A highly selective fluorescent sensor for Hg based on the water-soluble poly(p-phenyleneethynylene)

The conjugated polymer P-1 could be synthesized by the polymerization of 4,7-diethynyl-benzo[2,1,3]thiadiazole (M-1) and 1,4-bis[3′-(N,N-diethylamino)-1′-oxapropyl]-2,5-diiodobenzene (M-2) via Pd-catalyzed Sonogashira reaction. The water-soluble conjugated polyelectrolyte P-2 could be obtained by the reaction of P-1 with ethyl bromide. Both P-1 and P-2 can emit orange fluorescence. The responsive optical properties of P-1 and P-2 on Hg²⁺ were investigated by fluorescence spectra. Hg²⁺ can lead to nearly complete fluorescence quenching of P-1. On the contrary, Hg²⁺ can show the most pronounced fluorescence enhancement response of P-2 in aqueous solution without interference from those coexistent ions, such as K⁺, Mg²⁺, Pb²⁺, Co²⁺, Ni²⁺, Ag⁺, Cd²⁺, Cu²⁺, Fe³⁺ and Zn²⁺. The results also exhibit that this kind of water-soluble conjugated polyelectrolyte can be used as a highly sensitive and selective fluorescence sensor for Hg²⁺ detection in water.     

A fluorescence sensor based on chiral polymer for highly enantioselective recognition of phenylalaninol

The chiral polymer P-1 incorporating (S)-2,2′-binaphthol (BINOL) and (S)-2,2′-binaphthyldiamine (BINAM) moieties in the main chain of the polymer backbone was synthesized by the polymerization of (S)-6,6′-dibutyl-3,3′-diformyl-2,2′-binaphthol (S-M-1) with (S)-2,2′-binaphthyldiamine (S-M-2) via nucleophilic addition-elimination reaction, and the chiral polymer P-2 could be obtained by the reduction reaction of P-1 with NaBH₄. The fluorescence intensity of the chiral polymer P-1 exhibits gradual enhancement upon addition of (d)- or (l)-phenylalaninol and keeps nearly a linear correlation with the concentration molar ratios of (d)- or (l)-phenylalaninol. The value of enantiomeric fluorescence difference ratio (ef) is 6.85 for the chiral polymer on (d)-phenylalaninol. On the contrary, the chiral polymer P-2 shows no obvious fluorescence response toward either (d)- or (l)-phenylalaninol.     

Polybinaphthyls incorporating chiral 2,2′-binaphthyl and isoquinoline moieties by Sonogashira reaction

Polymers P-1, P-2, P-3, P-4 and P-5 were synthesized by the polymerization of 5,8-bis(ethynyl)isoquinoline (M-1) with (R)-3,3′-diiodo-2,2′-bisbutoxy-1,1′-binaphthyl ((R)-M-2), (S)-3,3′-diiodo-2,2′-bisbutoxy-1,1′-binaphthyl ((S)-M-2), (R)-6,6′-dibromo-2,2′-bisbutoxy-1,1′-binaphthyl ((R)-M-3), (S)-6,6′-dibromo-2,2′-bisbutoxy-1,1′-binaphthyl ((S)-M-3), and rac-6,6′-dibromo-2,2′-bisbutoxy-1,1′-binaphthyl (M-4) under Sonogashira reaction, respectively. Both monomers and polymers were analyzed by NMR, MS, FT-IR, UV-vis spectroscopy, DSC-TGA, fluorescence spectroscopy, GPC and circular dichroism (CD) spectroscopy. CD spectra of polymers P-1 and P-2, P-3 and P-4 are almost identical except that they gave opposite signals at each wavelength. The long wavelength CD effect of P-1 and P-2 can be regarded as the more extended conjugated structure in the repeating unit and the helical backbone in the polymer chain. All five polymers have strong blue-green fluorescence due to the efficient energy migration from the extended π-electronic structure of the repeating unit of the polymers to the chiral binaphthyl core and are expected to provide understanding of structure-property relationships of the chiral conjugated polymers.     

Synthesis and properties of chiral helical polymers based on optically active polybinaphthyls

The chiral polymer P-1 was synthesized by the polymerization of (R)-6,6′-dibutyl-3,3′-diiodo-2,2′-bisoctoxy-1,1′-binaphthyl (R-M-1) with 5,5′-divinyl-2,2′-bipyridine (M-1)via Pd-catalyzed Heck reaction. P-2 and P-2′ were prepared by Wittig-Horner reaction of (R)-6,6′-dibutyl-2,2′-bisoctoxy-1,1′-binaphthyl-3,3′-dicarbaldehyde (R-M-2) with 5,5′-bis (diethylphosphonomethyl)-2,2′-bipyridine (M-2) in the presence of EtONa or NaH, respectively. P-3 was synthesized by Wittig-Horner reaction of (R)-6,6′-di(4-trifluoromethylphenyl)-2,2′-bisoctoxy-1,1′-binaphthyl-3,3′-dicarbaldehyde (R-M-3) with M-2 using NaH as a base. The four polymers have strong blue-green fluorescence due to the extended π-electronic structure between the chiral model compounds (R)-6,6′-dibutyl-/di(4-trifluoromethylphenyl)-2,2′-bisoctoxy-1,1′-binaphthyl (R-1 or R-2) and the conjugated linker 2,2′-bipyridyl group via vinylene bridge. Both monomers and polymers were analyzed by NMR, MS, FT-IR, UV-vis spectroscopy, DSC-TGA, fluorescence spectroscopy, GPC and circular dichroism (CD) spectroscopy. Based on the great differences of specific rotation values and CD spectra, P-1 and P-2 may adopt a zigzag chain configuration, while P-2′ and P-3 may adopt a helical configuration. The responsive optical properties of the two chiral helical polymers P-2′ and P-3 on transition metal ions were investigated by fluorescence, UV-vis and CD spectra. The results show that Ag⁺ and Ni²⁺ lead to nearly complete fluorescence quenching of P-2′ and P-3, Cu²⁺ and Fe²⁺ can cause obvious fluorescence quenching, but Zn²⁺ and Cd²⁺ can only produce slight fluorescence quenching. Ag⁺, Ni²⁺, Cu²⁺ and Fe²⁺ can also lead to the obvious changes of UV-vis spectra of P-2′ and P-3. On the contrary, Zn²⁺ and Cd²⁺ cause little changes. Most importantly, the CD intensities and wavelengths of the chiral helical polymers P-2′ and P-3 exhibit the pronounced changes upon addition of Ag⁺ and Ni²⁺.     

(R,R)-salen/salan-based polymer fluorescence sensors for Zn detection

(R,R)-salen-based polymer fluorescence sensor P-1 could be synthesized by the polymerization of 5,5′-(isoquinoline-5,8-diylbis(ethyne-2,1-diyl))-bis(3-tert-butyl-2-hydroxybenzaldehyde) (M-1) with (R,R)-1,2-diaminocyclohexane (M-2) via nucleophilic addition-elimination reaction, and (R,R)-salan-based polymer sensor P-2 could be obtained by the reduction reaction of P-1 with NaBH₄. The fluorescence response behaviors of two chiral polymers P-1 and P-2 on Zn²⁺ were investigated by fluorescence spectra. The fluorescence intensities of P-1 and P-2 can exhibit gradual enhancement upon addition of Zn²⁺. Compared with other cations, such as Na⁺, K⁺, Mg²⁺, Ca²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Cd²⁺, Cr³⁺ and Pb²⁺, Zn²⁺ can lead to the pronounced fluorescence enhancement as high as 22.8-fold for P-1 and 3.75-fold for P-2, respectively. The results show that P-1 and P-2 incorporating (R,R)-salen/salan moieties as receptors in the polymer main chain backbone can exhibit high sensitivity and selectivity for Zn²⁺ detection.     

Hg detection by aniline-based conjugated copolymers with high selectivity

Conjugated polymers (P1, P1L and P2-P5) constructed by alkynyl-substituted aniline and substituted arene analogs could be synthesized through Pd-catalyzed Sonogashira coupling. The responsive optical properties of poly(2-ethynyl aniline) (P1 and P1L for different molecular weights, P1L with longer chains on average) toward various metal ions (including Ni²⁺, Ag⁺, Cu²⁺, Zn²⁺, Fe³⁺, Fe²⁺, Mn²⁺, Na⁺, Ca²⁺, Pb²⁺, K⁺, Cr³⁺, Al³⁺, Cd²⁺, Pt²⁺, Au³⁺ and Tl³⁺) were investigated. Hg²⁺ exhibited the most pronounced fluorescence response of both P1 and P1L without interference from those coexistent ions due to aniline in the polymer backbone as the metal binding ligand, while other metal ions does not cause obvious change of fluorescence. Compared with P1, P1L exhibits better sensitivity toward Hg²⁺. Introducing pyridyl, thienyl or phenyl groups into the polymer backbone would weaken the quenching responses to Hg²⁺ compared with P1. The results indicated P1 and P1L could be used as a selective fluorescence sensor toward Hg²⁺.     

Fluorescent chemosensor for metal ions based on optically active polybinaphthyls and 1,3,4-oxadiazole

Linear chiral polymers P-1 and P-2 were synthesized by the polymerization of (R)-5,5′-dibromo-6,6′-di(4-methylphenyl)-2,2′-bisoctoxy-1,1′-binaphthyl (R-M-1) with 2,5-di(4-vinylphenyl)-1,3,4-oxadiazole (M-2) and 2,5-di(4-tributylstannylphenyl)-1,3,4-oxadiazole (M-3) via Heck and Stille cross-coupling reaction, respectively. The chiral conjugated polymer P-1 can show strong green-blue fluorescence, and the chiral polymer P-2 shows strong blue fluorescence. While the conjugated polymers P-1 and P-2 were used as fluorescent chemosensor for metal ions, their fluorescence can be efficiently quenched on the addition of different metal ions. The obvious quenching effect of the polymers P-1 and P-2 indicates that the intramolecular photoinduced electron transfer (PET) or photoinduced charge transfer (PCT) between the polymer backbone and receptor-ions in the main chain of fluorescent chemosensor can lead to the pronounced fluorescence quenching. The results also show that the chiral polymers P-1 and P-2 incorporating 1,3,4-oxadiazole moiety as the recognition site can act as a special fluorescent chemosensor for the appropriate detection of the sensitive and selective sense of metal ions.     

Polybinaphthyls incorporating chiral (R) or (S)-2,2′-binaphthyland oxadiazole moieties by Stille reaction

Chiral polymers P-1 and P-2 were prepared by the polymerization of (R)-3,3′-diiodo-2,2′-bisbutoxy-1,1′-binaphthyl ((R)-M-1) and (S)-3,3′-diiodo-2,2′-bisbutoxy-1,1′-binaphthyl ((S)-M-1) with 2,5-bis[(4-tributylstannyl)phenyl]-1,3,4-oxadiazole (M-2) via Pd(PPh₃)₄ catalyzed Stille coupling reaction. 1,3,4-Oxadiazole unit not only has high electron affinity, high thermal and oxidative stability, but also serves as a good chromophore. Polymers have strong blue fluorescence due to the efficient energy migration from the extended π-electronic structure of the polymers to the chiral binaphthyl core and can be expected to have potential application in the materials of fluorescent sensors. Circular dichroism (CD) spectra of polymers P-1 and P-2 are almost identical except that they gave opposite signals at each wavelength. The long wavelengths CD effect of P-1 and P-2 can be regarded as the more extended conjugated structure in the repeating unit and a high rigidity of the polymer backbone.     

Fluorescence sensors based on chiral polymer for highly enantioselective recognition of phenylglycinol

Chiral polymer P-1 incorporating (R,R)-salen-type unit was synthesized by the polymerization of (R,R)-1,2-diaminocyclohexane with 2,5-dibutoxy-1,4-di(5-tert-butylsalicyclaldehyde)-phenylene (M-1) via nucleophilic addition-elimination reaction, and chiral polymer P-2 incorporating (R,R)-salan-type unit could be obtained by the reduction reaction of P-1 with NaBH₄. The fluorescence response of two chiral polymers P-1 and P-2 on (R)- or (S)-phenylglycinol were investigated by fluorescence spectra. The fluorescence intensities of two chiral polymers P-1 and P-2 show gradual enhancement upon addition of (R)- or (S)-phenylglycinol and keeps nearly linear correlation with the concentration molar ratios of (R)- or (S)-phenylglycinol. But both P-1 and P-2 exhibited more sensitive response signals for (S)-phenylglycinol. The values of enantiomeric fluorescence difference ratio (ef) are 1.84 and 2.05 for P-1 and P-2, respectively. The results also showed that two chiral polymers P-1 and P-2 can also be used as fluorescence sensors for enantiomer composition determination of phenylglycinol.     

Synthesis of 1,9-bis[glycidyloxypropyl]penta(1′H,1′H,2′H,2′H-perfluoroalkylmethylsiloxane)s and copolymerization with piperazine

A series of 1,9-bis[glycidyloxypropyl]pentasiloxanes (IV-VI) were prepared by the platinum catalyzed hydrosilylation of 1,9-dihydridodecamethylpentasiloxane (I), 1,9-dihydrido-3,5,7-tris(3′,3′,3′-trifluoropropyl)heptamethylpentasiloxane (II), and 1,9-dihydrido-3,5,7-tris(1′H,1′H,2′H,2′H-perfluorooctyl)heptamethylpentasiloxane (III) with allyl glycidyl ether. Subsequently, IV-VI were copolymerized with piperazine to form high molecular weight copoly(carbosiloxane)s (VII-IX). The structures of the 1,9-bis[glycidyloxypropyl]penta-siloxanes (IV-VI) and copoly(carbosiloxane)s (VII-IX) were determined by ¹H, ¹³C, ²⁹Si, and ¹⁹F NMR as well as IR spectroscopy. The molecular weight distributions (M_w/M_n) of VII-IX have been characterized by gel permeation chromatography and their thermal properties measured by differential scanning calorimetry and thermal gravimetric analysis.     

Polymer-based fluorescence sensor incorporating triazole moieties for Hg detection via click reaction

The polymer could be obtained by the polymerization of 1,4-dibutoxy-2,5-diethynylbenzene (M-1) with 1,4-diazidobenzene (M-2)via click reaction. The polymer show blue fluorescence. The responsive optical properties of the polymer on various transition metal ions were investigated by fluorescence spectra. Compared with other cations, such as Co²⁺, Ni²⁺, Ag⁺, Cd²⁺, Cu²⁺ and Zn²⁺, Hg²⁺ can exhibit the most pronounced fluorescence response of the polymer Hg²⁺ can exhibit the most pronounced fluorescence response of the polymer due to triazole moiety in the polymer main chain as the metal binding ligand. The results indicate this kind of conjugated polymer with triazole moiety synthesized by click reaction can be used as a selective fluorescence sensor for Hg²⁺ detection.     

Homo- and R/S-copolymerizations of chiral methylpropargyl esters carrying pyrene moieties, and optical properties of the formed polymers

Pyrene-functionalized chiral methylpropargyl esters, (R)-3-butyn-2-yl-1-pyrenebutyrate [(R)-1], (S)-3-butyn-2-yl-1-pyrenebutyrate [(S)-1], (R)-3-butyn-2-yl-1-pyrenecarboxylate [(R)-2], and 3-butyn-2-yl-1-pyrenecarboxylate [(R,S)-2] were polymerized with (nbd)Rh⁺[η⁶-C₆H₅B⁻(C₆H₅)₃] to obtain the corresponding polymers with moderate molecular weights (M_n: 10?500-66?500) in good yields (82-97%). All the polymers were soluble in CHCl₃, CH₂Cl₂, and THF. The polarimetric and CD spectroscopic data indicated that poly[(R)-1], poly[(S)-1], and poly[(R)-2] existed in a helical structure with predominantly one-handed screw sense in these solvents. The helical structure of poly[(R)-1] and poly[(S)-1] was stable upon heating and addition of MeOH, while that of poly[(R)-2] changed upon MeOH addition. The copolymerization of (R)-1 with (S)-1 was also conducted to obtain the copolymers satisfactorily. Poly[(R)-1], poly[(S)-1], and poly[(R)-2] emitted fluorescence smaller than the corresponding racemic copolymers. The fluorescence intensity was tuned by the addition of MeOH to THF solutions of the polymers.     

A polymer based fluorescent sensor for Zn detection and its application for constructing logic gates

A polymer-based fluorescent sensor was synthesized by polymerization of (S)-6,6′-dibutyl-3,3′-(di-5-salicylde-ethynyl)-2,2′-binaphthol (M-1) with (R,R)-1,2-diaminocyclohexane (M-2) via nucleophilic addition-elimination reaction. The responsive optical properties of the polymer on transition metal ions were investigated by fluorescence and UV-vis spectra. The polymer (1.0 × 10⁻⁵ mol/L in THF) could emit fluorescence at 550 nm and exhibit high selectivity for sensing Zn²⁺ with 36.1-fold fluorescence enhancement. Three logic gates were designed according to the different fluorescence responses of this polymer sensor to Zn²⁺ and Cu²⁺.     

Cationic phenyl-substituted poly(p-phenylenevinylene) related copolymers with efficient photoluminescence and synthetically tunable emissive colors

A series of amino-functionalized phenyl-substituted poly(p-phenylenevinylene) (PPV) related copolymers were synthesized by Wittig reaction. Their corresponding cationic conjugated polymers were successfully obtained via a post-polymerization approach. On the basis of FT-IR and ¹H NMR spectra, it was found that phenyl-substituted PPV related copolymers containing alkoxylated benzene (neutral polymer P1 and quaternized polymer P1′), phenylated benzene (neutral polymer P2 and quaternized polymer P2′) and fluorene (neutral polymer P3 and quaternized polymer P3′) moieties are of 55, 80, and 45% cis-vinylic linkage respectively while the polymer containing thiophene moiety (neutral polymer P4 and quaternized polymer P4′) is primarily of trans-vinylic linkage. Their photoluminescence (PL) were conveniently tuned from blue color to yellow color by introducing units with different optoelectronic properties into the PPV backbones. The polymer with fluorene unit and bulky phenylene-substituted benzene unit in the backbone exhibited the highest PL efficiency among these neutral and quaternized PPVs. P4′ containing little cis-vinylic linkage showed complete quenching while P1′-P3′ containing much more cis-vinylic linkage showed incomplete quenching, indicating that the quenching behavior of these cationic PPVs may be highly influenced by the content of cis-vinylic linkage in the PPV backbones.     

A facile galvanostatic method for the synthesis of quinoxalinediones

Electrochemical oxidation of catechols (1a-d) has been studied in the presence of N,N-dimethylethylendiamine (3) as a nucleophile in aqueous solutions, using cyclic voltammetry, constant-current coulometry and controlled-potential coulometry. The results indicate that the quinones derived from catechols (2a-d) participate in Michael addition reactions with N,N′-dimethylethylendiamine (3) via the ECECE mechanism to form the corresponding quinoxalinedione derivatives (6a-c).     

Synthesis and properties of cyclopentadithiophene-based poly(silarylenesiloxane) derivatives

Poly(silarylenesiloxane) derivatives with 4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene moiety, bearing dimethyl- (P1), methylphenyl- (P2) and diphenyl- (P3) substituents on silyl moieties, were prepared via polycondensation of the corresponding disilanol monomers, that is, 2,6-bis(dimethylhydroxysilyl)-4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene (M1), 2,6-bis(methylphenylhydroxysilyl)-4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene (M2), and 2,6-bis(diphenylhydroxysilyl)-4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene (M3), respectively. P1-P3 exhibited the good solubility in common organic solvents, such as benzene, toluene, chloroform, dichloromethane, THF, and so on. The glass transition temperatures (T_gs) of P1, P2 and P3 were determined by differential scanning calorimetry to be 56, 97 and 137 °C, respectively, depending on the substituent on the silyl moieties. No melting temperatures (T_ms) of P1, P2 and P3 were observed, suggesting the obtained P1-P3 are amorphous polymers. The temperatures at 5% weight loss (T_d5s) of P1, P2 and P3 were 460, 459 and 479 °C, respectively, indicating that the larger number of phenyl group on the silyl moieties resulted in the better thermostability. Bathochromic and hyperchromic effects were observed in the absorption and fluorescence spectra by introducing silyl substituents onto 4,4-dimethylcyclopenta[2,1-b:3,4-b′]dithiophene moiety. In addition, the bathochromic shift of the maximum absorption (λ_abs) and the increase in the fluorescence quantum yield (Φ_F) were observed by the introduction of phenyl group onto the silyl moieties.     

Aromatic diamine-based benzoxazines and their high performance thermosets

Four high-purity aromatic diamine-based benzoxazines (13-16), which could not easily be synthesized by traditional approaches, were successfully synthesized by a facile, widely useful three-step synthetic method using four typical aromatic diamines - 4,4′-diamino diphenyl methane (1), 4,4′-diamino diphenyl sulfone (2), 2,2-bis(4-(4-aminophenoxy)phenyl)propane (3), and bis(4-(4-aminophenoxy)phenyl)ether (4), respectively, as starting materials. The structures of the monomers (5-16) were confirmed by ¹H, ¹³C, ¹H-¹H and ¹H-¹³C NMR spectra. Their high performance thermosets, P(13-16), were obtained by thermal curing of benzoxazines (13-16), and their properties were studied and compared with polymer derived from bis(3,4-dihydro-2H-3-phenyl-1,3-benzoxazinyl)methane (F-a), a typical aromatic biphenol-based benzoxazine. Among the benzoxazines, 13 and F-a are constitutional isomers, but the T_g value and 5% decomposition temperature of P(13) are 53 and 111 °C, respectively, higher than those of P(F-a), demonstrating the power of the molecule-approach to enhance the thermal properties. Because of the large varieties of aromatic diamines, this approach can increase the molecule-design flexibility of benzoxazines.     

Tyrosine-based poly(m-phenyleneethynylene-p-phenyleneethynylene)s. Helix folding and responsiveness to a base

The Sonogashira-Hagihara polymerization of 3′,5′-diiodo-N-α-tert-butoxycarbonyl-l-tyrosine methyl ester (1) and 3′,5′-diiodo-N-α-tert-butoxycarbonyl-O-methyl-l-tyrosine methyl ester (2) with para-diethynylbenzene (3) was carried out to obtain optically active poly(m-phenyleneethynylene-p-phenyleneethynylene)s [poly(1) and poly(2)] with M_n’s ranging from 9900 to 15,000 in 80-87% yields. Poly(1) exhibited intense CD signals in DMSO and THF, but did not in CH₂Cl₂, indicating that it took a predominantly one-handed helical conformation in the former two solvents. On the other hand, there was no evidence for poly(2) to take a helical structure in these solvents. Poly(1) turned the CD sign at 390 nm from plus to minus in DMSO/H₂O = 9/1 (v/v) by the addition of NaOH. Alkaline hydrolysis of ester moieties of poly(1) and poly(2) gave the corresponding polymers having carboxy groups [poly(1a) and poly(2a)]. Poly(1a) and poly(2a) increased the CD intensity by the addition of NaOH.     

Pd-catalyzed hydrosilylation polymerization of a dihydrosilane with diyne/triyne mixed systems affording crosslinked silylene-divinylene polymers and their properties

Treatment of a dihydrosilane (methylphenylsilane, 1) with mixtures of a diyne (p- or m-diethynylbenzene, 2a or 2b) and a triyne (1,3,5-triethynylbenzene, 3a or B,B′,B″-triethynyl-N,N′,N″-trimethylborazine, 3b; 1:2:3=100:95:5, 100:90:10, 100:80:20) in the presence of Pd-PCy₃ (Cy=cyclohexyl) catalyst gave new crosslinked silylenedivinylene polycarbosilanes. In TGA the resulting crosslinked polymers tended to show higher Td₅ values and higher char yields than the corresponding linear polymers. On the other hand, UV/vis absorption spectra of the crosslinked polymers obtained in the reactions of 2a or 2b with 3a exhibited increased broad peaks around 390 nm for 2a or 360 nm for 2b. Coincidently, their fluorescence spectra showed significant increase of the emission peaks in 400-550 nm. The crosslinked polymer derived from 2a and 3b, however, showed decrease of the absorption peak around 390 nm and profound depression of fluorescence peaks in 400-550 nm.     

Synthesis of amphiphilic triblock copolymer of polystyrene and poly(4-vinylbenzyl glucoside) via TEMPO-mediated living radical polymerization

4-Vinylbenzyl glucoside peracetate 1 was polymerized with α,α′-bis(2′,2′,6′,6′-tetramethyl-1′-piperidinyloxy)-1,4-diethylbenzene 2 in chlorobenzene using (1S)-(+)-10-camphorsulfonic acid anhydrous (CSA) as an accelerator ([1]=0.4 M,[1]/[2]/[CSA]=75/1/1.3) at 125 °C for 5 h. The polymerization afforded poly(4-vinylbenzyl glucoside peracetate) having TEMPO moieties on both sides of the chain ends, 3, with a molecular weight (M_w,SLS) of 8500, a polydispersity index (M_w/M_n) of 1.09, and an average degree of polymerization of the 1 unit (x) of 17. Styrene (St) was polymerized with 3 in chlorobenzene at 125 °C (St/chlorobenzene=1/2, w/w). The polymerization successfully afforded polystyrene-poly(4-vinyl glucoside peracetate)-polystyrene, 4, when the polymerization time was below about 2 h. Polymer 4 with the M_w,SLS of 12,500, 17,900, and 29,400, the compositions (y-x-y) of 20-17-20, 45-17-45, and 100-17-100, and the M_w/M_n of 1.12, 1.14 and 1.17 were modified by deacetylation using sodium methoxide in dry-THF into polystyrene-poly(4-vinyl glucoside peracetate)-polystyrene, 5. The solubility of polymer 5 was examined using a good solvent for polystyrene such as toluene and for the saccharide such as H₂O.