Compounds having thiourea moiety as derivatization reagents in liquid chromatography/electrospray ionization–tandem mass spectrometry (LC/ESI‐MS/MS): synthesis of derivatization reagents for carboxylic acids

The derivatization reagents for carboxylic acids, N‐(Pyridin‐3‐yl)hydrazinecarbothioamide, N‐[4‐(dimethylamino)phenyl]hydrazinecarbothioamide, 1‐(2‐aminoethyl)‐3‐(pyridin‐3‐yl)thiourea, 1‐(2‐aminoethyl)‐3‐[4‐(dimethylamino)phenyl]thiourea and 4‐(2‐aminoethyl)‐N‐phenylpiperazine‐1‐carbothioamide were synthesized. These reagents reacted with carboxylic acids at 60°C for 45 min in the presence of the condensation reagents. The generated derivatives were favorably separated on the reversed‐phase column and sensitively detected by electrospray ionization tandem mass spectrometry. These reagents enhanced the electrospray ionization response of the analyte and generated a particular product ion efficiently by collision‐induced dissociation, and thus they were suitable for MS/MS detection. Copyright © 2010 John Wiley & Sons, Ltd.     

Spin dynamics in crystalline and amorphous DyAg

Crystalline (cr-) Dyag [CsC] structure] orders antiferro-magnetically with T_N≅60K; amorphous (am-) DyAg ferro-magnetically with T_C≈-18K. We measured the longitudinal field (LF) μ⁺SR relaxation functions G_ZZ(t) for 5K<T<300K using surface muons. In the paramagnetic state. cr-DyAg gives an exponential G_ZZ (t) in the relaxation rate rising first slowly then more rapidlynear T_N; no decoupling is observed in LF up to 0.4T. In the ordered state we see a Lorentzian Kubo-Toyabe G_ZZ(t), becoming nearly static at the lowest temperatures. Its static width is very narrow (Δ≈-7 MHz), and full dceoupling is achieved here in 0.1 T. On approaching T_N, the fluctuation rate and the static width increase mootonically bt the field distribution remains Loratzian. A LF of 0.4T is then insufficient to quench the fast exponential relaxation. In paramagnetic am-DyAg, the μ⁺ depolarization is always much faster then in cr-DyAg. At lower temperatures it is better described by a root-exponential than an exponential G_ZZ(t). Below T_C an exponentially relaxing signal with 1/3 amplitude is seen. The decoupling effect of LF up to 0.4T was negligible at all temperatures.     

Muon spin relaxation in diluted triangular‐lattice antiferromagnet

Zero and longitudinal field μSR measurements on diluted triangular‐lattice antiferromagnet LuFeMgO₄ have revealed gradual and highly anisotropic slowing‐down of spin fluctuation. Relaxation rate \lambda in the condition with initial muon spins perpendicular to the hexagonal c‐plane shows divergent behavior while that in the parallel configuration remains finite. At certain temperature range the fluctuation of spins is suppressed by a small external magnetic field. Monte Carlo calculation suggests that the correlation time for z(c)‐component of spins diverges first on cooling. This revised version was published online in July 2006 with corrections to the Cover Date.     

The low temperature hyperfine structure of quartz under uniaxial pressure

The uniaxial pressure dependence of the muonium hyperfine tensor was measured at 80 K. Uniaxial pressures (0 and 0.2 GPa) were applied along the a‐axis of quartz, and the hyperfine tensor was measured by applying various transverse fields between 0 and 7 G. The structure appears to be the result of the three chemically equivalent sites in quartz. When pressure is applied perpendicular to the crystallographic c‐axis of quartz, the symmetry of these sites is broken such that two chemically inequivalent sites are observed. The resulting hyperfine structure is discussed and qualitative explanations are proposed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Salt‐Free Reduction of Nonprecious Transition‐Metal Compounds: Generation of Amorphous Ni Nanoparticles for Catalytic C–C Bond Formation

A salt‐free procedure for the generation of a wide variety of metal(0) particles, including Fe, Co, Ni, and Cu, was achieved using 2,3,5,6‐tetramethyl‐1,4‐bis(trimethylsilyl)‐1,4‐diaza‐2,5‐cyclohexadiene ( 1 ), which reduced the corresponding metal precursors under mild conditions. Notably, Ni particles formed in situ from the treatment of Ni(acac)₂ (acac=acetylacetonate) with 1 in toluene exhibited significant catalytic activity for reductive C? C bond‐forming reactions of aryl halides in the presence of excess amounts of 1 . By examination of high‐magnification transmission electron microscopy images and electron diffraction patterns, we concluded that amorphous Ni nanoparticles (Ni aNPs) were essential for the high catalytic activity.     

Influence of RNA Strand Rigidity on Polyion Complex Formation with Block Catiomers

Polyion complexes (b‐PICs) are prepared by mixing single‐ or double‐stranded oligo RNA (aniomer) with poly(ethylene glycol)‐b‐poly(l ‐lysine) (PEG‐PLL) (block catiomer) to clarify the effect of aniomer chain rigidity on association behaviors at varying concentrations. Here, a 21‐mer single‐stranded RNA (ssRNA) (persistence length: 1.0 nm) and a 21‐mer double‐stranded RNA (small interfering RNA, siRNA) (persistence length: 62 nm) are compared. Both oligo RNAs form a minimal charge‐neutralized ionomer pair with a single PEG‐PLL chain, termed unit b‐PIC (uPIC), at low concentrations (<≈0.01 mg mL⁻¹). Above the critical association concentration (≈0.01 mg mL⁻¹), ssRNA b‐PICs form secondary associates, PIC micelles, with sizes up to 30–70 nm, while no such multimolecular assembly is observed for siRNA b‐PICs. The entropy gain associated with the formation of a segregated PIC phase in the multimolecular PIC micelles may not be large enough for rigid siRNA strands to compensate with appreciably high steric repulsion derived from PEG chains. Chain rigidity appears to be a critical parameter in polyion complex association.

     

Moment convergence of <Emphasis Type="Italic">Z</Emphasis>-estimators

The problem to establish the asymptotic distribution of statistical estimators as well as the moment convergence of such estimators has been recognized as an important issue in advanced theories of statistics. This problem has been deeply studied for M-estimators for a wide range of models by many authors. The purpose of this paper is to present an alternative and apparently simple theory to derive the moment convergence of Z-estimators. In the proposed approach the cases of parameters with different rate of convergence can be treated easily and smoothly and any large deviation type inequalities necessary for the same result for M-estimators do not appear in this approach. Applications to the model of i.i.d. observation, Cox’s regression model as well as some diffusion process are discussed.