Anion chromatography using on-line recycled eluents

Non-suppressed anion chromatography, using on-line recycled eluents, was investigated. Cations and anions from samples were excluded from the eluents using a mixture of strongly acidic cation-exchange resins and strongly basic anion exchange resins in the eluent reservoir. This exclusion was performed after determination of the anions in the non-suppressed anion chromatography, and the eluents were then recycled on-line. The performance of consecutive determinations was evaluated from the relative standard deviation (RSD) of peak heights and retention times of chloride, bromide, nitrite, nitrate, and sulfate ions, with a concentration of 3 microg ml(-1) each, compared to that of normal anion chromatography. Over 50 consecutive determinations could be achieved with an eluent volume of only 200 ml for a 100 microl sample volume. Almost all the RSD values for retention time, and peak heights of these anions, were smaller than 3%. Over fifty consecutive determinations of chloride, nitrate, and sulfate ions in a river water sample could be achieved with an eluent volume of only 100 ml. All the RSD values for retention time and peak heights of these anions were smaller than 3%. The eluent volume could be decreased to one tenth of that used in normal anion chromatography. The performance of the anion chromatography, using on-line recycled eluents, was the same as that for normal anion chromatography under the same conditions.     

Total synthesis of the duocarmycins

The total synthesis of (+)-duocarmycin A and SA through a common indoline intermediate is described. The key reactions include selective lithiation of a 2,6-dibromoiodobenzene derivative and diastereoselective addition to a chiral nitroalkene, copper-mediated aryl amination, and addition of aryllithium to azlactones.     

Stereocontrolled total synthesis of (-)-kainic acid. Regio- and stereoselective lithiation of pyrrolidine ring with the (+)-sparteine surrogate

[reaction: see text] A stereocontrolled total synthesis of (-)-kainic acid is described. cis-3,4-Disubstituted pyrrolidine ring was constructed by [3 + 2] cycloaddition of azomethine ylide with chiral butenolide. The crucial introduction of carboxyl group at the C-2 position was executed by regio- and stereoselective lithiation of the pyrrolidine ring in the presence of a (+)-sparteine surrogate followed by trapping with carbon dioxide.     

Alkyl group as entropy reservoir in an MMX chain complex, Pt2(n-PenCS2)4I

Heat capacity of halogen-bridged one-dimensional binuclear metal complex (so-called MMX chain) having four n-pentyl groups, Pt2(n-PenCS2)4I, was measured by adiabatic calorimetry. A first-order phase transition was observed at 207.4 K when measurement was made after cooling from room temperature. The enthalpy and entropy of transition were determined to be 10.19 kJ mol(-1) and 49.1 J K(-1) mol(-1), respectively. A monotropic phase transition was observed at 324 K on heating, and the entropy of transition was essentially null. The sample once heated above 324 K never returned to the initial phase at room temperature and underwent a higher-order phase transition at 173 K and a first-order phase transition at 220.5 K. The enthalpy and entropy of the first-order phase transition were estimated to be 11.6 kJ mol(-1) and 52.4 J K(-1) mol(-1), respectively. The magnitude of the entropy gain at the phase transition from the initial room-temperature phase to the high-temperature phase at 324 K shows that in Pt2(n-PenCS2)4I a large amount of entropy reserved in alkyl chain is transferred to dithiocarboxylato groups upon the phase transition, as in the cases of Pt2(n-PrCS2)4I and Pt2(n-BuCS2)4I.     

Ionization of long-lived highly excited atoms by collision with molecules. II

A theoretical treatment of the collisional ionization of a highly excited atom with a molecule is improved by use of the exact form factor of the hydrogen atom in highly excited states. The present treatment is still based on the previously proposed mechanism in which the Rydberg electron is ionized by gain of energy from rotational de-excitation of the molecule in a rotationally excited state. Closer comparison of experiment with theory is made for symmetric- as well as asymmetric-top molecules.     

On the theory of fluctuations around non-equilibrium steady states: A generalized time-convolutionless projector formalism

A new method of finding nonlinear Langevin type equations of motion for relevant macrovariables and the corresponding master equation for systems far from thermal equilibrium is presented by generalizing the time-convolutionless formalism proposed previously for equilibrium hamiltoian systems by Tokuyama and Mori. The Langevin type equation consists of a fluctuating force, and the nonlinear drift coefficients which are always identical to those of the master equation. A simple formula which relates the drift coefficients to the time correlation of the fluctuating forces is derived. This is a generalization of the fluctuation-dissipation theorem of the second kind in equilibrium systems and is valid not only for transport phenomena due to internal fluctuations but also for transport phenomena due to externally-driven fluctuations. A new cumulant expansion of the master equation is also obtained. The conditions under which a Langevin and a Fokker-Planck equation of a generalized type for non-equilibrium open systems can be derived are clarified.The theory is illustrated by studying hydrodynamic fluctuations near the Rayleigh-Bénard instability. The effects of two kinds of fluctuations, internal fluctuations of irrelevant macrovariables and external (thermal) noises, on the convective instability are investigated. A stochastic Ginzburg-Landau type equation for the order parameter and the corresponding nonlinear Fokker-Planck equation are derived.     

EFFECT OF CONTINUOUS FAR-RED PREIRRADIATION ON THE LAG PHASE OF CHLOROPHYLL A ACCUMULATION IN PHARBITIS NIL COTYLEDONS

In Pharbitis nil cotyledons, the lag phase of chlorophyll a (Chi a) accumulation which continues for about 2 h after the onset of continuous white light is eliminated by preirradiation with far-red light (FR) for 24 or 48 h. When the period of FR preirradiation is prolonged to 72 h or more, however, the lag phase is observed again (FR-induced lag phase) and the rate of Chi a accumulation during the rapid accumulation phase is lowered below the dark control level.
The application of exogenous 5-aminolevulinate (J-ALA) completely eliminates the FR-induced lag phase, but this treatment eliminates the normal lag phase in dark-grown cotyledons only partially (i.e. Chi a is accumulated but only slowly during the first few h). Application of a 5-ALA precursor, such as glycin + succinate. 2-ketoglutarate or glutamate, eliminates neither the FR-induced lag phase nor the normal lag phase.
A 24- or 48-h FR irradiation seems not only to enable the synthesis of 5-ALA but also to make the other regulatory factors favourable for Chi accumulation. When the period of FR irradiation is prolonged to 72 h or more, the ability to synthesize 5-ALA may be lost.     

K-Levels of Concave Surfaces

Abstract. We show that for any line l in space, there are at most k(k+1) tangent planes through l to the k -level of an arrangement of concave surfaces. This is a generalization of Lovász's lemma, which is a key constituent in the analysis of the complexity of k -levels of planes. Our proof is constructive, and finds a family of concave surfaces covering the ``laminated at-most-k -level.' As a consequence, (1) we have an O((n-k) ^2/3 n ² ) upper bound for the complexity of the k -level of n triangles of space, and (2) we can extend the k -set result in space to the k -set of a system of subsets of n points.     

The structure of the side chain of the frog alkaloid pumiliotoxin B

The E configuration at the double bond and $\text{threo}$ relation for diol moiety of the pumiliotoxin B side chain were defined, respectively, through nuclear- Overhauser effects and comparison with model $\text{threo}$- and $\text{erythro}$- diol compounds.     

Total synthesis of stevioside

Steviol 2 was transformed into stevioside 1 by applying the stereoselective methods of glycosidation.