Retro‐ene reactions in heterocyclic synthesis. v. a novel synthetic method for 1,3,5‐triazine‐2,4(1H,3H)‐diones

N‐t‐Butylamidines 1 on heating with diphenyl carbonate ( 2 ) at 150‐180° gave the 1,3,5‐triazine‐2,4(1H,3H)‐dione derivatives 5 . Acylation of amidines 1 and cyclocondensation of the resulting carbamates 3 gave [1,3,5,7]tetrazocine‐2,6‐dione derivatives 4 , and subsequent retro‐ene reaction and ring contraction afforded triazine derivatives 5 .     

Helical assembly of azobenzene-conjugated carbohydrate hydrogelators with specific affinity for lectins

Carbohydrate-mediated interactions are involved in various biological processes via specific molecular assembly and recognition. Such interactions are enhanced by multivalent effects of the sugar moieties, and thus supramolecular sugar-assembly, i.e., spontaneous association of glycoamphiphiles, is a promising approach to tailor glycocluster formation. In this study, novel sugar-decorated nanofibers were successfully prepared by self-assembly of low molecular weight hydrogelators composed of azobenzene and disaccharide lactones. Circular dichroism measurement of the as-prepared hydrogels indicated that the azobenzene amphiphile containing a lactose moiety possessed (R)-chirality, while the maltose-azobenzene conjugate exhibited (S)-chirality, even though the cellobiose-conjugated azobenzene existed in an achiral form. This suggests that the chiral orientation of the chromophoric azobenzene depended on both the glycosidic linkages and the steric arrangement of hydroxyl groups in the conjugated carbohydrates. Lectin-binding and cell adhesion assays revealed that the nonreducing ends of the conjugated sugar moieties were exposed on the surfaces of self-assembled nanofibrous hydrogels, allowing them to be effectively recognized by the corresponding lectins. In addition, photoisomerization of azobenzene under ultraviolet irradiation induced the sol-gel transitions of the hydrogels. These results demonstrate that the reversibly transformed fibrous glycohydrogels show potential for application as carbohydrate-decorated scaffolds for cell culture engineering.     

Two-dimensional Si photonic crystals on oxide using SOI substrate

Two-dimensional photonic crystals (2D-PhCs) on oxide can be easily incorporated into photonic integrated circuits. Although an asymmetrical structure (air/PhC/oxide) is advantageous in terms of ease of fabrication, it has been pointed out that such a structure may have no photonic band gap (PBG). To clarify the characteristics of the asymmetrical structure, we calculated the band structure using the three-dimensional (3D) FDTD method and measured the transmission characteristics of a fabricated 2D Si-PhC on oxide. The calculations show that we can use a quasi-PBG even in an asymmetrical structure when the PhC thickness satisfies the single-mode condition. The measured transmission characteristics correspond to the calculated band structure and reveal the existence of a quasi-PBG. These results show that the asymmetrical 2D Si-PhC-on-oxide structure can be applied to various optical devices.     

Linkage Determination of Linear Oligosaccharides by MSn (n > 2) Collision-Induced Dissociation of Z1 Ions in the Negative Ion Mode

Obtaining unambiguous linkage information between sugars in oligosaccharides is an important step in their detailed structural analysis. An approach is described that provides greater confidence in linkage determination for linear oligosaccharides based on multiple-stage tandem mass spectrometry (MSⁿ, n >2) and collision-induced dissociation (CID) of Z₁ ions in the negative ion mode. Under low energy CID conditions, disaccharides ¹⁸O-labeled on the reducing carbonyl group gave rise to Z₁ product ions (m/z 163) derived from the reducing sugar, which could be mass-discriminated from other possible structural isomers having m/z 161. MS³ CID of these m/z 163 ions showed distinct fragmentation fingerprints corresponding to the linkage types and largely unaffected by sugar unit identities or their anomeric configurations. This unique property allowed standard CID spectra of Z₁ ions to be generated from a small set of disaccharide samples that were representative of many other possible isomeric structures. With the use of MSⁿ CID (n = 3 – 5), model linear oligosaccharides were dissociated into overlapping disaccharide structures, which were subsequently fragmented to form their corresponding Z₁ ions. CID data of these Z₁ ions were collected and compared with the standard database of Z₁ ion CID using spectra similarity scores for linkage determination. As the proof-of-principle tests demonstrated, we achieved correct determination of individual linkage types along with their locations within two trisaccharides and a pentasaccharide.

Influence of oxygen plasma treatment on boron carbon nitride film composition

Variations in the composition and bonds of boron carbon nitride (BCN) film caused due to an oxygen (O₂) plasma ashing process are investigated for a low dielectric constant (low-k) insulating film for next generation LSI devices. The O₂ plasma treatment is preformed for BCN samples with various C compositions. The etching rate of BCN films with an O₂ plasma decreases with increasing C composition. The reaction of O atoms is suppressed in the BCN film with a high C composition. B-N and B-C bonds with lower bond energies are easily broken by the O₂ plasma and replaced by the generation of B-O, N-O, and C-O bonds. The B-atom concentration for all samples is decreased significantly by the O₂ plasma treatment. Ion bombardment may play a more dominant role than the O-atom reaction in the etching of the BCN film. The existence of C-N bonds with a high bonding energy may suppress etching and incorporation of O atoms.     

Performance improvement of Viterbi decoding for FM recording code

In high-density recording, the performance of the conventional Viterbi decoder for FM recording code is degraded by the influence of the correlation between samples of the noise at the discrimination point. A decoding method is therefore proposed which uses a Viterbi decoder whose form assumes a simple Markov process for the noise at the discrimination point. The error probability of this method is obtained by computer simulation and the performance is compared with that of a conventional decoder. The results show that a large improvement in performance is achieved     

Self-assembling monolayer formation of glucose oxidase covalently attached on 11-aminoundecanethiol monolayers on gold

Glucose oxidase (GOx) has been attached covalently to form uniform enzyme monolayers on self-assembled monolayers (SAMs) from 11-aminoundecanethiol (AUDT) by taking advantage of chemical oxidation of GOx carbohydrate residues followed by coupling the resulting 'aldehydic' enzyme with the terminal amino group in the SAM as characterized by AFM imaging, IR, QCM, and electrochemical measurements.     

Photometric reagents based on crown ether complex formation. VII

Summary Two new chromogenic crown reagents, 22-Kosh and 21-Kosh, have been synthesized by the condensation of Cryptand-22 and -21, respectively, with 2-hydroxy-5-nitrobenzyl bromide. Extraction of alkaline-earth metal ions with a dichloroethane solution of 22-Kosh or 21-Kosh has been investigated and their extraction coefficients have been evaluated. The relative ease of extraction is MgBa4 l·mole^–1·cm^–1 at 406 nm.

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Auf Kronenetherkomplexbindung basierende photometrische Reagenzien. VIIPhotometrische Bestimmung von Calcium in biologischem Material mit N,N-bis(2-hydroxy-5-nitrobenzyl)-1,10-diaza-4,7,13,16-tetraoxacyklooctadecan

Zusammenfassung Zwei neue chromogene Kronenetherreagenzien, 22-Kosh und 21-Kosh wurden durch Kondensation von Cryptand-22 bzw. -21 mit 2-Hydroxy-5-nitrobenzylbromid synthetisiert. Die Extraktion der Erdalkalimetallionen mit einer Dichlorethanlösung von 22-Kosh oder 21-Kosh wurde untersucht und ihre Extraktionskonstanten wurden bestimmt. Für die Leichtigkeit der Extrahierbarkeit mit den beiden Reagenzien ergibt sich folgende Reihenfolge: MgBa4 bei 406 nm.

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Part VI: M. Takagi, H. Nakamura, Y. Sanui, and K. Ueno, Analyt. Chim. Acta, in the press.

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Presented at the 8th International Microchemical Symposium; Graz, August 25–30, 1980.     

POSSIBLE ROLE OF METALLOTHIONEIN IN THE CELLULARDEFENSE MECHANISM AGAINST UVB IRRADIATION IN NEONATAL HUMAN SKIN FIBROBLASTS

Abstract –The role of metallothionein (MT) in protecting skin cells against UVB irradiation was investigated. Fibroblast strains from normal adult (HS-K) and neonatal (NB1RGB) human skins as well as keratinocyte strains from human skin (SV40-HSK) and newborn Balb/c mouse skin (Pam 212) were exposed to UVB irradiation.
The sensitivity of HS-K and NB1RGB cells to UVB irradiation was similar; those of SV40-HSK and Pam 212 cells were two- and six-fold as sensitive to UVB irradiation as HS-K cells, respectively. The HS-K cells contained the greatest cellular reduced form of glutathione (GSH) levels compared to the three other skin cells: the levels were 13-, 7- and 6-fold of those in NB1RGB, SV40-HSK and Pam 212 cells, respectively. These results indicated that the sensitivity of skin cells to UVB irradiation was not always associated with their endogenous GSH levels. In particular, despite the fact that NB1 RGB cells contained a relatively small amount of GSH, they were less sensitive to UVB irradiation.
NB1RGB cells contained 4–30 times more MT than those in other skin cells examined. The sulfhydryl residues of MT molecules in the NB1RGB cells were estimated to be mostly unoccupied by metals, suggesting they act in a similar way to those of GSH. Moreover, NB1RGB cells in which the MT content was elevated by dexamethasone (1 μg/mL ) or Zn²⁺ (7 μg/mL) treatment were more resistant to UVB irradiation than nontreated ones.
These results suggest that, at least in neonatal human skin fibroblasts, MT may play a role in protection against UVB irradiation.