On the entropy of fusion

The asymptotic value of the melting entropy, i.e. ΔS_f = R ln 2 for vanishing relative change of volume on melting, can be derived from the vibrational entropy due to vibrating dislocations, which are introduced into a material on melting.     

Synthesis of well‐defined syndiotactic poly(methyl methacrylate) with low‐temperature atom transfer radical polymerization in fluoroalcohol

The copper‐mediated atom transfer radical polymerization of methyl methacrylate (MMA) in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) was studied to simultaneously control the molecular weight and tacticity. The polymerization using tris[2‐(dimethylamino)ethyl]amine (Me₆TREN) as a ligand was performed even at ?78°C with a number‐average molecular weight (M_n) of 13,400 and a polydispersity (weight‐average molecular weight/number‐average molecular weight) of 1.31, although the measured M_n's were much higher than the theoretical ones. The addition of copper(II) bromide (CuBr₂) apparently affected the early stage of the polymerization; that is, the polymerization could proceed in a controlled manner under the condition of [MMA]₀/[methyl α‐bromoisobutyrate]₀/[CuBr]₀/[CuBr₂]₀/[Me₆TREN]₀ = 200/1/1/0.2/1.2 at ?20°C with an MMA/HFIP ratio of 1/4 (v/v). For the field desorption mass spectrum of Cu^IBr/Me₆TREN in HFIP, there were [Cu(Me₆TREN)Br]⁺ and [Cu(Me₆TREN)OCH(CF₃)₂]⁺, indicating that HFIP should coordinate to the Cu^I/Me₆TREN complex. The syndiotacticity of the obtained poly(methyl methacrylate)s increased with the decreasing polymerization temperature; the racemo content was 84% for ?78°C, 77% for ?30°C, 75% for ?20°C, and 63% for 30°C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1436–1446, 2006     

Catalytic property of Europium supported on alumina from its ammoniacal solution

Europium supported on alumina (Eu/Al₂O₃) was prepared by impregnation from an ammoniacal solution of the metal. The catalytic activity of Eu/Al₂O₃ for the isomerization of 2,3-dimethylbut-1-ene to 2,3-dimethylbut-2-ene was examined. Eu/Al₂O₃ showed the highest catalytic activity for the isomerization when heated under a vacuum at 523 K, the yield of 2,3-dimethylbut-2-ene in 20 min being 81.6% at 314 K. IR spectrum shows the presence of two kinds of Eu amides. The change of the IR spectra and the catalytic activities with evacuation temperature suggest that only one of the two Eu amides is catalytically active for this base-catalyzed isomerization.     

A construction of spherical 2-design

It is determined for which values ofn andd spherical 2-designs ofn points exist in ^d . And an explicit construction is given when they exist.     

New Chiral Kemp's Acid Diamides for Chiral Amine Recognition by 1 H NMR

Two Kemp's acid diamides were synthesized and applied to chiral amine recognition using ¹H NMR analysis. One derivative based on 1-(1-naphthyl)ethylamine had good chiral recognition of six amines and was useful to determine the optical purity for three amines, i.e., methylbenzylamine, 1-(1-naphthyl)ethylamine and 1- henylpropylamine,however, the cyclohexylethylamine derivative showed little discrimination for the amines studied. Together with the results for alkylamines, it was shown that aromatic structure was important for aromatic shielding anisotropy and –– interactions between host and guest. The structure of the 1-(1-naphthyl)ethylamine derivative in solution was also considered based on ¹H NMR data and computer simulation.     

Synthesis and evaluation of 1-arylsulfonyl-3-piperazinone derivatives as factor Xa inhibitor

Intravascular clot formation is an important factor in a number of cardiovascular diseases. Therefore, the prevention of blood coagulation has become a major target for new therapeutic agents. One attractive approach is the inhibition of factor Xa (FXa), which is a key enzyme in coagulation cascade responsible for the generation of thrombin by limited proteolysis of its zymogen, prothrombin. We have investigated 1-arylsulfonyl-3-piperazinone derivatives, containing a 4-(piperidino)pyridine group in place of guanidino and/or amidino groups, and discovered compound M55113 (30a: 4-[(6-Chloro-2-naphthalenyl)sulfonyl]-1-[[1-(4-pyridinyl)-4-piperidinyl]methyl]piperazinone), as a potent inhibitor of FXa (IC50=0.06 microM) with high selectivity for FXa over trypsin and thrombin.