Japanese version of voice handicap index for subjective evaluation of voice disorder

Recently, the Voice Handicap Index (VHI), developed in the United States, has been highlighted as a means to assess a patient's perceptions of the severity of his or her voice disorder. The VHI is based on a self-administered questionnaire that quantifies the degree of a patient's disability related to his/her voice disorder. The questionnaire was translated into Japanese and applied to Japanese patients with various kinds of disordered voice or dysphonia. The results were analyzed and the usefulness discussed. In this study, 546 patients (281 males and 265 females) were included. Mean VHI scores were 36.2/120 in males and 44.1/120 in females. In the male patients, VHI scores were the highest among teens. However, VHI scores did not vary with age in the female patients. Patients with vocal fold paralysis, functional dysphonia, psychological dysphonia, and spasmodic dysphonia showed relatively high VHI scores, whereas those with laryngeal granuloma and laryngopharyngeal reflux disease showed low scores. In most diseases, functional and physiological scores were higher than emotional scores. In any treated patients, those with vocal nodule, vocal polyp, polypoid vocal fold, and recurrent laryngeal nerve paralysis, VHI scores decreased after therapeutic intervention. These findings suggest that the Japanese VHI is a useful tool for monitoring a patient's psychological status, choosing appropriate treatment, and assessing the therapeutic outcome.     

Synthesis and photoinduced deprotection of calixarene derivatives containing certain protective groups

Calixarene derivatives 1a , 1b , and 1c containing pendant tert‐butoxycarbonyl (t‐BOC) groups were synthesized in 81, 93, and 83% yields, respectively, by the reaction of C‐methylcalix[4]resorcinarene (CRA), p‐methylcalix[6]arene (MCA), and p‐tert‐butylcalix[8]arene (BCA) with di‐tert‐butyl dicarbonate using triethylamine as a base in pyridine. Calixarene derivatives 2a , 2b , and 2c containing pendant trimethylsilyl ether (TMSE) groups were obtained in 58, 50, and 82% yields, respectively, by the reaction of CRA, MCA, and BCA with 1,1,1,3,3,3‐hexamethyldisilazane using chlorotrimethylsilane as an accelerator in tetrahydrofuran. Calixarene derivatives 3a , 3b , and 3c containing pendant cyclohexenyl ether (CHE) groups were also prepared in 65, 78, and 84% yields, respectively, by the reaction of CRA, MCA, and BCA with 3‐bromocyclohexene using potassium hydroxide as a base as well as tetrabutylammonium bromide as a phase‐transfer catalyst in N‐methyl‐2‐pyrolidone. The photoinduced deprotection of calixarene derivatives 1a – c was examined with bis‐[4‐(diphenylsulfonio)phenyl]sulfide bis(hexafluorophosphate) as a photoacid generator on UV irradiation followed by heating in the film state, and it was found that the deprotection of the t‐BOC groups of 1a proceeded smoothly in high conversion. The deprotection rates of the t‐BOC groups of 1b and 1c were much lower than that of 1a under the same irradiation conditions. The photoinduced deprotection of calixarenes 2b – c containing tetramethylsilane groups as well as 3a – c containing CHE groups were also examined under similar reaction conditions in the film state, and it was found that the deprotection rates of calixarenes 2b – c and 3a – c were lower than those of the corresponding 1a – c calixarenes. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1481–1494, 2001     

Synthesis of alkaline‐developable,photosensitive hyperbranched polyimides through the reaction of carboxylic acid dianhydrides and trisamines

Hyperbranched polyimides (HBPI)s with high glass‐transition temperatures and excellent thermal stability were synthesized through the reaction of commercially available carboxylic acid dianhydrides with tris[4‐(4‐aminophenoxy)phenyl]ethane (TAPE). In particular, hyperbranched polyimide HBPI(TAPE‐DSDA), prepared through the reaction of TAPE with 3,3′,4,4′‐diphenylsulfonetetracarboxylic dianhydride (DSDA), showed higher thermal stability and good solubility. Furthermore, alkaline‐developable, photosensitive HBPI(TAPE‐DSDA)‐MA‐CA was prepared through the reaction of HBPI(TAPE‐DSDA) with glycidyl methacrylate with tetrabutylammonium bromide as a catalyst in N‐methyl‐2‐pyrrolidinone (NMP) followed by the addition reaction of cis‐1,2,3,6‐tetrahydrophthalic anhydride with triphenylphosphine as a catalyst in NMP. The glass‐transition temperatures of HBPI(TAPE‐DSDA)‐MA‐CA were greater than 300 °C. A resist composed of 74 wt % HBPI(TAPE‐DSDA)‐MA‐CA, 22.2 wt % trimethylpropane triacrylate, and 3.8 wt % Irgacure 907 as a photoinitiator achieved a resolution of a 55‐μm line pattern and a 275‐μm space pattern by UV irradiation (1000 mJ/cm²). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3697–3707, 2004     

New thermo-crosslinking reactions of polymers containing pendant epoxide groups with various polyfunctional active esters

New thermo-crosslinking reactions of poly(glycidyl methacrylate), copolymers of glycidyl methacrylate with methyl methacrylate, styrene or ethyl acrlate with various active esters such as di[S-(2-benzothiazoly)] thioadipate (BTAD), di(S-phenyl) thioadipate (PTAD), di(4-nitrophenyl) adipate (NPAD), diphenyl adipate (PAD), and di(S-phenyl) thioisophthalate (PTIP), and other polyfunctional esters were carried out in the film state using various catalysts such as quarternary ammonium or phosphonium salts, tert amines, or the crown ether 18-crown-6 = potassium salts system. Addition reactions of pendant epoxide groups in the polymer with the active esters such as NPAD and PTAD proceeded selectively to give gel compounds without other side reactions. The rates of reaction with the thioesters such as BTAD and PTAD were relatively faster than those with the phenyl esters such as PAD and NPAD at 70°C. The rates of reactions with the esters having flexible segments such as PTAD were also faster than those with the esters having rigid skeletons such as PTIP. Furthermore, it was found that the rate of reaction was affected strongly by reaction temperature, catalyst concentration, length of alkyl chain in the catalyst, kind of counterion of quarternary ammonium salts as a catalyst, content of pendant epoxide groups in the polymer, and kind of copolymer unit in the polymer, respectively.     

Synthesis and photochemical reaction of cyclic oligomers: Synthesis and photopolymerization of novel C‐methylcalix[4]resorcinarene and p‐alkylcalix[n]arene derivatives containing spiro ortho ether groups

New photoreactive calixarene derivatives containing spiro ortho ester groups (calixarenes 3a–3c ) were synthesized by the reaction of 2‐bromomethyl‐1,4,6‐trioxaspiro[4.4]nonane with 2,8,14,20‐tetramethyl‐4,6,10,12,16,18,22,24‐octakis(carboxymethoxy)calix[4]resorcinarene, 5,11,17,23,29,35‐hexamethyl‐37,38,39,40,41,42‐hexakis(carboxymethoxy)calix[6]arene, and 5,11,17,23,29,35,41,47‐octa‐tert‐butyl‐49,50,51,52, 53,54,55,56‐octakis‐(carboxymethoxy)calix[8]arene, which were prepared by the reaction of C‐methylcalix[4]resorcinarene, p‐methylcalix[6]arene, and p‐tert‐butylcalix[8]arene, respectively. The thermal stability of the obtained calixarene derivatives containing spiro ortho ester groups was examined with thermogravimetric analysis, and it was found that these calixarene derivatives had good thermal stability. The photoinitiated cationic polymerization of spiro ortho ester groups in calixarene derivatives 3a–3c was examined with certain photoacid generators in the film state. Interestingly enough, the reaction of calixarene derivatives did not proceed with only photoirradiation; however, the reaction proceeded smoothly when the photoirradiation was followed by heating. Furthermore, calixarene 3a , composed of a C‐methylcalix[4]resorcinarene structure, showed the highest photochemical reactivity in this reaction system. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1293–1302, 2002     

Synthesis of polymer containing o-nitrobenzyl ether structure in the main chain

The polycondensation of nitrated xylenedihalides with diphenols was carried out under various conditions. The polycondensation of 2-nitro-1, 3-xylylenedibromide (NXDB) with 4,4′-isopropylidenediphenol proceeded in competition with the decomposition of polymer in the mixed solvent of tetrahydrofuran (THF) and dimethylsulfoxide (DMSO). The viscosity of the resulting polymer was markedly affected by the concentration of aqueous sodium hydroxide, reaction time, and reaction temperature. When dibromomethane was used as a solvent, the polycondensation proceeded very smoothly without the decomposition to give a higher reduced viscosity polymer than that in THF-DMSO at 60°C. The polymer obtained in dibromomethane contained a very small amount of formal bonds determined from the ¹H-NMR spectrum. The formation of formal bonds seems to cause the molecular weight in increase. Furthemore, the polycondensation of NXDB with 2,2-bis (4-hydroxyphenyl) hexafluoropropane afforded high molecular-weight polyether in dibromomethane. However, either high reaction temperatures or the high concentrations of aqueous potassium hydroxide solution casused the viscosity of the resulting polymer to decrease during the polycondensation in dibromomethane. The obtained polyethers with o-nitrobenzyl groups showed relatively good solubility, and decomposed smoothly upon the irradiation with UV light. Therefore, these polymers might be useful for positive type photoresists.     

Substitution and elimination reactions of poly(epichlorohydrin) and poly(2-chloroethyl vinyl ether) using phase transfer catalysis

The reactions of poly(epichlorohydrin) (PECH) and poly(2-chloroethyl vinyl ether) (PCEVE) with various reagents were investigated using phase transfer catalyst (PTC) such as tetra-n-butylammonium bromide (TBAB), 18-crown-6 (CR6), and dicyclohexyl-18-crown-6 (DCHC) is a solid—liquid two-phase system. Although the reactions of these polymers hardly occurred without PTC in nonpolar solvents such as toluene and diglyme under mild conditions, the addition of PTC caused the reactions to proceed smoothly under the same conditions. In addition, the reactions of PECH and PCEVE with a strong base such as potassium hydroxide proceeded selectively through β-elimination reaction to produce the polymers with pendant vinyl groups. These results suggested this method is useful for the syntheses of functional polymers. On the other hand, it turned out that quaternary ammonium salts such as TBAB have higher catalytic activity than crown ethers such as CRG and DCHE in these reactions. Furthermore, the catalytic activity of quaternary ammonium salts was strongly influenced by their chain length and the structure of the polymers.     

A novel insertion reaction of epoxy compounds into phenyl ester linkages in polymer chains

The insertion reaction of various epoxy compounds such as phenyl glycidyl ether (PGE), methyl glycidyl ether, butyl glycidyl ether (BGE), and styrene oxide into the phenyl ester linkage in the polymer chain was investigated using quaternary ammonium salts as catalysts in diglyme, anisole, sulfolane, o-dichlorobenzene, or DMSO at 100–150°C. The reaction of PGE with poly[4-(4-nitrobenzoyloxy)styrene] (polymer 1a ) proceeded almost quantitatively to give the corresponding polymer using tetrabutylammonium bromide (TBAB) as catalyst in diglyme at 100°C for 24 h. The reactions of BGE with poly(4-nitrophenyl methacrylate), and copolyarylate derived from 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and iso- and terephthaloyl chlorides also produced the corresponding polymers with 86 and 89 mol% new structural units, respectively, using TBAB in sulfolane at 150°C for 24 h. Furthermore, it was found that the degree of insertion of the epoxy compound into the ester linkage in the polymer chain was affected by the kind of epoxy compound, reaction solvent, catalyst concentration, substituent group on the phenyl ester, and structure of the polymer. Chiral polymers were also synthesized with high degrees of insertion by the reaction of chiral epoxides such as (R)-1,2-epoxyhexane, (R)-1,2-epoxyheptane, and (R)-1,2-epoxydecane with polymer 1a and poly(2,4-dichlorophenyl methacrylate) using TBAB in diglyme at 120°C for 24 h.     

Polycondensation of bis(p-nitrophenyl) β-truxinate with diamine

Model reaction of bis(4-nitrophenyl) β-truxinate (BNPT) with aliphatic amines proceeded quantitatively at room temperature. Accordingly, polycondensation of BNPT with various diamines was carried out at room temperature or 80°C. During the polycondensation of BNPT with diamines, the precipitation of polymer or the observed gelation of polymerization solution occurred, which may limit the molecular weight of the polymer. On the other hand, the reaction of BNPT with 1,3-(4-piperidyl)propane (DPP) proceeded homogeneously to give the polymer with relatively high molecular weight, and the obtained polyamide (P-1e) showed excellent solubility in many solvents. The study of TG and DTA indicated that the obtained polymers were stable at lower temperature than around 270°C. The polymer prepared from the polycondensation of BNPT with hexamethylenediamine showed melting point and decomposition due to the imidation at 282°C. The photochemical reaction of these polymers was carried out in the film state. The irradiation of 254 nm light caused an absorption at 272 nm to appear and the molecular weight to decrease. This meant that the scission of cyclobutane ring in the main chain occurred to give cinnamamide structures. Also, the absorption at 272 nm decreased by the irradiation of 302.5 nm light. However, the UV spectrum of irradiated polymer did not agree with that of the original polymer. These results suggested that the dimerization of the resulting cinnamamide moieties occurred in the competition of their trans–cis-isomerization. On the other hand, the rate of scission of cyclobutane ring of P-1e was faster than that of the corresponding polyamide containing α-truxillamide structure.     

One-step syntheses of alkyl glycosides and alkyl-substituted DNA oligomers by chemoselective glycosidations using DNA bases

The simple and practical synthesis of alkyl glycosides by novel chemoselective glycosidations using natural resources, DNA and RNA nucleosides, was realized, and the one-step synthesis of chemoselectively modified DNA oligomers using the glycosidation method was also demonstrated.