Green polymer chemistry: Telechelic poly(ethylene glycol)s via enzymatic catalysis

This article reports our discovery that poly(ethylene glycol) (PEG) can quantitatively be functionalized by transesterification using Candida antarctica lipase B (Novozyme 435) as the catalyst. α‐ω telechelic PEG‐methacrylates and PEG‐acetates were successfully prepared using commercially available PEGs with both narrow and broad molecular weight distribution. ¹H and ¹³C NMR together with MALDI‐TOF mass spectroscopy verified the expected structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3024–3028, 2008     

Precision synthesis and characterization of thymine‐functionalized polyisobutylene

A new two‐step synthesis of polyisobutylene (PIB) with precisely one thymine functionality per chain (PIB‐T) is reported. The primary hydroxyl‐functionalized PIB (PIB‐OH) precursor was prepared by direct functionalization via living carbocationic polymerization of isobutylene initiated by the α‐methylstyrene epoxide/TiCl₄ system. Matrix assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐ToF MS) of a low molecular weight PIB‐OH precursor demonstrated the effectiveness of direct functionalization by this method. A PIB‐acrylate precursor (PIB‐Ac) was obtained from such a PIB‐OH, and the PIB‐T was subsequently prepared by Michael addition of thymine across the acrylate double bond. MALDI‐ToF MS of the products verified that all polymer chains carried precisely one thymine group. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3501–3506, 2010     

Effect of size and protein environment on electrochemical properties of gold nanoparticles on carbon electrodes

We studied the electrochemical properties of gold nanoparticles (GNPs) and their complexes with proteins using square-wave voltammetry. Effect of the nanoparticle size and detection procedure was explored upon the oxidation of GNPs on a glassy carbon electrode (GCE). For pre-characterized GNPs of 13, 35 and 78 nm diameter, the oxidation peak potential was + 0.98, + 1.03 and + 1.06 V vs. Ag/AgCl, respectively. The conjugation of GNPs with four different proteins was verified by UV–Vis spectroscopy and atomic force microscopy indicated the formation of protein shells around GNPs. This process hampered the oxidation of GNPs on bare GCE causing pronounced decrease in the current response by an average factor of 72. GCE modification with carbon nanotubes weakly influenced the sensitivity of GNP detection but resulted in a 14.5-fold signal increase averaged for all GNP–protein complexes. The acidic dissolution and electrodeposition of GNPs or their complexes adsorbed on GCE allowed superior signal amplification directly proportional to nanoparticle size. The results are useful for the optimization of voltammetric analysis of GNP–protein complexes and can be extended to the characterization of other metal nanostructures and their complexes with biological components.     

Synthesis and characterization of novel flavonoid-substituted phthalocyanines using (±)naringenin

In this study, novel unsymmetrical mono- and di-substituted metal free and metallo phthalocyanines containing peripheral naringeninoxy moieties have been prepared. The naringenin-substituted phthalonitrile was synthesized from 4-nitrophthalonitrile and (±)naringenin in dimethylsulfoxide. Preparation of unsymmetrical mono- and di-substituted phthalocyanines, 2-naringenin-7-O-phthalocyaninatozinc, 2,9-bis-naringenin-7-O-phthalocyaninatozinc, 2,9-bis-naringenin-7-O-phthalocyaninatocobalt and 2,9-bis-naringenin-7-O-phthalocyanine was performed at 120-140 °C using the corresponding phthalonitrile in the presence of N,N-dimethylethanolamine (DMAE), ZnCl₂, CoCl₂ and LiCl, respectively. Synthesized new phthalocyanine compounds have been characterized by elemental analysis and ¹H NMR, ¹³C NMR, FT-IR, MS and UV-vis spectroscopy. These are the first known examples of flavonoid-substituted phthalocyanines.     

Synthesis and characterization of a novel water-soluble mid-chain macrophotoinitiator of polyacrylamide by Ce(IV)/HNO3 redox system

A new water-soluble mid-chain macrophotoinitiator of polyacrylamide (PAAm) has been synthesized by redox polymerization. The polymerization of acrylamide (AAm) initiated by dihydroxy functional photoinitiator namely, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl propan-1-one (HE-HMPP), Irgacure 2959, in combination with cerium(IV) ammonium nitrate has been investigated in aqueous nitric acid. The effects of HE-HMPP, AAm, and Ce(IV) concentrations on the polymerization rate were investigated. The photodegradation and IR, ¹H NMR, UV, and fluorescence spectroscopic studies revealed that polyacrylamide with desired photoinitiator functionality in the middle of the chain were obtained. This prepolymer was used in photoinduced free radical polymerization of methyl methacrylate (MMA) to produce PAAm-PMMA block copolymer.     

Kinetic interface roughening and magneto resistance of sputter-deposited Fe/Ni75B25 multilayers

The roughening of interfaces as a function of layer thickness and magneto transport properties have been investigated on sputter-deposited Fe/Ni₇₅B₂₅ multilayer films. X-ray reflectivity data were recorded for Ni₇₅B₂₅(72 nm) film and for [Fe(2 nm)/Ni₇₅B₂₅(2 nm)]₁₆ and [Fe(4 nm)/Ni₇₅B₂₅(4 nm)]₈ multilayer films. A power law dependence of the interfacial width of growing Fe/Ni₇₅B₂₅ interfaces was observed. The resulting growth exponents β were found to be in the range of 0.55–0.58 in the initial growth stage of the multilayer with lower Fe/Ni₇₅B₂₅ repetition thickness and at approximately 0.34 for multilayer with higher repetition thickness. The growth exponents were compared with theoretical calculations. High resolution electron microscopy revealed the columnar growth of the Fe/Ni₇₅B₂₅ multilayer. Additionally, an increase of magnetoresistance was observed by the multilayering of Ni₇₅B₂₅ films with Fe interlayers.     

On the ionic conductivity of polymer electrolytes in terms of hole fraction

A theoretical model to interpret the conductivity of ions through polymer electrolytes is established in terms of the temperature and pressure‐dependent hole fraction computed from Simha‐Somcynsky hole theory. The model successfully linearizes the logarithm of PPG and PEG conductivity data with NaCF₃SO₃ in a 20:1 ratio for a broad range of temperature and pressure. The conductivity parameter and transmission coefficient with an additive hole fraction constant are discussed and compared for both species. The derivative of the logarithm of conductivity with respect to the hole fraction decreases inversely with the hole fraction and saturates at about 0.08 and 0.12 hole fractions for PPG and PEG, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2249–2254, 2008     

Supplier diversification under binomial yield

We consider supplier diversification in an EOQ type inventory setting with multiple suppliers and binomial yields. We characterize the optimal policy for the model and show that, in this case, it does not pay to diversify, in contrast to previous results in the random yield literature.     

Generating the surface mapping class group by two elements

Wajnryb proved in 1996 that the mapping class group of an orientable surface is generated by two elements. We prove that one of these generators can be taken as a Dehn twist. We also prove that the extended mapping class group is generated by two elements, again one of which is a Dehn twist. Another result we prove is that the mapping class groups are also generated by two elements of finite order.