HPLC of antibiotics. 1. Streptolydigin and related compounds

Two new acyltetramic acids related to streptolydigin have been isolated from fermentations of Streptomyces lydicus. The principal members of this complex were resolved by TLC on silica gel. However, the methods of detection, permanganate spray or bioautography, were not suitable for both crude fermentation broths and purified extracts. Gas chromatography is unsuitable for the detection of either underivatized or silylated streptolydigins. High performance liquid chromatography (HPLC) particularly on triethylaminoethyl cellulose is rapid and sensitive and is the method of choice for the analysis of both crude and purified samples. Using high performance liquid chromatography, two components were detected in the complex, which are not observed using any of the other chromatographic procedures.     

Microemulsion photopolymerization of methacrylates stabilized with sodium dodecyl sulfate and poly(N-acetylethylenimine) macromonomers

Methyl methacrylate and butyl methacrylate were polymerized in oil-in-water microemulsions that were stabilized by sodium dodecyl sulphate (SDS). A poly(N-acetylethylenimine) (PNAEI) macromer was also included in the recipe, as a cosurfactant and a comonomer. Polymerizations were initiated by UV-irradiation. The average diameters of latex particles, obtained by STM, were in the range of 17-200 nm. The experimental data evidenced that the particle size was mainly dependent on the SDS/PNAEI ratio. Polymerization yields were around 75-85%. The synthesized copolymers have viscosity average molecular weights in the range of 2.1-2.4×10⁶ and glass transition temperatures of 38.0-43.5°C, lower than those obtained without using PNAEI. The investigation by means of FTIR and 1H-NMR techniques revealed that PNAEI was incorporated into the nanoparticles.     

Synthesis of Naturally Occurring Pyrazine and Imidazole Alkaloids from Botryllus LeachiRID=”a”ID=”a”?Dedicated to Prof. G. M?rkl on the occasion of his 75th birthday

The synthesis of the naturally occurring and biologically active alkaloids 1 and 2, first isolated from the red ascidian Botryllus leachi by Duran et al. [1], is described and the structure proposed for Botryllazine B (1) is confirmed. The analytical data for 2-(p-hydroxybenzoyl)-4-(p-hydroxyphenyl)imidazole (2) are discussed and compared with the literature. With special emphasis of ¹H NMR data the tautomerism of aroylimidazolemethanones is described.     

Mono- and Dioses of Glycyrrhiza glabra Root

Simple sugars were isolated from the ethanol extract of Glycyrrhiza glabra L. root. The component composition of the carbohydrate fraction was established using GC-MS (gas-chromatographic separation and mass-spectrometric analysis).     

A recycling technique for the chromatographic separation of enantiomers and diastereomers on triacetylcellulose

A simple and inexpensive equipment for the optical resolution of enantiomers (and separation of diastereomers) on triacetylcellulose in ethanol at elevated pressure is described. It involves a closed circuit of solvent (pump—column—detector—pump) allowing a continuous chromatography up to 16 cycles without stopping the flow or handling fractions.This useful and versatile method permitting also the determination of enantiomeric purities is illustrated by several examples of centro-, axial- and planarchiral arenes and metallocenes.Herrn Prof. Dr.U. Schmidt, Stuttgart, zum 60. Geburtstag gewidmet.     

Dynamics of the formation of two-dimensional ordered structures

The growth of ordered domains in lattice gas models, which occurs after the system is quenched from infinite temperature to a state below the critical temperatureT _c, is studied by Monte Carlo simulation. For a square lattice with repulsion between nearest and next-nearest neighbors, which in equilibrium exhibits fourfold degenerate (2×1) superstructures, the time-dependent energy E(t), domain size L(t), and structure functionS(q, t) are obtained, both for Glauber dynamics (no conservation law) and the case with conserved density (Kawasaki dynamics). At late times the energy excess and halfwidth of the structure factor decrease proportional tot ^–x, whileL(t) t ^x, where the exponent x=1/2 for Glauber dynamics and x1/3 for Kawasaki dynamics. In addition, the structure factor satisfies a scaling lawS(k,t)=t ^2xS(kt^x). The smaller exponent for the conserved density case is traced back to the excess density contained in the walls between ordered domains which must be redistributed during growth. Quenches toT>T _c, T=T_c (where we estimate dynamic critical exponents) andT=0 are also considered. In the latter case, the system becomes frozen in a glasslike domain pattern far from equilibrium when using Kawasaki dynamics. The generalization of our results to other lattices and structures also is briefly discussed.     

RELATIONSHIPS BETWEEN X—H STRETCHING OVERTONE FREQUENCIES AND BOND LENGTHS/BOND ANGLES

A relationship between the X-H (X = N, O, C, and so on) equilibrium bond length in a Morse oscillator and the X-H stretching overtone frequency shifts is obtained theoretically. We use the equation to discuss the empirical linear relationships that have been proposed for heterocyclics, alkanes and fluorinated benzenes. On the other hand, a unified relationship between the X-H bond angles and the experimental quantities (ω(?) and the coupling strength λ) is also presented for XH2, XH, and XH4 molecules or molecular fragments. Calculations of X-H bond angles for a number of molecules show that the results from our equations are in excellent agreement with the experimental values. Also we can extract the information of relative magnitude of bond coupling force field.     

Capillary electrophoresis separation of heterocyclic nitrosoamino acid-conformers at sub-ambient temperatures

The separation of a selected group of naturally occurring, heterocyclic nitrosoamino acids was achieved by capillary zone electrophoresis and the resolution of the syn and anti conformers improved as the temperature was lowered to 5 °C. The double peaks observed for each nitrosoamino acid are probably caused by the slow kinetics of conformational isomerism. The experimental setup consisted of a P/ACE 5510 electrophoresis system, a 57 cm polyacrylamidecoated capillary, and a 10 mM phosphate buffer, pH 7.2, containing 2 mM of 3-(N-N-dimethylmyristylammonio)propanesulfonate (DMMAPS) and 0.1% Tween 20. Our study shows that (a) the lower the temperature, the greater the resolution and the longer the migration times; and (b) different nitrosoamino acid conformers were resolved at different temperatures because of differences in the rate of isomerization. For example, the conformers of N-nitrosothiazolidine-4-carboxylic acid were partially resolved at 30 °C while those of N-nitrosoproline were well resolved at the same temperature.     

Functionalized naphthol[2,3-h] quinoline-7,12-diones

The addition of secondary and primary amines to ethyl (1-amino-9,10-anthraquinon-2-yl)propynoate affords an easily separable mixture of the corresponding ethyl 3-dialkylaminoor 3-alkylamino-3-(1-amino-9,10-anthraquinon-2-yl)acrylate and 3-dialkylamino- or 3-alkylaminonaphthol[2,3-h]quinoline-2(1H), 7,12-trione (in ∼4: 1 ratio). Intramolecular cyclization of the resulting substituted ethyl acrylates results in the formation of 4-dialkylaminoor 4-alkylamino-2-chlorinated pyridine rings. Subsequent nucleophilic substitution of the chlorine atom gives 2-functionalized 4-dialkylamino- or 4-alkylaminonaphtho[2,3-h]quinoline-7,12-diones. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2327–2332, November, 1998.     

Modeling and simulation of free radical polymerization of styrene under semibatch reactor conditions

The first part of this approach is concerned with the elaboration of a radical polymerization model of styrenne, based on a kinetic diagram that includes chemical and thermal initiation, propagation, termination by recombination and chain transfer to the monomer. Furthermore, volume contraction during polymerization is considered, as well as the gel and glass effects. The mathematical formalism that describes the model in terms of moments is explored in detail. The model was then used to predict the changes in monomer conversion and molecular weight after intermediate addition of initiator and monomer. The results of this operation are dependent on the conditions of the reaction mass, quantity, and moment of substance addition. Therefore, the simulations were performed at different times with respect to the gel effect; before, during and after this phenomenon, and also with respect to different temperatures and initiators. Increasing the initiator concentration before the gel effect leads to an earlier appearance of the phenomenon and to a decrease in molecular weight. The ratio reveals a polydispersity index smaller for the intermediate addition of initiator. No significant changes take place during or after the gel effect. If along with the initiator, unreacted monomver (used to dissolve the initiator) enters the reactor, a small dip in conversion is observed. The general conclusion of this paper reveals the intermediate addition of initiator as a method to control polymer properties and to prevent the “dead-end” polymerization of styrene.