Simple and rapid determination of hydrogen peroxide using phosphine-based fluorescent reagents with sodium tungstate dihydrate.

A simple batch method for the fluorometric determination of hydrogen peroxide using phosphine-based fluorescent reagents has been developed. A rapid, mild and selective derivatization reaction was achieved by adding sodium tungstate dihydrate to the reaction mixture of hydrogen peroxide and a phosphine-based fluorescent reagent. When 4-diphenylphosphino-7-methylthio-2,1,3-benzoxadiazole was used as a reagent, the derivatization reaction was completed after 2 min at room temperature. The calibration curve was linear between 12.5 and 500 ng hydrogen peroxide in a 10 microL sample solution. This method is accurate and has potential for on-line applications.     

Spectrophotometric determination of traces of hydrogen peroxide with the Ti(IV)-xylenol orange and the Ti(IV)-chromazurol S reagents

The formation of mixed ligand complexes in Ti(IV)-xylenol orange (XO)-H₂O₂ and Ti(IV)-chromazurol S (CAS)-H₂O₂ systems was studied by spectrophotometry. The former system gave constant absorbance (λ_max = 562 nm) under the condition of [XO]/[Ti(IV)] = 1 in the pH 2–4 region. In the latter system, a distinct maximum at 557 nm was observed when [CAS]/[Ti(IV)] = 4 in the pH range of 4.5–5.2. In both cases, the absorbance at λ_max was stable for a long time and proportional to the concentration of hydrogen peroxide. From those facts, the usefulness of the mixtures of Ti(IV)-XO and Ti(IV)-CAS as the colorimetric reagents for the determination of hydrogen peroxide can be expected. The conditions for the use of the Ti(IV)-XO and the Ti(IV)-CAS reagents were examined in detail, and both reagents were found to be available for trace analysis of hydrogen peroxide with high sensitivity.     

Solvents inducing oxidation of hydroxylamines

Hydroxylamines gradually undergo oxidation to their oximes on being dissolved in organic solvent (e.g. methanol). This phenomenon was followed by (1)H-NMR and liquid chromatography-mass spectrometry (LC-MS). The oxidation rate was estimated from the peak area observed on the mass chromatogram at the protonated molecule or fragment ion on LC-atmospheric pressure chemical ionization (APCI)-MS. The results showed that the oxidation rate of hydroxylamines depended on the solvent type.     

522—Catalytic oxydation of biological components on platinum electrodes modified by adsorbed metals: Anodic oxidation of glucose

The catalytic oxidation of glucose on Pt electrodes modified by adsorbed metals was studied in 1 M HClO₄ by linear sweep voltammetry. The adsorbed metals (denoted as M_ad, such as Bi_ad and Pb_ad) formed on Pt in the potential region more positive than the reversible potential of an M⁼⁺/M^o couple, lead to a marked increase in the anodic c?urrent of glucose by about one order of magnitude. The catalytic activity depends on the surface coverage by the M_ad. The strongly adsorbed species of lactone type, which are responsible for blocking the successive oxidation, are formed on the electrode surface in the anodic processes of glucose on a bare Pt electrode. The formation of such poisonous species is accelerated in the presence of adsorbed hydrogen on Pt. The effects of M_ad were discussed on the basis that M_ad plays its major role on the Pt electrode surface in removal of the adsorbed hydrogen which initiates the formation of the poisonous species.     

Catalytic effects of metal submonolayers formed by faradaic adsorption on the anodic oxidation of ascorbic acid at a platinum electrode

The catalytic effects of metal ions on the anodic oxidation of ascorbic acid on a Pt electrode in 1 M HClO₄ were studied by linear sweep voltammetry. The anodic peak due to a two-electron oxidation of ascorbic acid shifts to the negative potential side on the addition of Bi³⁺. This indicates the accelerating effect of Bi³⁺ on the oxidation of ascorbic acid. The presence of other metal ions, such as Pb²⁺, Hg²⁺, Tl⁺, Ag⁺ and Sb³⁺, also exerts similar effects. These metal ions were adsorbed on a Pt electrode at underpotentials and the adsorbed metals (denoted as M_ad) still remain on the electrode surface until the electrode potential goes up to and beyond the peak potential of the oxidation of ascorbic acid. On the other hand, metal ions forming no adsorbed layer on Pt, such as Co²⁺, Zn²⁺, Fe³⁺ and Ni²⁺, exhibit no catalytic effect. These facts suggest that the presence of a M_ad on Pt is essential for the promotion of the anodic oxidation of ascorbic acid. However, there is a difference in the catalytic action among the M_ad, for example, Cu_ad, Cd_ad, In_ad, Sn_ad and Mo_ad display no catalytic action.The catalytic activity depends on the degree of surface coverage by the M_ad. The maximal effect of the M_ad is attained in the submonolayer region. The effects of metal ions were discussed on the basis that the M_ad plays its major role in the removal of the adsorbed ascorbic acid occupying active sites on the electrode surface, and provides effective sites for the activation of adjacent water molecules. Furthermore, from the ¹³C NMR spectra for the oxidation products, the adsorbed water on the M_ad appears to function by promoting the subsequent hydration steps, following the electron-transfer step of ascorbic acid.     

Crystal violet combined with Merocyanine 540 for the ex vivo purging of hematopoietic stem cell grafts

The purpose of this study was to determine in a preclinical purging model, how effective crystal violet-mediated photodynamic therapy (CV-PDT) is against solid tumor and drug-resistant mutant tumor cells, and if certain limitations of CV-PDT can be overcome by using crystal violet (CV) in combination with the membrane-active photosensitizer, Merocyanine 540 (MC540). When used under conditions that preserved an adequate fraction of normal human granulocyte/macrophage progenitors (CFU-GM), CV-PDT failed to achieve meaningful reductions of DU145 prostate, H69 small cell lung cancer, and MDA-MB-435S breast cancer cells. Melphalan-resistant L1210/L-PAM1, adriamycin-resistant P388/ADR, and adriamycin-resistant HL-60/ADR leukemia cells were markedly less sensitive to CV-PDT than their wild-type counterparts, whereas cisplatin-resistant H69/CDDP cells were more sensitive than wild-type H69 cells. Sequential exposure to MC540- and CV-PDT under conditions that preserved an adequate fraction (73% and 29%, respectively) of normal CD34-positive hematopoietic stem cells and granulocyte/macrophage progenitors was highly effective against H69 (99.997% reduction) and H69/CDDP (99.999% reduction) cells, but ineffective against HL-60/ADR, MDA-MB-435S, and DU145 cells. CV thus shows only limited promise as a single-modality purging agent. However, in certain situations, clinically meaningful tumor cell depletions can be obtained by using CV in combination with a second photosensitizer such as MC540.     

Convenient Method for Dehalogenation of Aryl Halides

Reductive dehalogenation of aryl halides was achieved using hydrogen and a palladium catalyst. By using deuterium gas, the deuterated arenes were readily prepared.     

PET Imaging of Bacterial Infections with Fluorine‐18‐Labeled Maltohexaose

A positron emission tomography (PET) tracer composed of ¹⁸F‐labeled maltohexaose (MH¹⁸F) can image bacteria in vivo with a sensitivity and specificity that are orders of magnitude higher than those of fluorodeoxyglucose (¹⁸FDG). MH¹⁸F can detect early‐stage infections composed of as few as 10⁵ E. coli colony‐forming units (CFUs), and can identify drug resistance in bacteria in vivo. MH¹⁸F has the potential to improve the diagnosis of bacterial infections given its unique combination of high specificity and sensitivity for bacteria.     

Preferential inactivation of paediatric solid tumour cells by sequential exposure to Merocyanine 540-mediated photodynamic therapy and Edelfosine: implications for the ex vivo purging of autologous haematopoietic stem cell grafts

Paediatric solid tumours exhibit steep dose-response curves to alkylating agents and are therefore considered candidates for high-dose chemotherapy and autologous stem cell support. There is growing evidence that autologous stem cell grafts from patients with solid tumours are frequently contaminated with live tumour cells. The objective of this study was to perform, in a preclinical purging model, an initial assessment of the safety and efficacy of a two-step purging procedure that combined Merocyanine 540-mediated photodynamic therapy (MC540-PDT) with a brief exposure to the alkyl-lysophospholipid, Edelfosine. Human and murine bone marrow cells and Neuro-2a murine neuroblastoma, SK-N-SH human neuroblastoma, SK-ES-1 and U-2 OS human osteosarcoma, G-401 and SK-NEP-1 human Wilms' tumour, and A-204 human rhabdomyosarcoma cells were exposed to a fixed dose of MC540-PDT followed by a brief incubation with graded concentrations of Edelfosine. Survival was subsequently assessed by in vitro clonal assay or, in the case of CD34-positive haematopoietic stem cells, by an immunohistochemical method. Combination purging with MC540-PDT and Edelfosine depleted all tumour cells by >4 log while preserving at least 15% of murine granulocyte/macrophage progenitors (CFU-GM), 34% of human CFU-GM, and 31% of human CD34-positive cells. The data suggest that combination purging with MC540-PDT and Edelfosine may be useful for the ex vivo purging of autologous stem cell grafts from patients with paediatric solid tumours.     

Language specificity in the perception of voiceless sibilant fricatives in Japanese and English: implications for cross-language differences in speech-sound development

Both English and Japanese have two voiceless sibilant fricatives, an anterior fricative /s/ contrasting with a more posterior fricative /∫/. When children acquire sibilant fricatives, English children typically substitute [s] for /∫/, whereas Japanese children typically substitute [∫] for /s/. This study examined English- and Japanese-speaking adults' perception of children's productions of voiceless sibilant fricatives to investigate whether the apparent asymmetry in the acquisition of voiceless sibilant fricatives reported previously in the two languages was due in part to how adults perceive children's speech. The results of this study show that adult speakers of English and Japanese weighed acoustic parameters differently when identifying fricatives produced by children and that these differences explain, in part, the apparent cross-language asymmetry in fricative acquisition. This study shows that generalizations about universal and language-specific patterns in speech-sound development cannot be determined without considering all sources of variation including speech perception.