PREPARATION AND EVALUATION OF ACRYLIC ACID,ITACONIC ACID,AND N-METHACRYLOYLGLUTAMIC ACID COPOLYMERS FOR USE IN GLASS-IONOMER TYPE DENTAL RESTORATIVES

A series of copolymers containing various molar ratios of acrylic acid, itaconic acid and N-methacryloylglutamic acid were prepared in aqueous solution, using standard free-radical polymerization conditions. Specimens for mechanical property studies were prepared by mixing water solutions of the copolymers (50:50, wt:wt) with a commercial, calcium-fluoroaluminosilicate glass powder, with curing or hardening achieved by salt-bridge formation. The glass powder used in the formulation(s) was the same as that used in Fuji II (GC America) glass-ionomer. The working and setting times of the various formulations were evaluated. The compressive strength was used as the basic screening property to find the optimum molar ratio of the three monomers. The diametral tensile strength, flexural strength and Knoop surface hardness of the cured materials were also determined. All mechanical properties were measured after the specimens were conditioned in distilled water for 7 days at 37°C. Based on the compressive strength (CS), poly (AA-co-IA-co-MGA) with a monomers ratio of 8:1:1, respectively, showed the highest CS (269.9 MPa). The 8:1:1 copolymer with different molecular weights were also prepared to evaluate the effect of MW on the compressive strength. The optimum MW copolymer gave a glass-ionomer having the compressive strength improved by 30%, compared to Fuji II (293.9 MPa vs. 224.9 MPa). The same polymer solution was also mixed with glass powders used in other commercial glass-ionomers, i. e., Ketac-Molar (ESPE, Seefeld, Germany), α-Fil and α-Silver (DMG, Hamburg, Germany) to produce conventional glass-ionomers test specimens. The mechanical properties of these materials were also obtained and compared to the Fuji II, Ketac-Molar, α-Fil and α-Silver controls.     

Microhardness of N-Vinylpyrrolidone Modified Glass-Ionomer Cements

ABSTRACT

The water soluble N-vinylpyrrolidone (NVP) monomer was used to prepare poly(N-vinylpyrrolidone-co-itaconic acid-co-acrylic acid) glass-ionomer copolymers, using a free-radical polymerization process. NVP modified terpolymer was mixed with glass powders from four commercial glass ionomer systems. Microhardness from the set cement was measured and compared to several commercial glass-ionomer systems. The Knoop hardness number (KHN) values were recorded on polished specimens conditioned for 48 hours and 7 days. One-way analysis of variance and Tukey-Kramer tests were used to determine the significant differences among the materials tested in each group. Among the four commercial cements, Ketac-Molar (KM) showed the highest value and α-Silver (AS) snowed the lowest value in KHN. Fuji II (F2) and α-Fil (AF) showed much the same values in KHN. At the same P/L ratio, NVP modified glass-ionomers showed higher KHN values than the AS, similar to the AF and F2, and lower than the KM. The effect of P/L ratios was evident and highest KHN values for each group were basically presented by the one with a higher P/L ratio. Higher P/W ratio did not improve the KHN for the AS and KM group, but improved the F2 group.     

Improved Flexural Strength of N-Vinyl-Pyrrolidone Modified Acrylic Acid Copolymers for Glass-Ionomers

Abstract

The flexural strengths of N-vinylpyrrolidone modified glass-ionomer cements were investigated. The optimal molar ratio of the monomers in copolymers, composed of the three components acrylic acid, itaconic acid and N-vinylpyrrolidone, was determined using a SAS statistical program. The copolymers were prepared using a free-radical polymerization process. The viscosities of aqueous solutions of these polymers were determined. Cements were formed by the reaction of these solutions with glass particles. Flexural strength (FS) was used as the basic screening property to find the optimum molar ratio. Statistical models were applied to predict the optimum molar ratios. All strength values were recorded on the specimens conditioned in distilled water at 37°C for 7 days. The optimal molar ratio for these copolymers was 7:1:3 for poly(acrylic acid-co-itaconic acid-co-N-vinylpyrrolidone), based on flexural strength and viscosity. The effect of molecular weight (MW) on FS was also evaluated. Copolymer with a MW of 10, 800 (M_n) showed 85% higher FS than the Ketac-Molar (KM) system, along with a reasonable working viscosity.     

Synthesis and blend behavior of high performance homo- and segmented thermoplastic polyimides

New synthetic methodology was developed as part of an effort to increase the processibility of high Tg polyimide homo⁻ and copolymers, suitable as matrix resins and structural adhesives. Molecular weight and end group control together with solution imidization techniques were successfully employed to convert a variety of poly(amic acid) intermediates to fully cyclized polyimides. The solution imidization was conducted in N-methylpyrrolidone (NMP) with o-dichlorobenzene used as the azeotroping agent at 165–190°C. This technique has produced products which are more soluble than polyimides prepared previously by bulk thermal cyclization of poly(amic acids) at temperature of 300°C. They are also more stable than “chemically” imidized materials. In addition, incorporation of the monofunctional reagent phthalic anhydride provides nonreactive phthalimide end groups and controlled molecular weight. This latter feature significantly further improved the melt and solution processibility of the resulting polyimides. In this study thermoplastic, fully cyclized polyimides of 10 000, 20 000, and 30 000 M̄n were prepared which displayed glass transition temperatures ranging from 260–353°C, with the highest T_g observed with phthalimide capped polyimide systems derived from 6F-dianhydride and p-phenylene diamine. Tough, transparent films were prepared from polymers of 20 000 and 30 000 g/mol by casting from NMP solution or by compression molding at 50–70°C above the glass transition temperature. For purposes of molecular weight assessment, t-butyl phthalic anhydride was used as the end blocker. This permitted 400 M-Hertz proton NMR to be used for assessing the concentration of end groups. Comparison of the 18 aliphatic protons at the end of the chain allowed M̄n values to be determined, which agreed well with theory. A series of poly(arylene ether ketone)/aromatic polyimide blends were investigated to determine the influence of structural variation and composition on miscibility. As an extension to the PEEK^TM/Ultem^TM blend system, which has been reported to be miscible over all proportions, this study examined how structural variations in both the poly(arylene ether ether ketone) and the polyimide portions affect miscibility. In particular, replacement of the hydroquinone fraction in PEEK^TM with bisphenol A or sulfonyl diphenol produced an amorphous polymer which was no longer miscible with Ultem^TM. Polyimide structures modified by employing 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4′-[1,4-phenylene-bis-(1-methyl ethylidene)] bisaniline (Bis P) diamine to obtain higher glass transition temperatures were also investigated. This system afforded homogeneous blends with PEEK^TM when the (Bis P) diamine was utilized in the synthesis of the polyimide. Furthermore, up to 50 mole percent of hexafluoro-bis-dianhydride (6FDA) could be substituted for BTDA without loss of miscibility. However, when the more polar 3,3′-diaminodiphenylsulfone diamine was employed, immiscible blends resulted. An additional important variant has been to incorporate polyimide siloxane segmented copolymers into the PEEK^TM blend system. The polyimide segment can be designed to be miscible whereas the siloxane portion is homogeneously dispersed into a second phase which, in fact, enriches the surface behavior quite dramatically in siloxane content. The latter could be of some importance in allowing for atomic oxygen resistance and possibly improved flame resistance behavior.     

Synthesis of amino acid-containing polyacids and their application in self-cured glass-ionomer cement

Six methacrylate or acrylate derivatives of natural amino acids were synthesized and characterized. Based upon these monomers, six terpolymers [poly(acrylic) acid-co-itaconic acid-co-amino acid] were prepared and characterized. The synthesized polymers were used to formulate glass-ionomer cements (GICs) using Fuji II glass filler. The effects of the molecular weight (MW) and powder/liquid (P/L) ratio were evaluated. Scanning electron microscopy (SEM) was used to examine the fracture surfaces of the selected cement specimens. Results show that all the amino acid modified GICs exhibited higher compressive strengths (CS, 193-236 MPa) and much higher flexural strengths (FS, 55-71 MPa) as compared to commercial Fuji II GIC (191 in CS and 16 in FS). Both MW and P/L ratio affected the strength of the formed cement. It was important to find the optimal MW and P/L ratio to obtain the highest FS. In this study, optimized MW (number average) of the polyacids and P/L ratio were around 50,000 and 2.7/1, respectively. The microstructures of the fracture surfaces helped to explain the strength differences among the materials tested in the study. SEM analysis suggests that more integrated microstructures and fewer defects can lead to higher FS.     

SYNTHESIS OF POLY(ACRYLIC ACID-CO-ITACONIC ACID) IN CARBON DIOXIDE–METHANOL MIXTURES

ABSTRACT

High fluidity solvents, such as supercritical fluids, have several advantages over traditional solvents as polymerization media, such as offering a more environmentally-friendly reaction media, providing increased reaction rates, and simplifying the separation and purification of polymers. In this study, a traditional glass-ionomer polymer, poly(acrylic acid-co-itaconic acid) (PAA/IA) was synthesized by using mixtures of CO₂ and methanol as the reaction solvent and was characterized by ¹H-NMR, FT-IR, GPC, and viscometry. The mechanical and working properties of the glass-ionomer cements, prepared by mixing aqueous solutions of the polymers with Fuji II glass powder, were evaluated for compressive strength (CS), diametral tensile strength (DTS) and flexural strength (FS), as well as setting time and working time. The results showed that the polymerization reaction in CO₂/methanol mixtures was faster and had higher conversion than the polymerization reaction in water. The glass-ionomer formulations made from the copolymer prepared under SC conditions showed higher CS, comparable FS and DTS compared with those made from the same polymer prepared in water. Both of the synthesized copolymers had significantly higher CS and FS than Fuji II. The working properties of PAA/IA made in CO₂/methanol met the requirement of ANSI/ADA No. 96.     

Synthesis and formulation of vinyl-containing polyacids for improved light-cured glass-ionomer cements

Vinyl-containing poly(acrylic acid-co-itaconic acid) copolymers were synthesized and used to formulate light-curable cements containing reactive glass fillers (Fuji II LC). The conditions for light curing were studied and optimized. Effects of molecular weight (MW), grafting ratio, comonomer, liquid composition, powder/liquid (P/L) ratio, glass powder and aging were evaluated. The results show that the vinyl-containing glass-ionomer cements (GICs) prepared in this study exhibit higher compressive strength (CS, 225.6 MPa), diametral tensile strength (DTS, 28.4 MPa) and much higher flexural strength (FS, 116.4 MPa), as compared to commercial Fuji II LC GIC (186.6 in CS, 19.1 in DTS and 57.1 in FS). The optimal light-exposure time was found to be around 10 min, and concentrations of CQ and DC were 0.5% (by weight) and 1.0%, respectively. Effects of MW, grafting ratio, P/L ratio and content of polymer in the liquid formulation were significant. The highest strengths were found for the optimal formulations where the MW was 15,000 (weight average), grafting ratio 25 mol%, P/L ratio 2.7 and liquid composition 50:20:30. During aging, the cement showed an increase of strength over the first week and then no change for a month. SEM analysis suggests that more integrated microstructures and smaller glass particles can lead to higher FS and higher polymer content in GICs leads to tough fracture surface and plastic deformation.     

Random and block styrenic copolymers bearing both ammonium and fluorinated side‐groups

1H,1H,2H,2H‐Perfluorooctyloxymethylstyrene (FS) was prepared and copolymerized with chloromethylstyrene (CMS). Conventional radical copolymerization of both these aromatic monomers led to poly(CMS‐co‐FS) random copolymers for which CMS was shown to be more reactive than the fluorinated comonomer. Their controlled radical copolymerization based on degenerative transfer, namely iodine transfer polymerization (ITP), led to various poly(CMS)‐b‐poly(FS) block copolymers. Molecular weights of poly(CMS‐co‐FS) copolymers reached 33,000 g mol^?1 while those of poly(CMS)‐b‐ poly(FS) block copolymers were 22,000 g mol^?1. Their composition ranged from 18 to 61 mol.% in FS. These copolymers were modified via a cationization step, aiming at replacing the chlorine atom in CMS unit by a trimethylammonium group, leading to the formation of cationic sites. The resulting functionalized copolymers exhibited different solubilities. If both copolymerization techniques led to water‐insoluble copolymers, the block architecture enabled incorporating lower FS proportion, resulting in more cationic sites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Metal(II) Ion Complexes with 5‐(Pyrazin‐2‐yl)‐2,4‐dihydro‐3H‐1,2,4‐triazole‐3‐thione; Synthesis,Structural Characterization,Acid‐base,and Complexing Properties in Solution

The study reports the synthesis of complexes Co(HL)Cl₂ ( 1 ), Ni(HL)Cl₂ ( 2 ), Cu(HL)Cl₂ ( 3 ), and Zn(HL)₃Cl₂ ( 4 ) with the title ligand, 5‐(pyrazin‐2‐yl)‐1,2,4‐triazole‐5‐thione (HL), and their characterization by elemental analyses, ESI‐MS (m/z), FT‐IR and UV/Vis spectroscopy, as well as EPR in the case of the Cu^II complex. The comparative analysis of IR spectra of the metal ion complexes with HL and HL alone indicated that the metal ions in 1 , 2 , and 3 are chelated by two nitrogen atoms, N(4) of pyrazine and N(5) of triazole in the thiol tautomeric form, whereas the Zn^II ion in 4 is coordinated by the non‐protonated N(2) nitrogen atom of triazole in the thione form. pH potentiometry and UV/Vis spectroscopy were used to examine Co^II, Ni^II, and Zn^II complexes in 10/90 (v/v) DMSO/water solution, whereas the Cu^II complex was examined in 40/60 (v/v) DMSO/water solution. Monodeprotonation of the thione triazole in solution enables the formation of the L:M = 1:1 species with Co^II, Ni^II and Zn^II, the 2:1 species with Co^II and Zn^II, and the 3:1 species with Zn^II. A distorted tetrahedral arrangement of the Cu^II complex was suggested on the basis of EPR and Vis/NIR spectra.     

Palladium(II)‐Catalyzed Dehydroboration via Generation of Boron Enolates

The Pd^II‐catalyzed dehydroboration of boron enolates generated from ketones and 9‐iodo‐9‐borabicyclo[3.3.1]nonane was achieved, providing a synthetically versatile protocol from ketones to α,β‐unsaturated ketones. The Pd^II compound employed in this reaction worked catalytically in the presence of Cu(OAc)₂. The high trans‐selectivity of the olefinic moiety was observed. Aryl halide moieties (‐Br and ‐Cl) remained intact for this reaction in spite of the presence of a Pd species. An ester substrate could also be applied when a stoichiometric amount of Pd^II was used. The crossover reactions using boron and silyl enolates revealed that the oxidation reaction is much faster than the Saegusa‐Ito reaction.     

Inversion of DNA helicity induced by zinc (II)-macrocyclic polyamine complexes

Abstract

Exposure of synthetic polynucleotide poly(dG-dC)·poly(dG-dC) to Zn^II cyclen, 2 (cyclen = 1,4,7,10-tetraazacyclododecane), produces a dramatic change in its circular dichroism (CD) spectrum in H₂O at pH 7.2, 24°C: the CD spectrum of the initial B form changes to that of the Z form (or a non-Z structure with a left-handed helix) at very low concentrations ([Zn^II]/[base pair] in molar basis ≤ 1). By contrast, Zn^II-[12]aneN₃, 1 ([12]aneN₃ = 1,5,9-triazacyclododecane), and Zn^II-cyclam, 3 (cyclam = 1,4,8,11-tetraazacyclo-tetradecane), do not significantly have such a topological affect on the polynucleotide even at much higher concentrations. An increase in Na⁺ ionic strength nullified the effect of 2 on the CD spectrum, indicating an outside interaction (electrostatic and/or hydrogen bonding) of the DNA model. This study illustrates the significance of the macrocyclic ligand structure around the Zn^II ion for specific interaction with DNA.     

Synthesis and Characterization of α,ω‐bi[2,4‐dinitrophenyl (DNP)] poly(2‐methoxystyrene) Functional Polymers. Initial Evaluation of the Interaction of the Functional Polymers with RBL Mast Cells

Two series of functional polymers, α,ω‐bi[2,4‐dinitrophenyl][poly(ethylene oxide)‐b‐poly(2‐methoxystyrene)‐b‐poly(ethylene oxide)] (DNP‐PEO‐P2MS‐PEO‐DNP) and α,ω‐bi[2,4‐dinitrophenyl caproic][poly(ethylene oxide)‐b‐poly(2‐methoxystyrene)‐b‐poly(ethylene oxide)] (CDNP‐PEO‐P2MS‐PEO‐CDNP), were synthesized by anionic living polymerization. The polymers were characterized by FT‐IR, ¹H‐NMR and Gel Permeation Chromatography (GPC). The molecular weight distributions for the lower molecular weight functional polymers were slightly broad (1.3–1.5). However, the molecular weight distributions for higher molecular weight polymers were narrower (1.1–1.2). Differential scanning calorimetry (DSC) studies showed thermal transitions indicative of the presence of microphases in the polymer solid state. The polymers were white powders and soluble in tetrahydrofuran. The binding affinity of DNP‐PEO‐P2MS‐PEO‐DNP ligands towards anti DNP IgE was determined by titrations with fluorescently labeled FITC‐IgE. A water soluble CDNP‐PEO‐P2MS‐PEO‐CDNP/DMEG (dimethoxyethylene glycol) complex binds and achieves steady state binding with solution IgE within a few seconds. This strongly suggests that CDNP functional polymers with improved water solubility have potential in therapeutics. Higher molecular weight (water insoluble) CDNP‐PEO‐P2MS‐PEO‐CDNP polymers were electrosprayed as fibers (500 nm) on silicon surface. Fluorescence spectroscopy clearly showed that RBL mast cells were interacting with the fibers suggesting that the cell‐surface receptors were clustered along the fiber surface. These observations suggest that the functional polymers hold promise for developing an antibody detection device.     

The N Terminus of α‐Synuclein Forms CuII‐Bridged Oligomers

The oligomerization of α‐synuclein (αSyn) is one of the defining features of Parkinson’s disease. Binding of divalent copper to the N terminus of αSyn has been implicated in both its function and dysfunction. Herein, the molecular details of the Cu^II/αSyn binding interface have been revealed using a library of synthetic 56‐residue αSyn peptides containing site‐specific isotopic labels. Using electron paramagnetic resonance spectroscopy, αSyn is shown to coordinate Cu^II with high affinity via two pH‐dependent coordination modes between pH 6.5–8.5. Most remarkably, the data demonstrate that the dominant mode is associated with binding to oligomers (antiparallel dimers and/or cyclic trimers) in which Cu^II ions occupy intermolecular bridging sites. The findings provide a molecular link between Cu^II‐bound αSyn and its associated quaternary oligomeric structure.     

Efficient Removal of Cobalt(II) and Strontium(II) Metals from Water using Ethylene Diamine Tetra‐acetic Acid Functionalized Graphene Oxide

Graphene oxide (GO) with high specific surface area was prepared and functionalized with ethylene diamine tetra‐acetic acid (EDTA). The as‐prepared GO and the functionalized one (GO‐EDTA) were characterized using high resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), and Raman spectroscopy. The as‐prepared and EDTA funcationalized GO were applied as adsorbent to remove strontium(II) and cobalt(II) from water. The results indicated that the prepared materials are efficient adsorbents for strontium(II) and cobalt(II) removal. The adsorption of Co^II and Sr^II under effects of contact time, temperature, and pH was investigated It is concluded that the maximum adsorption capacities of GO for Co^II and Sr^II were about 168 and 140 mg · g^–1, whereas of GO‐EDTA the values were about 197 and 158 mg · g^–1, respectively. It is indicated that pH 6 and temperature 40 °C are the best condition for Co^II and Sr^II removal from water. The application of Langmuir and Freundlich isotherms indicated that Langmuir isotherm is best fit for Co^II and Sr^II equilibrium adsorption. Adsorption kinetics were studied by applying pseudo first‐order, pseudo second‐order, and intraparticle diffusion models on the experimental data. The results proved that pseudo second‐order model is the best represented adsorption kinetics. Appling the intraparticle diffusion regressions on the experimental data indicated that intraparticle diffusion involved in adsorption process, which was not the only rate‐controlling step.     

Electrochemical and Spectral Studies of Sterically Hindered Water-Soluble Iron Tetrakis(Sulfonatomesityl)Porphine

Sterically hindered water-soluble iron(III) tetrakis(sulfonatomesityl)porphine (FeTSMP) exists exclusively in its monomer form in neutral and basic aqueous solutions. The acid dissociation constant (pKa) for Fe^IIITSMP is 6.6. The Fe^III/IITSMP couple has a formal reduction potential at ?0.22 V (vs. Ag/AgCl) in an acidic buffer solution. The E°-pH diagram shows that E° is independent of pH until the pH is larger than the pKa. The acid dissociation constant for Fe^IITSMP is 11.7. The redox potential of Fe^III/IITSMP shifts positively when imidazole is present, indicating the ligation of imidazole to Fe^IITSMP. At pH 4.0 and 10.2 buffer solutions, two imidazoles are found to ligate at the iron(III) center with β₂ = 10^4.7 and 10^4.1, respectively. The E°-pH diagram indicates that the pKa of (ImH)₂Fe^IIITSMP is 11.3 at 0.03 M imidazole solution. The oxidation of Fe^IIITSMP could involve two one-electron transfer processes, namely, one electron oxidation at the iron center, while another at the porphyrin ring. The two one-electron oxidations are found to overlap at pH = 5.5 and separate as the pH increases by shifting of the potential at the iron center, which is pH dependent. The radical cation of porphyrin ring is not stable and decomposes rapidly in water.     

N-Confused Phlorin-Prodigiosin Chimera: meso-Aryl Oxidation and π-Extension Triggered by Peripheral Coordination

An N-confused phlorin isomer bearing a dipyrrin moiety at the α-position of the confused pyrrole ring ( 1 ) was synthesized. Pd^II and B^III coordination at the peripheral prodigiosin-like moiety of 1 afforded the corresponding complexes 2 and 3 . Reflux of 2 in triethylamine (TEA) converted the meso-phenyl into the Pd^II-coordinating phenoxy group to afford 4 . Under the same reaction conditions, TEA was linked to the α-position of the dipyrrin unit in 3 as an N,N-diethylaminovinyl group to afford 5 . Furthermore, peripheral coordination of B^III in 3 and 5 improved the planarity of the phlorin macrocycle and thus facilitated the coordination of Ag^III at the inner cavity to afford 3-Ag and 5-Ag , respectively. These results provide an effective approach for developing unique porphyrinoids through peripheral coordination.     

A convenient synthesis of α,α′‐ homo‐ and α,α′‐hetero‐bifunctionalized poly(ε‐caprolactone)s by ring opening polymerization: The potentially valuable precursors for miktoarm star copolymers

Two new ring opening polymerization (ROP) initiators, namely, (3‐allyl‐2‐(allyloxy)phenyl)methanol and (3‐allyl‐2‐(prop‐2‐yn‐1‐yloxy)phenyl)methanol each containing two reactive functionalities viz. allyl, allyloxy and allyl, propargyloxy, respectively, were synthesized from 3‐allylsalicyaldehyde as a starting material. Well defined α‐allyl, α′‐allyloxy and α‐allyl, α′‐propargyloxy bifunctionalized poly(ε‐caprolactone)s with molecular weights in the range 4200–9500 and 3600–10,900 g/mol and molecular weight distributions in the range 1.16–1.18 and 1.15–1.16, respectively, were synthesized by ROP of ε‐caprolactone employing these initiators. The presence of α‐allyl, α′‐allyloxy and α‐allyl, α′‐propargyloxy functionalities on poly(ε‐caprolactone)s was confirmed by FT‐IR, ¹H, ¹³C NMR spectroscopy, and MALDI‐TOF analysis. The kinetic study of ROP of ε‐caprolactone with both the initiators revealed the pseudo first order kinetics with respect to ε‐caprolactone consumption and controlled behavior of polymerization reactions. The usefulness of α‐allyl, α′‐allyloxy functionalities on poly(ε‐caprolactone) was demonstrated by performing the thiol‐ene reaction with poly(ethylene glycol) thiol to obtain (mPEG)₂‐PCL miktoarm star copolymer. α‐Allyl, α′‐propargyloxy functionalities on poly(ε‐caprolactone) were utilized in orthogonal reactions i.e copper catalyzed alkyne‐azide click (CuAAC) with azido functionalized poly(N‐isopropylacrylamide) followed by thiol‐ene reaction with poly(ethylene glycol) thiol to synthesize PCL‐PNIPAAm‐mPEG miktoarm star terpolymer. The preliminary characterization of A₂B and ABC miktoarm star copolymers was carried out by ¹H NMR spectroscopy and gel permeation chromatography (GPC). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 844–860     

Syntheses and reactions of optically active polymers. II. Preparations of optically active polymers containing quinine,L-ephedrine,and L-histidine residues and their reactions with α-cyanoethylaquocobaloxime

Preparations of polymers with bis(dimethylglyoximato)cobalt (cobaloxime) were investigated. 4-Vinylpyridine was reacted with α-cyanoethylaquocobaloxime to produce α-cyanoethyl-4-vinylpyridinatocobaloxime (I) in 72% yield. It did not, however, polymerize by the use of azobisisobutyronitrile (AIBN) as an initiator. Polymers containing α-cyanoethylcobaloxime were obtained by reactions of polymers with α-cyanoethylaquocobaloxime (II). Poly(9-O-methacryloylquinine) (III), poly(O-methacryloyl-N-methyl-L -ephedrine) (IV), poly[N^α-(o-vinylbenzyl)-L -histidine] (V), and poly(4-vinylpyridine) (VI) were prepared and used in these reactions. Polymers V and VI were reacted with II to give polymers X, XI, XII, and XIII containing α-cyanoethylcobaloxime.     

Silsesquioxane Modified with PAMAM Dendrimer and a Bimetallic Complex for Electrochemical Detection of Ascorbic Acid

Octakis(3-chloropropyl)octasilsesquioxane (S) was organofunctionalized with the PAMAM Dendrimer G.0 (SPD). After functionalization, silsesquioxane interacts with copper chloride and subsequently with potassium hexacyanoferrate (III) to produce the structure CuHSPD. The silsesquioxane functionalized with the PAMAM dendrimer (SPD) and the obtained novel hybrid composite (CuHSPD) were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). The CuHSP voltammogram showed two well-defined redox pairs with E^θ′= 0.27 and 0.74 V, that are assigned to the Cu^I/Cu^II and Fe^II(CN)₆/Fe^III(CN)₆ redox pairs, respectively. The graphite paste electrode containing CuHSPD allowed the electrocatalytic determination of ascorbic acid using various electrochemical techniques such as cyclic voltammetry, differential pulse voltammetry, and chronoamperometry.     

Synthesis and complex formation of stereoisomers of 1,3-Diphenyl-2-thioxo-4,5-bis(hydroxyimino)-Imidazoline

The new α-dioxime, 1,3-diphenyl-2-thioxo-4,5-bis-(hydroxyimino)-imidazoline, DTIH₂, has been synthesized. Anti- and amphi-forms of DTIH₂ could be separated. The anti- and amphi-forms of Cu^II, Ni^II, Co^II, and Co^III complexes have been isolated and their structures identified by using IR, UV-Visible and elemental analyses. The interconversion of anti- and amphi-Ni^II complexes has been studied.