Far‐ and Deep‐Ultraviolet Surface Plasmon Resonance Sensor

Plasmonics in the UV region has been widely focused because of the higher energy and the abundant electronic resonances compared to the conventional visible plasmonics. Recently, we have investigated the surface plasmon resonance (SPR) properties of the Al film, aiming for the application as refractive index sensors. Utilizing the UV lights, we expect three advantages: high sensitivity, material selectivity, and surface selectivity. By using an original attenuated total reflectance spectroscopic instrument, Al‐SPR angle and wavelength were investigated with changing environments on the Al film. Al film thickness and materials of prisms on which Al was evaporated were also important factors for the SPR properties. By optimizing the conditions, the Al film worked as a sensor both in air and in liquids. In addition, our established system expands the plasmonics into an even higher energy region than 200 nm, while the UV‐plasmonics have been studied in the wavelength region longer than 200 nm.     

Conversion of ammonia to dinitrogen in wastewater by Nitrosomonas europaea

Because Nitrosomonas europaea contains ammonia-oxidizing enzyme, nitrite reductase, and nitrous oxide reductase, the conversion of ammonia to dinitrogen was tried with different reaction conditions. In aerobic reaction conditions, ammonium was converted to nitrite (NO ₂ ⁻ ), while under oxygen-limiting or oxygen-free conditions, NO ₂ ⁻ -N formed from ammonia oxidation by N. europaea was reduced to N₂O and dinitrogen with 22% conversion. During denitrification, optimal pH for the production of N₂O and dinitrogen was found to be 7.0–8.0. Dinitrogen was not produced in acidic pH<7.0. A low partial oxygen pressure as well as oxygen-free conditions are favorable for high production of dinitrogen.     

Syntheses of amphiphilic block copolymers by living cationic polymerization of vinyl ethers and their selective solvent‐induced physical gelation

Amphiphilic diblock copolymers were prepared by the living cationic polymerization of vinyl ethers in the presence of added bases, and their selective solvent‐induced physical gelation behavior was investigated. The block copolymerization of 2‐phenoxyethyl vinyl ether (PhOVE) and 2‐methoxyethyl vinyl ether (MOVE) was carried out in the presence of ethyl acetate with Et_1.5AlCl_1.5 in toluene at 0 °C. Despite the rate difference, diblock copolymers with a very narrow molecular weight distribution were obtained, quantitatively. By adding the selective solvent, water, to the acetone solution of the diblock copolymer, PhOVE₂₀₀‐b‐MOVE₄₀₀, physical gelation occurred suddenly and the system ceased to flow, maintaining transparency. Viscoelastic measurements and transmission electron microscopic observations were performed to examine the characteristic gelation behavior and structure of the obtained gels. Various gelation conditions and physical gelation by other amphiphilic block copolymers were also designed on the basis of the solubility of each block segment. Further, new forms of physical gelation, accompanied by the solubilization of immiscible organic compounds, were achieved using similar diblock copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3190–3197, 2001     

Angioarchitecture of tumors induced by two different cloned cell lines established from a transplantable rat malignant fibrous histiocytoma.

Angiogenesis, a biologic process whereby endothelial cells divide and migrate to form new blood vessels, is a key step in tumor growth, invasion, and metastasis. In the present study, we investigated the differences in angioarchitecture between two different tumors induced by cloned cell lines (MT-8 and MT-9), derived from a transplantable rat malignant fibrous histiocytoma, by scanning electron microscopy of vascular corrosion casts. During a 3-week observation period after implantation, the growth of MT-8 tumors appeared to be faster than that of MT-9 tumors. Histologically, MT-8 tumors were of the uniformly undifferentiated sarcoma type arranged in characteristic organoid structures, and MT-9 tumors showed a storiform growth pattern. In MT-8 tumors, neovascularization occurred by sprouting at postimplantation (PI) week 1, and the newly formed capillaries gradually became more tortuous. In MT-9 tumors, at PI week 1, the corrosion casts of newly formed capillaries mainly showed a wavy course but no finger-like outgrowths of capillaries were seen. At PI weeks 2 and 3, the sprouting was seen specifically in MT-9 tumors, forming basket-like structures and glomeruloid structures of capillaries. These results indicate that angiogenesis or angioarchitecture of MT-8 tumors is different from that of MT-9 tumors, depending on the differences in their tumor histology and by the features like absence or presence of basket-like structures and glomeruloid structures of capillaries.     

[2.2.2.2](2,7)‐1‐Bromonaphthalenophane from a Desymmetrized Building Block Bearing Electrophilic and Masked Nucleophilic Functionalities

In search of 2,7‐ethylene‐bridged naphthalenophanes with desymmetrized naphthalene cores as inherently chiral cyclophanes, nucleophilic substitution of 1‐bromo‐7‐(bromomethyl)‐2‐[(trimethylsilyl)methyl]naphthalene, a desymmetrized building block bearing an electrophilic group (CH₂Br) and a masked nucleophilic functionality (CH₂TMS) which can be activated by fluoride anion, was examined. As a result, in contrast to the case of parent naphthalenophanes wherein the smallest [2.2]naphthalenophane was obtained as the major product, only [2.2.2.2](2,7)‐1‐bromonaphthalenophane was obtained albeit in low yields, whereas the corresponding [2.2]‐ or [2.2.2]naphthalenophanes were not obtained. Though the [2.2.2.2]‐1‐bromonaphthalenophane can adopt four idealized geometries of different symmetry, among which three are inherently chiral, theoretical calculations predict that three conformers have almost equal energy and may equilibrate in solution. The X‐ray crystallographic study shows that it adopts a C₂ conformation with anti,anti,anti orientation of the C?Br bonds at least as a major component in crystal.     

Antiadhesive Nanosomes Facilitate Targeting of the Lysosomal GlcNAc Salvage Pathway through Derailed Cancer Endocytosis

Activated endocytosis of extracellular macromolecules and their intracellular trafficking to lysosomes is an essential metabolic mechanism in cancer cells during their rapid proliferation. Cancer cells reuse a vast amount of N‐acetylglucosamine (GlcNAc) supplied from the GlcNAc salvage pathway for the accelerated synthesis of a pivotal uridine diphosphate (UDP)‐GlcNAc. A method to inactivate key glycosidases in lysosomes could critically contribute to the development of potent anticancer therapy. Here we demonstrate that “nanosomes” made of core metals covered by an antiadhesive mixed self‐assembled monolayer allow for avoiding nonspecific surface protein corona and targeted molecular delivery through activated endocytosis. Nanosomes carrying suicide substrates showed that lysosomal glycosidases such as β‐hexosaminidase and β‐galactosidase in cancer cells are promising targets for novel anticancer therapeutic nanomedicine that induce apoptotic cell death through lysosomal membrane permeabilization. The advantage of this method is evident because multivalent surface loading by antiadhesive nanosomes makes it possible to highlight “weak interactions” such as carbohydrate–lectin interactions independent of surface protein corona.