Several types of bilayer smectic liquid crystals with ferroelectric and antiferroelectric properties in binary mixture of dimeric compounds

The mesomorphic behavior and phase structure were examined in the mixture of two kinds of dimeric compounds, alpha,omega-bis(4-alkoxyanilinebenzylidene-4'-carbonyloxy)pentane (mOAM5AMOm), by optical microscopy, X-ray diffraction, polarization switching, and second-harmonic generation measurements. One compound is 4OAM5AMO4 with a short terminal alkyl chain that forms a single-layer smectic phase (SmCAs) with a random mixing of spacer and tail groups. Another compound is 16OAM5AMO16 with a long terminal alkyl chain that forms a chiral, anticlinic, and antiferroelectric bilayer phase (SmCAb) with the bent molecules tilted to the bilayer. By mixing these two compounds, the SmCAs phase of 4OAM5AMO4 is easily destabilized, leading to the wide content region of the bilayer phases. In the bilayer regime, three other smectic phases are newly induced. Two of them are antiferroelectric and ferroelectric phases in which the molecules lie perpendicularly with respect to the layer. The other shows no polar response to an external electric field and behaves like a smectic A. The new appearance of these bilayer phases is discussed as a mixing effect of long and short tail groups.     

Global stability of extended multi-group sir epidemic models with patches through migration and cross patch infection

In this article, we establish the global stability of an endemic equilibrium of multi-group SIR epidemic models, which have not only an exchange of individuals between patches through migration but also cross patch infection between different groups. As a result, we partially generalize the recent result in the article [16].     

Temperature dependence of the photoinduced fatigue-recovery phenomena of photoluminescence under prolonged irradiation in GeS2 chalcogenide glass

We report the time-dependent intensities for the photoluminescence (PL) at various temperatures (10 K ? T ? 300 K) in amorphous GeS₂, which is known to exhibit not only PL fatigue but also PL recovery behavior. A difference in reversibility in fatigue-recovery process was found between room temperature (RT) and those at 110 K or below. Another small band of PL was also observed at 10 K or less, which also showed a time-dependence in intensity. A functional form to describe the time dependence was adopted based on a simplified model which have been obtained in a previous study and extended to describe the fatigue-recovery behaviors for all temperature range which have measured below RT.     

Construction of a High‐Mannose‐Type Glycan Library by a Renewed Top‐Down Chemo‐Enzymatic Approach

A comprehensive method for the construction of a high‐mannose‐type glycan library by systematic chemo‐enzymatic trimming of a single Man9‐based precursor was developed. It consists of the chemical synthesis of a non‐natural tridecasaccharide precursor, the orthogonal demasking of the non‐reducing ends, and trimming by glycosidases, which enabled a comprehensive synthesis of high‐mannose‐type glycans in their mono‐ or non‐glucosylated forms. It employed glucose, isopropylidene, and N‐acetylglucosamine groups for blocking the A‐, B‐, and C‐arms, respectively. After systematic trimming of the precursor, thirty‐seven high‐mannose‐type glycans were obtained. The power of the methodology was demonstrated by the enzymatic activity of human recombinant N‐acetylglucosaminyltransferase‐I toward M7–M3 glycans, clarifying the substrate specificity in the context of high‐mannose‐type glycans.     

Chemical-Synthesis-Based Approach to Glycoprotein Functions in the Endoplasmic Reticulum

The introduction of Asn-linked glycans to nascent polypeptides occurs in the lumen of the endoplasmic reticulum of eukaryotic cells. After the removal of specific sugar residues, glycoproteins acquire signals in the glycoprotein quality control (GPQC) system and enter the folding cycle composed of lectin-chaperones calnexin (CNX) and calreticulin (CRT), glucosidase II (G-II), and UDP-Glc:glycoprotein glucosyltransferase (UGGT). G-II initiates glycoproteins’ entry and exit from the cycle, and UGGT serves as the “folding sensor”. This account summarizes our effort to analyze the properties of enzymes and lectins that play important roles in GPQC, especially those involved in the CNX/CRT cycle. To commence our study, general methods for the synthesis of high-mannose-type glycans and glycoproteins were established. Based on these, various substrates to analyze components of the GPQC were created, and properties of CRT, G-II, and UGGT have been clarified.     

Second-generation total synthesis of haterumalide NA using B-alkyl Suzuki-Miyaura coupling

Second-generation total synthesis of haterumalide NA, a potent cytotoxic marine macrolide, was achieved by using B-alkyl Suzuki-Miyaura coupling and Nozaki-Hiyama-Kishi coupling as key steps (1.2% in 33 steps). Compared to our first-generation approach, the second-generation synthesis is much improved in the yield of key intermediate.     

Relative and absolute stereochemistry of quinadoline B, an inhibitor of lipid droplet synthesis in macrophages

New fungal metabolites, designated quinadolines A (1) and B (2), were isolated from culture broth of Aspergillus sp. FKI-1746, and their structures were elucidated by NMR spectroscopy. The complete relative and absolute stereochemistry of 2 was determined by X-ray crystallography and amino acid analysis using a chiral column. Quinadolines moderately inhibited lipid droplet synthesis in mouse macrophages.     

Koshikamide B, a cytotoxic peptide lactone from a marine sponge Theonella sp

Koshikamide B (1) has been isolated from two separate collections of the marine sponge Theonella sp. as the major cytotoxic constituent. Koshikamide B is a 17-residue peptide lactone composed of six proteinogenic amino acids, two D-isomers of proteinogenic amino acids, seven N-methylated amino acids, and two unusual amino acid residues. The unusual amino acids are N(delta)-carbamoylasparagine and 2-(3-amino-2-hydroxy-5-oxopyrrolidin-2-yl)propionic acid (AHPP); the former is first found as the constituent of peptides, whereas the latter is a new amino acid residue. The N-terminus of koshikamide B is blocked by a methoxyacetyl group. The structure of koshikamide B (1) has been determined by interpretation of spectral data and analysis of chemical degradation products. Koshikamide B (1) exhibits cytotoxicity against P388 murine leukemia cells and the human colon tumor (HCT-116) cell line with an IC50 value of 0.45 and 7.5 microg/mL, respectively.     

Approaches toward High‐Mannose‐Type Glycan Libraries

Asparagine‐linked (N‐linked) sugar chains are widely found in the rough endoplasmic reticulum (ER), which has attracted renewed attention because of its participation in the glycoprotein quality control process. In the ER, newly formed glycoproteins are properly folded to higher‐order structures by the action of a variety of lectin chaperones and processing enzymes and are transported into the Golgi, while terminally misfolded glycoproteins are carried into the cytosol for degradation. A group of proteins related to this system are known to recognize subtle differences in the high‐mannose‐type oligosaccharide structures of glycoproteins; however, their molecular foundations are still unclear. In order to gain a more precise understanding, our group has established a strategy for the systematic synthesis of high‐mannose‐type glycans. More recently, we have developed “top‐down” chemoenzymatic approaches that allow expeditious access to theoretically all types of high‐mannose glycans. This strategy comprehensively delivered 37 high‐mannose‐type glycans, including G1M9–M3 glycans, and opened up the possibility of the elucidation of structure–function relationships with a series of high‐mannose‐type glycans.