Adsorption and photochemical behaviors of the novel cationic xanthene derivative on the clay surface

Novel tetra-cationic xanthene derivative (Flu) was synthesized. Its adsorption and photochemical behaviors on the clay surface were investigated. Fluorescence quantum yield (?_f) and fluorescence lifetime were 0.50 and 2.9 ns for Flu/clay complex. ?_f of Flu was enough high (>0.1) even at high density conditions (0.080 molecules nm⁻²). It is supposed that the strong interaction between clay and Flu by the ‘Size-Matching Effect’ realizes the highly emissive clay complexes at high density adsorption condition by a suppression of a molecular aggregation, which tends to decrease the photochemical activity.     

A Dual Functional-Group Derivatization Liquid Chromatography–Tandem Mass Spectrometry Method: Application for Quantification of Human Insulin

Chromatographia - Recently, we developed a sensitive and accurate quantification method for short-chain peptides using dual functional-group derivatization. Sensitive and accurate quantification...     

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.     

α-Trifluoromethyl Chalcones as Potent Anticancer Agents for Androgen Receptor-Independent Prostate Cancer

α-Trifluoromethyl chalcones were prepared and evaluated for their antiproliferative activities against androgen-independent prostate cancer cell lines as well as five additional types of human tumor cell lines. The most potent chalcone 5 showed superior antitumor activity in vivo with both oral and intraperitoneal administration at 3 mg/kg. Cell-based mechanism of action studies demonstrated that 5 induced cell accumulation at sub-G1 and G2/M phases without interfering with microtubule polymerization. Furthermore, several cancer cell growth-related proteins were identified by using chalcone 5 as a bait for the affinity purification of binding proteins.     

Serine‐Selective Aerobic Cleavage of Peptides and a Protein Using a Water‐Soluble Copper–Organoradical Conjugate

The site‐specific cleavage of peptide bonds is an important chemical modification of biologically relevant macromolecules. The reaction is not only used for routine structural determination of peptides, but is also a potential artificial modulator of protein function. Realizing the substrate scope beyond the conventional chemical or enzymatic cleavage of peptide bonds is, however, a formidable challenge. Here we report a serine‐selective peptide‐cleavage protocol that proceeds at room temperature and near neutral pH value, through mild aerobic oxidation promoted by a water‐soluble copper–organoradical conjugate. The method is applicable to the site‐selective cleavage of polypeptides that possess various functional groups. Peptides comprising D ‐amino acids or sensitive disulfide pairs are competent substrates. The system is extendable to the site‐selective cleavage of a native protein, ubiquitin, which comprises more than 70 amino acid residues.     

Copper–Oxygen Dynamics in the Tyrosinase Mechanism

The dinuclear copper enzyme, tyrosinase, activates O₂ to form a (μ-η²:η²-peroxido)dicopper(II) species, which hydroxylates phenols to catechols. However, the exact mechanism of phenolase reaction in the catalytic site of tyrosinase is still under debate. We herein report the near atomic resolution X-ray crystal structures of the active tyrosinases with substrate l -tyrosine. At their catalytic sites, CuA moved toward l -tyrosine (CuA1 → CuA2), whose phenol oxygen directly coordinates to CuA2, involving the movement of CuB (CuB1 → CuB2). The crystal structures and spectroscopic analyses of the dioxygen-bound tyrosinases demonstrated that the peroxide ligand rotated, spontaneously weakening its O−O bond. Thus, the copper migration induced by the substrate-binding is accompanied by rearrangement of the bound peroxide species so as to provide one of the peroxide oxygen atoms with access to the phenol substrate's ϵ carbon atom.     

Acyl Fluorides in Late‐Transition‐Metal Catalysis

In this Review, we summarize the current state of the art in late‐transition‐metal‐catalyzed reactions of acyl fluorides, covering both their synthesis and further transformations. In organic reactions, the relationship between stability and reactivity of the starting substrates is usually characterized by a trade‐off. Yet, acyl fluorides display a very good balance between these properties, which is mostly due to their moderate electrophilicity. Thus, acyl fluorides (RCOF) can be used as versatile building blocks in transition‐metal‐catalyzed reactions, for example, as an “RCO” source in acyl coupling reactions, as an “R” source in decarbonylative coupling reactions, and as an “F” source in fluorination reactions. Starting from the cleavage of the acyl C?F bond in acyl fluorides, various transformations are accessible, including C?C, C?H, C?B, and C?F bond‐forming reactions that are catalyzed by transition‐metal catalysts that contain the Group 9–11 metals Co, Rh, Ir, Ni, Pd, or Cu.     

Heterogeneous continuous flow synthetic system using cyclohexane-based multiphase electrolyte solutions

The discovery that supporting electrolytes can be effectively confined in typical organic solvents in a c-Hex-based multiphase electrolyte solution has led to the development of a novel heterogeneous continuous flow synthetic system. PTFE fiber functions as a separation filter that can efficiently isolate the c-Hex phase from multiphase electrolyte solutions. This system has demonstrated both electrochemical solvating and carbon-carbon bond forming reactions. Hydrophobic substrates can be introduced into the reactor as c-Hex solutions, which are then electrochemically transformed into the target hydrophobic products that pass through the PTFE fiber as c-Hex solutions.     

Reductive coupling of N-methoxycarbonyl lactams with benzophenone and 9-fluorenone by low-valent titanium

The reductive coupling of N-methoxycarbonyl lactams with benzophenone by Zn-TiCl₄ in THF gave cross-coupled products as cyclic α-diphenylidene-N-methoxycarbonylamines and ring-opening α,α-diphenyl-α-hydroxy-ω-(N-methoxycarbonyl)amino ketones selectively depending on the reduction conditions. The reductive coupling of N-methoxycarbonyl lactams with 9-fluorenone by Zn-TiCl₄ gave cyclic α-(9H-fluoren-9-ylidene)-N-methoxycarbonylamines preferentially irrespective to the conditions.