Photoelectron and penning ionization electron spectroscopic investigation of trimethylsilyl- and t-butyl-thiophenes

Penning ionization electron spectroscopy and CNDO/S calculations have been successfully applied to the analyses of the UV photoelectron spectra of 2- and 2,5-bistrimethylsilylthiophene and 2-t-butylthiophene. The relative intensities of the π type bands are greatly enhanced in the Penning spectra compared with those of the UV photoelectron spectra.     

Synthesis and Systematic Structural Analysis of Cationic Half-Sandwich Ruthenium Chalcogenocarbonyl Complexes

Although the chemistry of transition-metal complexes with carbonyl (CO) and thiocarbonyl (CS) ligands has been well developed, their heavier analogues, namely selenocarbonyl (CSe) and tellurocarbonyl (CTe) complexes remain scarce. The limited availability of such CSe and CTe complexes has so far hampered our understanding of the differences between such chalcogenocarbonyl (CE: E=O, S, Se, Te) ligands. Herein, we report the synthesis and properties of a series of cationic half-sandwich ruthenium CE complexes of the type [CpRu(CE)(H₂IMes)(CNCH₂Ts)][BAr^F₄] (Cp=η⁵-C₅H₅⁻; H₂IMes=1,3-dimesitylimidazolin-2-ylidene; Ar^F=3,5-(CF₃)₂C₆H₃). A combination of X-ray diffraction analyses, NMR spectroscopic analyses, and DFT calculations revealed an increasing π-accepting ability of the CE ligands in the order O<S<Se<Te. A variable-temperature NMR analysis of the thus obtained chiral-at-metal CE complexes indicated high stereochemical stability.     

Thermodynamically Induced Conformational Changes of the Cyanobacterial Circadian Clock Protein KaiB

Site-directed spin labeling electron spin resonance (ESR) was applied to investigate the local environment of the cyanobacterial circadian clock protein KaiB. We prepared five cysteine residue-substituted mutants of KaiB labeled with maleimide spin label (MSL). By comparing the ESR spectra of KaiBs carrying MSL at different positions (Thr64, Lys67, Tyr94, Gly98, and Ala101), local conformational changes were identified. The ESR spectra of MSL-T64C and MSL-K67C showed the relatively slow motion of MSL characterized by τ?=?79 and 59?ns at 4°C, respectively. The spectra of MSL-Y94C, MSL-G98C and MSL-A101C showed relatively fast motion characterized by τ?=?8.0, 4.1 and 3.1?ns at 4°C, respectively. These differences were explained by the local environments of the position in KaiB. On incubation at 40°C for 24?h, all ESR spectra of the labeled KaiBs changed, which can be explained by the structural relaxation of KaiB.     

Observation of the "self-healing" of an error field island in the large helical device

It was observed that the vacuum magnetic island produced by an external error magnetic field in the large helical device shrank in the presence of plasma. This was evidenced by the disappearance of flat regions in the electron temperature profile obtained by Thomson scattering. This island behavior depended on the magnetic configuration in which the plasmas were produced.     

A Normal Force on the Free Surface of a Coated Material

The three-dimensional theoretical solution of a concentrated normal force acting on the free surface of a coated material has been deduced by applying the reflection method. It is found that all stress functions defined in the local coordinate systems with their origins placed at each mirror point can be deduced from the fundamental solution of a concentrated normal force acting on the free surface of a semi-infinite homogeneous medium. The structure of the elastic solution has been illustrated by numerical analysis. It is found that only the stress functions corresponding to the first few mirror points are influential. It is also found that the effect of material combination on the stress field shall be described by three parameters, the two Dundurs' parameters and one additional parameter.     

Tuning the Electronic Properties and Acid‐Response Behavior of N‐Heteroacene‐Based π‐Conjugated Liquids by Changing the Number of π‐Conjugated Substituents

We have designed and synthesized two room‐temperature‐fluorescent π‐conjugated liquids based on the N‐heteroacene framework ( 1 and 2 ). These two π‐conjugated liquids, which contained one and two thiophene rings, respectively, exhibited different electronic properties and rheology behaviors. Single‐crystal X‐ray analysis of dithiophene‐appended compound 4 revealed that two thiophene rings hindered the interactions of the imino N atoms with acids through the formation of interactions between the S atoms of the thiophene rings and the imino N atoms of the pyrazine group. On the other hand, monothiophene‐appended molecules 1 and 3 each contained an unhindered imino N atom on the opposite site to the thiophene ring. Upon dissolving various acids with different pK_a values in compounds 1 and 2 , these slight structural differences gave rise to marked differences in their acid‐response behaviors, thereby resulting in the emission of variously colored fluorescence in the liquid state. Furthermore, when acids with lower pK_a values was dissolved in compounds 1 and 2 , phase transition occurred from an isotropic liquid state to a self‐organized liquid‐crystalline phase.     

Difference systems of sets and cyclotomy

Difference systems of sets (DSS) are combinatorial configurations that arise in connection with code synchronization. A method for the construction of DSS from partitions of cyclic difference sets was introduced in [V.D. Tonchev, Difference systems of sets and code synchronization, Rend. Sem. Mat. Messina, Ser. II, t. XXV 9 (2003) 217–226] and applied to cyclic difference sets (n,(n-1)/2,(n-3)/4) of Paley type, where is a prime number. This paper develops similar constructions for prime numbers that use partitions of the set of quadratic residues, as well as more general cyclotomic classes.     

Reduction of ion thermal diffusivity associated with the transition of the radial electric field in neutral-beam-heated plasmas in the large helical device

Recent large helical device experiments revealed that the transition from ion root to electron root occurred for the first time in neutral-beam-heated discharges, where no nonthermal electrons exist. The measured values of the radial electric field were found to be in qualitative agreement with those estimated by neoclassical theory. A clear reduction of ion thermal diffusivity was observed after the mode transition from ion root to electron root as predicted by neoclassical theory when the neoclassical ion loss is more dominant than the anomalous ion loss.     

Fracture theory based on the concept of characteristic fracture length of materials

Fracture theory is a classic, but not a well-dealt with, difficulty in solid mechanics. This paper has proposed the concept of characteristic fracture length of materials from the fact that fracture happens with area failure rather than point failure in materials. A unified theory is then proposed, which can be applied both to smooth and defected materials (whether with micro or macro defects). Brittle fracture tests with specimens of different sizes of holes are carried out to examine the fracture theory. It is found that the fracture stresses obtained by experiments agree well with those predicated by the presented fracture theory. Though the brittle fracture is the focus of the paper, the concept of characteristic length can be easily extended to fatigue or other failure problems.     

Mössbauer spectroscopic study of frozen solutions of57Co using a specially designed cryostat for time differential coincidence emission Mössbauer spectroscopy of237Np

Experiments on the⁵⁷Fe Mössbauer effect in frozen solutions were carried out in order to demonstrate the capabilities of a cryostat which was developed for the emission Mössbauer spectroscopy of²³⁷Np. We confirmed the existence of an aliovalent state of⁵⁷Fe in the temperature range from 5.5 to 35 K. However, the relative amounts of Fe(II) and Fe(III) in the frozen matrix were almost constant for the temperature range from 5.5 to 150 K. The design, operation and capabilities of the cryostat are also described.