Isoprene functionalization : Hydroxy sulfone terpene building blocks by ring opening of cyclic alkoxy oxosulfonium intermediates

Hydroxy sulfoxide 1 reacts with SO₂Cl₂ to give the (Z)-C₅ terpene building block 3b via cyclic alkoxy oxosulfonium salt 2. The conversion of 1 via the corresponding sulfone 4 leads to the (E) isomer 6b. An explanation is offered for the stereoselective course of the reactions.     

The M gamma chain of human fetal hemoglobin; its identification and occurrence

High-performance liquid chromatographic procedures have been used in the detection and identification of a new gamma chain of human fetal hemoglobin (Hb). This M gamma chain is characterized by a Leu----Met replacement at position gamma 141; no other structural variations have been observed. The M gamma chain has been detected in red cell lysates of subjects with a heterozygosity for one of many types of so-called hereditary persistence of fetal hemoglobin conditions, which are characterized by an increased level of Hb F in adult life, in sickle cell anemia, and in a few cord blood samples. At present it is not possible to definitely identify the genetic cause of this newly discovered heterogeneity; an infidelity in translation or the existence of an unrecognized gamma globin gene should be considered.     

Quantities of adult, fetal and embryonic globin chains in the blood of eighteen- to twenty-week-old human fetuses

The prenatal diagnostic program, established at Hacettepe University in Ankara for the purpose of detecting beta-thalassemia (beta-thal), sickle cell anemia (SS), and Hb S-beta-thal, offered the opportunity of evaluating the relative quantities of adult (beta A, beta S), fetal (G gamma, A gamma, A gamma T), and embryonic (epsilon, zeta) chains in 26 fetuses, aged 18-20 weeks. Methodology involved micro high-performance liquid chromatographic (HPLC) procedures and immunology using an mAb, specific for the embryonic epsilon chain. A good correlation was observed between the beta/gamma in vitro chain synthesis ratio and the level of beta A and/or beta S chains determined by reversed-phase HPLC; the combination of these two sets of data strengthens the prenatal diagnostic approach of detecting beta-thal major but not beta-thal trait. The levels of the different gamma chains were about as observed in newborn babies; the frequency of the A gamma T variant in the 26 fetuses was the same as observed for a larger group of Turkish newborn babies. The level of the embryonic zeta chain was higher than seen in full-term babies and varied between 0 and 1.3%; 5 of the 26 fetuses showed the complete absence of zeta. The embryonic epsilon chain was not detectable, not even in babies with beta-thal major. These data indicate that the synthesis of epsilon is completely turned off in fetuses at the age of 18-20 weeks, while that of zeta continues, albeit at a low level.     

Isoprene functionalization : E/Z-isomerism of 1-sulfonyl substituted 2-methylbutadienes

The isomeric chlorosulfones 3, 4 and 5 are prepared by 1,4-addition of sulfonyl chlorides to isoprene, Dehydrohalogenation affords the corresponding 2- and 3-methylbutadienyl sulfones in a configuration which is dependent on the configuration of the chlorosulfone. Pure Z-2-methylbutadienyl sulfones 1 are obtained by displacement of primary halides by the Z-sulfinate anion 2. The Z-sulfones 1 are isomerized to E/Z-mixtures. The E/Z-mixtures are separated into their components and the configuration of the isomers is established by the NMR-NOE technique.     

Imaginary automorphisms on real hyperelliptic curves

A real hyperelliptic curve X is said to be Gaussian if there is an automorphism such that , where [-1] denotes the hyperelliptic involution on X. Gaussian curves arise naturally in several contexts, for example when one studies real Jacobians. In the present paper, we study the properties of Gaussian curves and we describe their moduli spaces.     

Adjusting a railway timetable in case of partial or complete blockades

Unexpected events, such as accidents or track damages, can have a significant impact on the railway system so that trains need to be canceled and delayed. In case of a disruption it is important that dispatchers quickly present a good solution in order to minimize the nuisance for the passengers. In this paper, we focus on adjusting the timetable of a passenger railway operator in case of major disruptions. Both a partial and a complete blockade of a railway line are considered. Given a disrupted infrastructure situation and a forecast of the characteristics of the disruption, our goal is to determine a disposition timetable, specifying which trains will still be operated during the disruption and determining the timetable of these trains. Without explicitly taking the rolling stock rescheduling problem into account, we develop our models such that the probability that feasible solutions to this problem exist, is high. The main objective is to maximize the service level offered to the passengers. We present integer programming formulations and test our models using instances from Netherlands Railways.     

Inhibited spontaneous emission of quantum dots observed in a 3D photonic band gap

We present time-resolved emission experiments of semiconductor quantum dots in silicon 3D inverse-woodpile photonic band gap crystals. A systematic study is made of crystals with a range of pore radii to tune the band gap relative to the emission frequency. The decay rates averaged over all dipole orientations are inhibited by a factor of 10 in the photonic band gap and enhanced up to 2× outside the gap, in agreement with theory. We discuss the effects of spatial inhomogeneity, nonradiative decay, and transition dipole orientations on the observed inhibition in the band gap.     

Approaches to Total Synthesis of Heterocyclic Steroidal Systems

In heterocyclic steroids the carbon atoms of the steroid skeleton (positions I to 17) are replaced in part by hetero atoms. The term generally denotes compounds containing one or two nitrogen, oxygen, and/or sulfur atoms. The part of the molecule containing the hetero atom is either introduced as a preformed unit or is constructed by stepwise synthesis. The examples given in the present article contain the hetero atoms in ring A, ring B, between rings A and B, and/or between rings C and D.