Uptake and excretion of total inorganic arsenic by the freshwater alga Chlorella vulgaris

Arsenic-tolerant freshwater alga Chlorella vulgaris which had been collected from an arsenicpolluted environment were tested for uptake and excretion of inorganic arsenic. Approximately half the quantity of arsenic taken up by C. vulgaris was estimated to be adhered to the extraneous coat (10 wt %) of the cell. The remainder was bioaccumulated by the cell. Both adhered and accumulated arsenic concentrations increased with an increase in arsenic(V) concentration of the aqueous phase. Arsenic(V) accumulation was affected by the growth phse: arsenic was most actively accumulated when the cell was exposed to arsenic during the early exponential phase and then accumulation decreased with an increase in culture time exposed to arsenic. The alga grew well in the modified Detmer (MD) medium containing 1 mg As(III) dm^?3 and the growth curve was approximated by a ‘logistic equation’. Arsenic(III) was accumulated up to the second day of the culture time and arsenic(III) accumulation decreased with an increase in the culture time after that. Arsenic accumulation was also largely affected by various nutrients, especially by managanese, iron and phosphorus compounds. A modified MD medium with the three nutrients was proposed for the purpose of effective removal of arsenic from the aqueous phase. Using radioactive arsenate (Na₂H⁷⁴AsO₄), the arsenic accumulated was found to be readily excreted under conditions which were unfavourable for the multiplication of C. vulgaris.     

Conformational effects on lipase-mediated acylations of 2-substituted cyclohexanols

Lipase-mediated acetylations of trans- and cis-2-substituted cyclohexanols gave the corresponding (1R)-cyclohexyl acetates and (1S)-cyclohexanols in high yields and ee, but c-4-tert-butyl-c-2-ethenyl-r-1-cyclohexanol was unreactive owing to the steric interaction between the axial OH group and the axial H atoms at the 3- and 5-positions. In the cis-isomer the OH group occupies an equatorial position to bind to the lipase, and less bulky axial alkenyl and alkynyl groups might not so much prevent acetylations than an alkyl group.     

Lead-selective poly(vinyl chloride) membrane electrodes based on acyclic dibenzopolyether diamides

Lipophilic acyclic dibenzopolyether diamides, 12 kinds, have been designed to prepare solvent polymeric membrane ion-selective electrodes (ISEs) for Pb(2+). The ionophores include 1,5-bis[2-(N,N-dialkylcarbamoylmethoxy)phenoxy]-3-oxapentanes1-4, 1,5-bis[2-(N,N-dialkylcarbamoylpentadecyloxy)phenoxy]-3-oxapentanes 5-8, and 1,2-bis[2-(2'-N,N-dialkylcarbamoylpentadecyloxy)phenoxy]ethanes 9-12. Linear response concentration range of the ISE based on 9 is 3 x 10(-2) - 1 x 10(-6) M of Pb(2+) (average slope = 28.5 mV decade(-1)). Potentiometric selectivities of the ISEs based on 1-12 for Pb(2+) over other heavy metal cations, alkali metal cations, and alkaline earth metal cations have been assessed. These ISEs exhibit remarkably high selectivities for Pb(2+) relative to heavy metal cations, such as Cu(2+), Fe(2+), and Ni(2+), the selectivity coefficients (K(Pot)(Pb,Cu)) being 5 x 10(-5) - 6 x 10(-5) for 1-4 and ca. 6 x 10(-4) for 9. For the Pb(2+) selectivities over alkali metal cations, such as Na(+) and K(+), 9 which has an ethylene glycol spacer and a N,N-diethyl group is superior to other dibenzopolyether diamide ionophores 1-8 and 10-12.     

[2]Paracyclo[2](3,7)-p-tropoquinonophane

The title compound $\text{1}$ a novel cyclophane containing p-tropoquinone, was synthesized starting from 5-methoxytropolone and its physical properties were discussed comparing with those of 3,7-dimethyl-p-tropoquinone and p-benzoquinonophane. The reduced quinone character exhibited by $\text{1}$ was ascribed to the intramolecular CT interaction and the deformation of the quinone ring.     

Studies on palytoxins

The complete structure of palytoxin (1) was elucidated by us in 1982.¹ Our continuous interests in palytoxin led us to examine minor constituents of Okinawan Palythoa tuberculosa. In this paper, we describe successful isolation and structural elucidation of four minor toxins, which were named homopalytoxin (2), bishomopalytoxin (3), neopalytoxin (4) and deoxypalytoxin (5).     

Synthesis, structure, and physical properties of 1,11-o-benzeno[2]orthocyclo[2](1,2)tropyliophane

The title compound (2) has been synthesized, the structure and the physical properties of which are investigated by X-ray, spectroscopic analyses, and MO calculations. There exists charge transfer (CT) interaction between the tropylium ion and the facing phenyl ring. From the pK_R⁺ value of 2, it can be clear that the cation 2 is stabilized by the CT interaction. In spite of the presence of bond weakening σ-π orbital mixing, the cation 2 withstands retro[4+4]type bond cleavage, which is quite interesting when compared to a facile cleavage for the congener with anthracene photodimer type structure.     

Anodic cyanation of 1-methylpyrazole

The electrooxidation of 1-methylpyrazole in methanol containing sodium cyanide produced 1-methyl-pyrazole-4-carbonitrile 2 and ?5-carbonitrile 3 in yields of 23 and 8%, respectively (2e-oxidation products), together with 4-methoxy-1-methylpyrazole-5-carbonitrile 4 (4e-oxidation product, 4%).     

Gas chromatographic-mass spectrometric profile of organic acids in urine and serum of diabetic ketotic patients

The organic acids in the urine and serum of diabetic patients with ketoacidosis and disturbance of consciousness were studied using acidification, extraction, evaporation, methoxime formation and trimethylsilylation, gas chromatographic separation and mass spectrometric identification procedures. The organic acid profile of 1 ml of serum ultrafiltrate was obtained with good separation using a gas chromatograph equipped with a glass capillary column and a splitless injector. 5-Hydroxyhexanoic acid and 3-hydroxyvaleric acid were identified for the first time in the urine of diabetic patients with ketoacidosis. Urinary excretion and serum concentrations of 2,3-dideoxypentonic acid were increased in diabetic patients.     

Effect of HF addition on the microwave-assisted acid-digestion for the determination of metals in coal by inductively coupled plasma-atomic emission spectrometry

The microwave-assisted acid-digestion for the determination of metals in coal by ICP-AES was investigated, especially focusing on the necessity of adding HF. By testing five certified reference materials, BCR-180, BCR-040, NIST-1632b, NIST-1632c, and SARM-20, it was found that the two-stage digestion without HF (HNO₃ + H₂O₂ was used) was very effective for the pretreatment of ICP-AES measurement. Both major metals (Al, Ca, Fe, and Mg) and minor or trace metals (Co, Cr, Cu, Mn, Ni, Pb, and Zn) in coal gave good recoveries for their certified or reference values. The possibility of ‘HF-memory effect’ was cancelled by the use of a set of vessels which had been never contacted with HF. Twenty-four Japanese standard coals (SS coals) were analyzed by the present method, and the concentrations of major metals measured by the present method provided very high accordance with those from the authentic JIS (Japanese Industrial Standard) method.