Synthesis and antitumour and antiangiogenesis activity of polymers containing methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid

A new monomer, methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid (MTCA), was synthesized from citric acid and methacrylic anhydride. Poly(methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid) and poly(methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid)‐co‐(maleic anhydride) were prepared by radical polymerizations. Terpoly(methacryloyl‐2‐oxy‐1,2,3‐propane tricarboxylic acid–maleic anhydride–furan) was obtained by in situ terpolymerization of MTCA and exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalic anhydride. The synthesized samples were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The number‐average molecular weights of the fractionated polymers determined by GPC were in the range 14 900–16 600 and polydispersity indices were less than 1.14. The in vitro IC₅₀ values of the monomer and polymers against cancer and normal cell lines were much higher than those of 5‐fluorouracil (5‐FU). The in vivo antitumour activities of the synthesized samples at a dosage of 0.8 mg kg⁻¹ against mice bearing the sarcoma 180 tumour cell line decreased in the order terpoly(MTCA‐MAH‐FUR) > poly(MTCA‐co‐MAH) > poly(MTCA) > MTCA > 5‐FU. The synthesized samples inhibited DNA replication and angiogenetic activity more than did 5‐FU. © 2001 Society of Chemical Industry     

Synthesis,antitumour and DNA replication activities of polymers containing vinyl‐(5‐fluorouracil)‐ethanoate

A new monomer, vinyl‐(5‐fluorouracil)‐ethanoate (VFUE), was synthesized by reaction of 5‐fluorouracil (5‐FU) and vinyl iodoacetate. The homopolymer of VFUE and its copolymers with acrylic acid (A, A) and maleic anhydride (MAH) were prepared by photopolymerization. The synthesized VFUE and polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The contents of VFUE unit in poly(VFUE‐co‐AA) and poly(VFUE‐co‐MAH) were 21 mol% and 16 mol%, respectively. The number average molecular weights of the polymers determined by gel permeation chromatography were in the range 9600–17900 g mol^?1. The in vitro cytotoxicities of the samples against a normal cell line decreased as follows: 5‐FU > VFUE > poly(VFUE) > poly(VFUE‐co‐AA) > poly(VFUE‐co‐MAH). The in vivo antitumour activities of the polymers against Balb/C mice bearing the sarcoma 180 tumour cells were greater than those of 5‐FU at all concentrations. The inhibition of simian virus 40 DNA replication by the samples was much greater than that of the control. © 2002 Society of Chemical Industry     

Synthesis and biological activity of phthalimide‐based polymers containing 5‐fluorouracil

The attachment of anticancer agents to polymers is a promising approach towards reducing the toxic side‐effects and retaining the potent antitumour activity of these agents. A new tetrahydrophthalimido monomer containing 5‐fluorouracil (ETPFU) and its homopolymer and copolymers with acrylic acid (AA) and with vinyl acetate (VAc) have been synthesized and spectroscopically characterized. The ETPFU contents in poly(ETPFU‐co‐AA) and poly(ETPFU‐co‐VAc) obtained by elemental analysis were 21 mol% and 20 mol%, respectively. The average molecular weights of the polymers determined by gel permeation chromatography were as follows: M_n = 8900 g mol^?1, M_w = 13 300 g mol^?1, M_w/M_n = 1.5 for poly(ETPFU); M_n = 13 500 g mol^?1, M_w = 16 600 g mol^?1, M_w/M_n = 1.2 for poly(ETPFU‐co‐AA); M_n = 8300 g mol^?1, M_w = 11 600 g mol^?1, M_w/M_n = 1.4 poly(ETPFU‐co‐VAc). The in vitro cytotoxicity of the compounds against FM3A and U937 cancer cell lines increased in the following order: ETPFU > 5‐FU > poly(ETPFU) > poly(ETPFU‐co‐AA) > poly(ETPFU‐co‐VAc). The in vivo antitumour activities of all the polymers in Balb/C mice bearing the sarcoma 180 tumour cell line were greater than those of 5‐FU and monomer at the highest dose (800 mg kg^?1). © 2002 Society of Chemical Industry     

Synthesis and biological activity of medium molecular weight polymers containing 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl‐5‐fluorouracil

A new monomer, 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl‐5‐fluorouracil (ETBFU), was synthesized by reaction of 3,6‐endo‐methylene‐1,2,3,6‐tetrahydrophthalimidobutanoyl chloride and 5‐fluorouracil. The homopolymer of ETBFU and its copolymers with acrylic acid (AA) or vinyl acetate (VAc) were prepared by photopolymerization using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETBFU and its polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The ETBFU content in poly(ETBFU‐co‐AA) and poly(ETBFU‐co‐VAc) was 43 and 14 mol%, respectively. The apparent number‐average molecular weight (M_n) of the polymers determined by GPC ranged from 8400 to 11 300. The in vitro cytotoxicity of the samples against mouse mammary carcinoma (FM3A), mouse leukaemia (P388), and human histiocytic lymphoma (U937) cancer cell lines decreased in the order 5‐FU ≥ ETBFU > poly(ETBFU) > poly(ETBFU‐co‐AA) > poly(ETBFU‐co‐VAc). The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐fluorouracil at all doses tested. © 2000 Society of Chemical Industry     

Syntheses,antitumour activities and antiangiogenesis of 1,2,3‐tris(ethoxycarbonyl)‐2‐propyl acrylate and its polymers

A new monomer, 1,2,3‐tris(ethoxycarbonyl)‐2‐propyl acrylate (TPA), was synthesized by reaction of acryloyl chloride and triethyl citrate. The homopolymer of TPA and its copolymers with acrylic acid (AA), vinyl acetate (VAc) and maleic anhydride (MAH) were prepared by polymerization using lauroyl peroxide (LPO) at 70 °C for 24 h. The structures of TPA and its polymers were identified by FTIR, ¹H NMR, ¹³C NMR spectroscopies, and elemental analysis. The number average molecular weights and polydispersity indices of the synthesized polymers determined by GPC were in the range 4200–23 000 g mol^?1 and 1.1–2.1, respectively. The IC₅₀ values of the synthesized samples against cancer cell lines were greater than those of 5‐fluorouracil (5‐FU). The percentage inhibition values of SV40 DNA replication were 82.2 for TPA, 34.3 for poly (TPA), 81.9 for poly(TPA‐co‐AA), 82.0 for poly(TPA‐co‐VAc), 35.6 for poly(TPA‐co‐MAH) and 12.7 for 5‐FU. The inhibitions of SV40 DNA replication and antiangiogenesis for the synthesized TPA and its polymers are much greater than those of the control. © 2001 Society of Chemical Industry     

Syntheses and antitumor activities of polymers containing 2-acrylamido-2-methyl-1-propanesulfonic acid or 5-fluorouracil

Summary The polymers containing 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPA) were prepared by radical polymerizations. The polymers were identified by FT-IR, ¹H-, and ¹³C-NMR spectroscopies. The contents of AMPA unit in poly(AMPA-co-MAH), terpoly(AMPA-MAH-FUR), and poly(AMPA-co-EETFU) were 67, 73 and 49 mol %, respectively. The number average molecular weights of the polymers determined by GPC were in range from 5,600 to 9,200. The IC₅₀ values of the synthesized polymers against cancer cell lines were in the range of 0.02 to 127. The in vivo antitumor activities of polymers against Balb/C mice bearing the sarcoma 180 tumor cells were greater than those of 5-FU. Received: 6 September 2000/Revised version: 12 March 2001/Accepted: 22 March 2001     

Synthesis and biological activity of medium range molecular weight polymers containing exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid

A new monomer, exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid (ETCA), was prepared by reaction of maleimidocaproic acid and furan. The homopolymer of ETCA and its copolymers with acrylic acid (AA) or with vinyl acetate (VAc) were obtained by photopolymerizations using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETCA and its polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The apparent average molecular weights and polydispersity indices determined by gel permeation chromatography (GPC) were as follows: M_n = 9600 g mol^?1, M_w = 9800 g mol^?1, M_w/M_n = 1.1 for poly(ETCA); M_n = 14 300 g mol^?1, M_w = 16 200 g mol^?1, M_w/M_n = 1.2 for poly(ETCA‐co‐AA); M_n = 17 900 g mol^?1, M_w = 18 300 g mol^?1, M_w/M_n = 1.1 for poly(ETCA‐co‐VAc). The in vitro cytotoxicity of the synthesized compounds against mouse mammary carcinoma and human histiocytic lymphoma cancer cell lines decreased in the following order: 5‐fluorouracil (5‐FU) ≥ ETCA > polymers. The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐FU at all doses tested. © 2001 Society of Chemical Industry     

Synthesis and photopolymerization of 4‐(1‐propenyl)oxybutyl acrylate

Hybrid monomer, 4‐(1‐propenyl)oxybutyl acrylate, with cationic and free radical polymerizable group was synthesized. Real‐time Fourier transform infrared spectroscopy (FTIR) was used to monitor the photopolymerization kinetics of the monomer. Photopolymerization processing conditions, such as light intensity, photoinitiator concentrations have been evaluated. It was found that hybrid monomer showed higher efficiency of photopolymerization in comparison with the blend system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Syntheses and biological activities of novel diheterocyclic compounds containing 1,2,4‐triazolo[1,5‐a]pyrimidine and 1,3,4‐oxadiazole

In a search for novel agrochemicals with high activity and low toxicity, a series of diheterocyclic compounds containing 1,2,4‐triazolo[1,5‐a]pyrimidine and 1,3,4‐oxadiazole rings were designed and synthesized by a four‐step synthetic route starting from 2‐mercapto‐5,7‐dimethyl‐1,2,4‐triazolo[1,5‐a]pyrimidine. The structures of all the compounds synthesized were confirmed by ¹H NMR, mass spectroscopy and elemental analysis. The preliminary bioassay against Brassica campestris L and Echinochloa crusgalli Beavu indicated that the title compounds displayed herbicidal activity at the concentration of 100 ppm and that compounds 5a (R = CH₃), 5d (R = C₂H₅) and 5f (R = i‐Bu) were found to have particularly high activities. In addition, the results of an in vivo test at a concentration of 50 ppm showed that all the compounds prepared were highly active against Rhizoctonia slain, but not active against Fusarium oxysporum, Gibberella zeave and Phoma sparagi. A further in vivo test showed that compound 5j possessed better fungicidal activity against Rhizoctonia solani at a concentration of 200 ppm than Carbendazim and Validamycin A, which are well known for their fungicidal activity against Rhizoctonia solani. To our knowledge, this is the first report that 1,2,4‐triazolo[1,5‐a]pyrimidine derivatives display fungicidal activity against Rhizoctonia solani. © 2001 Society of Chemical Industry     

含氨基酸结构的磺酰胺衍生物合成与生物活性

采用分子杂交策略，设计合成15个氨基酸结构的磺酰胺衍生物进行抗菌活性评价。首先，苯磺酰氯与氨基酸反应制得苯磺酰氨基酸（中间体Ⅰ），然后，以芳香醛、亚磷酸酯、乙酸铵和三氟甲磺酸铝为原料，一锅法制得α-氨基膦酸酯（中间体Ⅱ），最后，中间体Ⅰ与Ⅱ缩合，制得目标物，经1H NMR 、13C NMR和MS确认结构。结果表明，该类化合物对大肠杆菌（E. coli）和耐氟喹诺酮大肠杆菌（FREC）活性最为显著。其中，化合物Ⅲb〔{(2-氟苯基) [2-(苯基磺酰氨基)苯丙酰氨基]甲基}膦酸二乙酯〕、Ⅲc〔{(2-氟苯基) [2-(苯基磺酰氨基)苯丙酰氨基]甲基}膦酸二乙酯〕、Ⅲh〔{(2-氟苯基) [2-(苯基磺酰基氨)异戊酰氨基]甲基}膦酸二乙酯〕和Ⅲm〔{(苯基) [2-(苯基磺酰基氨)乙酰氨基]甲基}膦酸二乙酯〕对E. coli的MIC（Minimum Inhibitory Concentration）均为16 μg/mL，化合物Ⅲn〔{(2-氟苯基) [2-(苯基磺酰氨基)乙酰氨基]甲基}膦酸二乙酯〕对E. coli的MIC为8 μg/mL，抗菌活性不低于对照药苯唑西林；化合物Ⅲb、Ⅲh、Ⅲm和Ⅲn对FREC的MIC分别为32、32、32和16 μg/mL，优于对照药苯唑西林和诺氟沙星。     

Synthesis and photopolymerization of 2‐(acryloyloxy)ethyl piperidine‐1‐carboxylate and 2‐(acryloyloxy)ethyl morpholone‐4‐carboxylate

Two low‐viscosity monomers, 2‐(acryloyloxy)ethyl piperidine‐1‐carboxylate (AEPC II) and 2‐(acryloyloxy)ethyl morpholone‐4‐carboxylate (AEMC), were synthesized with a non‐isocyanate route. The photopolymerization kinetics was monitored by real‐time infrared spectroscopy with a horizontal sample holder. The results indicated that AEPC II and AEMC had high ultraviolet curing rates and final double‐bond conversions, which could reach 90 and 95%, respectively. The glass‐transition temperatures of AEPC II/urethane acrylate resin (1/4 w/w), AEMC/urethane acrylate resin (1/4 w/w), and isobornyl acrylate/urethane acrylate resin (1/4 w/w) mixtures were 37.5, 45.6, and 57°C, respectively. The crosslink density of the AEMC/urethane acrylate resin (1/4 w/w) mixture was lower than that of the isobornyl acrylate/urethane acrylate resin (1/4 w/w) mixture. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Reactivity of temperature‐sensitive,protein‐conjugating polymers prepared by a photopolymerization process

This study was carried out to characterize the reactivity of temperature‐sensitive, protein‐conjugating polymers prepared by a photopolymerization process. Polymers were based on N‐isopropylacrylamide (NiPAM) and N‐acryloxysuccinimide (NASI). A photoinitiator, 2,2‐dimethoxy‐2‐phenyl‐acetophenone, and monomers at desired ratios were polymerized in a glass flask using an UV source. Polymers were characterized for composition, molecular weight (MW), cloud point temperature (CPT), hydrolysis and aminolysis rates (using ethanolamine as a model compound), and protein conjugation. The monomer feed ratio was found to effectively control the composition of the synthesized polymers. The polymer MWs were between 10 and 20 kD, depending on the polymerization solvent. The CPT of NiPAM/NASI polymers did not depend on NASI content (≤5.6%), nor did the hydrolysis and aminolysis rates. Compared to NASI monomer, the polymerized NASI exhibited a 6‐ and 120‐fold slower rates of hydrolysis and aminolysis, respectively. Although hydrolysis and aminolysis rates were higher at higher pHs, the relative aminolysis : hydrolysis rate was highest at a pH of 7.4, which also gave the most effective protein conjugation. We conclude that characterizing the polymer reactivity is useful for predicting the optimal conditions for protein conjugation and may facilitate the design of polymers with improved protein conjugation kinetics. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 583–592, 2000     

Synthesis and photopolymerization of ethylene glycol 3‐morpholine‐propionate methacrylate for potential dental composite application

2,2‐Bis[4‐(2‐hydroxy‐3‐methacryloxypropoxy) phenyl]‐propane (bis‐GMA), triethylene glycol dimethylacrylate (TEGDMA), camphorquinone (CQ), ethyl‐4‐dimethylaminobenzoate (EDMAB), or 2‐(dimethylamine)ethyl methacrylate (DMEM) were composed of the modern dental composite system and acted as resin, diluent, photoinitiator, and coinitiator, respectively. In this study, ethylene glycol 3‐morpholine‐propionate methacrylate (EGMPM) was synthesized via Michael addition reaction to replace both the TEGDMA as a diluent and the nonpolymerizable amine EDMAB as a coinitiator. Mixtures of bis‐GMA/TEGDMA/CQ/EGMPM and bis‐GMA/TEGDMA/CQ/DMEM were found to have almost the same rate of polymerization and reach final double bond conversion at 58%, slightly lower than that of the bis‐GMA/TEGDMA/CQ/EDMAB (63%) and bis‐GMA/EGMPM/CQ (60%) under comparable visible light irradiation conditions. In addition, the results of dynamic mechanical analysis showed that all of the four samples had approximately the same modulus and the glass transition temperature. The water sorption and solubility of bis‐GMA/TEGDMA/CQ with different amines (EDMAB, DMEM, and EGMPM) had almost the same value except that the water sorption of bis‐GMA/EGMPM/CQ was out of the range of the ISO 4049 (2000) standards. The results indicated that EGMPM was potentially a coinitiator for dental composite, because there are no significant differences in photopolymerization characteristic and physical properties when compared with traditional system (bis‐GMA/TEGDMA/CQ/EDMAB). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4589–4594, 2006     

6,7‐Dimethoxy‐2‐{2‐[4‐(1H‐1,2,3‐triazol‐1‐yl)phenyl]ethyl}‐1,2,3,4‐tetrahydroisoquinolines as Superior Reversal Agents for P‐Glycoprotein‐Mediated Multidrug Resistance

P‐glycoprotein (P‐gp)‐mediated multidrug resistance (MDR) is a major obstacle for successful cancer chemotherapy. Based on our previous study, 17 novel compounds with the 6,7‐dimethoxy‐2‐{2‐[4‐(1H‐1,2,3‐triazol‐1‐yl)phenyl]ethyl}‐1,2,3,4‐tetrahydroisoquinoline scaffold were designed and synthesized. Among them, 2‐[(1‐{4‐[2‐(6,7‐dimethoxy‐3,4‐dihydroisoquinolin‐2(1H)‐yl)ethyl]phenyl}‐1H‐1,2,3‐triazol‐4‐yl)methoxy]‐N‐(p‐tolyl)benzamide (compound 7 h ) was identified as a potent modulator of P‐gp‐mediated MDR, with high potency (EC₅₀=127.5±9.1 nM ), low cytotoxicity (TI>784.3), and long duration (>24 h) in reversing doxorubicin (DOX) resistance in K562/A02 cells. Compound 7 h also enhanced the effects of other MDR‐related cytotoxic agents (paclitaxel, vinblastine, and daunorubicin), increased the accumulation of DOX and blocked P‐gp‐mediated rhodamine 123 efflux function in K562/A02 MDR cells. Moreover, 7 h did not have any effect on cytochrome (CYP3A4) activity. These results indicate that 7 h is a relatively safe modulator of P‐gp‐mediated MDR that has good potential for further development.     

Metal ion retention properties of water‐insoluble polymers containing carboxylic acid groups

Crosslinked poly(acrylic acid), PAA, and poly(2‐acrylamidoglycolic acid), PAAG, were synthesized by radical polymerization. Both resins contain carboxylic acid groups. PAA at basic pH exists basically as an acrylate anion and PAAG shows three atoms or groups, carboxylic acid, hydroxyl, and amide groups, that can act as ion exchanger or chelating groups. Both resins are studied as adsorbents to trace metal ions from saline aqueous solutions and natural sea water and their properties by Batch equilibrium procedure are compared. The metal ions studied under competitive and noncompetitive conditions were Cu(II), Pb(II), Cd(II), and Ni(II). The effects of pH, time of contact, amount of resin, temperature, and salinity were studied. Resin PAA shows a high affinity (>80%) for Cu(II) and Cd(II) and resin PAAG shows also a high affinity for Ni(II), Pb(II), and Cd(II). By treatment of the metal ion‐loaded resin with 4M HNO₃ it is possible to recover completely the Cu(II) ions from resin PAA and Ni(II) and Pb(II) from resin PAAG. The metal ion retention properties were studied with natural sea water. For those natural sea waters containing Cu(II) and Cd(II), the resins showed a high affinity for Cd(II) ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 697–705, 2006     

Biodegradable polymers based on renewable resources. III. copolyesters composed of 1,4:3,6‐dianhydro‐D‐glucitol, 1,1‐bis(5‐carboxy‐2‐furyl)ethane and aliphatic dicarboxylic acid units

Various copolyesters were synthesized by bulk polycondensation of the respective combinations of 1,4;3,6‐dianhydro‐D ‐glucitol (1) as the diol component and 1,1‐bis[5‐(methoxycarbonyl)‐2‐furyl]ethane (3b) and seven dimethyl dialkanoates with methylene chain lengths of 4, 5, 6, 7, 8, 10, and 12 (4a–4g) as the dicarboxylic acid components. Most of the copolyesters were amorphous, while a copolyester composed of 1, 3b, and dodecanedioic acid (4g) (3b:4g = 25:75) units as well as homopolyesters derived from 1 and azelaic acid (4d), sebacic acid (4e), and dodecandioic acid (4g), respectively, were partially crystalline. All these homo‐ and copolyesters were soluble in chloroform, dichloromethane, pyridine, trifluoroacetic acid, and m‐cresol. The number‐average molecular weights of these polyesters were estimated to be in the range of 10,000–20,000 by SEC using chloroform as an eluent and standard polystyrene as a reference. The biodegradability of these copolyesters was assessed by enzymatic degradation using four different enzymes in a phosphate buffer solution at 37°C and by soil burial degradation tests in composted soil at 27°C. In general, biodegradability of the copolyesters decreased with increase in the difuran dicarboxylate 3b content. Copolyesters containing sebasic acid 4e units showed higher biodegradability. Soil burial degradation in the soil that was treated with antibiotics, together with electron microscopic observation, indicated that actinomycetes are mainly responsible for the degradation of the copolyesters containing 3b units in the present soil burial test. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3342–3350, 1999     

Preparation and characterization of an amphiphilic macrophotoinitiator based on 2‐hydroxyl‐2‐methyl‐1‐phenylpropanone

On the basis of 2‐hydroxyl‐2‐methyl‐1‐phenylpropanone (HMPP) and poly(ethylene glycol) (PEG), we prepared amphiphilic macrophotoinitiators (HMPP–PEG–HMPP) by first reacting HMPP with isophorone diisocyanate and subsequently reacting it with PEGs with different chain lengths. Fourier transform infrared spectroscopy, high‐performance liquid chromatography, and ¹H‐NMR were used to confirm the structure of the amphiphilic macrophotoinitiators. Ultraviolet (UV) absorption spectra showed that the amphiphilic macrophotoinitiators had maximum absorption wavelengths that were similar to those of the low‐molecular‐weight photoinitiator HMPP. The photolysis rate of the amphiphilic macrophotoinitiators was slightly lower than that of HMPP, but the migration rate of the amphiphilic macrophotoinitiators from a UV‐cured matrix was much lower compared to that of HMPP. Because of their amphiphilic nature, these macrophotoinitiators may play roles as both photoinitiators and emulsifiers, and they have been applied to the solution polymerization of water‐soluble monomer acrylamide in water and the emulsion polymerization of methyl methacrylate. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43910.     

Blends containing amphiphilic polymers IV. Poly(N‐1‐alkyl itaconamic acids) with poly(2‐vinylpyridine) and poly(4‐vinylphenol)

The phase behavior of blends containing Poly(N‐1‐alkyl itaconamic acids) (PNAIA) with Poly(2‐vinylpyrindine) (P2VPy) and Poly(4‐vinylphenol) (P4VPh) were analyzed by Diferential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR). Miscibility over the whole range of compositions is observed in both systems. All the blends show thermograms exhibiting distinct single glass transition temperatures (T_g), which are intermediate to those of the pure components. The Calorimetric Analysis using Gordon Taylor, Couchman, and Kwei treatments allows conclusion that interactions between the components is favorable to the miscibility. FTIR analysis of the blends suggests that the driving force for miscibility is hydrogen bonding formation. The variation of the absorptions of the carbonyl groups of PNAIA and the hydroxyl groups of P4VPh allows one to attribute the miscibility to weak acid base like interactions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1245–1250, 2002; DOI 10.1002/app.10453     

Synthesis and characterization of the soluble fluorescent poly[2‐decyloxy‐5‐(2′‐(6′‐dodecyloxy)naphthyl)‐1,4‐phenylenevinylene]

A new soluble fluorescent polymer, poly[2‐decyloxy‐5‐(2′‐(6′‐dodecyl‐oxy)naphthyl)‐1,4‐phenylenevinylene] (DDN‐PPV), with no tolane‐bisbenzyl (TBB) structure defects is prepared by the dehydrohalogenation of 1,4‐bis(bromomethyl)‐2‐decyloxy‐5‐(2′‐(6′‐dodecyloxy)naphthyl)benzene (as monomer) in this study. The aforementioned monomer is synthesized via such chemical reactions as alkylation, bromination, and Suzuki coupling reactions. The structure and properties of the DDN‐PPV are examined by ¹H NMR, FTIR, UV/vis, TGA, photoluminescence (PL), and electroluminescence (EL) analyses. The two asymmetric decyloxy and 6′‐dodecyloxynaphthyl substituents on the phenylene ring make the DDN‐PPV soluble in organic solvents and eliminate the TBB structure defects. With the DDN‐PPV acting as a light‐emitting polymer, a device is fabricated with a sequential lamination of ITO/PEDOT/DDN‐PPV/Ca/Ag. The EL spectrum of the device shows a maximum emission at 538 nm. The turn on voltage of the device is about 16.6 V. Its maximum brightness is 14 cd/m² at a voltage of 18.2 V. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2734–2741, 2007     

Chiral Resolution and Pharmacological Characterization of the Enantiomers of the Hsp90 Inhibitor 2‐Amino‐7‐[4‐fluoro‐2‐(3‐pyridyl)phenyl]‐4‐methyl‐7,8‐dihydro‐6H‐quinazolin‐5‐one Oxime

Heat‐shock protein 90 (Hsp90) is a molecular chaperone involved in the stabilization of key oncogenic signaling proteins, and therefore, inhibition of Hsp90 represents a new strategy in cancer therapy. 2‐Amino‐7‐[4‐fluoro‐2‐(3‐pyridyl)phenyl]‐4‐methyl‐7,8‐dihydro‐6H‐quinazolin‐5‐one oxime is a racemic Hsp90 inhibitor that targets the N‐terminal adenosine triphosphatase site. We developed a method to resolve the enantiomers and evaluated their inhibitory activity on Hsp90 and the consequent antitumor effects. The (S) stereoisomer emerged as a potent Hsp90 inhibitor in biochemical and cellular assays. In addition, this enantiomer exhibited high oral bioavailability in mice and excellent antitumor activity in two different human cancer xenograft models.