Syndiotactic‐specific radical polymerization of N,N‐dimethylacrylamide in the presence of tartrates: A proposed mechanism for the polymerization

Radical polymerization of N,N‐dimethylacrylamide (DMAAm) was investigated in the presence of tartrates, such as diethyl L ‐tartrate, diisopropyl L ‐tartrate, and di‐n‐butyl L ‐tartrate, in toluene at low temperatures. Syndiotactic polymers were obtained in the presence of tartrates, whereas isotactic polymers were obtained in the absence of tartrates. The syndiotactic‐specificity increased with increasing amount of tartrates and with decreasing polymerization temperature. NMR analysis suggested that DMAAm and tartrates formed a 1:1 complex through double hydrogen bonding. A mechanism for the syndiotactic‐specific radical polymerization of DMAAm is proposed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1192–1203, 2009     

The effect of the N‐substituent s‐trans to the carbonyl group of N‐methylacrylamide derivatives on the stereospecificity of radical polymerizations

Radical polymerization of N‐methylacrylamide (NMAAm), N,N‐dimethylacrylamide (DMAAm), and N‐methyl‐N‐phenylacrylamide (MPhAAm) was investigated in toluene at low temperatures. Atactic, isotactic, and syndiotactic polymers were obtained by the polymerization of NMAAm, DMAAm, and MPhAAm, respectively, indicating that the stereospecificity of the radical polymerization of acrylamide derivatives depended on the N‐substituents of the monomer used. From the viewpoint of monomer structure, the origin of the stereospecificity of radical polymerization of NMAAm derivatives is discussed. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6534–6539, 2009     

Stereospecificity of 1H, 13C and 15N shielding constants in the isomers of methylglyoxal bisdimethylhydrazone: problem with configurational assignment based on 1H chemical shifts

In the ¹³C NMR spectra of methylglyoxal bisdimethylhydrazone, the ¹³C‐5 signal is shifted to higher frequencies, while the ¹³C‐6 signal is shifted to lower frequencies on going from the EE to ZE isomer following the trend found previously. Surprisingly, the ¹H‐6 chemical shift and ¹J(C‐6,H‐6) coupling constant are noticeably larger in the ZE isomer than in the EE isomer, although the configuration around the –CH═N– bond does not change. This paradox can be rationalized by the C–H?N intramolecular hydrogen bond in the ZE isomer, which is found from the quantum‐chemical calculations including Bader's quantum theory of atoms in molecules analysis. This hydrogen bond results in the increase of δ(¹H‐6) and ¹J(C‐6,H‐6) parameters. The effect of the C–H?N hydrogen bond on the ¹H shielding and one‐bond ¹³C–¹H coupling complicates the configurational assignment of the considered compound because of these spectral parameters. The ¹H, ¹³C and ¹⁵N chemical shifts of the 2‐ and 8‐(CH₃)₂N groups attached to the –C(CH₃)═N– and –CH═N– moieties, respectively, reveal pronounced difference. The ab initio calculations show that the 8‐(CH₃)₂N group conjugate effectively with the π‐framework, and the 2‐(CH₃)₂N group twisted out from the plane of the backbone and loses conjugation. As a result, the degree of charge transfer from the N‐2– and N‐8– nitrogen lone pairs to the π‐framework varies, which affects the ¹H, ¹³C and ¹⁵N shieldings. Copyright © 2012 John Wiley & Sons, Ltd.     

Steady-State and Time-Resolved Fluorescence Spectroscopic Studies on Interaction of the N-terminal Region with the Hairpin Loop of the Phytocystain Scb

The steady-state and time-resolved fluorescece spectroscopy is one of the most powerful method to detect and analyze subtle conformation change and interaction between peptide elements in protein. Phytocystatin Scb isolated from sunflower seeds includes a single Trp residue at position 85. In an attempt to investigate the interaction of the N-terminal region of Scb with the first and second hairpin loops by fluorescence spectroscopy of Trp residue, two Scb mutants in which single Trp locates at position 52 and 58, respectively, and their N-terminal removed mutants were generated. The N-terminal truncation changed the fluorescence decay kinetics of Trp52 from the triple exponential to double. Furthermore, the time-resolved fluorescence anisotropy residue indicated that the segmental motion of Trp52 was significantly enhanced by its N-terminal truncation. In contrast, Trp58 and Trp85 had little influence. The N-terminal successive truncations of Scb and its mutants resulted in the weaken inhibitors to papain. These results suggested that the N-terminal region of Scb interacts with the peptide segment preceding the first hairpin loop, thereby stabilizing the conformation of the hairpin loop structure.     

57Fe CEMS study on the surface damage of alloys produced by He+ ion bomabardment

Using the⁵⁷Fe conversion electron Mössbauer spectroscopy (CEMS), the structural and compositional changes at near surface of the amorphous Fe-13%B-9%Si and Fe-15%Cr-9%Ni stainless steel specimens have been clarified after the bombardment of 25kV accelerated He⁺ ions.     

Magnetic behavior of Fe0.2Mg0.8TiO3 and Fe0.3Mg0.7TiO3 probed by Mössbauer timescale

Magnetization and Mössbauer measurements have been made on a diluted antiferromagnets Fe_xMg_1?xTiO₃ with x=0.2, 0.3 and 0.7. It has been demonstrated that this system exhibits a spin glass or a reentrant spin glass like behavior in the samples with x around the percolation concenrration x_c≈0.25. It has been shown that various sizes of magnetic clusters are formed well above the transition temperatures determined by the magnetization measurements in the samples with x near x_c. The behavior of Fe_0.2Mg_0.8TiO₃ is discussed as a typical cluster glass.     

57Fe and57Co Mössbauer studies of highT c Y-Ba-Cu oxides

The⁵⁷Co emission Mössbauer spectra from YBa₂Cu₃O_6.92 (1-2-307) and YBa₂Cu₃O_6.00 (1-2-306) have been measured and compared with the⁵⁷Fe absorption spectra from YBa₂Cu_2.95Fe_0.05O_7?δ in order to clarify decisively the site assignments for the⁵⁷Fe quadrupole-split doublets in these compounds. Mössbauer spectra obtained from both specimens consist of four components whose hyperfine interaction parameters well agree with each other. It is shown that the Co and Fe atoms mainly substitute at Cu1 chain sites in 1-2-307, but in 1-2-306 the Co atoms occupy randomly the Cu2 plane sites and indicate magnetically-split sextet which converts to a paramagnetic doublet of S-state Fe³⁺ in 1-2-307 by a post-annealing in O₂ gas.     

Mössbauer spectroscopy of the high-pressure phase of pure iron;ɛ-Fe

Hyperfine Interactions - First off-line tests at the ion trap facility SHIPTRAP took place. The facility is being set up to deliver very clean and cooled beams of singly-charged recoil ions (Rare...