Facilitated sulfate transfer across the nitrobenzene-water interface as mediated by hydrogen-bonding ionophores.

Facilitated SO4(2-) transfers by hydrogen bond-forming ionophores are investigated across the nitrobenzene (NB)-water interface by using polarography with a dropping electrolyte electrode. Bis-thiourea 1, alpha,alpha'-bis(N'-p-nitrophenylthioureylene)-m-xylene, is found to significantly facilitate the transfer of the highly hydrophilic SO4(2-) whereas its counterpart, N-(p-nitrophenyl)-N'-propylthiourea (ionophore 2), cannot. In contrast to the predominant formation of a 1:1 complex with SO4(2-) in the bulk NB phase, the SO4(2-) transfer assisted by 1 is indeed based on the formation of a 1:2 complex between SO4(2-) and ionophore, even under the condition of [SO4(2-)]aq > [1]org. Such an exclusive formation of the 1:2 (SO4(2-) to ionophore) complex at the NB-water interface is not observed with structurally similar bis-thiourea 3, alpha,alpha'-bis(N'-phenylthioureylene)-m-xylene, where p-nitrophenyl moietes of bis-thiourea 1 are simply replaced by phenyl groups. The facilitated transfer of SO4(2-) with bis-thiourea 1 is further compared to that of HPO4(2-) and H2PO4- across the NB-water interface, which was previously shown to be assisted by 1 through the formation of the 1:1 and 2:1 (anion to ionophore) complexes, respectively. On the basis of these examinations, unique binding behaviors of hydrogen bond-forming ionophores at the NB-water interface are discussed, with a view towards development of ionophore-based anion-selective chemical sensors.     

A new route for the construction of the AB-ring core of Taxol

A new method for the construction of the AB-ring core of Taxol was developed utilizing a new skeletal transformation protocol as a pivotal step. The acid-catalyzed rearrangement of the cyclopentenone-allene photoadduct gave a bridged seven-membered ketone, which was easily transformed, using the intramolecular Suzuki reaction and the oxidative cleavage of the vicinal diol, to the bicyclic diketone.     

Highly sensitive determination of haloperidol in human serum by capillary gas chromatography using a surface ionization detector

A method has been developed for highly sensitive determination of haloperidol in human serum involving a simple extraction procedure followed by gas chromatographic separation. Target components were separated from the extracting solvents with a Van den Berg type solventless sample injector before introduction Into a DB-1 capillary separation column. A surface ionization detector (SID), which has highly selective sensitivity for Substituted amines, was employed for quantitation using bromperidol as an internal standard. Chloroform proved to be the best extracting solvent, yielding a quantitative detection limit of 5 ng/ml (S/N = 2). Comparison of the response to target compounds obtained by the SID, FTD (flame thermionic detector), and FID (flame ionization detector) showed the SID to be superior.     

Classical trajectory calculations of intramolecular vibrational energy redistribution. I. Methanol-water complex

Intramolecular vibrational energy redistributions of the O-H stretching (nuOH) vibration for the methanol monomer and its water complex, the methanol-water dimer, are investigated by using ab initio full-dimensional classical trajectory calculations. For the methanol monomer, in the high-energy regime of the 5nuOH overtone, the time dependence of the normal-mode energies indicates that energy flowed from the initial excited O-H stretching mode to the C-H stretching mode. This result confirms the experimental observation of energy redistribution between the O-H and C-H stretching vibrations [L. Lubich et al., Faraday Discuss. 102, 167 (1995)]. Furthermore, a lot of dynamical information in the time domain is contained in the power spectra, whose density is given by the Fourier transformation of the total momentum obtained from trajectory calculations. For the methanol-water hydrogen-bonded complex, at the high-energy level of the 5nuOH overtone, the calculated power spectrum shows considerable splitting and broadening, indicating significant energy redistribution through strong coupling between the O-H stretching vibration and other vibrations. It is thus clear that the A-H...B hydrogen-bond formation facilitates energy redistribution subsequent to the vibrational excitation of the hydrogen-bonded A-H stretching mode.     

Effect of polycondensation methods on molecular weight distribution of nylon 610

Polycondensation methods greatly influence the molecular weight distribution of poly(hexamethylene sebacamide) (nylon 610) as determined by gel permeation chromatography (GPC). The ratio of weight average molecular weight to number average molecular weight (M_w/M_n) was used as a measure for estimating the molecular weight distribution. The M_w/M_n ratios of nylon 610 obtained from melt, solid phase, and high temperature polycondensation methods were 2 to 3.5, which were expected values for the most probable distribution. However, those for polymers obtained from the direct polycondensation in the presence of triphenylphosphine, interfacial polycondensation and low temperature polycondensation using an acid chloride varied over a wide range from 3.5 to 8.5. The effect of the kind of organic solvents in the interfacial method on the M_w/M_n ratios was especially large, and the molecular weight distribution could be controlled to some extent by selecting an appropriate solvent.     

One-pot oxidative Mannich-type reaction of lactams with alkyl malonates

One-pot substitution of a C-H bond at the position next to the nitrogen atom of lactams with alkyl malonates proceeded effectively by dehydrogenation of lactams with N-tert-butylbenzenesulfinimidoyl chloride, followed by Mannich-type addition of alkyl malonates.     

Dynamic stability of carbonyl ylides

The non- and fluorine-substituted singlet carbonyl ylides are studied by using ab initio MCSCF calculations. The thermodynamic stability of the carbonyl ylides and the intramolecular stability to isomerization or fragmentation reaction coordinates is demonstrated in terms of the topological structure of the ab initio potential energy surfaces. The allylic resonance is found to be dynamically unstable, considering out-of-plane vibrational mode. The instability is studied by the symmetries of the low-lying excitations out of the MCSCF wave function.     

Mononuclear nonheme ferric-peroxo complex in aldehyde deformylation

A mononuclear nonheme ferric-peroxo complex bearing a macrocyclic tetradentate N4 ligand, [(TMC)Fe(III)-O2]+, was prepared and used in mechanistic studies of aldehyde deformylation; a catalytic aldehyde deformylation by a nonheme iron(II) complex, [Fe(II)(TMC)]2+, and molecular oxygen is reported as well.     

Design of Supramolecular Cyclodextrin Complex Sensors for Ion and Molecule Recognition in Water

The design and function of novel supramolecular fluoroionophore/cyclodextrin (CyD) complex sensors for ion and molecule recognition in water are reviewed. For the crown ether fluoroionophore/-CyD complex, the dimerization of the fluoroionophore inside the -CyD is found to be selectively promoted by alkali metal ion binding, thereby resulting in metal-ion-selective pyrene dimer emission in water. This supramolecular function is successfully utilized in the design of a podand fluoroionophore/-CyD complex for sensing toxic lead ion in water. The boronic acid fluoroionophore/-CyD complex binds sugars and produces increased fluorescence emission in water. The response mechanism appears to be due to the suppression of the photoinduced electron transfer (PET) from pyrene donor to trigonal phenylboronic acid acceptor. This is a novel emission function provided by the boronic acid fluoroionophore/-CyD complex sensors in water.