High-Throughput Analysis of Bacterial Toxic Lipopolysaccharide in Water by Dual-Wavelength Monitoring Using a Ratiometric Fluorescent Chemosensor.

Lipopolysaccharide (LPS) is a bacterial toxin that causes fever in humans. Our small-molecule chemosensor named Zn-dpa-C2OPy shows rapid ratiometric fluorescence response to LPS in water with a detection limit of 11 pM, which is lower than that of our previously reported sensor. Spectroscopic measurements (fluorescence, absorbance, 1H NMR, and fluorescence lifetime), dynamic light scattering measurements, and transmission electron microscopy observations revealed that the fluorescence response was induced by the changes in the aggregation state via multi-point recognition of LPS through hydrophobic and electrostatic interactions, in addition to the coordination between the zinc(II)-dipicolylamine moiety of the chemosensor and the phosphate group of LPS. The proposed Zn-dpa-C2OPy chemosensor was applied to an original flow injection analysis (FIA) system with a self-developed dual-wavelength fluorophotometer, and a high throughput of 36 samples per hour was achieved. These results demonstrate the feasibility of this unique methodology combining a ratiometric fluorescent chemosensor and FIA for continuous online monitoring of LPS in water.

Electrochemical detection of boric acid using gallacetophenonato-(ß-diketonato) ruthenium complex in water.

A simple and practical method for boron detection in water is desired in various fields such as seawater desalination, water conservation, and plant production. To develop a method for detecting boron as boric acid in water, we synthesized [Ru(acac)2(H2thap)] (acac = acetylacetonat ion, thap = 2',3',4'-trihydroxyacetophenonate (gallacetophenonate) ion) possessing a cis-diol moiety that interacts with boric acid. A comparison of UV-visible (UV-vis) absorption spectra measured in the presence and absence of boric acid at various pH values revealed that [Ru(acac)2(H2thap)] shows the highest response to boric acid at pH 8.5. Cyclic voltammograms (CVs) and differential pulse voltammograms (DPVs) of [Ru(acac)2(H2thap)] aqueous solution at pH 8.5 with varying boric acid concentrations showed a decrease in the peak current value at 0.032 V (vs. Ag|AgClaq.) and an increase in the peak current value at 0.444 V with increasing boric acid concentration. On the basis of the relationship between the ratio of current values (at 0.032 V and 0.444 V) and boric acid concentrations, the binding constant (assuming a 1:1 binding model) for the interaction between [Ru(acac)2(H2thap)] and boric acid was estimated to be 135.1 ± 9.1 mol-1 dm3, and the Limit of Detection (LOD) was calculated to be 1.03 mg B L-1.

Simple and Rapid Endotoxin Recognition Using a Dipicolylamine-Modified Fluorescent Probe with Picomolar-Order Sensitivity.

Endotoxin is a lipopolysaccharide (LPS) that is found in the outer membrane of the cell wall of Gram-negative bacteria. Due to its high toxicity, the allowable endotoxin limit for water for injection is set at a very low value. Conventional methods for endotoxin detection are time-consuming and expensive and have low reproducibility. A previous study has shown that dipicolylamine (dpa)-modified pyrene-based probes exhibit fluorescence enhancement in response to LPS; however, the application of such probes to the sensing of LPS is not discussed. Against this backdrop, we have developed a simple and rapid endotoxin detection method using a dpa-modified pyrenyl probe having a zinc(II) center (Zn-dpa-C4Py). When LPS was added into Zn-dpa-C4Py solution, excimer emission of the pyrene moiety emerged at 470 nm. This probe can detect picomolar concentrations of LPS (limit of detection = 41 pM). The high sensitivity of the probe is ascribed to the electrostatic and hydrophobic interactions between the probe and LPS, which result in the dimer formation of the pyrene moieties. We also found that Zn-dpa-C4Py has the highest selectivity for LPS compared with other phosphate derivatives, which is probably caused by the co-aggregation of the probe with LPS. We propose that Zn-dpa-C4Py is a promising chemical sensor for the detection of endotoxin in medical and pharmaceutical applications.

Cyclization of Hindered Fluorinated Dichloro(5- and 6-)alkenyl Radicals. Structural Effects of Olefins on the Selective Formation of 5-exo and 6-endo Cyclization Products.

Reaction of 3-butenyl radicals generated by photolysis of variously substituted Barton esters (both open-chain 1a-d and cyclohexyl 1e-h) with CF(2)=CCl(2) gave a mixture of cyclized products (cyclopentanes 6 and 8 and cyclohexanes 7 and 9) as well as noncyclized products (4and 5) in various ratios depending on the substitution pattern at the olefinic moiety. The product ratios of [cyclization (6 + 7 + 8 + 9):noncyclization (5)] for 1 with more alkyl substituents on the CC double bond were greater than those for 1 with fewer substituents. The products ratio of [5-exo (6 + 8):6-endo (7 + 9)] was influenced by a steric effect. Photoreaction of Barton ester 2 with CF(2)=CCl(2) gave a mixture of cyclohexanes 16 and 17 as well as noncyclized 14 and 15. Dehydrochlorination of decalins 7g and 7h followed by oxidation of sulfide and [2,3]sigmatropic rearrangement of the allyl sulfoxide gave octahydronaphthalenones 23 and 27, respectively.

[Consideration concerning a care orientated medicine for the patient with terminal stage of cancer].

Home care medicine plays an important role in the care of terminal patients with redundant diseases such as cancer. In this study, we propose a "simple-style medicine" consisting in the participation of both medical and co-medical staffs and the use of Kampo medicine. This system satisfied various and individual requests from terminal patients. We present 2 terminal patients for whom this "simple-style", home care-orientated medicine was effective. This system can contribute to the quality of life of patients who need palliative, home care medicine.