Construction of optically active CF3-containing quaternary carbon centers via stereospecific S(N)2' reaction

[reaction: see text] Phosphates from 3-substituted 4,4,4-trifluorobut-2-en-1-ols were found to be effective for construction of CF3-containing quaternary carbon centers by way of Cu(I)-catalyzed Grignard reactions in the presence of catalytic amounts of CuCN and trimethylsilyl chloride (TMSCl) in an anti S(N)2' manner.     

Stereoblock poly(lactic acid): synthesis via solid-state polycondensation of a stereocomplexed mixture of poly(L-lactic acid) and poly(D-lactic acid)

Stereoblock poly(lactic acid) consisting of D- and L-lactate stereosequences can be successfully synthesized by solid-state polycondensation of a 1:1 mixture of poly(L-lactic acid) and poly(D-lactic acid). In the first step, melt-polycondensation of L- and D-lactic acids is conducted to synthesize poly(L-lactic acid) and poly(D-lactic acid) with a medium-molecular-weight, respectively. In the next step, these poly(L-lactic acid) and poly(D-lactic acid) are melt-blended in 1:1 ratio to allow formation of their stereocomplex. In the last step, this melt-blend is subjected to solid-state polycondensation at temperature where the dehydrative condensation is allowed to promote chain extension in the amorphous phase with the stereocomplex crystals preserved. Finally, stereoblock poly(lactic acid) having high-molecular-weight is obtained. The stereoblock poly(lactic acid) synthesized by this way shows a higher melting temperature in consequence of the controlled block lengths and the resulting higher-molecular-weight. The product characterization as well as the optimization of the polymerization conditions is described. Changes in M(w) of stereoblock poly(lactic acid) (sb-PLA) as a function of the reaction time.     

New hydroxyl protecting groups of a safety-catch type removable by reductive acidolysis.

New hydroxyl protecting groups of a safety-catch type, i.e., 4-methylsulfinylbenzyl-oxycarbonyl (Msz) group for Tyr and 4-methylsulfinylbenzyl (Msob) ether for Thr, have been developed. O-Msz and O-Msob groups are stable under both acidic and basic conditions and can be removed by a one-pot reaction involving reductive acidolysis using tetrachlorosilane-trifluoroacetic acid (TFA)-scavengers. Using these new protecting groups, a 17 residue-peptide, gamma-endorphin, was successfully synthesized by the efficient solid phase method.     

Small-Angle electron scattering and electron density in carbon dioxide

The total (elastic and inelastic) intensity of electrons scattered by CO₂ was measured in the s range of 1 to 12 Å^?1 and compared with the theoretical intensity calculated from the Hartree-Fock molecular wave function and those calculated for the independent-atom-model (IAM ) molecule. In the range of s ? 4 Å^?1 the electron correlation effect on the total scattered intensity was found to be represented by that for the IAM molecule.     

Preconcentration of trace elements from pure manganese and manganese compounds with activated carbon as collector

A method is described for separation of traces of Bi, Cd, Co, Cu, Fe, In, Ni. Pb, Tl, and Zn from pure manganese and manganese compounds and their determination by flame a.a.s. After the metal or manganese dioxide samples have been dissolved in acid (and manganese salts in water) the trace elements are compleed with potassium xanthogenate. The solution is then filtered through a small filter paper covered with activated carbon, whereby complex compounds are separated from the matrix. When the charcoal is treated with acid, a trace concentrate is obtained which is nearly free of manganese. The detection limits for the analysis of 10-g samples of manganese metal are <0.5 p.p.m., and for 30-g samples of MnCl₂-4H₂O are ? 0.1 p.p.m. The relative standard deviation, in general,is lower than 5%.     

Palladium-catalyzed allylation of imines with allyl alcohols

A catalytic system, Pd(OAc)2 (10 mol %)-P(n-Bu)3 (20 mol %)-Et3B (360 mol %), promotes allylic alcohols to undergo the allylation of anisidine-imines of aromatic and aliphatic aldehydes and furnishes homoallylamines in good to moderate yields. The reaction shows unique stereoselectivity, giving anti-isomers selectively. [reaction: see text]     

Mechanism for the inhibition of the acid degradation of ampicillin by 2-hydroxypropyl- β -cyclodextrin

The formation of inclusion complexes between amoxicillin (AMPC) and 2-hydroxypropyl-β-cyclodextrin (HPCD) was investigated by isothermal microcalorimetry and molecular dynamics simulation to evaluate the inhibitory effects on the degradation of AMPC in aqueous solutions at various pH. The process depended significantly on the ionic species of AMPC in the solution. In a strong acid solution, cationic AMPC and HPCD formed two different types of inclusion complexes with a 1:1 stoichiometry: the first-type had a high association constant K ₁ of 4.0-8.0·10³ M^-1 and included the penam ring of AMPC in the HPCD cavity (Mode I), while the second-type with a K ₂ of 1.0·10³ M^-1 contained the phenyl group of AMPC (Mode II). Furthermore, a complex with a 1:2 (AMPC:HPCD) stoichiometry was realized in a two-step reaction and was characterized by a smaller K _1:2of 4.0·10² M^-1 and larger negative enthalpy and entropy changes than the complexes with a 1:1 stoichiometry. Since the β-lactam ring of AMPC could be protected by inclusion with HPCD in the 1:2 complex and Mode I of 1:1 complexes, the degradation of AMPC in the presence of HPCD was approximately four times slower than in its absence at pH 1.2 and 37°C. In weak acid and neutral solutions, zwitterionic AMPC and HPCD formed only one type of inclusion complex with a 1:1 stoichiometry, where the phenyl group was included (Mode II). AMPC was very stable in these solutions (t _1/2=226 h at pH=6.0) and there is little significant difference in the degradation rate between complexed AMPC and uncomplexed AMPC. Thus, the results indicated that the inclusion complex of AMPC with HPCD, effectively increasing the stability of AMPC in a strong acidic solution like that the stomach, would be useful for eradicating Helicobacter pylori infection and as a drug delivery system. This revised version was published online in July 2006 with corrections to the Cover Date.     

Gas chromatography of manganese(II) and manganese(III) trifluoroacetylacetonates by the ligand vapour technique

The thermal properties and gas Chromatographie behaviour of manganese(II) and manganese(III) trifluoroacetylacetonates (TFA) were investigated by using the ligand vapour technique. The two chelates, Mn(TFA); and Mn(TFA)₃, can be quantitatively eluted on a mixed-liquid phase (1.9% OV-17 ÷ 0.1% PEG-20M) at column temperatures above 210°C and 130–150°C, respectively; Mn(TFA)₃ is completely converted to Mn(TFA)₂ by thermal dissociation at column temperatures above 180°C and completely eluted as Mn(TFA)₂ above 210°C. The chelates can be determined separately within errors of about 1% after a preliminary extraction.     

Refining Cosmetatos' Approximation for the Mean Waiting Time in the M/D/s Queue

This paper deals with refining Cosmetatos's approximation for the mean waiting time in an M/D/s queue. Although his approximation performs quite well in heavy traffic, it overestimates the true value when the number of servers is large or the traffic is light. We first focus on a normalized quantity that is a ratio of the mean waiting times for the M/D/s and M/M/s queues. Using some asymptotic properties of the quantity, we modify Cosmetatos's approximation to obtain better accuracy both for large s and in light traffic. To see the quality of our approximation, we compare it with the exact value and some previous approximations. Extensive numerical tests indicate that the relative percentage error is less than 1% for almost all cases with s ≤ 20 and at most 5% for other cases.     

Approximating the Mean Waiting Time in the <Emphasis Type="Italic">GI/G/s</Emphasis> Queue

We provide two distribution-dependent approximations for the mean waiting time in a GI/G/s queue. Both approximations are weighted combinations of the exact mean waiting times for the GI/M/s and M/D/s queues each of which has the same mean service time and traffic intensity as in the approximating GI/G/s queue. The weights in the approximations are expressed by the service-time c.d.f. and the first two moments of interarrival and service times. To examine the performance of our approximations, they are numerically compared with exact solutions and previous two-moment approximations for various cases. Extensive numerical comparisons indicate that the relative percentage errors of the approximations are of the order of 5% in moderate traffic and 1% in heavy traffic, except for extreme cases.