Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess

Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2/(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and ¹H nuclear magnetic resonance (¹H-NMR) methods. Chiral configurations could also be differentiated using CD or ¹H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10⁻⁶ mol·L⁻¹). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers.     

Thermodynamics-inspired inverse halftoning viamultiple halftone images

Based on an analogy between thermodynamics and Bayesian inference,inverse halftoning was formulated using multiple halftone images based on Bayesian inference using the maximizer of the posterior marginal(MPM) estimate.Applying Monte Carlo simulation to a set of snapshots of the Q-Ising model,it was demonstrated that optimal performance is achieved around the Bayes-optimal condition within statistical uncertainty and that the performance of the Bayes-optimal solution is superior to that of the maximum-a-posteriori(MAP) estimation which is a deterministic limit of the MPM estimate.These properties were qualitatively confirmed by the mean-field theory using an infinite-range model established in statistical mechanics.Additionally,a practical and useful method was constructed using the statistical mechanical iterative method via the Bethe approximation.Numerical simulations for a 256-grayscale standard image show that Bethe approximation works as good as the MPM estimation if the parameters are set appropriately.     

Extraction and implementation of muscle synergies in neuro-mechanical control of upper limb movement

This work faces the redundancy problem, a central concern in robotics, in a particular force-producing task by using muscle synergies to simplify the control. We extracted muscle synergies from human electromyograph signals and interpreted the physical meaning of the identified muscle synergies. Based on the human analysis results, we hypothesized a novel control framework that can explain the mechanism of the human motor control. The framework was tested in controlling a pneumatic-driven robotic arm to perform a reaching task. This control method, which uses only two synergies as manipulated variables for driving antagonistic pneumatic artificial muscles to generate desired movements, would be useful to deal with the redundancy problem; thus, suggesting a simple but efficient control for human-like robots to work safely and compliantly with humans.     

Catching a molecule at the air-water interface: Dynamic pore array for molecular recognition

As a soft and flexible porous structure, a pore array of a steroid cyclophane SC(OH), which consists of the rigid 1,6,20,25-tetraaza[6.1.6.1]paracyclophane ring connected to four steroid moieties (cholic acid) through flexible L-lysine spacers, was prepared at the air-water interface. As confirmed by surface pressure (π)-molecular area (A) isotherms, transition between open conformation and cavity conformation of the SC(OH) molecule was reversibly induced upon repeated compression and expansion of its monolayer at pH 11 where amino groups of the lysine residues are not fully deprotonated. Capture and release of an aqueous fluorescent guest (TNS) by SC(OH) was observed upon dynamic cavity formation through surface fluorescence spectroscopy. At pH 12, dynamic cavity formation of SC(OH) was sufficiently suppressed, and the capture and release of an aqueous TNS by the monolayer was not virtually observed. Lessened electrostatic repulsion between the SC(OH) molecules due to conversion of ammonium to free amine may prevent the cavity from reopening. The importance of dynamic nature of cavity formation on the guest binding was also proved by control experiments using SC(H), which cannot form cavity conformation at any surface pressures at both pH 11 and 12.     

Halogen-free acylation of toluene over FeSBA-1 molecular sieves

Three-dimensional cage type iron substituted mesoporous silica with different iron contents (FeSBA-1) was synthesized in a highly acidic media using cetyltriethylammonium bromide and tetraethylorthosilicate as a template and a silica source, respectively. Acylation of toluene with acetic anhydride (AA) was carried out over FeSBA-1 mesoporous catalysts with different n_Si/n_Fe ratios in the temperature range 80–180 °C for a time-on-stream of 1–6 h under liquid phase conditions. The important factors affecting the conversion and the selectivity of the reaction, such as the reaction temperature, feed ratio, catalyst weight and time-on-stream were studied and the results are discussed in detail. The reaction conditions were optimized and the n_AA/n_Toluene ratio of 2 and catalyst weight of 0.1 g (3.3 wt% of total reaction mixture) were maintained for all catalytic runs. It was found that the catalytic activity is strongly influenced by the amount of tetrahedral iron in the catalysts. Among the catalysts used in the present study, FeSBA-1(36) showed a high toluene conversion and selectivity to p-methylacetophenone (p-MAP) under the optimized reaction conditions. It was also found that the selectivity for p-MAP was always higher than m-MAP and o-MAP for all the catalysts and the activity of the catalysts changes in the following order: FeSBA-1(36) > FeSBA-1(90) > FeSBA-1(120).     

Free primary alcohols in oils and waxes from germs,kernels and other components of nuts,seeds, fruits and cereals

The composition of free primary alcohols in oils and waxes obtained from the germ, kernel, seed coat, shell and skin (peel) of various nuts, seeds, fruits and cereals and from the chrysalis of silkworm was examined. These alcohols are usually present in small amounts, along with large quantities of hydrocarbons, esters and glycerides in oils and waxes. Thus, it is necessary to remove hydrocarbons, esters and glycerides to analyze the alcohols. We found that preparative reverse-phase thin-layer chromatography (TLC) was the best way to isolate alcohols from oils and waxes. Gas liquid chromatography (GLC) then detected hexacosanol, octacosanol and triacontanol in the oils and waxes. Octacosanol usually was the predominant alcohol. Relationships between the organs from nuts, seeds, fruits and cereals and the contents of octacosanol are suggested. For example, degermed kernels contained two times more octacosanol than the germ, and the skin coat and shell contained one-half and one-fortieth the octacosanol of the germ, respectively.     

Higher order structures and mechanical properties of bacterial homo poly(3-hydroxybutyrate) fibers prepared by cold-drawing and annealing processes

Pure bacterial homo poly(3-hydroxybutyrate) (PHB) fibers were prepared by melt spinning, followed by cold-drawing in an amorphous state at a temperature just above its glass transition temperature. Cold drawn fibers obtained were further drawn at higher temperatures, followed by annealing at various temperatures under tension. Relations among the processing conditions, higher order structures and mechanical properties were investigated using wide- and small-angle X-ray diffractions (WAXD and SAXD, respectively), birefringence, differential scanning calorimetry (DSC), and tensile measurements. PHB has two different crystalline forms, 2₁ helix conformation (α-form) and planar zigzag conformation (β-form). A single broad reflection of β-form was detected even in a PHB fiber drawn once at a temperature just above its T_g immediately after quenching and it tended to be stronger after 2nd drawing at higher temperatures. Annealing under low temperature and high tension facilitates the occurrence of β-form. It is suggested that the β-form crystal is formed not only from the tie chains between α-form lamella, but also from completely free amorphous chains. Changes in the amount of two types of crystals were analyzed using the WAXD integrated intensity. Birefringence of these fibers shows negative and positive values, depending on process conditions. Changes in higher order structure on the mechanical properties are also discussed.     

Additional kernel observer: privilege escalation attack prevention mechanism focusing on system call privilege changes

International Journal of Information Security - Cyberattacks, especially attacks that exploit operating system vulnerabilities, have been increasing in recent years. In particular, if administrator...