New general guidance method in constrained optimal control,part 2: Application to space shuttle guidance

The application and the performance of the neighboring optimal feedback scheme presented in Part 1 of this paper is demonstrated for the heating-constrained cross-range maximization problem of a space-shuttle-orbiter-type vehicle. This problem contains five state variables, two control variables, and a state variable inequality constraint of order zero.This research was supported in part by the Deutsche Forschungsgemeinschaft under the Schwerpunktprogramm Anwendungsbezogene Optimierung und Steuerung.The authors wish to express their sincere and grateful appreciation to Professor Roland Bulirsch who encouraged this work.     

Transfer matrix analysis of the two-dimensional ANNNI model

The two-dimensional axial next-nearest neighbour Ising (ANNNI) model is studied for the first time by a transfer matrix method for semi-infinite strips (N×;N13). One obtains the thermodynamic properties and, more important, the correlation functions, which display directly the various magnetic structures. In one part of the phase diagram where a disorder line is believed to follow closely the ferromagnetic transition line the critical exponents appear to deviate from the expected ones. ForN13 a variational procedure is proposed.     

A new concept for isotope ratio monitoring liquid chromatography/mass spectrometry

A new interface for the on-line coupling of a liquid chromatograph to a stable isotope ratio mass spectrometer has been developed and tested. The interface is usable for (13)C/(12)C determination of organic compounds, allowing measurement of small changes in (13)C abundance in individual analyte species. All of the carbon in each analyte is quantitatively converted into CO(2) while the analyte is still dissolved in the aqueous liquid phase. This is accomplished by an oxidizing agent such as ammonium peroxodisulfate. The CO(2) is separated from the liquid phase and transferred to the mass spectrometer. It is shown that the whole integrated process does not introduce isotope fractionation. The measured carbon isotope ratios are accurate and reproducible. The sensitivity of the complete system allows isotope ratio determination down to 400 ng of compound on-column. By-passing the high-performance liquid chromatography (HPLC) separation allows bulk isotopic analysis with substantially lower sample amounts than those required by conventional elemental analyzers. The results of the first applications to amino acids, carbohydrates, and drugs, eluted from various types of HPLC columns, are presented. The wide range of chromatographic methods enables the analysis of compounds never before amenable to isotope ratio mass spectrometry techniques and may lead to the development of many new assays.     

A case study in conformation design: learning by doing

Efforts are described to design simple, fully flexible but conformationally preorganised omega-hydroxy-nonanoic acids that could serve as the conformation controlling unit in analogues of the potent protein-kinase C activator aplysiatoxin. Such analogues are macrodilactones incorporating the designed omega-hydroxy-nonanoic acid and 3,4-dihydroxy-pentanoic acid, which contains the pharmacophoric groups. The design process (replacement of CH(2) groups by an oxygen atom, annelation of a six-membered ring and placement of alkyl substituents) of the omega-hydroxy-nonanoic acids was monitored by force-field calculations. In the end of this process simple analogues of aplysiatoxin are proposed in which the proper disposition of the pharmacophoric groups is secured by a conformationally flexible but preorganised template structure as part of the macrodilactone ring.     

Toward the synthesis of reidispongiolide a: stereocontrolled synthesis of the C17-C22 and C23-C35 degradation fragments

[structure: see text] By relying on the asymmetric aldol reactions of chiral ketones, a highly stereocontrolled synthesis of each of the C(17)-C(22) and C(23)-C(35) degradation fragments of reidispongiolide A has been achieved. This permits a configurational assignment of the complete C(17)-C(36) region of this antimitotic macrolide, along with providing advanced intermediates for a projected total synthesis.     

The influence of a surface on Ising and conjugate model spin correlations atT=T c

We calculate rigorously the two-point correlation function in the 2-d Ising model on a quasi-cylindrical lattice at the critical temperatureT _c .The scaling predictions for the surface critical exponents = 5/8, = 1 are confirmed and the change from surface to bulk behavior is studied. By a correspondence relation the results are mapped to the conjugate model, a subcase of the 8-vertex model. We find in this model = 5/4, = 2.     

Stable Mesoionic N-Heterocyclic Olefins (mNHOs)

We report a new class of stable mesoionic N-heterocyclic olefins, featuring a highly polarized (strongly ylidic) double bond. The ground-state structure cannot be described through an uncharged mesomeric Lewis-structure, thereby structurally distinguishing them from traditional N-heterocyclic olefins (NHOs). mNHOs can easily be obtained through deprotonation of the corresponding methylated N,N′-diaryl-1,2,3-triazolium and N,N′-diaryl-imidazolium salts, respectively. In their reactivity, they represent strong σ-donor ligands as shown by their coordination complexes of rhodium and boron. Their calculated proton affinities, their experimentally derived basicities (competition experiments), as well as donor abilities (Tolman electronic parameter; TEP) exceed the so far reported class of NHOs.