3-Tetrahydrofurfuryloxy-2-Hydroxypropyl Methacrylate: Synthesis,Characterization, Homopolymerization,and Copolymerization

Abstract

3-Tetrahydrofurfuryloxy-2-hydroxypropyl methacrylate monomer was prepared from methacrylic acid, tetrahydrofurfuryl alchol, and epichlorhydrin. Homopolymerization and copolymerization with (2-phenyl-1,3-dioxolane-4-yl)methyl methacrylate and N-vinyl pyrrolidone monomers were carried out in 1,4-dioxane solution at 60°C using benzoyl peroxide as initiator. Infrared, proton and carbon-13 nuclear magnetic resonance techniques were used in characterizations of the monomer, the homopolymer and the copolymers were determined by DSC technique. The copolymer compositions were estimated from 1H-NMR spectra. The reactivity ratios in copolymerization of 3-tetrahydrofurfuryloxy-2-hydroxypropyl methacrylate and (2-phenyl-1,3-dioxolane-4-yl) methyl methacrylate were calculated by both Kelen-Tüdos and Fineman-Ross methods.     

A Grafting Study on Partially Dehydrochlorinated Poly(vinyl chloride) by Atom Transfer Radical Polymerization

HCl elimination in low ratio was first carried out from poly(vinyl chloride) to increase allylic chlorines. Partially dehydrochlorinated poly(vinyl chloride), having a macroinitiator effect, was grafted with tert‐butyl methacrylate via atom transfer radical polymerization in the presence of CuBr/2,2′‐bipyridine at 64°C in tetrahydrofuran. Original poly(vinyl chloride) was also grafted with tert‐butyl methacrylate under the same conditions to compare with that of partially dehydrochlorinated poly(vinyl chloride). The graft copolymers were characterized by elemental analysis, FTIR, ¹H and ¹³C‐NMR, differential scanning calorimetry, and gel permeation chromatography (GPC). Thermal stabilities of the graft copolymers were investigated by thermogravimetric analysis as compared with those of the macroinitiators.     

Dielectric Properties of Polymer Composites Filled with Different Metals

Electrically conductive composite systems based on polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA) filled with metal powders of Al and Cu have been studied. The composite preparation conditions allow the formation of a random distribution of metallic particles in the polymer matrix. Dependence of the dielectric and conductivity properties of the PVC and PMMA/fillers was studied over a broad range of frequency and volume fraction of metal fillers. The experimental results could be explained by means of the conductivity of fillers and the interface polarization between polymers and fillers. Percolation was also seen in this study when the volume fraction of conducting fillers was close to critical value, in which the composites undergo an insulator‐conductor transition. The relation among the dielectric property and the fillers with different conductivity was proposed.     

Preparation,Characterization and Electromagnetic Shielding Effectiveness of Conductive Polythiophene/Poly(ethylene terephthalate) Composite Fibers

Conductive polythiophene (PTh)/poly(ethylene terephthalate) (PET) composite fibers were prepared by polymerization of thiophene in the presence of PET fibers in acetonitrile medium using FeCl₃. The effects of polymerization conditions such as oxidant/monomer mol ratio and polymerization temperature and time on PTh content and surface electrical resistivity of PTh/PET composite fiber were investigated in detail. It was observed that the usage of preswelled PET fibers in dichloromethane increased the PTh content and decreased surface resistivity of composite fiber. Composite fiber having the highest PTh content (5.7%) and the lowest surface resistivity (80 kΩ) was obtained at 20°C with 1.25 M FeCl₃ and 0.42 M thiophene concentrations. The washing effects of laundering detergent and dry cleaning liquid on surface resistivity of composite fibers were investigated. The electromagnetic shielding effectiveness (EMSE) and relative shielding efficiency by absorption and reflection of composite fibers were measured in the radio and microwave frequency range. The results show that the EMSE values decreased with increasing frequency from radio waves to microwaves with an attenuation of 21 dB to 4 dB.     

A Ready‐to‐Use Electrochemical Kit Design for the Diagnosis of Single Nucleotide Polymorphisms

In this study, for the first time a model electrochemical kit was constructed for the detection of a functional polymorphism in catechol‐O‐methyl transferase (COMT) gene which is important for diagnosis of neuropsychiatric disorders as Alzheimer disease. The disposable pencil graphite electrode (PGE) is designed as a “kit” and the probe DNA covered PGE can detect single nucleotide polymorphisms (SNPs) from real samples based on the guanine oxidation signal even after 5 months of kit preparation (150 days durability).The detection limit (S/N=3) of the biosensor was calculated as 1.18 pmol of synthetic target sequence and 6.09×10⁵ molecules of real samples in 30 min detection time.     

Molecularly Imprinted Polypyrrole for DNA Determination

In this study graphite electrodes modified by a thin DNA‐imprinted polypyrrole layer, which was able to bind specific target‐DNA, are reported. For this aim, electrochemical synthesis of polypyrrole was performed on a pencil graphite electrode by cyclic voltammetry (CV) or by potential pulse sequences (PPS). The modified electrode surface was used for electrochemical determination of target‐DNA by differential pulse voltammetry. According to our best knowledge this is a first report on the application of DNA‐imprinted polymer for the determination of target‐DNA. The results showed that the molecularly imprinted polypyrrole (MIPPy) layer that formed on the carbon electrode surface was sensitive for target‐DNA, while the nonimprinted polypyrrole layer was not sensitive to the same target‐DNA. Comparison of electrodes modified using PPS and CV techniques is presented.     

A Sensitive and Selective RP-LC Method for the Simultaneous Determination of the Antihypertensive Drugs,Enalapril, Lercanidipine,Nitrendipine and Their Validation

A RP-LC method is presented, which is sensitive and selective for the simultaneous determination of enalapril–lercanidipine and enalapril–nitrendipine binary mixtures in their pharmaceutical dosage forms. The analyte peaks were detected using the LC method with the mobile phase ratio of methanol: water (70:30 v/v, pH 3.0) and a 1.0 mL min⁻¹ flow rate. The detection wavelength was selected at 210 nm using photo diode array detector and column temperature was optimized to 30 °C. Linearity was obtained at different concentration ranges for all working pharmaceutically active compounds between 0.5 and 25 μg mL⁻¹. The proposed methods were extensively validated according to USP 27 requirements and ICH guidelines. The methods were applied to the analysis of pharmaceutical dosage forms containing binary mixtures of enalapril–lercanidipine and enalapril–nitrendipine. Moreover, the proposed methods were applied for the degradation studies of the selected compounds. Degradation studies were conducted using stress conditions such as UV light, acidic and alkaline hydrolysis, oxidation and heat in oven, to evaluate the ability of the separation of the response of standard compounds from their degradation products.

     

Synthesis of 2,3‐Dihydro‐4H‐furo[3,2‐c] chromen‐4‐ones and 2,3‐Dihydronaphtho[2,3‐b]furan‐4,9‐diones by the Radical Cyclizations of Hydroxyenones with Electron-Rich Alkenes using Manganese(III) Acetate

We have obtained dihydrofurans 3a–j in the radical cyclization of 4‐hydroxycoumarin 1a and 2‐hydroxy‐1,4‐naphtoquinone 1b with electron rich alkenes 2a–i by manganese(III) acetate. Methods A and B, which have different molar ratios were studied comparatively in these reactions, and we observed that method B (molar ratio 2:1:3) gave the best results. Treatment of 4‐hydroxycoumarin 1a and electron rich alkenes 2a–e gave 2,3‐dihydro‐4H‐furo[3,2‐c]chromen‐4‐ones 3a–e in 36–86% yields by the method B. Under the same conditions, the reactions of 2‐hydroxy‐1,4‐naphtaquinone 1b with conjugated alkenes 2b and 2f–i afforded 2,3‐dihydronaphtho[2,3‐b]furan‐4,9‐diones 3f–j in an excellent yields.     

Synthesis of C 2-Symmetric Chiral Amino Alcohols: Their Usage as Organocatalysts for Enantioselective Opening of Epoxide Ring

A series of β-amino alcohols derivatives were synthesized from (R)-2-amino-1-butanol and (S)-1,2-propanediol, and they have been used as organocatalaysts in the racemic ring opening of epoxide in good yields with high enantiomeric excess (up to 97%).