A fast atom bombardment mass spectrometric analysis of crown ether complexes [1]

Analyses of crown ether complexes of alkali metal ions and characterization of the complexes formed inm-nitrobenzyl alcohol have been carried out by fast atom bombardment (FAB) mass spectrometry. By using m-nitrobenzyl alcohol as a matrix for measurements, the stoichiometry of the complexes was assessed on the basis of the observed FAB peaks. In addition, the formation of crown ether-alkali metal complexes at a 2 : 1 molar ratio was enhanced by increasing the ionic radius of the metal ion in agreement with previous observations. On these grounds, FAB mass spectrometry may provide a rapid means for investigation of the complexation behavior of crown ethers and the stoichiometry of the complexes.     

Numerical analysis of finite amplitude motion of waves and a moored floating body under severe storm conditions

The motion of a moored floating body under the action of wave forces, which is influenced by fluid forces, shape of the floating body and mooring forces, should be analysed as a complex coupled motion system. Especially under severe storm conditions or resonant motion of the floating body it is necessary to consider finite amplitude motions of the waves, the floating body and the mooring lines as well as non-linear interactions of these finite amplitude motions. The problem of a floating body has been studied on the basis of linear wave theory by many researchers. However, the finite amplitude motion under a correlated motion system has rarely been taken into account. This paper presents a numerical method for calculating the finite amplitude motion when a floating body is moored by non-linear mooring lines such as chains and cables under severe storm conditions.     

Bioavailability study of commercial sustained-release preparations of diclofenac sodium in gastrointestinal physiology regulated-dogs.

The gastrointestinal (GI) physiology of beagle dogs was regulated with a combined-treatment of intramuscular pentagastrin (10 micrograms/kg x 2) and intravenous atropine sulfate (0.02 mg/kg x 1). Here, the gastric acidity, the gastric emptying time and the small intestinal transit time in the regulated-dogs were respectively around pH 2, 0.7h and 4h, approximating those in healthy humans. The superiority of the regulated-dogs over the intact dogs was confirmed in comparative bioavailability studies by using two classes of commercial preparations. Both the conventional tablet and the sustained-release capsule of diclofenac sodium exhibited simple and similar average plasma concentration-time curves of free diclofenac in the intact dogs, while the latter preparation is reported to reveal a bimodal plasma curve of the drug in healthy humans. The regulated-dogs, however, permitted a bimodal average plasma pattern of the drug for the capsules due to an approximation of the GI physiology between humans and these classes of the dogs. The combined-treatment of beagle dogs with pentagastrin and atropine sulfate seems to supply a useful animal model in predicting the absorption characteristics of the sustained-release preparations and poor water-soluble drugs.     

Quasi-distribution of tunneling time

Using real time Feynman histories, a quasi-distribution of tunneling time Q(τ) is introduced. For the tunneling time of resident time type, an explicit expression for Q is shown for square barriers. Q becomes oscillatory as the barrier becomes opaque. Some well-known tunneling times fall within the range of τ where Q takes non-negligible values. The formal “average” and the “variance” of the tunneling time are found to be related to known tunneling times. It is thus demonstrated that the quasi-distribution extracts the temporal information about tunneling from real time Feynman histories.     

Synthesis and characterization of 6‐ and 12‐arm star polymers by nitroxide‐mediated radical polymerization of St and MA from dendritic TIPNO‐based hexafunctional and dodecafunctional macroinitiators

Dendritic multifunctional macroinitiators having six and 12 TIPNO‐based alkoxyamines, TIPNO‐6 and TIPNO‐12 , were synthesized and used in the living radical polymerization of styrene (St), methyl acrylate (MA), N,N‐dimethylacrylamide (DMAAm), and isoprene (IP). The polymerizations of St initiated with TIPNO‐6 gave 6‐arm star polymers with narrow polydispersities of 1.14–1.18. In the polymerizations of MA initiated with TIPNO‐6 and TIPNO‐12 , the influences of added TIPNO on the polydispersity indexes (PDIs) of the resulting star polymers were first investigated, and this led to the successful formation of poly(MA) star polymers with narrow polydispersities (1.10–1.18). Moreover, the polymerizations of DMAAm and IP from TIPNO‐6 in the presence or absence of TIPNO were briefly investigated. The benzyl ether bonds of the poly(St) and poly(MA) star polymers were cleaved by treating with Me₃SiI or Pd/C, and the resulting arm's parts were analyzed with SEC. The PDIs of the resulting arm parts were low (1.19–1.23), and the M_ns agreed with the M_n,theor, indicating that the poly(St) and poly(MA) star polymers had well‐controlled arms. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4364–4376, 2007     

Preparation of a cyclodextrin dimer linked with a bis(picolinyl)cystine moiety and its intra- and intermolecular inclusion behavior

A novel cyclodextrin (CD) dimer linked with a bis(picolinyl)cystine (Cys) moiety was prepared by the coupling of Boc-protected Cys with amino-modified CDs, followed by deprotection of the Boc groups and bispicolinylation. The dimer showed less affinity to an organic guest molecule compared to that of a native CD monomer. It was attributed to an intramolecular inclusion of the pyridine moiety into CD cavity. The dimer caused significant increase of its organic guest affinity by an addition of a copper ion. The included pyridine group may come out of a CD cavity to bind the copper ion and the two CDs included cooperatively and intermolecularly a guest molecule with high affinity.     

Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006