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Biomedical subjects

T Korenaga

Publications and source records attributed to T Korenaga.

At least 19 recordsLinked to original sources

General synthetic route to chiral flexible biphenylphosphine ligands: the use of a chiral additive enables the preparation and observation of metal complexes incorporating the enantiopure form.

[figure: see text] The enantio- and diastereomerically pure metal complex of a chirally flexible BIPHEP ligand is obtained through enantiomer-selective coordination of a BIPHEP-Ru complex with enantiopure 3,3'-dimethyldiaminobinaphthyl, DM-DBN, followed by epimerization of the remaining BIPHEP-Ru enantiomer to complex with DM-DABN. Thus, an efficient and general synthetic route to a variety of substituted BIPHEP ligands from biphenol and observation of the enantiomerically pure BIPHEP ligands in their Ru(II) complexes are described.

Journal Article↗

Simultaneous determination of D-lactic acid and 3-hydroxybutyric acid in rat plasma using a column-switching HPLC with fluorescent derivatization with 4-nitro-7-piperazino-2,1,3-benzoxadiazole (NBD-PZ).

A highly sensitive method for the determination of D-lactic acid and 3-hydroxybutyric acid (3-HB) in rat plasma was developed using high-performance liquid chromatography with octadecylsilica (ODS) connected to a chiral column. At first, (D + L)-lactic acid and 3-HB in the plasma were derivatized with a fluorescent reagent, 4-nitro-7-piperazino-2,1,3-benzoxadiazole (NBD-PZ), separated on the ODS column and determined fluorimetrically at 547 nm with 491 nm of excitation wavelength. During the separation step on the ODS, the peak fraction of (D + L)-lactate derivative was introduced directly to a phenylcarbamoylated beta-cyclodextrin chiral column by changing the flow of the eluent via a six-port valve. Then, D-lactate derivative was separated enantiomerically from the L-lactate derivative, and the enantiomeric ratio was determined from the chromatogram. Intra- and inter-day accuracy values for the determination of D-lactic acid in 10 microL of rat plasma were 97.8-109.2 and 98.4-109.9%, and those for 3-HB were 99.8-108.4 and 99.8-103.8%, respectively. The intra- and inter-day precision values were within 4.6 and 5.1% for D-lactic acid, and 2.7 and 2.4% for 3-HB, respectively. The detection limits for D-lactic acid and 3-HB were approximately 2.0 and 0.04 microM, respectively (signal-to-noise ratio 3). The proposed method was applied to the plasma of diabetic rats induced by intraperitoneal administration of streptozotocin, and the significant increases of both D-lactic acid and 3-HB concentrations were observed in the diabetic rats as compared to the normal rats.

3-Hydroxybutyric Acid↗

A new fluorimetric method for the determination of formaldehyde in air based on the liquid droplet sampling technique.

A new, simple, sensitive, selective and in-field fluorimetric method for the determination of formaldehyde is proposed. The reaction of formaldehyde with hydralazine in acidic medium, heating on a boiling water-bath for 25 min, produces s-triazolo[3,4-a]phthalazine (Tri-P). The fluorescence intensity of the product formed (Tri-P) was determined at lambda em = 389 nm with lambda ex = 236 nm. The fluorescence intensity is linear over a formaldehyde concentration range of 1.2-33.0 micrograms l-1. The proposed method was applied successfully to the determination of formaldehyde sampled from the atmosphere using the liquid droplet technique. Formaldehyde vapour in a wind tunnel was produced by a mean of permeater. A linear curve was obtained between the concentration in the wind tunnel and that in the droplet. The detection limit for formaldehyde was 2.0 micrograms l-1 with RSDs varying from 3 to 12% in ambient air, using a droplet correction solution (boric acid and hydralazine). The effect of interfering substances on the determination shows that most cations and anions did not interfere. The results obtained were satisfactory compared with a reference method.

Air Pollutants↗

Extrahepatic expression of apolipoprotein A-II in mouse tissues: possible contribution to mouse senile amyloidosis.

Apolipoprotein A-II (apoA-II), an apolipoprotein in serum high-density lipoprotein, is a precursor of mouse senile amyloid fibrils. The liver has been considered to be the primary site of synthesis. However, we performed nonradioactive in situ hybridization analysis in tissue sections from young and old amyloidogenic (R1.P1-Apoa2C) and amyloid-resistant (SAMR1) mice and revealed that other tissues in addition to the liver synthesize apoA-II. We found a strong hybridization signal in the basal cells of the squamous epithelium and the chief cells of the fundic gland in the stomach, the crypt cells and a small portion of the absorptive epithelial cells in the small intestine, the basal cells of the tongue mucosa, and the basal cells of the epidermis and hair follicles in the skin in both mouse strains. Expression of apoA-II mRNA in those tissues was also examined by RT-PCR analysis. Immunolocalization of apoA-II protein also indicated the cellular localization of apoA-II. ApoA-II transcription was not observed in the heart. Amyloid deposition was observed around the cells expressing apoA-II mRNA in the old R1.P1-Apoa2C mice. These results demonstrate that the apoA-II mRNA is transcribed and translated in various extrahepatic tissues and suggest a possible contribution of apoA-II synthesized in these tissues to amyloid deposition.

Aging↗

Fluorescent derivatization of nitrite ions with 2,3-diaminonaphthalene utilizing a pH gradient in a Y-shaped microchannel.

The on-chip derivatization of nitrite ions with 2,3-diaminonaphthalene (DAN) utilizing a pH gradient formed in a Y-shaped microchannel was investigated. Nitrite ions react with DAN at low pH, and strongly fluoresced at high pH. Therefore, a reaction at low pH followed by the addition of a strong alkaline solution is the usual procedure in a batch scheme. However, a strong alkaline solution, like an NaOH aqueous solution, erodes the wall of the microchannels in substrates made of glass or polymers, and has not been considered suitable for use in microchannels. We first investigated the derivatization reaction and fluorescent properties of nitrite ions with DAN. We found that the on-chip fluorescent derivatization reaction and detection without the addition of an alkaline solution is possible by controlling the pH values of the nitrite solution and the DAN solution to form a suitable pH gradient by utilizing a buffering effect of triethanolamine solution, which is used as an NO2 gas-absorption medium. These results have suggested the feasibility of novel reaction schemes which can provide the desired products due to a controlled pH gradient in the microchannels, as well as the possibility of an on-site monitoring microchip device for ambient NO2.

Journal Article↗

Asymmetric Activation.

While nonracemic catalysts can generate nonracemic products with or without the nonlinear relationship in enantiomeric excesses between catalysts and products, racemic catalysts inherently give only a racemic mixture of chiral products. Asymmetric catalysts, either in nonracemic or racemic form, can be further evolved into highly activated catalysts with association of chiral activators. This asymmetric activation process is particularly useful in racemic catalysis through selective activation of one enantiomer of the racemic catalyst. Recently, a strategy whereby a racemic catalyst is selectively deactivated by a chiral additive has been reported to yield nonracemic products. However, reported herein is an alternative and conceptually opposite strategy in which a chiral activator selectively activates, rather than deactivates, one enantiomer of a racemic chiral catalyst. The advantage of this activation strategy over the deactivation counterpart is that the activated catalyst can produce a greater enantiomeric excess in the products-even with the use of a catalytic amount of activator relative to chiral catalyst-than that attained by the enantiomerically pure catalyst on its own. Therefore, asymmetric activation could provide a general and powerful strategy for not only the use of atropisomeric, racemic ligands but also chirally flexible and proatropisomeric ligands without enantiomeric resolution!

Journal Article↗

Ion chromatographic method for simultaneous determination of nitrate and nitrite in human saliva.

A simple, rapid, accurate and sensitive method is proposed for the simultaneous determination of nitrite and nitrate in human saliva. Nitrite and nitrate present in the human saliva were determined after 10- to 100-fold dilution with ion chromatography (IC) using suppressed conductivity detection. Recoveries of nitrite and nitrate were found to be ranged between 95% and 101%. The method was linear (r2=0.9991) over the concentration working range. The detection limits were found to be 15.0 microg/l and 33.5 microg/l, for nitrite and nitrate, respectively. Ions that are present in human saliva and several other ions that are suspected to affect nitrite and nitrate determination were checked. It was found that most of the ions did not cause any interference in the determination. The method allows simultaneous determination of nitrite and nitrate in human saliva.

Chromatography, Liquid↗

Optical rotation per refractive index unit, or enantiomeric (e) factor, for screening enantioselective catalysts through asymmetric activation or carbohydrates.

A super high-throughput screening (SHTS) system can be constructed by combining high-performance liquid chromatography (HPLC), optical rotation (OR), and refractive index unit (RIU) to determine not only the enantioselectivity of the addition of diethylzinc to an aliphatic aldehyde catalyzed by a binaphthol-zinc complex through asymmetric activation with chiral Schiff bases, but also the enantiopurity of a carbohydrate. The enantiomeric (e) factor, which we define here as optical rotation per refractive index unit, is linearly related to the percent enantiomeric excess (%ee) and is independent of concentration.

Acetonitriles↗

Enantiomer-selective activation of racemic catalysts.

Asymmetric catalysts can be evolved into highly activated catalysts by association with chiral activators. This asymmetric activation process is particularly useful in racemic catalysis through selective activation of one enantiomer of the racemic catalysts. Recently, a strategy whereby a racemic catalyst is selectively deactivated by a chiral additive has been reported to yield nonracemic products. However, we have reported a strategy that is an alternative to asymmetric catalysts but is conceptually opposite, in which a chiral activator selectively activates rather than deactivates one enantiomer of a racemic chiral catalyst. The advantage of this activation strategy over the deactivation counterpart is that the activated catalyst can produce a greater enantiomeric excess (x(act)% ee) in the products than the ee attained by the enantiomerically pure catalyst on its own. Therefore, 'asymmetric activation' could provide a general and powerful strategy for the use of not only atropisomeric and, hence, racemic ligands but also chirally flexible and 'pro-atropisomeric' ligands without enantiomeric resolution!

Catalysis↗

CT-Guided acetic acid injection therapy for aldosterone-producing adrenocortical adenoma: a preliminary report of three cases.

We reported the preliminary outcomes of CT-guided percutaneous injection therapy for aldosterone-producing adrenocortical adenoma (APA). Five sessions of injection therapy, 4 percutaneous acetic acid injections (PAI) and 1 percutaneous ethanol injection (PEI) were performed in 3 patients with APA. A small amount of acetic acid or ethanol solution was injected via a needle placed precisely inside the tumor. The procedure was frequently monitored by repetitive CT scanning. The follow-up period ranged from 5 to 27 months. After the treatment, hypertension was normalized or controlled by a low dose of conventional anti-hypertensive drug. In 2 of 3 cases the plasma aldosterone levels were normalized. Although temporary symptoms of alcoholic intoxication were observed in the single session of PEI, the 4 sessions of PAI were associated with no adverse symptoms or complications. Although this study covers only short-term results in 3 patients, CT-guided PAI appears to be a safe and effective treatment and may be a promising alternative as a simple and far less invasive therapy for APA.

Acetic Acid↗

Plant cis-acting regulatory DNA elements (PLACE) database: 1999.

PLACE (http://www.dna.affrc.go.jp/htdocs/PLACE/) is a database of nucleotide sequence motifs found in plant cis-acting regulatory DNA elements. Motifs were extracted from previously published reports on genes in vascular plants. In addition to the motifs originally reported, their variations in other genes or in other plant species in later reports are also compiled. Documents for each motif in the PLACE database contains, in addition to a motif sequence, a brief definition and description of each motif, and relevant literature with PubMed ID numbers and GenBank accession numbers where available. Users can search their query sequences for cis-elements using the Signal Scan program at our web site. The results will be reported in one of the three forms. Clicking the PLACE accession numbers in the result report will open the pertinent motif document. Clicking the PubMed or GenBank accession number in the document will allow users to access to these databases, and to read the of the literature or the annotation in the DNA database. This report summarizes the present status of this database and available tools.

Arabidopsis↗

Malignant lymphoma of the gingiva: MR evaluation.

PURPOSE: Our purpose was to document the MR imaging findings of malignant lymphoma of the gingiva. METHODS: Five patients with histologically proved malignant lymphoma of the gingiva were studied by MR imaging. The MR images were analyzed for tumor size, extent, and signal characteristics, bone involvement, and associated cervical lymph node enlargement. RESULTS: Clinical examination tended to underestimate the size of lymphomatous lesions. The signal intensity of the lesions was isointense to hyperintense relative to muscle on noncontrast T1-weighted images and showed variable contrast enhancement patterns. On T2-weighted images, signal intensity was isointense to hypointense relative to the oral mucosa. In one case, the mass extended to the submandibular space; in the remaining cases, the masses were limited to the gingiva and the adjacent bone. MR imaging revealed that gingival lymphomatous masses were broad-based along the mandible or maxilla and eroded through the cortex into the marrow space, but the cortex was still recognizable. No nodal involvement was noted in any of the patients with malignant lymphoma. CONCLUSION: The signal characteristics of gingival lymphoma overlap those of other tumors. The cortex separating marrow involvement from the broad-based gingival mass generally appears to be permeated with small erosions but is still recognizable.

Aged↗

Squamous cell carcinoma of the oral cavity: MR findings and value of T1-versus T2-weighted fast spin-echo images.

OBJECTIVE: The purposes of this study were to describe the characteristics of squamous cell carcinomas of the oral cavity on unenhanced and contrast-enhanced T1-weighted spin-echo (SE) MR images and unenhanced T2-weighted fast spin-echo (FSE) MR images and to determine which sequences best delineate the margins and extent of the tumors. MATERIALS AND METHODS: Forty-four patients with proved squamous cell carcinoma of the oral cavity (tongue, 24; floor of mouth, seven; buccal mucosa, four; maxillary gingiva, two; and mandibular gingiva, seven) underwent unenhanced axial T2-weighted FSE MR imaging and unenhanced and enhanced axial and coronal T1-weighted SE MR imaging. The appearance, signal characteristics, and extent of the tumors were assessed, and the delineation of tumor margins with each sequence or combination of sequences was evaluated by use of a grading system ranging from 1 (poor) to 3 (excellent). Three patients were excluded because of artifacts on the MR images caused by dental restorations. RESULTS: Tumors in all 41 patients were depicted on unenhanced T1-weighted SE images, but in four patients, tumors were not visible on T2-weighted FSE images. Except for tumors that invaded the maxillary gingiva, the tumors generally had homogeneous, low signal intensity on unenhanced T1-weighted images and nonhomogeneous, high signal intensity on T2-weighted FSE images. All tumors showed enhancement, 76% with a nonhomogeneous appearance. The delineation of tumor margins was excellent (grade 3) in 31 cases and fair (grade 2) in 10 cases. The highest rating was given for unenhanced T1-weighted images in 10 cases, for contrast-enhanced T1-weighted images in 10 cases, for the combination of both unenhanced and contrast-enhanced T1-weighted images in 18 cases, for the combination of unenhanced T1-weighted and T2-weighted FSE images in five cases, and for T2-weighted FSE images in one case. In three cases, the highest rating was given for both combinations of pulse sequences. CONCLUSION: An unenhanced T1-weighted sequence should be used as the basic pulse sequence for MR imaging of tumors of the oral cavity. When tumor margins are not clearly delineated with this sequence, T2-weighted FSE and contrast-enhanced T1-weighted sequences should be added. Although both of these sequences provide supplementary information, the contrast-enhanced T1-weighted sequence is more useful in delineating the margins and extent of tumors than is the T2-weighted FSE sequence.

Adult↗

Phosphorylation of farnesol by a cell-free system from Botryococcus braunii.

Farnesol was incorporated into squalene as well as botryococcenes when the alcohol was fed to the culture of Botryococcus braunii B race strain. In in vitro experiments with a 10,000 x g supernatant of cell homogenate, squalene was synthesized from farnesyl diphosphate in the presence of NADPH or NADH, but botryococcenes were not synthesized under the same conditions. A 100,000 x g pelet fraction was able to phosphorylate farnesol to give its mono- and diphosphate esters in a CTP dependent manner.

Cytidine Triphosphate↗

Purification of geranylgeranyl diphosphate synthase from bovine brain.

Geranylgeranyl diphosphate (GGPP) synthase was purified to homogeneity from bovine brain in a one-step affinity column procedure. For the construction of the affinity column, a farnesyl diphosphate (FPP) analog, O-(6-amino-1-hexyl)-P-farnesylmethyl phosphonophosphate, was synthesized and linked to the spacer of the matrix of Affigel 10 via the amino group. The native enzyme appeared to be homooligomer (150-195 kDa) with a molecular mass of the monomer of 37.5 kDa. The pI for the enzyme was 6.2. The Km values for dimethylallyl diphosphate (DMAPP), geranyl diphosphate (GPP) and FPP were estimated to be 33 microM, 0.80 microM and 0.74 microM, respectively. The Km value for isopentenyl diphosphate (IPP) in the presence of both IPP and FPP mixture was 2 microM. The ratio of the reaction velocity for formation of GGPP from DMAPP, GPP or FPP was 0.004:0.145:1. The intermediate FPP was formed in the reaction with GPP as an allylic primer. FPP synthase catalyzing the formation of FPP from DMAPP and IPP was also purified to homogeneity from the same organ by a similar affinity chromatography procedure using a GPP analog, O-(6-amino-1-hexyl)-P-geranylmethyl phosphonophosphate as a ligand. The enzyme was a homodimer with a monomeric molecular mass of 40.0 kDa. These results indicate that GGPP, a lipid precursor for the biosynthesis of a majority of prenylated proteins, is synthesized from DMAPP and IPP by the action of FPP synthase catalyzing the reactions C5-->C15 followed by the action of GGPP synthase catalyzing the reaction C15-->C20.

Alkyl and Aryl Transferases↗