New compounds Yb2Fe3O7 and Lu2Fe3O7

New compounds A₂Fe₃O₇ (A = Yb and Lu) were synthesized under low oxygen partial pressures at 1200°C, and their possible space group and lattice constants were determined.     

Development of laser ablation assisted resonant ionization mass spectrometry for isotope analysis

Stable isotope analysis using Laser Ablation Assisted Resonant Ionization Mass Spectrometry (LA-RIMS) is discussed. For the case of the ⁸⁷Sr/⁸⁶Sr isotope ratio measurements with a single color two-photon excitation scheme, the mass discrimination effects, which occur in LA-RIMS, are analyzed and a precision of 0.6% was extracted. For preparation of LA-RIMS on Hf isotopes, a novel two-color resonant excitation scheme with subsequent non-resonant ionization has been established using a high repetition-rate Ti:Sapphire laser system.     

Hydrodynamic Limit for an Evolutional Model of Two-Dimensional Young Diagrams

We construct dynamics of two-dimensional Young diagrams, which are naturally associated with their grandcanonical ensembles, by allowing the creation and annihilation of unit squares located at the boundary of the diagrams. The grandcanonical ensembles, which were introduced by Vershik [17], are uniform measures under conditioning on their size (or equivalently, area). We then show that, as the averaged size of the diagrams diverges, the corresponding height variable converges to a solution of a certain non-linear partial differential equation under a proper hydrodynamic scaling. Furthermore, the stationary solution of the limit equation is identified with the so-called Vershik curve. We discuss both uniform and restricted uniform statistics for the Young diagrams.     

Preparation of porous biodegradable microspheres with direct melting dispersion method

Porous biodegradable microspheres can be prepared by using the direct melting dispersion method without any noxious organic solvents, in which the biodegradable polymer is directly melted and stirred to form the liquid–liquid dispersion followed by cooling in the continuous phase, such as ethylene glycol with the higher melting temperature than polymer. In the experiment, polyhydroxybutyrate (PHB) was adopted as the biodegradable polymer. As particulate porogen, magnetite powder was pre‐mixed into the melted polymer and removed by hydrochloric acid aqueous solution after preparation of the microspheres to make them porous. It was found that the inner surface area was significantly increased by removing magnetite powder. Copyright © 2007 John Wiley & Sons, Ltd.     

Radical and cationic polymerizations of 3‐ethyl‐3‐methacryloyloxymethyloxetane

3‐Ethyl‐3‐methacryloyloxymethyloxetane (EMO) was easily polymerized by dimethyl 2,2′‐azobisisobutyrate (MAIB) as the radical initiator through the opening of the vinyl group. The initial polymerization rate (R_p) at 50 °C in benzene was given by R_p = k[MAIB]^0.55 [EMO]^1.2. The overall activation energy of the polymerization was estimated to be 87 kJ/mol. The number‐average molecular weight (M?_n) of the resulting poly(EMO)s was in the range of 1–3.3 × 10⁵. The polymerization system was found to involve electron spin resonance (ESR) observable propagating poly(EMO) radicals under practical polymerization conditions. ESR‐determined rate constants of propagation (k_p) and termination (k_t) at 60 °C are 120 and 2.41 × 10⁵ L/mol s, respectively—much lower than those of the usual methacrylate esters such as methyl methacrylate and glycidyl methacrylate. The radical copolymerization of EMO (M₁) with styrene (M₂) at 60 °C gave the following copolymerization parameters: r₁ = 0.53, r₂ = 0.43, Q₁ = 0.87, and e₁ = +0.42. EMO was also observed to be polymerized by BF₃OEt₂ as the cationic initiator through the opening of the oxetane ring. The M?_n of the resulting polymer was in the range of 650–3100. The cationic polymerization of radically formed poly(EMO) provided a crosslinked polymer showing distinguishably different thermal behaviors from those of the radical and cationic poly(EMO)s. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1269–1279, 2001     

Radical heterogeneous polymerization behavior of N‐methyl‐α‐fluoroacrylamide in benzene

The polymerization of N‐methyl‐α‐fluoroacrylamide (NMFAm) initiated with dimethyl 2,2′‐azobisisobutyrate (MAIB) in benzene was studied kinetically and with electron spin resonance. The polymerization proceeded heterogeneously with the highly efficient formation of long‐lived poly(NMFAm) radicals. The overall activation energy of the polymerization was 111 kJ/mol. The polymerization rate (R_p) at 50 °C is given by R_p = k[MAIB]^0.75±0.05 [NMFAm]^0.44±0.05. The concentration of the long‐lived polymer radical increased linearly with time. The formation rate (R_p?) of the long‐lived polymer radical at 50 °C is expressed by R_p? = k[MAIB]^1.0±0.1 [NMFAm]^0±0.1. The overall activation energy of the long‐lived radical formation was 128 kJ/mol, which agreed with the energy of initiation (129 kJ/mol), which was separately estimated. A comparison of R_p? with the initiation rate led to the conclusion that 1‐methoxycarbonyl‐1‐methylethyl radicals (primary radicals from MAIB), escaping from the solvent cage, were quantitatively converted into the long‐lived poly(NMFAm) radicals. Thus, this polymerization involves completely unimolecular termination due to polymer radical occlusion. ¹H NMR‐determined tacticities of resulting poly(NMFAm) were estimated to be rr = 0.34, mr = 0.48, and mm = 0.18. The copolymerization of NMFAm(M₁) and St(M₂) with MAIB at 50 °C in benzene gave monomer reactivity ratios of r₁ = 0.61 and r₂ = 1.79. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2196–2205, 2001     

Kinetic study of the radical polymerization behavior of N‐(1‐phenylethylaminocarbonyl)methacrylamide

Polymerization of N‐(1‐phenylethylaminocarbonyl)methacrylamide (PEACMA) with dimethyl 2,2′‐azobisisobutyrate (MAIB) was kinetically studied in dimethyl sulfoxide (DMSO). The overall activation energy of the polymerization was estimated to be 84 kJ/mol. The initial polymerization rate (R_p) is given by R_p = k[MAIB]^0.6[PEACMA]^0.9 at 60 °C, being similar to that of the conventional radical polymerization. The polymerization system involved electron spin resonance (ESR) spectroscopically observable propagating poly(PEACMA) radical under the actual polymerization conditions. ESR‐determined rate constants of propagation and termination were 140 L/mol s and 3.4 × 10⁴ L/mol s at 60 °C, respectively. The addition of LiCl accelerated the polymerization in N,N‐dimethylformamide but did not in DMSO. The copolymerization of PEACMA(M₁) and styrene(M₂) with MAIB in DMSO at 60 °C gave the following copolymerization parameters; r₁ = 0.20, r₂ = 0.51, Q₁ = 0.59, and e₁ = +0.70. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2013–2020, 2005     

A New Desulfurization Method: Application to the Synthesis of 11-Deoxyprostaglandin E2

Alkylation at carbon attached to sulfur of α-phenylthio or α-alkylthioketones, or reductive-alkylation of α-phenylthioketones provided a new regiospecific alkylation method of ketones.^1,2 In these procedures, desulfurization was effected either by reduction with lithium in liquid ammonia^1,2 or by use of Raney Ni-W-2.² Recently, buffered sodium amalgam method has been reported to be effective for desulfurization of β-ketosulfides as well as for desulfonylation of aryl alkyl sulfones.³ We wish to report here that desulfurization of α-phenylthioketones was achieved by treatment of the ketones with zinc and chlorotrimethylsilane. This observation would lead to a facile synthesis of α-substituted ketones.