Cyclodextrin polymers as highly effective adsorbents for removal and recovery of polychlorobiphenyl (PCB) contaminants in insulating oil.

A total of 179 countries (parties) ratified the Stockholm Convention on persistent organic pollutants (POPs) and agreed to destroy polychlorobiphenyls (PCBs) and develop a sound management plan by 2028. Currently, still 3 million tons of PCB-contaminated oil and equipment need to be managed under the Stockholm Convention. Thus, the development of a facile and environmentally benign method to treat large amounts of oil stockpiles contaminated with PCBs is a crucial subject. Herein, we report that cyclodextrin (CD) polymers, which are easily prepared by cross-linking the renewable cyclic oligosaccharide γ-cyclodextrin (γ-CD) with dibasic acid dichlorides, are a new selective and powerful adsorbent to remove PCB contaminants in oil. When PCB (100 ppm)-contaminated oil was passed through a column packed with the terephthaloyl-cross-linked γ-CD polymer (TP-γ-CD polymer) at 80-110 °C, the PCB contaminants were completely removed from the oil. Additionally, methyl esterification of the free carboxylic groups of the TP-γ-CD polymer enabled the complete recovery of the PCBs adsorbed on the polymer (with >99.9% recovery efficiency) by simply washing with acetone. The methyl-esterified TP-γ-CD polymer could be recycled at least 10 times for PCB adsorption without any loss in the adsorption capability. These results revealed that the γ-CD polymers can function as highly effective and powerful adsorbents for the removal and recovery of PCBs from PCB-contaminated oil and, thus, significantly contribute to the protection of the global environment.

6-O-Modified beta-cyclodextrin enabling inclusion complex formation in nonpolar media.

Heptakis(6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (TBDMS-beta-CD) effectively forms inclusion complexes with chlorinated benzenes in nonpolar solvents such as benzene-d(6) and cyclohexane-d(12). The inclusion selectivity toward 1,2- and 1,3-dichlorobenzenes can be switched by changing the solvent from benzene-d(6) to cyclohexane-d(12). Moreover, 1,2,4-trichlorobenzene (90 ppm) is perfectly removed from insulating oil by using TBDMS-beta-CD as an adsorbent.

Unique organogel formation with a channel-type cyclodextrin assembly.

A channel-type assembly of gamma-cyclodextrin (gamma-CD(channel)) forms organogels in a variety of oils and organic solvents at ambient temperature through the construction of a three-dimensional network of micrometer-sized cubic particles composed of gamma-CD(channel).

Complete removal of chlorinated aromatic compounds from oils by channel-type gamma-cyclodextrin assembly.

This paper describes the complete removal of chlorinated aromatic compounds from insulating oil by a channel-type gamma-cyclodextrin (gamma-CD) assembly as a new adsorbent. Using this type of adsorbent (50-60 wt % of oil), 1,2,4- and 1,3,5-trichlorobenzenes, 2- and 4-chlorobiphenyls (2- and 4-MCBs), 4,4'-dichlorobiphenyl (4,4'-DiCB), and 3,4,4'-trichlorobiphenyl (3,4,4'-TrCB), whose initial concentrations were 100 ppm, were completely removed from the insulating oil. Competitive adsorption experiments using a mixture of 2-MCB and 4-MCB or a mixture of 4-MCB, 4,4'-DiCB, and 3,4,4'-TrCB revealed that selective adsorption based on the shape and size of the chlorinated aromatics was achieved by the channel-type gamma-CD assembly, implying that inclusion into the cavity of the channel-type gamma-CD was responsible for the removal of chlorinated aromatics from insulating oil. It was also found that more than 70% of adsorbed chlorinated aromatics was easily recovered from the channel-type gamma-CD by simply washing with n-hexane, and chlorinated aromatics were completely removed from the insulating oil even by the regenerated adsorbent, indicating that the gamma-CD assembly can be easily regenerated and recycled.

Novel metabolism of nitrogen in plants.

Our previous study showed that approximately one-third of the nitrogen of 15N-labeled NO2 taken up into plants was converted to a previously unknown organic nitrogen (hereafter designated UN) that was not recoverable by the Kjeldahl method (Morikawa et al., 2004). In this communication, we discuss metabolic and physiological relevance of the UN based on our newest experimental results. All of the 12 plant species were found to form UN derived from NO2 (about 10-30% of the total nitrogen derived from NO2). The UN was formed also from nitrate nitrogen in various plant species. Thus, UN is a common metabolite in plants. The amount of UN derived from NO2 was greatly increased in the transgenic tobacco clone 271 (Vaucheret et al., 1992) where the activity of nitrite reductase is suppressed less than 5% of that of the wild-type plant. On the other hand, the amount of this UN was significantly decreased by the overexpression of S-nitrosoglutathione reductase (GSNOR). These findings strongly suggest that nitrite and other reactive nitrogen species are involved in the formation of the UN, and that the UN-bearing compounds are metabolizable. A metabolic scheme for the formation of UN-bearing compounds was proposed, in which nitric oxide and peroxynitrite derived from NO2 or endogenous nitrogen oxides are involved for nitrosation and/or nitration of organic compounds in the cells to form nitroso and nitro compounds, including N-nitroso and S-nitroso ones. Participation of non-symbiotic haemoglobin bearing peroxidase-like activity (Sakamoto et al., 2004) and GSNOR (Sakamoto et al., 2002) in the metabolism of the UN was discussed. The UN-bearing compounds identified to date in the extracts of the leaves of Arabidopsis thaliana fumigated with NO2 include a delta2-1,2,3-thiadiazoline derivative (Miyawaki et al., 2004) and 4-nitro-beta-carotene.

Attempted reduction of 1,2,3-thiadiazole-4-carboxylates with samarium/iodine in methanol. Unexpected ring enlargement to 1,2,5-trithiepan-4,6-dicarboxylates.

When stirred with powdered samarium and iodine in methanol at ice-cold temperature, ethyl 1,2,3-thiadiazole-4-carboxylate 5 underwent unusual reduction involving the dimeric ring enlargement with a sulfur addition, giving dimethyl 1,2,5-trithiepan-4,6-dicarboxylates 7a,b as a cis/trans-isomeric mixture in acceptable yield. The 1,2,3-thiadiazole ring of 5 proved to resist reduction by ordinary reducing agents, where the only choice in most cases was either recovery of the unchanged substrate or decomposition to an intractable mixture of unidentified products and tar.