Glycopolymeric inhibitors of β‐glucuronidase. III. Configurational effects of hydroxy groups in pendant glyco‐units in polymers upon inhibition of β‐glucuronidase

Two kinds of new glycopolymers, (P(VB‐1‐GlcaH‐co‐AAm), 9 ) and (P(VB‐1‐Glco‐co‐AAm), 10 ), were synthesized through the radical copolymerization of styrene derivatives bearing pendant D ‐glucaric and D ‐gluconic moieties, N‐(p‐vinylbenzyl)‐1‐D ‐glucaramide (VB‐1‐GlcaH, 7 ), and N‐(p‐vinylbenzyl)‐D ‐gluconamide (VB‐1‐Glco, 8 ), with acrylamide (AAm). Glycopolymer 9 bearing the pendant glucaric moiety at the first position inhibited the hydrolysis of a model compound for xenobiotics‐β‐glucuronide conjugates, p‐nitrophenyl β‐D ‐glucuronide, uncompetitively, in contrast to the competitive inhibition in the presence of the corresponding isomeric glycopolymer bearing the pendant D ‐glucaric unit at the sixth position (P(VB‐6‐GlcaH‐co‐AAm), 3 ) reported in our previous article. On the other hand, another copolymer 10 bearing the gluconic moiety was found not to inhibit the hydrolysis as well as the corresponding copolymer bearing pendant gulonic unit (P(VB‐6‐Glco‐co‐AAm), 4 ). These results indicate that the hydrolysis is influenced not only by existence of pendant carboxyl units but also by the direction on the linkage of the glyco‐units to the polymer frame. Therefore the configurational position of hydroxy groups in pendant glyco‐units in macromolecular inhibitors may be essential for the interaction with β‐glucuronidase. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4895–4903, 2006     

Isobutylene‐rich macromonomers: Dynamics and yields of peroxide‐initiated crosslinking

New isobutylene‐rich elastomers bearing multiple pendant styrenic, acrylic, maleimidic, vinylic, and allylic functional groups have been prepared and examined in the context of peroxide‐initiated crosslinking. Halide displacement from brominated poly(isobutylene‐co‐isoprene) (BIIR) by the requisite carboxylate nucleophiles in homogeneous toluene solutions provide the desired esters in quantitative yield without complications from dehydrohalogenation or premature crosslinking. Heating the resulting macromonomers with dicumyl peroxide to 160 °C under solvent‐free conditions gives thermoset derivatives, with reaction rates and yields depending markedly on functional group structure. In general, high cure extents can only be achieved using highly reactive pendant functional groups, owing to the competitive balance between crosslinking through C?C oligomerization, and degradation through β‐scission of backbone macroradical intermediates. Independent control of crosslinking rates and cure extents is gained through the use of nitroxyl radical traps bearing acrylate functionality. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 123–132     

Reversible fixation and release of carbon dioxide with a binary system consisting of polyethylene glycol and polystyrene‐bearing cyclic amidine pendant group

In this study, we investigated the CO₂‐capture/release behavior of the polystyrene‐bearing cyclic amidine pendant groups, which was synthesized via free radical polymerization of HCl salt of the corresponding styrene monomer followed by neutralization. For comparison, we also prepared the polystyrene bearing N‐formyl‐1,3‐propanediamine pendant groups through the hydrolysis of the cyclic amidine group by treatment with an alkaline solution. First, we examined the CO₂‐capture/release behaviors of the amidine and amine monomers in aqueous solution in terms of conductivity. The conductivity of a wet DMSO solution of the amidine monomer increased upon CO₂ bubbling at 25 °C and reached a stationary value of about 11 mS/m, which indicated the formation of the bicarbonate salt. Conversely, the conductivity decreased to its original value upon N₂ bubbling at 50 °C, reflecting the complete release of the trapped CO₂ molecules. Both solutions showed the changes in the conductivity with quick responses, and no appreciable difference was observed between them. We then investigated the CO₂‐capture/release behaviors of the amidine and amine polymers, by taking advantage of the binary system with polyethylene glycol, and found that the binary system with the amidine polymer captured and released CO₂ more efficiently than that with the amine polymer. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2025–2031     

Regiospecific design strategies for 3‐arylpolythiophenes with pendant stable radical groups

Carbon—carbon bond‐forming polymerization of 2‐bromo‐3‐(3′,5′‐di‐t‐butyl‐4′‐methoxyphenyl)‐thiophene yields poly[3‐(3′,5′‐di‐t‐butyl‐4′‐methoxyphenyl)‐2,5‐thienylene] with regiospecific connectivity and a degree of polymerization of about six. Lewis‐acid‐moderated‐cleavage of the methoxy groups on the pendant phenyl group yield the corresponding polyphenolic polymer, which is oxidized under solution conditions to yield the title polyradical. Poly[3‐(3′,5′‐di‐t‐butyl‐4′‐oxyphenyl)‐2,5‐thienylene] exhibits a strong, persistent electron spin resonance spectrum and a UV–visible spectrum consistent with formation of the pendant phenoxyl spin‐bearing units. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 779–788, 1999     

Assorted Phenoxyl‐Radical Polymers and Their Application in Lithium‐Organic Batteries

The synthesis and electrochemical characterization of novel polymers bearing phenoxyl‐radicals as redox‐active side chains is described. The monomers are synthesized from the corresponding phenols and quinones, respectively. These compounds are subsequently poly­merized via ring‐opening metathesis polymerization. The electrochemical properties of the phenoxyl‐radical polymers are characterized using cyclic voltammetry and the most promising polymer is investigated as active material in a lithium coin‐cell, creating the first phenoxyl‐lithium battery. These phenoxyl‐containing polymers represent interesting anode materials for organic radical and lithium batteries due to their suitable redox‐potentials and possibility to create batteries with higher potentials as well as straightforward synthesis procedures.

     

Pendant groups fine‐tuning thermal gelation of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) aqueous solution

Novel poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) (PCL‐PEG‐PCL) bearing pendant hydrophobic γ‐(carbamic acid benzyl ester) groups (PECB) and hydrophiphilic amino groups (PECN) were synthesized based on the functionalized comonomer γ‐(carbamic acid benzyl ester)‐ε‐caprolactone (CABCL). The thermal gelation behavior of the amphiphilic copolymer aqueous solutions was examined. The phase transition behavior could be finely tuned via the pendant groups, and an abnormal phenomenon occurred that the sol–gel transition temperature shifted to a higher temperature for PECB whereas a lower temperature for PECN. The micelles percolation was adopted to clarify the hydrogel mechanism, and the effect of the pendant groups on the micellization was further investigated in detail. The results demonstrated that the introduction of γ‐(carbamic acid benzyl ester) pendant groups significantly decreased the crystallinity of the copolymer micelles whereas amino pendant groups made the micelles easy to aggregate. Thus, the thermal gelation of PEG/PCL aqueous solution could be finely tuned by the pendant groups, and the pendant groups modified PEG/PCL hydrogels are expected to have great potential biomedical application. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2571–2581     

Novel Cross‐Linked Conducting Polythiophene with Yellow‐Green‐Light‐Emitting Properties and Good Thermal Stability

A novel conjugated polythiophene derivative with polymethacrylate attaching to the polymer backbone via an alkyl spacer was successfully synthesized. A methacrylate‐substituted thiophene monomer, 3‐(hexyl methacrylate)thiophene was prepared and polymerized by free radical polymerization, followed by an electrochemical polymerization. The resulting polymer as a yellow‐green‐light emitter, has potential applications in photoelectronics area.     

Synthesis of phosphate‐pendant polymers and their application to thermally latent polymeric initiators

A novel phosphate monomer, O‐p‐(methacryloyloxymethyl)benzyl O,O‐diethyl phosphate (MDP) was synthesized by the reaction of diethyl phosphorochloridate with 1,4‐benzenedimethanol, followed by the reaction with methacryloyl chloride in the presence of triethylamine. The radical polymerization of MDP and copolymerization with methyl methacrylate were carried out in the presence of 2,2′‐azobisisobutyronitrile (3 mol %) in dimethylacetamide at 60 °C for 20 h to afford phosphate‐pendant polymers. The polymerization of glycidyl phenyl ether (GPE) was carried out with the phosphate‐pendant polymer as an initiator in the presence of ZnCl₂. The polymerization did not proceed below 90 °C but rapidly proceeded above 90 °C to afford polyGPE. The phosphate‐pendant polymer served as a good thermally latent polymeric initiator. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3365–3370, 2001     

Preparation and utilization of poly(methacryloylsilatrane) as a salt‐dissociation enhancer in PEO‐based polymer electrolytes

Polymers containing silatrane units were prepared by the free radical polymerization of methacryloylsilatrane (MPS), and their conductivities were evaluated. We confirmed that MPS can be polymerized without excessive decomposition of the silatrane units by the radical polymerization initiated by azobisisobutyronitrile. The chemical structure of the polymerized MPS (pMPS) was characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy. The pMPS formed a homogeneous complex with lithium trifluoromethyl sulfonate (LiOTf), although the obtained pMPS/LiOTf complex did not show conductivity. The negligible conductivity was caused by the high glass transition temperature (T_g) of the pMPS matrix, which exceeded 70°C. The pMPS was subsequently utilized as a salt‐dissociation enhancer for the poly(ethylene oxide)‐based polymer electrolyte. MPS was copolymerized with poly[methacryloyl oligo(ethylene oxide)] (pMEO) by free radical polymerization. When the pMEO incorporated a small amount of MPS units (i.e. lower than 15 mol%), the elevation in T_g was not observed, and the conductivity markedly improved. Among the series of copolymers and when compared with pristine pMEO, the copolymer containing 6.3% of MPS units had the maximum conductivity (3.1 × 10^?4 S cm^?1 at 80°C). The Vogel–Fulcher–Tammann fitting parameters showed that the conductivity was improved by the increase in the number of carrier ions. The enhancement in salt dissociation was presumably due to the homogeneous incorporation of polar MPS units. However, when the MPS unit content exceeded 15 mol%, the conductivity was lowered because of the increase in T_g. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and characterization of proton‐conducting copolyimides bearing pendant sulfonic acid groups

A series of sulfonated copolyimides (co‐SPIs) bearing pendant sulfonic acid groups were synthesized from 1,4,5,8‐naphthalenetetracarboxylic dianhydride (NTDA), bis(3‐sulfopropoxy) benzidines (BSPBs), and common nonsulfonated diamines via statistical or sequenced polycondensation reactions. Membranes were prepared by casting their m‐cresol solutions. The co‐SPI membrane had a microphase‐separated structure composed of hydrophilic and hydrophobic domains, but the connecting behavior of hydrophilic domains was different from that of the homo‐SPIs. The co‐SPI membranes displayed clear anisotropic membrane swelling in water with negligibly small dimensional changes in the plane direction of the membrane. With water uptake values of 39–94 wt %, they showed dimensional changes in membrane thickness of about 0.11–0.58, which were much lower than those of homo‐SPIs. The proton conductivity σ values of co‐SPI membranes with ion exchange capacity values ranging from 1.95–2.32 meq/g increased sigmoidally with increasing relative humidity. They displayed σ values of 0.05–0.16 S/cm at 50 °C in liquid water. Increasing temperature up to 120 °C resulted in further increase in proton conductivity. The co‐SPI membranes showed relatively good conductivity stability during the aging treatment in water at 100 °C for 300 h. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1545–1553, 2005     

Photoluminescent behavior of poly(3‐hexylthiophene) derivatives with a high azobenzene content in the side chains

A series of polythiophene derivatives with substantially higher azobenzene contents in the side chains were prepared via copolymerization of 3‐hexylthiophene with four different types of 4‐((4‐(phenyl)azo)phenoxy)alkyl‐3‐thienylacetate. The alkyl spacers with different lengths, i.e. butyl, hexyl, octyl and undecyl groups were used between the azobenzene group and the thiophene ring. The compositions, structures and thermal properties of these polythiophene derivatives were characterized. The structural dependence of photoluminescent emission, photochromic behavior of these copolymers were systematically studied and compared with poly(3‐hexylthiophene). The results show that the azobenzene substitution renders the polythiophene some interesting optical properties that can be modulated by UV light irradiation. In the azobenzene modified polythiophene, the intensity of photoluminescent emission associated with the conjugated polythiophene main chain was found to decrease significantly upon UV irradiation. The finding suggests that the photo‐induced trans‐cis isomerization of the azobenzene pendant groups has a significant effect on photoluminescent emission, particularly when short spacers are used between azobenzene groups and the main chain. However, the effect becomes less prominent when longer spacers are used between the azobenzene group and the main chain. Furthermore, UV irradiation of the copolymers also resulted in an increase in intensity and broadening of bandwidth for the absorption peak associated with the polythiophene backbones. Again the magnitude of intensity changes upon UV irradiation were found to be dependent on the spacer length between the azobenzene group and polythiophene main chain. Copyright © 2005 John Wiley & Sons, Ltd.     

Constructing novel double‐bond‐containing well‐defined amphiphilic graft copolymers via successive Ni‐catalyzed living coordination polymerization and SET‐LRP

A series of polyallene‐based well‐defined amphiphilic graft copolymers, poly(6‐methyl‐1,2‐heptadiene‐4‐ol)‐g‐poly(2‐(diethylamino)ethyl methacrylate) (PMHDO‐g‐PDEAEMA), was synthesized through the grafting‐from technique. First, double‐bond‐containing PMHDO backbone bearing pendant hydroxyls was prepared via [(η³‐allyl)NiOCOCF₃]₂‐initiated living coordination polymerization of 6‐methyl‐1,2‐heptadiene‐4‐ol (MHDO). The pendant hydroxyls in the homopolymer were then reacted with 2‐chloropropionyl chloride to give PMHDO‐Cl macroinitiator. Finally, hydrophilic PDEAEMA side chains were formed by single electron transfer‐living radical polymerization (SET‐LRP) of 2‐(diethylamino)ethyl methacrylate (DEAEMA) in THF/H₂O initiated by the macroinitiator using CuCl/Me₆TREN as catalytic system to afford PMHDO‐g‐PDEAEMA graft copolymers. The narrow molecular weight distributions (M_w/M_n ≤ 1.35) and kinetics experiment showed the controllability of SET‐LRP graft copolymerization of DEAEMA. The critical micelle concentration (cmc) of PMHDO‐g‐PDEAEMA amphiphilic graft copolymer in aqueous media was determined by fluorescence probe technique and the relationships between cmc and pH or salinity were also investigated. Micellar morphologies were preliminarily explored using transmission electron microscopy. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis of helical polyisocyanides bearing aza‐crown ether groups as pendant

We, herein, present a novel synthesis of responsive helical poly(aryl isocyanide)s bearing aza‐crown ethers as pendant groups. Chiral aryl isocyanide monomers bearing an aza‐crown ether as a pendant were designed and synthesized, piror to polymerization using a Pd‐Pt µ‐ethynediyl complex as an initiator to give the corresponding polymers in good yield. The resulting polyisocyanides adopted a stable helical structure in solution, as confirmed by circular dichroism spectroscopic analysis. In addition, the polymers were soluble in various solvents. Furthemore, the addition of suitable alkali metal ions to the crown ether of the sidechain on the helical polyisocyanide to form host‐gest complexes resulted in deformation of the helix due to electrostatic repulsion, and these phenomena depended on the size of metal cations. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 496–504.     

Polymerization of the new double‐charged monomer bis‐1,3(N,N,N‐trimethylammonium dicyanamide)‐2‐propylmethacrylate and ionic conductivity of the novel polyelectrolytes

The achievement of high ionic conductivity in single‐ion conducting polymer electrolytes is one of the important aims for various electrochemical devices including modern lithium batteries. One way to enhance the ionic conductivity in polyelectrolyte systems is to increase the quantity of charge carriers in each monomer unit. Highly charged poly(bis‐1,3(N,N,N‐trimethylammonium)‐2‐propylmethacrylate) with one of the most conducting anions, namely dicyanamide, was prepared via free radical bulk polymerization or using ionic liquids as reaction medium. The cationic polymers of the double‐charged monomer have molar masses up to = 1,830,000 g/mol and the ionic conductivity equal to 5.51 × 10^?5 S / cm at 25°C. The film forming ability, crystallinity, thermal stability, and glass transition temperatures of the new polymeric ionic liquids obtained from detailed studies are presented. Copyright © 2009 John Wiley & Sons, Ltd.     

Controlled synthesis and functionalization of PEGylated methacrylates bearing cyclic carbonate pendant groups

Homopolymer bearing cyclic carbonate (CC) group, ABA type triblock copolymers, and (AC)B(AC) type terpolymers with statistical arrangement of A and C monomers bearing side chain CC groups are reported here. Difunctional poly(ethylene glycol) macroinitiators (PEGMIs) were prepared from PEG of three different molecular weights. PEGMIs were subsequently used for the preparation of polymers bearing CC pendant groups from cyclic carbonate methacrylate (CCMA) under atom transfer radical polymerization to yield polymers with low polydispersity index. Homopolymer and ABA type triblock copolymers were obtained by polymerizing CCMA monomer and (AC)B(AC) type statistical terpolymers were obtained when methyl methacrylate was included as a comonomer. No polymer was obtained when styrene was used as comonomer. The cyclic carbonate groups were subjected to ring‐opening reaction with monoamine to yield side chain hydroxyurethane polymers with increased solubility and diamines to yield crosslinked insoluble materials. Changes in wettability characteristics were studied by following the water contact angle of the polymers before and after ring‐opening reaction involving the cyclic carbonate pendant group. The polymers which composed of electrolyte in the form of PEG and coordinating species in the form of pendant cyclic carbonate groups showed conductivity in the range of 2–5 × 10^?6 Scm^?1 at 23 °C after doping with lithium bis(trifluoromethane)sulfonimide as characterized by impedance spectroscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1622–1632, 2010     

An approach to one‐dimensional conductive polymer composites

A substantial approach to one‐dimensional (1D) electrically conductive composites was proposed which was based on the thermodynamic analysis of electric‐field‐induced particle alignment in a nonpolar thermoplastic polymer matrix. The process condition window was based on the real‐time exploration of dynamic percolation under different electric fields with carbon black (CB)‐filled polyethylene as a model. The CB content was the main factor of the process condition. Its upper limit was set as the critical percolation concentration at the thermodynamic equilibrium state without an electric field to eliminate the possibility of conductive network formation perpendicular to the electric‐field direction, whereas its lower limit the critical percolation concentration at the thermodynamic equilibrium state under a critical electric field (E*). A composite with CB content in this window, isothermally treated in an electric field not less than E*, showed conductivity in the electric‐field direction about 10⁵ times larger than that in the perpendicular direction. A 1D cluster structure in the direction of the electric filed was confirmed with scanning electron microscopy morphology observations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 184–189, 2005     

Synthesis of poly(o‐phenylenediamine) nanofiber with novel structure and properties

The poly(o‐phenylenediamine) (PoPD) was synthesized from the monomer o‐phenylenediamine in various organic solvent medium viz. dimethyl sulfoxide (DMSO), N,N‐dimethyl formamide (DMF) and methanol using ammonium per sulfate as a radical initiator. The structure just like polyaniline derivative with free ?NH functional groups of the synthesized polymers confirmed by various standard characterizations was explained from the proposed polymerization mechanism. All the synthesized polymers were completely soluble in common organic solvent like DMSO and DMF because of the presence of polar free ?NH functional groups in its structure. The formation of polymer nanofiber by reverse salting‐out process was confirmed, and the synthesized polymer in DMSO medium was the best polymer in terms of nano‐morphology as well as conducting properties. Interestingly, the average DC conductivity of undoped polymer film was recorded as 2.21 × 10^?6 Scm^?1 because of induced doping through self charge separation. Moreover, the conductivity of the polymer film was further increased to 1.16 × 10^?3 Scm^?1 after doping by sulfuric acid. Copyright © 2016 John Wiley & Sons, Ltd.     

Correlating backbone‐to‐backbone distance to ionic conductivity in amorphous polymerized ionic liquids

The morphology and ionic conductivity of poly(1‐n‐alkyl‐3‐vinylimidazolium)‐based homopolymers polymerized from ionic liquids were investigated as a function of the alkyl chain length and counterion type. In general, X‐ray scattering showed three features: (i) backbone‐to‐backbone, (ii) anion‐to‐anion, and (iii) pendant‐to‐pendant characteristic distances. As the alkyl chain length increases, the backbone‐to‐backbone separation increases. As the size of counterion increases, the anion‐to‐anion scattering peak becomes apparent and its correlation length increases. The X‐ray scattering features shift to lower angles as the temperature increases due to thermal expansion. The ionic conductivity results show that the glass transition temperature (T_g) is a dominant, but not exclusive, parameter in determining ion transport. The T_g‐independent ionic conductivity decreases as the backbone‐to‐backbone spacing increases. Further interpretation of the ionic conductivity using the Vogel–Fulcher–Tammann equation enabled the correlation between polymer morphology and ionic conductivity, which highlights the importance of anion hoping between adjacent polymer backbones. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis and characterization of a π‐conjugated hybrid of oligothiophene and porphyrin

5‐(3‐Thienyl)‐10,15,20‐triethyl‐21H,23H‐porphine (H₂(ttep)) was synthesized and characterized. Oxidative polymerization of H₂(ttep) gave a novel oligomeric porphyrin linked at the 2,5‐positions of the thienyl group. Electric conductivity of 4 × 10^?1 S/cm after I₂ doping indicated that the oligomer had a π‐conjugated structure with a delocalization of π electrons over the thienylene backbone. PM3 calculations revealed a low HOCO‐LUCO gap, which was consistent with the relatively high electric conductivity. Regioregular (head‐to‐tail) structure was inferred from spectroscopic and calculational results. The pendant porphyrin groups formed a regular J‐type array along the thienylene backbone, which was indicated by a significant red shift of the Soret band maximum. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5403–5412, 2006     

Radical copolymerization of chlorotrifluoroethylene with 4‐bromo‐3,3,4,4‐tetrafluorobut‐1‐ene

The radical copolymerization of chlorotrifluoroethylene (CTFE) with 3,3,4,4‐tetrafluoro‐4‐bromobut‐1‐ene (BTFB) initiated by tert‐butylperoxypivalate is presented. The microstructures of the obtained copolymers are determined by means of NMR spectroscopies and elemental analysis and show that random copolymers were obtained. A wide range of poly(CTFE‐co‐BTFB) copolymers is synthesized, containing from 17 to 89 mol % of CTFE. In all the cases, CTFE is the less reactive of both comonomers. T_d^10% values, ranging from 163 up to 359 °C, are dependent on the BTFB content. These variations of thermal property are attributed to the increase in the number of C‐H and C‐Br bonds breakdown when the BTFB molar percentage in the copolymer is higher. T_g values range from 19 to 39 °C and a decreasing trend is observed when increasing the amount of BTFB in the copolymer. This observation arises from the higher flexibility of the copolymer when increasing the number of fluorobrominated lateral chains. These original fluoropolymers bearing reactive pendant bromo groups are suitable candidates for various applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1714–1720