Re-revision of the stereo structure of piperidine lactone,an intermediate in the synthesis of febrifugine

The stereo structure of piperidine lactone (3), an intermediate of the antimalarial agent febrifugine ((+)-1) prepared by a synthetic method, was re-revised to the cis-form from the trans-form.     

The effect of various substances on the suppression of the bitterness of quinine-human gustatory sensation,binding, and taste sensor studies

The purpose of this study was to quantify the degree of suppression of the perceived bitterness of quinine by various substances and to examine the mechanism of bitterness suppression. The following compounds were tested for their ability to suppress bitterness: sucrose, a natural sweetener; aspartame, a noncaloric sweetener; sodium chloride (NaCl) as the electrolyte; phosphatidic acid, a commercial bitterness suppression agent; and tannic acid, a component of green tea. These substances were examined in a gustatory sensation test in human volunteers, a binding study, and using an artificial taste sensor. Sucrose, aspartame, and NaCl were effective in suppressing bitterness, although at comparatively high concentrations. An almost 80% inhibition of bitterness (calculated as concentration %) of a 0.1 mM quinine hydrochloride solution required 800 mM of sucrose, 8 mM of aspartame, and 300 mM NaCl. Similar levels of bitterness inhibition by phosphatidic acid and tannic acid (81.7, 61.0%, respectively) were obtained at much lower concentrations (1.0 (w/v)% for phosphatidic acid and 0.05 (w/v)% for tannic acid). The mechanism of the bitterness-depressing effect of phosphatidic acid and tannic acid was investigated in terms of adsorption and masking at the receptor site. With phosphatidic acid, 36.1% of the bitterness-depressing effect was found to be due to adsorption, while 45.6% was due to suppression at the receptor site. In the case of 0.05 (w/v)% tannic acid, the total bitterness-masking effect was 61.0%. The contribution of the adsorption effect was about 27.5% while the residual masking effect at the receptor site was almost 33%. Further addition of tannic acid (0.15 (w/v)%), however, increased the bitterness score of quinine, which probably represents an effect of the astringency of tannic acid itself. Finally, an artificial taste sensor was used to evaluate or predict the bitterness-depressing effect. The sensor output profile was shown to reflect the depressant effect at the receptor site rather well. Therefore, the taste sensor is potentially useful for predicting the effectiveness of bitterness-depressant substances.     

Synthesis of novel phosphinic acid-containing polymers

Three arylene difluoride monomers containing phosphine oxide ( 1 ), phosphinic acid ( 2 ), or phosphinate ester ( 3 ) groups were prepared and polymerized with bisphenol A to give novel poly-(arylene ether)s ( 4 , 5 , and 6 ). The polymers obtained had moderate molecular weights (η_inh: 0.14–0.30 dL g⁻¹ in N-methylpyrrolidinone) and glass-transition temperatures (T_g: 102–200 °C), depending on the phosphine group in the main chain. Using bis(4-fluorophenyl)sulfone as a comonomer improved the polymerization to give copolymers with higher solution viscosities. The stoichiometric investigation revealed that 7 mol % excess of fluoride monomer gave the highest molecular weight copolymer 8 with η_inh of 0.78 dL g⁻¹, which had a T_g of 176 °C, a T of 432 °C, and formed a hard film by casting from solution. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1854–1859, 2001     

Strain energy function of an uncross-linked butadiene rubber estimated from planar extension

The derivatives of the strain energy function u with respect to the invariants of the strain tensor (I₁ and I₂) are estimated for uncross-linked butadiene rubber by using the BKZ constitutive equation. The derivatives at small deformations show anomalous behavior; namely, an upturn for ∂u/∂I₁ and a downturn for ∂u/∂I₂ take place, as is the case of cross-linked rubbers. At large deformations, u is well described by u = A₁(I₁ −3) + A₂(I₂ −3) with numerical constants A₁ and A₂. This behavior is also quite similar to that for cross-linked rubbers. The non-zero positive constant A₂ for the melt suggests that the non-zero value is due to neither the inhomogeneity in network structure nor high extension of constituent polymer chains.     

Determination of Permeability Distributions Using NMR Velocity Imaging

This study develops a methodology for determining the absolute permeability distribution in a porous media sample using velocity data obtained from NMR imaging experiments. An objective function describing the discrepancy between observed and simulated data is reduced by iteratively updating the permeability. This parameter estimation scheme is based on an iterative method which uses optimal control theory to refine the estimates. Although this theory is developed for both isotropic and anisotropic porous media, the permeability reconstructions examined in this paper are restricted to the isotropic case. Synthetic data are used to investigate the impact of varying the noise in the experimental data, the degree of parameterization, the relative weighting of the regularization term in the objective function, and the amount and type of data required to obtain a satisfactory permeability reconstruction. These synthetic data are extracted from the solution of numerical experiments that have utilized an assumed permeability distribution. The methodology is also applied to data gathered in laboratory experiments for water flow in a sandstone sample.     

Polycyclic N‐Heterocyclic Compounds. 56 Reaction of N‐(5,6‐Dihydro[1]benzoxepino[5,4‐d]pyrimidin‐4‐yl)amidine or Its Amide Oxime Derivatives with Hydroxylamine Hyrdochloride

The reactions of N‐(5,6‐dihydro[1]benzoxepino[5,4‐ d]pyrimidin‐4‐yl)amidines or its amide oxime derivatives with hydroxylamine hydrochloride gave abnormal cyclization products via a ring cleavage of pyrimidine component accompanied with a ring closure of [1,2,4]oxadiazole.     

Synthesis of 5,6‐dihydrothieno(and furo)pyrimidines bearing an active methine group at the 4‐position

The reactions of 2‐benzamido‐4,5‐dihydro‐3‐thiophene(and ‐3‐furan)carbonitriles ( 1a‐c and 4a‐c ) with ethyl acetoacetate in the presence of tin(IV) chloride and triethylamine provided the corresponding ethyl 2‐(5,6‐dihydro‐2‐phenylthieno(and furo)[2,3‐d]pyrimidin‐4‐yl)‐3‐oxobutanoates ( 2a‐c and 9a‐c ). Similarly, compounds 1a‐c and 4a‐c reacted with dialkyl malonates to give the corresponding dialkyl(5,6‐dihydro‐2‐phenylthieno(and furo)[2,3‐d]pyrimidin‐4‐yl)propanedioates ( 5a‐c, 6a‐c, 10a‐c and 11a‐c ).     

Measurement and correlation of excess molar enthalpies for the partially miscible systems 2-butanone+water and methanol+hexane

The excess molar enthalpies of the systems 2-butanone+water and methanol+hexane which show limited miscibility were measured at 283.15–298.15 K using a flow microcalorimeter. The experimental data were correlated using three local-composition (LC) models (NRTL, modified Wilson and modified EBLCM). These models were also used to predict the liquid–liquid equilibria for both systems with the parameters obtained from the excess enthalpy data.     

Smoothing Property for Schrödinger Equations¶with Potential Superquadratic at Infinity

We prove a smoothing property for one dimensional time dependent Schr?dinger equations with potentials which satisfy at infinity, k≥ 2. As an application, we show that the initial value problem for certain nonlinear Schr?dinger equations with such potentials is L ₂ well-posed. We also prove a sharp asymptotic estimate of the L ^p -norm of the normalized eigenfunctions of H=−Δ+V for large energy. Dedicated to Jean-Michel Combes on the occasion of his Sixtieth Birthday Received: 10 October 2000 / Accepted: 29 March 2001     

Coulometric titrations of electrolytes in water by a solid state ionic device using Nafion and Tosflex membranes

A solid state ionic device to titrate electrolytes in water was produced, and the performance of the device was examined. The device named the coulometric titration apparatus is a three-component electrochemical cell like an electrodialyzer. The central component, the analyzing room, is a container of the sample solution. The sample solution, 10⁻¹ M H₂SO₄, NaOH, Na₂SO₄, or 10⁻⁷–10⁻² M Na₂SO₄, is separated from the cathode and the anode room solutions, 10⁻² M H₂SO₄, NaOH, or Na₂SO₄, by Nafion-117 and Tosflex IE-SF34 membranes working as the anion and the cation blocking electrodes, respectively. The quantity of electricity to extract whole electrolytes in the sample solution is evaluated from the peak area of the titration curve. The sample concentration is successfully determined by the calibration curve method, with the quantity of electricity and the sample volume (6 ml) in the range from 10⁻¹ to 10⁻⁵ M.