ATR-IR spectroscopic study of L-lysine adsorption on amorphous silica

Attenuated total reflectance infrared (ATR-IR) spectroscopy was employed to quantitatively evaluate the dissociation states (di-cationic, cationic, zwitterionic, and anionic) of lysine adsorbed on amorphous silica. To determine the relationship between the ATR-IR spectra and each dissociation state, we first measured pH-induced spectral changes of dissolved lysine and correlated these changes with the thermodynamically calculated dissociation states of lysine. This procedure yielded calibration curves with good linearity; we used these curves for the quantitative analysis of adsorbed lysine. Our analysis revealed that 81+/-5% of the lysine adsorbed on amorphous silica was present in a cationic state and 19+/-5% was in a zwitterionic state; these percentages remained mostly unchanged over the whole range of pH values tested (pH = 7.1-9.8). We interpret the values obtained to indicate that lysine adsorption is mainly driven by electrostatic interaction with the negatively charged silica surface (SiO(-)...Lys(+), SiO(-)...Lys(+/-)).     

A note on disjoint arborescences

Recently Kamiyama, Katoh, and Takizawa have shown a theorem on packing arc-disjoint arborescences that is a proper extension of Edmonds’ theorem on disjoint spanning branchings. We show a further extension of their theorem, which makes clear an essential rôle of a reachability condition played in the theorem. The right concept required for the further extension is “convexity” instead of “reachability”.     

Using HDC to evaluate signal similarity for information masking

In the many studies done on informational masking, interfering speech reduces speech intelligibility. This effect is often used to secure privacy in public spaces. These applications require estimates of how much masking is required. In general, masking effects are estimated by using spectrum information as excitation patterns. However, estimates of informational masking can hardly be obtained by only using spectrum information. Therefore, we estimated the effects of informational masking using time-domain information. Then, we calculated the cepstra of the envelopes’ magnitude histograms. If these cepstra are different between the target and the masker, the signals are not similar in the time-domain. Furthermore, the effect of informational masking would be low. Therefore, we considered the histograms’ cepstra distances (HCD) to estimate signal similarities. The signal similarities in our first experiment were estimated using five maskers by utilizing the HCD. These maskers were random noise, music, female speech, male speech, and target speaker’s speech. Male and female speech were more similar to the target speech than music and noise. Also, the same speaker’s speech was the most similar in the set of maskers. A listening test was carried out in the second experiment to verify the HCD. A double masker was used in this experiment as an effective informational masker. It has similar characteristics to reversal speech. The listening test results suggest the double-masker’s masking effects has the same relation with HCD. This suggests informational masking can be estimated by signal similarity using the HCD.     

High-Field and Multifrequency ESR in the Two-Dimensional Triangular Lattice Antiferromagnet NiGa2S4

We report the experimental results of electron spin resonance in high magnetic fields up to about 53 T on the quasi-two-dimensional triangular lattice antiferromagnet NiGa₂S₄. The temperature dependence of the resonance field at 584.8 GHz shows a steep change below about 30 K, indicating a development of the short-range correlation. The frequency dependence of the resonance field at the lowest temperature for H∥c is explained by one of the helical resonance modes. These experimental results suggest that the short-range order is well developed at low temperatures, and the resonance mode is described by a conventional spin wave theory.     

Quadruple Role of Pd Catalyst in Domino Reaction Involving Aryl to Alkyl 1,5-Pd Migration to Access 1,9-Bridged Triptycenes

A Pd-catalyzed domino reaction of 1,8,13-tribromo-9-methoxytriptycenes is reported. Under conventional Suzuki coupling conditions, the triptycenes underwent multiple transformations to give 1,9-bridged triptycenes. Based on mechanistic investigations, a single Pd catalyst functions as Pd⁰, Pd^II and Pd^IV species to catalyze four distinct processes: (1) aryl to alkyl 1,5-Pd migration, (2) intramolecular arylation, (3) homocoupling of phenylboronic acid and (4) Suzuki coupling. DFT calculations revealed that 1,5-Pd migration likely proceeds via both concerted Pd^II and stepwise Pd^IV routes. Asymmetric synthesis of the chiral triptycenes, as well as optical resolution, and further transformation are also reported.     

Molecular Dynamics Simulation Studies on the Aggregation of Amyloid-β Peptides and Their Disaggregation by Ultrasonic Wave and Infrared Laser Irradiation

Alzheimer’s disease is understood to be caused by amyloid fibrils and oligomers formed by aggregated amyloid-β (Aβ) peptides. This review article presents molecular dynamics (MD) simulation studies of Aβ peptides and Aβ fragments on their aggregation, aggregation inhibition, amyloid fibril conformations in equilibrium, and disruption of the amyloid fibril by ultrasonic wave and infrared laser irradiation. In the aggregation of Aβ, a β-hairpin structure promotes the formation of intermolecular β-sheet structures. Aβ peptides tend to exist at hydrophilic/hydrophobic interfaces and form more β-hairpin structures than in bulk water. These facts are the reasons why the aggregation is accelerated at the interface. We also explain how polyphenols, which are attracting attention as aggregation inhibitors of Aβ peptides, interact with Aβ. An MD simulation study of the Aβ amyloid fibrils in equilibrium is also presented: the Aβ amyloid fibril has a different structure at one end from that at the other end. The amyloid fibrils can be destroyed by ultrasonic wave and infrared laser irradiation. The molecular mechanisms of these amyloid fibril disruptions are also explained, particularly focusing on the function of water molecules. Finally, we discuss the prospects for developing treatments for Alzheimer’s disease using MD simulations.     

Scale-up of high shear granulation based on agitation power

Scale-up of wet granulation in a vertical high shear mixer was conducted. Pharmaceutical excipient mixtures composed of lactose, cornstarch and micro-crystalline cellulose, and hydroxypropylecellulose as a binder were mixed together and then granulated with purified water under various operating conditions and vessel scales. Torque of agitator shaft was continuously measured and then agitation power per unit vessel volume was calculated. The agitation power per unit vessel volume showed a good correlation with physical properties of obtained granules, such as mass median diameter, strength and compressibility. This implied that the scale-up characteristics could be well analyzed by means of the agitation power per unit vessel volume. In addition, the effects of agitator tip speed and Froude number on the agitation power per unit vessel volume were investigated. The results showed that the agitation power per unit vessel volume was well characterized by the tip speed rather than the Froude number. This meant that the granule growth mainly progressed by the shear stress from the agitator blade. Dynamic characteristics of high shear granulation were also discussed here.     

Direct Observation of a Li‐Ionic Space‐Charge Layer Formed at an Electrode/Solid‐Electrolyte Interface

When two different materials come into contact, mobile carriers redistribute at the interface according to their potential difference. Such a charge redistribution is also expected at the interface between electrodes and solid electrolytes. The redistributed ions significantly affect the ion conduction through the interface. Thus, it is essential to determine the actual distribution of the ionic carriers and their potential to improve ion conduction. We succeeded in visualizing the ionic and potential profiles in the charge redistribution layer, or space‐charge layer (SCL), formed at the interface between a Cu electrode and Li‐conductive solid electrolyte using phase‐shifting electron holography and spatially resolved electron energy‐loss spectroscopy. These electron microscopy techniques clearly showed the Li‐ionic SCL, which dropped by 1.3 V within a distance of 10 nm from the interface. These techniques could contribute to the development of next‐generation electrochemical devices.     

Kinetic Study on Alpha-Form Crystallization of Mixed-Acid Triacylglycerols POP,PPO, and Their Mixture

The crystallization behavior of the metastable α form of triacylglycerols (TAGs) plays a critical role as a precursor for the crystallization of more stable β′ and β forms for various applications in food and pharmaceutical products. However, precise analysis of the crystallization kinetics of α has not been performed, likely due to its rapid and complex behavior. This paper presents the observation results of the initial stages of the isothermal crystallization kinetics of α forms of 1,3-dipalmitoyl-2-oleoyl-glycerol (POP), 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (rac-PPO), and molecular compound (MC) crystals of a POP/rac-PPO (1/1) mixture (MCPOP/PPO) using synchrotron radiation time-resolved X-ray diffraction and polarized optical microscopy. In all the TAGs, α crystals with a worm-like morphology started to grow rapidly in the first stage. Then, the α crystals slowly transformed into more stable forms in different manners for different TAG samples. In POP, the conversion was simple, as the α-2 form transformed into γ-3, whereas in rac-PPO, the lamellar distance values of the α-2 form continuously decreased with time and changed into the α-3 form. In the MCPOP/PPO crystals, in contrast, separate crystallization of α-2 of a rac-PPO fraction initially occurred, followed by the crystallization of α-2 of POP, and the two α forms merged into α-2 of MCPOP/PPO. This separate crystallization was caused by large differences in the crystallization kinetics of the α forms of POP and rac-PPO.     

DNA-Mediated Stack Formation of Nanodiscs

Membrane-scaffolding proteins (MSPs) derived from apolipoprotein A-1 have become a versatile tool in generating nano-sized discoidal membrane mimetics (nanodiscs) for membrane protein research. Recent efforts have aimed at exploiting their controlled lipid protein ratio and size distribution to arrange membrane proteins in regular supramolecular structures for diffraction studies. Thereby, direct membrane protein crystallization, which has remained the limiting factor in structure determination of membrane proteins, would be circumvented. We describe here the formation of multimers of membrane-scaffolding protein MSP1D1-bounded nanodiscs using the thiol reactivity of engineered cysteines. The mutated positions N42 and K163 in MSP1D1 were chosen to support chemical modification as evidenced by fluorescent labeling with pyrene. Minimal interference with the nanodisc formation and structure was demonstrated by circular dichroism spectroscopy, differential light scattering and size exclusion chromatography. The direct disulphide bond formation of nanodiscs formed by the MSP1D1_N42C variant led to dimers and trimers with low yield. In contrast, transmission electron microscopy revealed that the attachment of oligonucleotides to the engineered cysteines of MSP1D1 allowed the growth of submicron-sized tracts of stacked nanodiscs through the hybridization of nanodisc populations carrying complementary strands and a flexible spacer.