Iron‐catalyzed living radical polymerization of acrylates: Iodide‐based initiating systems and block and random copolymerizations

A half‐metallocene iron iodide complex [Fe(Cp)I(CO)₂] induced living radical polymerization of methyl acrylate (MA) in conjunction with an iodide initiator [(CH₃)₂C(CO₂Et)I, 1 ] and Al(Oi‐Pr)₃ to give polymers of controlled molecular weights and narrow molecular weight distributions (MWDs) (M_w/M_n < 1.2). With the use of chloride and bromide initiators, the MWDs were broader, whereas the molecular weights were similarly controlled. Other acrylates such as n‐butyl acrylate (nBA) and tert‐butyl acrylate (tBA) can be polymerized with 1 /Fe(Cp)I(CO)₂ in the presence of Ti(Oi‐Pr)₄ and Al(Oi‐Pr)₃, respectively, to give living polymers. The 1 /Fe(Cp)I(CO)₂ initiating system is applicable for the synthesis of block and random copolymers of acrylates (MA, nBA, and tBA) and styrene of controlled molecular weights and narrow MWDs (M_w/M_n = 1.2–1.3). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2033–2043, 2002     

Determination of palladium(II) with alpha-(2-benzimidazolyl)-alpha',alpha'-(N-5-nitro-2-pyridylhydrazone)-toluene by adsorptive cathodic stripping voltammetry

The determination of palladium(II) complexed with alpha-(2-benzimidazolyl)-alpha',alpha'-(N-5-nitro-2-pyridylhydrazone)-Toluene (BINPHT) was investigated by adsorptive cathodic stripping voltammetry using hanging mercury drop electrode. Palladium(II) in the sample solution can be determined in BINPHT and ethylenediaminetetraacetic acid (EDTA). Accumulation is achieved by adsorption of Pd(II)-BINPHT complex on a hanging mercury drop electrode. Optimal conditions were found to be: supporting electrolyte; 0.01 M sodium acetate buffer at pH 5.0, accumulation potential; -590 mV versus Ag/AgCl, accumulation time; 180 s, scan rate; 50 mV s(-1), concentration of BINPHT; 2x10(-5) M. The linear range of Pd(II) was observed over the concentration range 20-100 ng ml(-1) The detection limit (S/N=3) is 2 ng ml(-1). A good reproductivity shows RSD of 2.0% (n=7). This procedure offers high selectivity with the presence of EDTA masking some metallic ions. River water sample spiking with palladium was determined.     

Colorimetric anion chemosensor based on 2-aminobenzimidazole: naked-eye detection of biologically important anions

We synthesized a novel colorimetric anion chemosensor bearing benzimidazole motifs as recognition sites in the pods of the receptor. The addition of tetrabutylammonium salts of F⁻ or AcO⁻ to the solution of receptor caused dramatic color changes from colorless to yellow, which was clearly visible to the naked eye. The receptor showed no significant changes on addition of other anions such as Cl⁻, Br⁻, I⁻, NO₃⁻, and H₂PO₄⁻.     

Interaction potentials of the RG-I anions, neutrals, and cations (RG = He, Ne, Ar)

Interaction potentials of the iodine atom, atomic cation, and anion with light rare-gas atoms from He to Ar are calculated within the unified ab initio approach using the unrestricted coupled-cluster with singles and doubles and perturbative treatment of triples correlation treatment, relativistic small-core pseudopotential, and an extended basis set. Ab initio points are fit to a flexible analytical function. The calculated potentials are compared with available literature data, assessed in the I(-)-and I+-ion mobility calculations and the Ar-I(-)-anion zero electron kinetic-energy spectra simulations, and analyzed using the correlation rules. The results indicate a high precision of the reported potentials.     

Adsorption of atomic hydrogen on single-walled carbon nanotubes

We have investigated atomic and electronic structures of hydrogen-chemisorbed single-walled carbon nanotubes (SWCNTs) by density functional calculations. We have searched for relative stability of various hydrogen adsorption geometries with coverage. The hydrogenated SWCNTs are stable with coverage of H/C, theta >/= 0.3. The circular cross sections of nanotubes are transformed to polygonal shapes with different symmetries upon hydrogen adsorption. We find that the band gap in carbon nanotubes can be engineered by varying hydrogen coverage, independent of the metallicity of carbon nanotubes. This is explained by the degree of sp(3) hybridization.     

Role of sphingomyelin-MAPKs pathway in heat-induced apoptosis

The role of sphingomyelinase (SMase) activation and mitogen activated protein kinases (MAPKs) activation in cellular apoptosis was investigated during the hyperthermic treatment of HL-60 human leukemia cells. Treating the cells for 1 h at 43(o)C caused more than 50% of cellular apoptosis within several hours. The neutral-SMase activity in the cells treated for 1 h at 42(o)C was slightly increased but decreased in the cells treated at 43(o)C or 44(o)C for the same period whereas the acid SMase activity was slightly increased after heating the cells at 42(o)C and 43(o)C and markedly increased at 44(o)C for 1 h. Treatment of cells with inhibitors of SMase activation and ceramide formation significantly reduced the heat-induced apoptosis. Three major families of mitogen-activated protein kinases (MAPKs), i.e. ERK1/2, p38 and JNK, were activated by the hyperthermic treatment of cells. Inhibition of ERK1/2 with PD98059 exerted little effect on the heat-induced apoptosis and p38 inhibition with SB203580 slightly lessened apoptosis whereas, inhibition of JNK with SP600125 markedly suppressed the heat-induced apoptosis. These results indicate that heat-shock induced the activation of SMase, particularly acid-SMase, thereby causing apoptosis and that JNK played a pivotal role in heat-induced apoptosis in HL-60 leukemia cells.