Conformation of Peptides Containing a Chiral α‐Ethylated α,α‐Disubstituted α‐Amino Acid: (S)‐α‐Ethylleucine (=(2S)‐2‐Amino‐2‐ethyl‐4‐methylpentanoic Acid) within Sequences of Dimethylglycine and Diethylglycine Residues

An optically active (S)‐α‐ethylleucine ((S)‐αEtLeu) as a chiral α‐ethylated α,α‐disubstituted α‐amino acid was synthesized by means of a chiral acetal auxiliary of (R,R)‐cyclohexane‐1,2‐diol. The chiral α‐ethylated α,α‐disubstituted amino acid (S)‐αEtLeu was introduced into the peptides constructed from 2‐aminoisobutyric acid (=dimethylglycine, Aib), and also into the peptide prepared from diethylglycine (Deg). The X‐ray crystallographic analysis revealed that both right‐handed (P) and left‐handed (M) 3₁₀‐helical structures exist in the solid state of CF₃CO‐(Aib)₂‐[(S)‐αEtLeu]‐(Aib)₂‐OEt ( 14 ) and CF₃CO‐[(S)‐αEtLeu]‐(Deg)₄‐OEt ( 18 ), respectively. The IR, CD, and ¹H‐NMR spectra indicated that the dominant conformation of pentapeptides 14 and CF₃CO‐[(S)‐αEtLeu]‐(Aib)₄‐OEt ( 16 ) in solution is a 3₁₀‐helical structure, and that of 18 in solution is a planar C₅ conformation. The conformation of peptides was also studied by molecular‐mechanics calculations.     

Laser-induced fluorescence spectroscopy of NC3S

In a discharged supersonic jet of acetonitrile and carbon disulfide, we have for the first time observed an electronic transition of the NC(3)S radical using laser-induced fluorescence (LIF) spectroscopy. A progression originating from the C-S stretching mode of the upper electronic state appears in the excitation spectrum. Each band of the progression has a polyad structure due to anharmonic resonances with even overtones of bending modes. Rotationally resolved spectra have been observed by high-resolution laser scans, and the electronic transition is assigned to A 2Pii-X 2Pii. For the vibronic origin band, the position and the effective rotational constant of the upper level have been determined to be 21 553.874(1) and 0.046 689(4) cm(-1), respectively. The dispersed fluorescence spectrum from the zero vibrational level of A 2Pi3/2 has also been observed; its vibrational structure is similar to that of the LIF excitation spectrum, showing a prominent C-S stretching progression with polyad structures. The vibrational frequencies of the C-S stretching mode in the ground and excited electronic states are determined to be 550 and 520 cm(-1), respectively. Fluorescence decay profiles have been measured for several vibronic levels of the A state.     

Enzymatic cyclization reactions of geraniol, farnesol and geranylgeraniol, and those of truncated squalene analogs having C20 and C25 by recombinant squalene cyclase

The substrate specificity of squalene-hopene cyclase was investigated using the C10-C25 analogs including naturally occurring substances, e.g. geraniol (C10), farnesol (C15) and geranylgeraniol (C20). No cyclization occurred for geraniol, but a significantly high conversion ratio (64%) was observed for farnesol, yielding the cyclic sesquiterpenes consisting of 6/6-fused bicyclic ring systems. Among them, an attractive compound having C30 was produced, in the structure of which acyclic the farnesol unit is linked to the bicyclic skeleton through ether linkage. Conversion of geranylgeraniol was low (ca. 12%). The squalene analogs having C20 and C25 also were cyclized in yields of ca. 33-36%, but the analogs having the methyl group at C7 and/or at C11 underwent no cyclization; the large steric bulk size of C7-Me and/or C11-Me, which is arranged in [small alpha]-disposition for all the pre-chair conformation, would have interacted repulsively with the cyclase recognition site near to the C7 and/or C11, resulting in no construction of the all-chair conformation inside the reaction cavity. A relatively low yield of geranylgeraniol indicated that a less bulky hydrogen atom must be located at C14 for the efficient polycyclization reaction. The squalene cyclase shows remarkably broad substrate specificity to accept the truncated analogs having carbon-chain lengths of C(15)-C25 in addition to C30.     

Picosecond IR-UV pump-probe spectroscopic study of the dynamics of the vibrational relaxation of jet-cooled phenol. I. Intramolecular vibrational energy redistribution of the OH and CH stretching vibrations of bare phenol

The intramolecular vibrational energy redistribution (IVR) of the OH stretching vibration of jet-cooled phenol-h6 (C6H8OH) and phenol-d8 (C6D8OH) in the electronic ground state has been investigated by picosecond time-resolved IR-UV pump-probe spectroscopy. The OH stretching vibration of phenol was excited with a picosecond IR laser pulse, and the subsequent temporal evolutions of the initially excited level and the redistributed ones due to the IVR were observed by multiphoton ionization detection with a picosecond UV pulse. The IVR lifetime for the OH stretch vibration of phenol-h6 was determined to be 14 ps, while that of the OH stretch for phenol-d8 was found to be 80 ps. This remarkable change of the IVR rate constant upon the dueteration of the CH groups strongly suggests that the "doorway states" for the IVR from the OH level would be the vibrational states involving the CH stretching modes. We also investigated the IVR rate of the CH stretching vibration for phenol-h6. It was found that the IVR lifetime of the CH stretch is less than 5 ps. The fast IVR is described by the strong anharmonic resonance of the CH stretch with many other combinations or overtone bands.     

Isomerization reactions of allylic alcohols into ketones with the Grubbs reagent

Allylic alcohols were isomerized into ketones by the action of the Grubbs reagent. Some model alcohols were prepared and tested under similar conditions to reveal that less substituted alkenes rearrange more easily. More hindered alcohols are stable under these conditions, however, the simple allylic alcohols tend to isomerize producing ethyl ketone and the corresponding degraded methyl ketone.     

Sulfur-bridged Co(III)Pt(II)Co(III) trinuclear complexes with mixed aliphatic and aromatic thiolate ligands: effect of nonbridging ligands on the homochiral linkage of cobalt(III) octahedrons by platinum(II)

The reaction of [Ni[Co(aet)(2)(pyt)](2)](2+) (aet = 2-aminoethanethiolate, pyt = 2-pyridinethiolate) with [PtCl(4)](2)(-) gave an S-bridged Co(III)Pt(II)Co(III) trinuclear complex composed of two [Co(aet)(2)(pyt)] units, [Pt[Co(aet)(2)(pyt)](2)](2+) ([1](2+)). When a 1:1 mixture of [Ni[Co(aet)(2)(pyt)](2)](2+) and [Ni[Co(aet)(2)(en)](2)](4+) was reacted with [PtCl(4)](2)(-), a mixed-type S-bridged Co(III)Pt(II)Co(III) complex composed of one [Co(aet)(2)(pyt)] and one [Co(aet)(2)(en)](+) units, [Pt[Co(aet)(2)(en)][Co(aet)(2)(pyt)]](3+) ([2](3+)), was produced, together with [1](2+) and [Pt[Co(aet)(2)(en)](2)](4+). The corresponding Co(III)Pt(II)Co(III) trinuclear complexes containing pymt (2-pyrimidinethiolate), [Pt[Co(aet)(2)(pymt)](2)](2+) ([3](2+)) and [Pt[Co(aet)(2)(en)][Co(aet)(2)(pymt)]](3+) ([4](3+)), were also obtained by similar reactions, using [Ni[Co(aet)(2)(pymt)](2)](2+) instead of [Ni[Co(aet)(2)(pyt)](2)](2+). While [Pt[Co(aet)(2)(en)](2)](4+) formed both the deltalambda (meso) and deltadelta/lambdalambda (racemic) forms in a ratio of ca. 1:1, the preferential formation of the deltadelta/lambdalambda form was observed for [1](2+) (ca. deltalambda:deltadelta/lambdalambda = 1:3) and [2](3+) (ca. delta(en)lambda(pyt)/lambda(en)delta(pyt):deltadelta/lambdalambda = 1:2). Furthermore, [3](2+) and [4](3+) predominantly formed the deltadelta/lambdalambda form. These results indicate that the homochiral selectivity for the S-bridged Co(III)Pt(II)Co(III) trinuclear complexes composed of two octahedral [Co(aet)(2)(L)](0 or +) units is enhanced in the order L = en < pyt < pymt. The isomers produced were separated and optically resolved, and the crystal structures of the meso-type deltalambda-[1]Cl(2).4H(2)O and the spontaneously resolved deltadelta-[4](ClO(4))(3).H(2)O were determined by X-ray analyses. In deltalambda-[1](2+), the delta and Lambda configurational mer(S).trans(N(aet))-[Co(aet)(2)(pyt)] units are linked by a square-planar Pt(II) ion through four aet S atoms to form a linear-type S-bridged trinuclear structure. In deltadelta-[4](3+), a similar linear-type trinuclear structure is constructed from the delta-mer(S).trans(N(aet))-[Co(aet)(2)(pymt)] and delta-C(2)-cis(S)-[Co(aet)(2)(en)](+) units that are bound by a Pt(II) ion with a slightly distorted square-planar geometry through four aet S atoms.     

Biodegradable Poly(3-hydroxybutyrate) Nanocomposite

This work seeks bringing a technological and social contribution by searching blends and composites of poly(3-hydroxybutyrate) (PHB) and polyethylene widely used in packaging films, and colloidal silica. The mixtures were prepared by extrusion using a single-screw extruder and were analyzed regarding their thermal and mechanical properties and morphology. The results have shown PHB toughness in the studied compositions, which elongation at break was in the range 5–80% compared to 2% for neat PHB. The small amount (0.2 to 0.4%) of added silica seemed to increase in 20% the tensile strength. The thermal degradation by thermogravimetry from room temperature to 800 °C revealed a mixed behavior for the composites between PHB and polyethylene.     

Calorimetric study on the effect of Co γ-rays on the growth of microorganisms

Using a calorimeter equipped with 24 sample units, the heat evolution from growing Saccharomyces cerevisiae, Escherichia coli and spores of Bacillus pumilus and Bacillus stearothermophilus was detected in the form of growth thermograms. Irradiation with ⁶⁰Co γ-rays affected the growth pattern, which was used for a quantitative analysis of the effect on microorganisms. Irradiation of B. pumilus and B. stearothermophilus spores led to dose-dependent delays in growth, indicating a bactericidal effect. In case of ⁶⁰Co γ-irradiated S. cerevisiae, a dose-dependent reduction of the growth rate constant was observed together with the retardation in growth, indicating a combination of bactericidal and bacteriostatic effects. An equation to determine the number of survivors on the basis of the retardation in growth t and the growth rate constant μ was developed, which proved the opportunity to use the calorimetric technique in predictive microbiology.     

Hysteretic behavior of diamagnetic molecular assembly: Magnetic field-induced deformation of tubular self-assemblies composed of amphiphilic molecules

Real-time observation of a morphologies of a multi-component tubular giant vesicle (tGV), which is a self-assembly composed of plural amphiphiles with different packing parameters, was carried out under application of a magnetic field. A tGV, one of the terminals of which was fixed to a bottom of a cell, exhibited the bending deformation under a magnetic field along the perpendicular direction of the long axis. Moreover, the hysteretic behavior in this deformation was observed associated with the increase and decrease of the magnetic fields repeatedly, regardless of the presence or absence of a paramagnetic species. To understand the hysteretic behavior, the molecular cooperative effect, which stabilizes the bending deformation by replacing of the plural kinds of amphiphiles with different packing parameters within a membrane, must be taken into consideration.     

The effects of the crystallization rate of the mesoporous TiO2 on the stability of the mesoporous structure after reflux

A simple synthetic method was employed to prepare mesoporous titania with anatase crystalline walls and high photocatalytic activity. The properties and structures of mesoporous titania were characterized by means of low angle and wide angle X-ray diffraction (XRD), Fourier transform (FT)-IR spectra, transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and N₂ adsorption–desorption. The characteristic results clearly show that crystallization rate of the mesoporous titania affects the stability of the mesoporous structure after reflux, and that the anatase crystal in the mesoporous wall of mesoporous titania can stabilize the mesoporous structure. The photocatalytic activity of titania powder was evaluated from an analysis of the photodegradation of methyl orange under UV irradiation. The results indicate that the titania powder with mesoporous structure shows the highest photocatalytic activity.