A bicyclic cispentacin derivative as a novel reverse turn inducer in a GnRH mimetic

A cispentacin-derived bicyclic beta-amino acid (Bic) has been synthesized and incorporated into the 6-position of GnRH. The new GnRH analogue has been characterized with respect to its structure in solution and its activity and affinity toward the human GnRH receptor.     

The Dynamics of Populating The Lowest Triplet State Of Benzophenone Following Singlet Excitation

Measurements of the build-up of triplet-triplet absorption at 5300 A have been made during and subsequent to the excitation of benzophenone by 5 psec pulses of 3545 A radiation (frequency tripled Nd³⁺: glass fundamental). The data were fitted to a simple model that included the finite gaussian pulse width and results for the assumed process S_i

T₁ are: K^?1=16.5±3 psec for benzophenone in ethanol; k^?1 = 30 ±5 psec for benzophenone in benzene. This new type of solvent effect on triplet build-up is discussed.     

Geometry optimization inab initio SCF calculations

The floating orbital geometry optimization (FOGO) described previously [1, 2] for atoms without polarized inner-shell electrons, is extended to the general case. Instead of the Hellmann-Feynman force a special gradient is calculated analytically and utilized in a variable metric procedure simultaneously with the ordinary energy gradient. Test calculations on a sample of 12 molecules were performed to check the efficiency of the method. The geometries obtained are better than those obtained with the corresponding double-zeta basis set. The most striking results, however, are excellent dipole moments.     

[4+2]-Cycloadditionen von 1,2-Dicyanocyclobuten und seine thermische Ringöffnung zum 2,3-Dicyanobutadien-1,3

Facile synthetic routes to 1,2-dicyanocyclobutene ( 3 ), cyclobutene-1,2-dicarboxylic acid ( 56 ) and derivatives thereof are presented, starting from 1,2-dicyanocyclobutane ( 1 ), a commercially available acrylonitrile cyclodimer. The favored mode of [4+2]-cycloadditions of 3 to cyclic dienes with sp³carbon atoms is the endo-addition (above 90% relative yields of adducts with endo-cyclobutane ring). Exo-cycloaddition, however, is preferred by dienes having no sp³-carbon atom (e.g. furane). Cyclisation reactions involving cis-vicinal substituents in [4+ 2]-cycloadducts afford (m.n. 2)-azapropellanes 18 , 74 and 77 . ¹H- and ¹³C-NMR. spectra of the stereoisomeric adducts are discussed in detail. The structures of the furane adducts 14 and 15 were determined by ¹H-NMR. using the shift reagent Eu(dpm)₃. Reactive butadienes 32 , 53 - 55 are obtained in high yield and purity by gasphase thermolysis (380–420°) of the correspondingly substituted cyclobutenes. 2,3-Dicyanobutadiene-l, 3 ( 32 ) gives good yields of [4 + 2]-cycloadducts with strained cycloolefines, moderate yields with vinylethers and non-activated olefins, and no adducts at all with electrophilic dienophiles (8.g. maleic anhydride, fumaronitrile). Thus, reactions of 32 are typical Diels-Alder reactions with ‘inverse electron demand’. Some of these primary [4+2]-cycloadducts ( 38 , 39 and 45 ) were dehydrogenated to new aromatic ortho-dinitriles 46 - 48 .     

C45 und C50-Carotinoide. 6. Mitteilung. Synthese eines optisch aktiven cyclischen C20-Bausteins und von Decaprenoxanthin (= (2R, 6R, 2′R, 6′R)-2,2′-Bis(4-hydroxy-3-methylbut-2-enyl)-ϵ, ϵ-carotin)

C₄₅- and C₅₀-Carotenoids: Synthesis of an Optically Active Cyclic C₂₀-Building Block and of Decaprenoxanthin ( = (2R, 6R, 2′R, 6′R)-2,2′-Bis(4-hydroxy-3-methylbut-2-enyl)-?, ?-carotene) The synthesis of the optically active cyclic C₂₀-building block (R, R) -15 and of the optically active C₅₀-carotenoid (2R, 6R, 2′R, 6′R)-decaprenoxanthin ( 1 ) starting from (-)-β-pinene ((S)- 2 ) is reported.     

Comparison of biomechanical modeling of register transitions and voice instabilities with excised larynx experiments

Voice instabilities were studied using excised human larynx experiments and biomechanical modeling. With a controlled elongation of the vocal folds, the experiments showed registers with chest-like and falsetto-like vibrations. Observed instabilities included abrupt jumps between the two registers exhibiting hysteresis, aphonic episodes, subharmonics, and chaos near the register transitions. In order to model these phenomena, a three-mass model was constructed by adding a third mass on top of the simplified two-mass model. Simulation studies showed that the three-mass model can vibrate in both chest-like and falsetto-like patterns. Variation of tension parameters which mimic activities of laryngeal muscles could induce transitions between both registers. For reduced prephonatory areas and damping constants, extended coexistence of chest and falsetto registers was found, in agreement with experimental data. Subharmonics and deterministic chaos were observed close to transitions between the registers. It is concluded that the abrupt changes between chest and falsetto registers can be understood as shifts in dominance of eigenmodes of the vocal folds.     

Preparation and (E/Z)‐Isomerization of the Diastereoisomers of Violaxanthin

Violaxanthin A (=(all‐E,3S,5S,6R,3′S,5′S,6′R)‐5,6 : 5′,6′‐diepoxy‐5,6,5′,6′‐tetrahydro‐β,β‐carotene‐3,3′‐diol =syn,syn‐violaxanthin; 5 ) and violaxanthin B (=(all‐E,3S,5S,6R,3′S,5′R,6′S)‐5,6 : 5′,6′‐diepoxy‐5,6,5′,6′‐tetrahydro‐β,β‐carotene‐3,3′‐diol=syn,anti‐violaxanthin; 6 ) were prepared by epoxidation of zeaxanthin diacetate ( 1 ) with monoperphthalic acid. Violaxanthins 5 and 6 were submitted to thermal isomerization and I₂‐catalyzed photoisomerization. The structure of the main products, i.e., (9Z)‐ 5 , (13Z)‐ 5 , (9Z)‐ 6 , (9′Z)‐ 6 , (13Z)‐ 6 , and (13′Z)‐ 6 , was determined by their UV/VIS, CD, ¹H‐NMR, ¹³C‐NMR, and mass spectra.     

Use of molecular dynamics simulations with ab initio SCF calculations for the determination of the deuterium quadrupole coupling constant in liquid water and bond lengths in ice

The deuterium quadrupole coupling constant and asymmetry parameter in heavy water were determined using ab initio SCF calculations. Snapshots from a molecular dynamics simulation were used to give liquid water cluster configurations and the influence of simulation parameters on the quadrupole coupling constant was investigated. The electronic potential model and the number of molecules in the molecular dynamics simulation and the pressure of the system were found to have only a small influence on the quadrupole coupling constant. The average value of the quadrupole coupling constant at room temperature, corrected for the known deficiency of the ab initio calculation in the gas phase, yields a quadrupole coupling constant of 253 kHz, in perfect agreement with the most recent experiments. The oxygen—deuterium bond lengths in ice Ih, ice II, and ice IX were determined using experimental quadrupole coupling constants and a model equation. An averaged bond length of 98.9 pm was obtained for the Ih form, which is approximately 2 pm shorter than that determined by neutron diffraction studies, whereas the bond lengths for the four deuterium sites in ice II and the three sites in ice IX are in fair agreement with experiment. © John Wiley & Sons, Inc.     

Synthese von ‘D-Isothreonin’ und ‘L-Alloisothreonin’ aus L-Alanin

Synthesis of ‘D -Isothreonine’ and ‘L -Alloisothreonine’ Starting from L -Alanine Starting from L -alanine, ‘D -isothreonine’ ( = (2R, 3S)-3-amino-2-hydroxybutanoic acid) and ‘L -alloisothreonine’ ( = (2S, 3S)-3-amino-2-hydroxybutanoic acid) were synthesized.