FT-IR Spectroscopic Investigation of Hofmann Td-Type Complexes of 2-, and 3-Chloropyridine

Hofmann-type modified clathrate hosts containing 2- or 3-chloropyridine molecules attached to metal (II) tetracyanocadmate frame, with a given formula: M(Clpy)₂Cd(CN)₄ where M = Mn, Ni or Cd; Clpy = 2- or 3-chloropyridine, have been synthesised for the first time. Their FT-IR spectra are reported in the 400–4000 cm^-1 region. All the vibrational modes of coordinated Clpy are characterised. The spectral features of the compounds studied are found to be similar to each other indicating that they have analogous structures. The coordination effect on the Clpy modes is analyzed.     

Self‐curable polyester by a reaction of glycidol with maleic anhydride

The controlled reaction of equimolar quantities of maleic anhydride and glycidol in dimethoxyethane gives soluble polyesters with one hydroxyl group in each repeating unit. The reaction proceeds with stepwise ring opening of the components and gives highly viscous clear solutions in relatively short periods. In the first step, monomaleate ester formation takes place around 80 °C. The ring opening of the oxirane group is the second step, and it occurs at 120 °C. The overall reaction is the formation of soluble polyesters with moderate molecular weights (6000–18,000), without the elimination of water. The soluble polyesters can be crosslinked tightly by direct heating at 190 °C without additional vinyl monomer. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2549–2555, 2003     

Air‐stable and recoverable catalyst for copper‐catalyzed controlled/living radical polymerization of styrene; In situ generation of Cu(I) species via electron transfer reaction

Copper‐catalyzed controlled/living radical polymerization (LRP) of styrene (St) was conducted using the silica gel‐supported CuCl₂/N,N,N′,N′,N″‐pentamethyldiethylenetriamine (SG‐CuCl₂/PMDETA) complex as catalyst at 110 °C in the presence of a definite amount of air. This novel approach is based on in situ generation and regeneration of Cu(I) via electron transfer reaction between phenols and Cu(II). Sodium phenoxide or p‐methoxyphenol was used as a reducing agent of Cu(II) complexes in LRP. The number–average molecular weight, M_n,GPC, increases linearly with monomer conversion and agrees well with the theoretical values up to 85% conversion The molecular weight distribution, M_w/M_n, decreases as the conversion increases and reaches values below 1.2. The catalyst was recovered in aerobic condition and reused in copper‐catalyzed LRP of St. For the second run, the number–average molecular weights increased with monomer conversion and the polydispersities decreased as the polymerization proceeded and reached to the value <1.3 at 81% conversion. The recycled catalyst retained 90% of its original activity in the subsequent polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 77–87, 2006     

An experimental and theoretical study of vibrational spectra of picolinamide, nicotinamide, and isonicotinamide

The molecular structures and vibrational spectra of the three isomers of pyridinecarboxamide (picolinamide, nicotinamide, isonicotinamide) were calculated with the Density Functional Theory (DFT) method using the B3LYP function and the 6-31++G(d,p), Z2PolX, Z3PolX basis sets. The calculations were performed by using the Gaussian98W packet program set. The total energy distributions (TED) of the vibrational modes of these molecules were calculated by using the Scale 2.0 program and the vibrational modes of the molecules were determined. The Scaled Quantum Mechanical (SQM) method was used in the scaling procedure. In the experimental part of the study, the solid phase FT-IR and Micro Raman spectra of the three isomers of pyridinecarboxamide have been recorded in the range of 4000-650 and 1200-100 cm⁻¹, respectively. The calculated wavenumbers were compared to the corresponding experimental values. As a result, the observed bands of the three isomers of pyridinecarboxamide were assigned with good accuracy.     

The First Example of Dinuclear Co(III) Complexes Containing Crown Ether Moieties

The new dinuclear, octahedral cobalt(III) complexes have been synthesized and then their ability to interact with 4,4′-trimethylene dipyridine investigated. The ¹H and ¹³C-NMR, IR and elemental analysis data indicated that the cobalt(III) complexes are dinuclear.     

A Comparison of Four Different Electrode Matrices on the Performance of Amperometric Hydrogen Peroxide (Bio)Sensors

A comparison of the analytical performances of four different (bio)sensor designs in H₂O₂ determination is discussed. The (bio)sensor designs developed were based on the use of (i) multiwalled carbon nanotubes (MWCNT), zinc oxide nanoparticles (ZnONP), prussian blue (PB); (ii) MWCNT, ZnONP, PB and ionic liquid (IL); (iii) MWCNT, ZnONP and horseradish peroxidase (HRP) and (iv) MWCNT, ZnONP, HRP and IL modified glassy carbon electrode (GCE). A performance comparison of (bio)sensors showed that the one based on HRP/IL-MWCNT-ZnONP/GCE showed the best analytical characteristics with a linear dynamic range of 9.99×10⁻⁸–7.55×10⁻⁴ M, detection limit of 1.37×10⁻⁸ M and sensitivity of 17.00 μA mM⁻¹.     

One‐pot synthesis of star‐block copolymers using double click reactions

3‐Arm star‐block copolymers, (polystyrene‐b‐poly(methyl methacrylate))₃, (PS‐b‐PMMA)₃, and (polystyrene‐b‐poly(ethylene glycol))₃, (PS‐b‐PEG)₃, are prepared using double‐click reactions: Huisgen and Diels–Alder, with a one‐pot technique. PS and PMMA blocks with α‐anthracene‐ω‐azide‐ and α‐maleimide‐end‐groups, respectively, are achieved using suitable initiators in ATRP of styrene and MMA, respectively. However, PEG obtained from a commercial source is reacted with 3‐acetyl‐N‐(2‐hydroxyethyl)‐7‐oxabicyclo[2.2.1]hept‐5‐ene‐2‐carboxamide (7) to give furan‐protected maleimide‐end‐functionalized PEG. Finally, PS/PMMA and PS/PEG blocks are linked efficiently with trialkyne functional linking agent 1,1,1‐tris[4‐(2‐propynyloxy)phenyl]‐ethane 2 in the presence of CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) at 120 °C for 48 h to give two samples of 3‐arm star‐block copolymers. The results of the peak splitting using a Gaussian deconvolution of the obtained GPC traces for (PS‐b‐PMMA)₃ and (PS‐b‐PEG)₃ displayed that the yields of target 3‐arm star‐block copolymers were found to be 88 and 82%, respectively. © Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7091–7100, 2008     

Preparation of 3‐arm star polymers (A3) via Diels–Alder click reaction

Diels–Alder click reaction was successfully applied for the preparation of 3‐arm star polymers (A₃) using furan protected maleimide end‐functionalized polymers and trianthracene functional linking agent (2) at reflux temperature of toluene for 48 h. Well‐defined furan protected maleimide end‐functionalized polymers, poly (ethylene glycol), poly(methyl methacrylate), and poly(tert‐butyl acrylate) were obtained by esterification or atom transfer radical polymerization. Obtained star polymers were characterized via NMR and GPC (refractive index and triple detector detection). Splitting of GPC traces of the resulting polymer mixture notably displayed that Diels–Alder click reaction was a versatile and a reliable route for the preparation of A₃ star polymer. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 302–313, 2008     

A2B2 type miktoarm star copolymers via alkyne homocoupling reaction

The terminal alkyne homocoupling reaction (oxidative alkyne coupling) is presented here as a new route for the preparation of A₂B₂ type 4‐miktoarm star copolymer. The block copolymer with terminal alkyne at the junction point prepared by NMP‐ATRP and ROP‐NMP sequential routes is coupled via diyne formation to give (PS)₂‐(PMMA)₂ and (PCL)₂‐(PS)₂ 4‐miktoarm star polymers, respectively, by using a combination of (PPh₃)₂PdCl₂/PPh₃/CuI in a solvent mixture of Et₃N/CH₃CN at room temperature for 72 h. The molecular weight, intrinsic viscosity ([η]), radius of gyration (R_g), and hydrodynamic radius (R_h) of A₂B₂ 4‐miktoarm star copolymers were calculated using triple‐detection GPC as results of three detectors response. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6703–6711, 2008     

Star polymers with POSS via azide–alkyne click reaction

Azidopropyl‐heptaisobutyl‐substituted polyhedral oligomeric silsesquioxane (POSS‐N₃) was reacted with 1,1,1‐tris[4‐(2‐propynyloxy)phenyl]‐ethane ( 1 ) and poly(ethylene glycol) (PEG)‐b‐poly(methyl methacrylate) (PMMA) copolymer with alkyne at its center (PEG‐PMMA‐alkyne) affording the first time synthesis of 3‐arm star POSS and PEG‐PMMA‐POSS 3‐miktoarm star terpolymer, respectively, in the presence of CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as catalyst and N,N‐dimethylformamide/tetrahydrofuran as solvent at room temperature. The precursors and the target star polymers were characterized comprehensively by ¹H NMR, GPC, and DSC. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5947–5953, 2009