especially those sensitized by natural dyes. The efficiency and stability of devices based on natural sensitizers such as mulberry ( Morus alba Lam), blueberry ( Vaccinium myrtillus Lam), and jaboticaba's skin ( Mirtus cauliflora Mart) were investigated. Dye-Cells prepared with aqueous mulberry extract presented the highest P max value (1.6 mW cm −2 ) with J sc = 6.14 mA cm −2 and V oc = 0.49 V. Photoelectrochemical parameters of 16 cm 2 active area devices sensitized by mulberry dye were constant for 14 weeks of continuous evaluation. Moreover, the cell remained stable even after 36 weeks with a fairly good efficiency. Therefore, mulberry dye opens up a perspective of commercial feasibility for inexpensive and environmentally friendly Dye-Cells.

Rb 1 C 60 is studied by ESR as a function of frequency from several tenth MHz to 26 GHz and by heat capacity, to reveal the nature of the phase transition around 50 K. Above the transition temperature, the electronic states are consistent with a metallic state. Below it, the ESR linewidth increases linearly with decreasing T , which is ascribed to a development of short-range order (SRO) based on its frequency dependence. Furthermore, the present analysis of the EPR spectra suggested a distribution of the linewidth that was consistent with broadly distributed transition temperatures of the spin density wave (SDW) or antiferromagnetism. The heat capacity shows a broad anomaly from 50 K down to 30 K The apparent entropy change of such a magnetic anomaly suggests that only one fourth of spins are in the ordered state at 30 K, which is consistent with the reported intensity of AFMR.

Ultraviolet photoemission spectra were measured for two conducting polymers; PF − 6 doped polypyrrole and camphorsulfonic acid doped polyaniline. The valence band structures at the binding energies between 5 eV and 15 eV are attributed to the π and σ bands on both samples. Although the finite spectral intensity at the Fermi level was observed in polypyrrole, that of polyaniline was extremely small. This shows that the electronic state is more metallic in polypyrrole than in polyaniline, which is consistent with the results obtained through magnetic resonance, electrical resistance and X-ray measurements.

ESR linewidth ( ΔH pp ) of as-grown polypyrrole, PPy-PF 6 − , was measured as a function of temperature under both helium and oxygen atmospheres to study an effect of oxygen on the ESR linewidth. Houze and Nechtschein reported that an interaction between the charge carriers on a polymer backborn and paramagnetic spins of the oxygen molecules could cause an additional ESR broadening that is proportional or inversely proportional to the carrier diffusion rate D ∥ in the case of storng or weak interaction, respectively. The present experimental data demonstrate that only the ESR linewidth under oxygen atmosphere are not enough, but other information is indispensable to discriminate the above two cases. On the present PPy-PF 6 − case, supplemental data on d.c. conductivity, the ESR linewidth under helium atmosphere, VSC resistance, etc. make it possible to conclude mechanism of oxygen effect.

Magnetic susceptibility and ESR linewidth are measured as a function of temperature in polypyrrole (PPy) doped with PF 6 −, AsF 6 −, ClO 4 −, BF 4 −, ToS − . Spin susceptibility by Schumacher-Slichter (ESR-NMR) technique shows both the temperature independent Pauli term ranging from 0.7 to 1.4×10 −5 emu/mol-ring and the Curie term of 1 spin per 600~1500 rings, which is consistent with that obtained by SQUID measurement in the same sample. The temperature dependence of ESR linewidth is ascribed to the Elliott mechanism typical for the metallic electron spins, increasing monotonically with the temperature. This interpretation is also consistent with the ESR linewidth in polythiophene doped with ClO 4 − and AsF 6 −. Therefore, both the susceptibility and the ESR linewidth demonstrate the PPy's doped with several dopants to have a metallic electronic state.