Formation of toxic arsenical in roasted muscles of marine animals

Arsenobetaine, an organo‐arsenic compound known to be non‐toxic, occurs ubiquitously in marine animals. To elucidate the food hygiene safety of the degradation products of arsenobetaine formed on cooking, arsenicals generated by roasting the muscles of the starspotted shark Mustelus manazo and of the red crayfish Panulirus longipes femoristriga were investigated. ­As a result, both muscle types were found to contain the tetramethylarsonium ion, which is reported to show a higher acute toxicity than dimethylarsinic acid (cacodylic acid) or methanearsonic acid. As a minor compound, arsenate was also detected in the muscle of M. manazo. Copyright © 2001 John Wiley & Sons, Ltd.     

Effect of the melting system sizes on the temperature and concentration combined melting of a vertical ice plate in a rectangular cavity

This paper is concerned with the melting of a vertical ice plate into a calcium chloride aqueous solution inside a rectangular cavity. The initial temperature of the ice plate and the mixture are both −5°C and the initial concentration of the mixture is 20 wt%. The effect of the liquid height H, the width W, the aspect ratio of the liquid region A (=H/W) and the initial ice plate thickness δ _i on the transient melting mass per unit melting front area, M, is mainly considered numerically. M keeps a similar value in spite of H varied for A = 1 at early melting stage, however, becomes considerably influenced by H as melting progresses. The ice plate melts influenced by A for H = 20 mm fixed at early melting stage due to the fast development of the stagnant region and M decreases with increasing A (=1∼ 10). A dimensionless correlation of the transient melting mass, the aspect ratio and the melting time was presented under the restricted condition of H = 20 mm.     

Production of no-carrier-added 64Cu and applications to molecular imaging by PET and PETIS as a biomedical tracer

Copper-64 was produced by the ⁶⁴Ni(p, n)⁶⁴Cu reaction using enriched ⁶⁴NiO target. We investigated and compared the production yield of ⁶⁴Cu for proton beams of various energies by using a thick target. Enriched ⁶⁴Ni was recovered with high yield by simple procedures. Imaging studies using positron emission tomography (PET) and positron emitting tracer imaging system (PETIS) were performed. We obtained clear images in PET and PETIS studies. The results of this study indicate that ⁶⁴Cu can be utilized as a biomedical tracer for the molecular imaging both in animals and plants.     

Fluorescence probe for lysophospholipase C/NPP6 activity and a potent NPP6 inhibitor

Nucleotide pyrophosphatases/phosphodiesterases (NPPs) are ubiquitous membrane-associated or secreted ectoenzymes that have a role in regulating extracellular nucleotide and phospholipid metabolism. Among the members of the NPP family, NPP1 and -3 act on nucleotides such as ATP, while NPP2, -6, and -7 act on phospholipids such as lysophosphatidylcholine and sphingomyelin. NPP6, a recently characterized NPP family member, is a choline-specific glycerophosphodiester phosphodiesterase, but its functions remain to be analyzed, partly due to the lack of highly sensitive activity assay systems and practical inhibitors. Here we report synthesis of novel NPP6 fluorescence probes, TG-mPC and its analogues TG-mPC(3)C, TG-mPC(5)C, TG-mPENE, TG-mPEA, TG-mPhos, TG-mPA, TG-mPMe, and TG-mPPr. Among the seven NPPs, only NPP6 hydrolyzed TG-mPC, TG-mPC(3)C, and TG-mPENE. TG-mPC was hydrolyzed in the cell lysate from NPP6-transfected cells, but not control cells, showing that it is suitable for use in cell-based NPP6 assays. We also examined the usefulness of TG-mPC as a fluorescence imaging probe. We further applied TG-mPC to carry out high-throughput NPP6 inhibitor screening and found several NPP6-selective inhibitors in a library of about 80,000 compounds. Through structure-activity relationship (SAR) analysis, we identified a potent and selective NPP6 inhibitor with an IC(50) value of 0.21 μM. Our NPP6-selective fluorescence probe, TG-mPC, and the inhibitor are expected to be useful to elucidate the biological function of NPP6.     

Time-resolved long-lived luminescence imaging method employing luminescent lanthanide probes with a new microscopy system

Superior fluorescence imaging methods are needed for detailed studies on biological phenomena, and one approach that permits precise analyses is time-resolved fluorescence measurement, which offers a high signal-to-noise ratio. Herein, we describe a new fluorescence imaging system to visualize biomolecules within living biological samples by means of time-resolved, long-lived luminescence microscopy (TRLLM). In TRLLM, short-lived background fluorescence and scattered light are gated out, allowing the long-lived luminescence to be selectively imaged. Usual time-resolved fluorescence microscopy provides fluorescence images with nanosecond resolution and has been used to image interactions between proteins, protein phosphorylation, the local pH, the refractive index, ion or oxygen concentrations, etc. Luminescent lanthanide complexes (especially europium and terbium trivalent ions (Eu3+ and Tb3+)), in contrast, have long luminescence lifetimes on the order of milliseconds. We have designed and synthesized new luminescent Eu3+ complexes for TRLLM and also developed a new TRLLM system using a conventional fluorescence microscope with an image intensifier unit for gated signal acquisition and a xenon flash lamp as the excitation source. When the newly developed luminescent Eu3+ complexes were applied to living cells, clear fluorescence images were acquired with the TRLLM system, and short-lived fluorescence was completely excluded. By using Eu3+ and Tb3+ luminescent complexes in combination, time-resolved dual-color imaging was also possible. Furthermore, we monitored changes of intracellular ionic zinc (Zn2+) concentration by using a Zn2+-selective luminescent Eu3+ chemosensor, [Eu-7]. This new imaging technique should facilitate investigations of biological functions with fluorescence microscopy, complementing other fluorescence imaging methodologies.     

A Single Fluorescent Probe to Visualize Hydrogen Sulfide and Hydrogen Polysulfides with Different Fluorescence Signals

Hydrogen sulfide (H₂S) and hydrogen polysulfides (H₂S_n, n>1) are endogenous regulators of many physiological processes. In order to better understand the symbiotic relationship and cellular cross‐talk between H₂S and H₂S_n, it is highly desirable to develop single fluorescent probes which enable dual‐channel discrimination between H₂S and H₂S_n. Herein, we report the rational design, synthesis, and evaluation of the first dual‐detection fluorescent probe DDP‐1 that can visualize H₂S and H₂S_n with different fluorescence signals. The probe showed high selectivity and sensitivity to H₂S and H₂S_n in aqueous media and in cells.     

Chiral separation membranes from modified polysulfone having myrtenal-derived terpenoid side groups

Novel polymeric materials, having a chiral environment, were obtained by the reaction of lithiated polysulfone with chiral terpenoid myrtenal. The resulting polymers gave self-standing durable membranes. Molecularly imprinted membranes were prepared from the novel myrtenal-containing polysulfones by the presence of print molecules during the membrane preparation process. The d-isomer imprinted membrane showed d-isomer adsorption and diffusivity selectivity, and vice versa. As a result, the d-isomer imprinted membrane transported the d-isomer in preference to the l-isomer, and vice versa. The control non-imprinted membrane also showed permselectivity toward racemic glutamic acid mixtures. The expression of permselectivity for the molecularly imprinted membranes was synergistically due to adsorption and diffusivity selectivity.     

Zeolite Catalyzed Alkylation of Biphenyl. Where Does Shape-Selective Catalysis Occur?

Liquid-phase alkylation of biphenyl (BP) was studied over large-pore zeolites. Selective formation of the least bulky products, 4,4-diisopropylbiphenyl (4,4-DIPB) occurred only in the isopropylation of BP over one- or two-dimensional zeolites, H-mordenite (HM), ZSM-12, SSZ-24, SAPO-5, SSZ-31, and CIT-5. These shape-selective catalyses are ascribed to steric restriction of transition state and to easiness of the substrates to enter into the pores. HM gave the highest selectivity among them. The dealumination of HM enhanced catalytic activity and the selectivity for 4,4-DIPB because of the decrease of coke deposition. Non-regioselective catalysis occurs on external acid sites over HM with the low SiO₂/Al₂O₃ ratio because severe coke deposition deactivates the acid sites inside the pores by blocking pore openings. The selectivity of DIPB isomers was changed with propylene pressure and/or with reaction temperature. Selective formation of 4,4-DIPB was observed at moderate temperatures such as 250°C, whereas the decrease of the selectivity of 4,4-DIPB occurred at higher temperatures as 300°C. 4,4-DIPB yielded selectively under high propylene pressure (<0.3 MPa) at 250°C, while the selectivity of 4,4-DIPB decreased under low propylene pressure as 0.2 MPa. However, 4,4-DIPB was almost exclusive isomer in the encapsulated DIPB isomers inside the pores under every temperature and pressure. The decrease of the selectivity of 4,4-DIPB is due to the isomerization of 4,4-DIPB on the external acid sites. The deactivation of external acid sites of HM was examined by the modification with cerium and other rare earth metal oxide on HM. Selectivities of 4,4-DIPB were improved over modified HM even at high temperatures because of the suppression of non-regioselective alkylation and isomerization at the external acid sites. The ethylation of BP to ethylbiphenyls (EBPs) and diethylbiphenyls (DEBPs) was non-regioselective. The ethylation of BP to EBPs was controlled kinetically. However, there was difference in reactivities of EBPs and DEBPs for their further ethylation. 4-EBP was ethylated preferentially among the isomers, although the formation of 4,4-DEBP was less selective. 4-EBP and 4,4-DEBP have the highest reactivities among EBPs and DEBPs for the ethylation to polyethylbiphenyls (PEBPs). These results show that the environments of HM pores are too loose for shape-selective formation of the least bulky isomers, 4-EBP and 4,4-DEBP, in the ethylation of BP, and that HM pores have enough space for the further ethylation of 4,4-DEBP.     

Arsenobetaine-decomposing Ability of Marine Microorganisms Occurring in Particles Collected at Depths of 1100 and 3500 Meters

The arsenobetaine-decomposing ability of microorganisms occurring in sinking particles, which play a main role in the vertical transport of organic substances produced in the photic zone, was investigated. The microorganisms in particles collected in the deep sea, 1100 and 3500 m in depth, clearly showed decomposing ability. With the particles from 1100 m, the degradation products were the same as those produced by microorganisms occurring in sources in the photic zone, i.e. trimethylarsine oxide (TMAO), dimethylarsinic acid (DMA) and inorganic arsenic(V). At 3500 m, the degradation activity was diminished, smalls amount of DMA and TMAO being produced. These results suggest that arsenobetaine contained in the animals starts to degrade immediately after the death of the animals and their transformation to particles. The degradation of arsenobetaine to inorganic arsenic in our tentative arsenic cycle in marine ecosystems (inorganic arsenic to inorganic arsenic via the biosynthesis of arsenobetaine) may apply to the deep sea as well as to the photic zone. © 1997 by John Wiley & Sons, Ltd.     

Chosen ciphertext secure keyed-homomorphic public-key cryptosystems

In homomorphic encryption schemes, anyone can perform homomorphic operations, and therefore, it is difficult to manage when, where and by whom they are performed. In addition, the property that anyone can “freely” perform the operation inevitably means that ciphertexts are malleable, and it is well-known that adaptive chosen ciphertext (CCA) security and the homomorphic property can never be achieved simultaneously. In this paper, we show that CCA security and the homomorphic property can be simultaneously handled in situations that the user(s) who can perform homomorphic operations on encrypted data should be controlled/limited, and propose a new concept of homomorphic public-key encryption, which we call keyed-homomorphic public-key encryption (KH-PKE). By introducing a secret key for homomorphic operations, we can control who is allowed to perform the homomorphic operation. To construct KH-PKE schemes, we introduce a new concept, transitional universal property, and present a practical KH-PKE scheme with multiplicative homomorphic operations from the decisional Diffie-Hellman (DDH) assumption. For \(\ell \)-bit security, our DDH-based KH-PKE scheme yields only \(\ell \)-bit longer ciphertext size than that of the Cramer–Shoup PKE scheme. Finally, we consider an identity-based analogue of KH-PKE, called keyed-homomorphic identity-based encryption and give its concrete construction from the Gentry IBE scheme.