Effect of Photoinduced Size Changes on Protein Refolding and Transport Abilities of Soft Nanotubes

Self‐assembly of azobenzene‐modified amphiphiles (Gly_nAzo, n=1–3) in water at room temperature in the presence of a protein produced nanotubes with the protein encapsulated in the channels. The Gly₂Azo nanotubes (7 nm internal diameter [i.d.]) promoted refolding of some encapsulated proteins, whereas the Gly₃Azo nanotubes (13 nm i.d.) promoted protein aggregation. Although the 20 nm i.d. channels of the Gly₁Azo nanotubes were too large to influence the encapsulated proteins, narrowing of the i.d. to 1 nm by trans‐to‐cis photoisomerization of the azobenzene units of the Gly₁Azo monomers packed in the solid bilayer membranes led to a squeezing out of the proteins into the bulk solution and simultaneously enhanced their refolding ratios. In contrast, photoinduced transformation of the Gly₂Azo nanotubes to short nanorings (<40 nm) with a large i.d. (28 nm) provided no further refolding assistance. We thus demonstrate that pertubation by the solid bilayer membrane wall of the nanotubes is important to accelerate refolding of the denatured proteins during their transport in the narrow nanotube channels.     

Deformation Luminescence in gamma-irradiated KCl single crystals

Abstract

Deformation Luminescence(DL) is studied on KCl crystal colored by γ-irradiation. The spectra analysis of DL and thermoluminescence reveals that F-center plays a role as electron donor through the interaction with moving dislocation and V₂-center is a probable luminescence center. A theory is presented for understanding the deformation rate and temperature dependences of DL intensity.     

Selective Formation of Intramolecular Hydrogen-Bonding Palladium(II) Complexes with Nucleosides Using Unsymmetrical Tridentate Ligands

Three palladium(II) complexes with amino-amidato-phenolato-type tridentate ligands were synthesized and characterized by ¹H NMR spectroscopy and X-ray crystallography. The strategic arrangement of a hydrogen-bond donor and acceptor adjacent to the substitution site of the Pd^II complex allowed the selective coordination of nucleosides. Among two pyrimidine-nucleosides, cytidine and 5-methyluridine, cytidine was successfully coordinated to the Pd^II complex while 5-methyluridne was not. On the other hand, both purine-nucleosides, adenosine and guanosine, were coordinated to the Pd^II complex. As purines have several coordination sites, adenosine afforded three kinds of coordination isomers expected from the three different donors. However, guanosine afforded a sole product according to the ligand design such that the formation of double intramolecular hydrogen-bond strongly induced the specific coordination by N1-position of guanine moiety. Furthermore, the preference of the nucleosides was evaluated by scrambling reactions. It was found that the preference of guanosine is nearly twice as high as adenosine and cytidine, owing to the three-point interaction of a coordination bond and two hydrogen bonds. These results show that the combination of a coordination and hydrogen bonds, which is reminiscent of the Watson–Crick base pairing, is an effective tool for the precise recognition of nucleosides.     

Solving Generalized Polyomino Puzzles Using the Ising Model

In the polyomino puzzle, the aim is to fill a finite space using several polyomino pieces with no overlaps or blanks. Because it is an NP-complete combinatorial optimization problem, various probabilistic and approximated approaches have been applied to find solutions. Several previous studies embedded the polyomino puzzle in a QUBO problem, where the original objective function and constraints are transformed into the Hamiltonian function of the simulated Ising model. A solution to the puzzle is obtained by searching for a ground state of Hamiltonian by simulating the dynamics of the multiple-spin system. However, previous methods could solve only tiny polyomino puzzles considering a few combinations because their Hamiltonian designs were not efficient. We propose an improved Hamiltonian design that introduces new constraints and guiding terms to weakly encourage favorable spins and pairs in the early stages of computation. The proposed model solves the pentomino puzzle represented by approximately 2000 spins with >90% probability. Additionally, we extended the method to a generalized problem where each polyomino piece could be used zero or more times and solved it with approximately 100% probability. The proposed method also appeared to be effective for the 3D polycube puzzle, which is similar to applications in fragment-based drug discovery.     

A head‐to‐head isomer of di‐μ‐pivalamidato‐κ4N,O‐bis­[(1,10‐phenanthroline‐κ2N,N′)­platinum(II)] dinitrate dihydrate

In the title compound, [Pt₂(C₅H₁₀NO)₂(C₁₂H₈N₂)₂](NO₃)₂·2H₂O, the intradimer Pt—Pt distance is relatively short [2.8489 (17) Å], which must be due to the strong intramolecular π–π‐stacking interactions between the phenanthroline moieties. The dimers stack along the c axis, forming one‐dimensional columns in which very intriguing d–d, π–π and d–π interactions exist. Although the dimer–dimer Pt...Pt distances are very long [4.340 (2) and 4.231 (2) Å], some short interdimer Pt...C contacts leading to strong interdimer associations are found [3.325 (19) and 3.402 (19) Å].     

Proof-of-Principle Experiment of the Pseudorandom Multiplexing of White-Pump Light for Spectral Photothermal Microscopy

Absorption spectroscopy, coupled with photothermal super-resolution microscopy, is enabled by the frequency division multiplexing of the pump-light (Pu) wavelength whose spectral component is discriminated by the modulation frequency. This demonstrates a great advantage in availing multicolor image information. However, the response gain of the thermal lens signal to the spectral components is not uniform because of the limited relaxation rate of the thermal lens, i.e., the gains of the components assigned to the high-frequency modulations are diminished, thus resulting in a distorted absorption spectrum. In this study, white-pump light (Pu) is multiplexed by pseudonoise sequences (PNSs) to avoid the distortion. The frequency bandwidth of the PNSs is equalized, and the gains of the thermal lens generation to the respective wavelength components are balanced. The obtained results indicate that the modulation-waveform deformation due to the slow responses of the sample can also distort spectra. To mitigate the problem, the countermeasures required to compensate for this distortion are also discussed.     

Interesterification activity of Rhizopus delemar lipase in phospholipid microemulsions

The interesterification of olive oil with palmitic acid catalyzed by Rhizopus delemar lipase was investigated in phospholipid microemulsion systems. Soybean lecithin was used as the amphiphilic component. The maximal reaction rate was obtained at a buffer pH of 5.5–6.0. The reaction rate was also dependent on the W_L (= [H₂O]/[lecithin]) value and attained a maximum at W_L = 5. The reaction rate reached a maximum at a palmitic acid concentration of 350 mM. The molar fraction of the interesterified product 1,3-dipalmitoyl-3-oleoyl glycerol (POP) in the olive oil was enhanced from 2.8 to 65.6 mol% after 24 h of the reaction.