Localization of the Grover Walks on Spidernets and Free Meixner Laws

In the first part, we have constructed several families of interacting wedge-local nets of von Neumann algebras. In particular, we discovered a family of models based on the endomorphisms of the U(1)-current algebra ${\mathcal{A} ^{(0)}}$ of Longo-Witten. In this second part, we further investigate endomorphisms and interacting models. The key ingredient is the free massless fermionic net, which contains the U(1)-current net as the fixed point subnet with respect to the U(1) gauge action. Through the restriction to the subnet, we construct a new family of Longo-Witten endomorphisms on ${\mathcal{A} ^{(0)}}$ and accordingly interacting wedge-local nets in two-dimensional spacetime. The U(1)-current net admits the structure of particle numbers and the S-matrices of the models constructed here do mix the spaces with different particle numbers of the bosonic Fock space.     

AlCl3-catalyzed tandem acetylation of hydroarylated [60]fullerenes

The AlCl3-catalyzed acetylation of 1,2-hydrophenylated [60]fullerenes, HC60-Ar, proceeded via a sequential manner involving the acetylation at the hydrogenated fullerene carbon, the following intramolecular cyclization with the adjacent aryl group, the facile loss of water, and the second acetylation of the generated indenylidene double bond. However, the similar reaction of the hydrobiphenylated analogue brought about the normal acetylation at the terminal aromatic ring prior to the same sequential reactions as did hydrophenylated fullerenes.     

Scale-up of wet kneading in a novel vertical high shear kneader

A novel multi-functional vertical high shear kneader has been developed and its performance in wet kneading has previously been reported [Watano et al., Chem. Pharm. Bull., 50(3), 341-345 (2002)]. In this study, scale-up of wet kneading in the novel vertical high shear kneader was conducted. Pharmaceutical excipients composed of lactose, cornstarch and micro-crystalline cellulose were used as powder samples. Kneading operations were conducted under various operating conditions and three different vessel scales. The dried pellets were then prepared by extruding the wet kneaded masses through a dome-type extruder and their drying by a fluidized bed. The physical properties such as strength and disintegration time of the dried pellets were evaluated. It was found that the properties of the dried pellets and their scale-up characteristics were well expressed by an agitation power per unit vessel volume and dimensionless Froude number.     

Concise Synthesis of Potassium Acyltrifluoroborates from Aldehydes through Copper(I)‐Catalyzed Borylation/Oxidation

Potassium acyltrifluoroborates (KATs) were prepared through copper(I)‐catalyzed borylation of aldehydes and subsequent oxidation. This synthetic route is characterized by the wide range of aldehydes accessible, favorable step economy, mild reaction conditions, and tolerance of various functional groups, and it enables the facile generation of a range of KATs, for example, bearing halide, sulfide, acetal, or ester moieties. Moreover, this method was applied to the three‐step synthesis of various α‐amino acid analogues that bear a KAT moiety on the C‐terminus by using naturally occurring amino acids as the starting material.     

Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

Production of Alkyl Aryl Sulfides from Aromatic Disulfides and Alkyl Carboxylates via a Disilathiane–Disulfide Interchange Reaction

The results of this study show that disilathiane is an effective mediator in the synthesis of alkyl aryl sulfides with disulfides and alkyl carboxylates. Mechanistic studies suggest that disilathiane promotes cleavage of the sulfur–sulfur bond of disulfides to generate thiosilane as a key intermediate. Diselenides were also applicable to this transformation to produce the corresponding selenides.     

A Light-Harvesting/Charge-Separation Model with Energy Gradient Made of Assemblies of meta-Pyridyl Zinc Porphyrins

Self-assembly of porphyrins is a fascinating topic, not only for mimicking chlorophyll assemblies in photosynthetic organisms, but also for the potential of creating molecular-level devices. Herein, zinc porphyrin derivatives bearing a meta-pyridyl group at the meso position were prepared and their assemblies studied in chloroform. Among the porphyrins studied, one with a carbamoylpyridyl moiety gave a distinct ¹H NMR spectrum in CDCl₃, which allowed the supramolecular structure in solution to be probed in detail. Ring-current-induced chemical-shift changes in the ¹H NMR spectrum, together with vapor-pressure osmometry and diffusion-ordered NMR spectroscopy, among other evidence, suggested that the porphyrin molecules form a trimer with a triangular cone structure. Incorporation of a directly linked porphyrin–ferrocene dyad with the same assembling properties in the assemblies led to a rare example of a light-harvesting/charge-separation system in which an energy gradient is incorporated and reductive quenching occurs.     

The Bioactive Peptide SL-13R Expands Human Umbilical Cord Blood Hematopoietic Stem and Progenitor Cells In Vitro

Hematopoietic stem and progenitor cell (HSPC) transplantation is a curative treatment of hematological disorders that has been utilized for several decades. Although umbilical cord blood (UCB) is a promising source of HSPCs, the low dose of HSPCs in these preparations limits their use, prompting need for ex vivo HSPC expansion. To establish a more efficient method to expand UCB HSPCs, we developed the bioactive peptide named SL-13R and cultured UCB HSPCs (CD34+ cells) with SL-13R in animal component-free medium containing a cytokine cocktail. Following 9 days of culture with SL-13R, the numbers of total cells, CD34+, CD38− cells, and hematopoietic stem cell (HSC)-enriched cells were significantly increased relative to control. Transplantation of cells cultured with SL-13R into immunodeficient NOD/Shi-scid/IL-2Rγ knockout mice confirmed that they possess long-term reconstitution and self-renewal ability. AHNAK, ANXA2, and PLEC all interact with SL-13R. Knockdown of these genes in UCB CD34+ cells resulted in reduced numbers of hematopoietic colonies relative to SL-13R-treated and non-knockdown controls. In summary, we have identified a novel bioactive peptide SL-13R promoting expansion of UCB CD34+ cells with long-term reconstitution and self-renewal ability, suggesting its clinical use in the future.