The oxidative degradation of Calmagite using added and in situ generated hydrogen peroxide catalysed by manganese(II) ions: Efficacy evaluation, kinetics study and degradation pathways.

Manganese (II) ions (Mn(II)) catalyse the oxidative degradation of Calmagite (CAL, 2-hydroxy-1-(2-hydroxy-5methylphenylazo)-4-naphthalenesulfonic acid) at room temperature using added and in situ generated hydrogen peroxide (H2O2), using 1,2-dihydroxybenzene-3,5-disulfonate, disodium salt and monohydrate (Tiron) as the co-catalyst for the in situ generation of H2O2. The percentage of CAL degradation with the in situ generated H2O2 was 91.1 % after 30 min which is lower than that in the added H2O2/Mn(II) system (96.0 %). A one-eighth-lives method was applied to investigate the kinetic parameters in the added H2O2 system, with and without Mn(II), involving phosphate, carbonate, and two biological buffers at different pHs. Percarbonate (HCO4-) was found to be the main reactive species for CAL degradation in the added H2O2 system buffered by carbonate in the absence of Mn(II). Manganese (IV) = O (Mn(IV) = O) and manganese(V) = O (Mn(V) = O) are the main reactive species in the added H2O2/Mn(II) system buffered by carbonate and non-carbonate buffers respectively. pH 8.5 was the optimum pH for CAL degradation when buffered by carbonate, while pH 10.0 is the best pH for the systems not using carbonate buffer. Using a high performance liquid chromatography/electrospray ionisation mass spectrometer (HPLC/ESI-MS), the degradation intermediates of CAL were identified as 1-amino-2-naphthol-4-sulfonate ion, 1-amino-2-naphthol-4-sulfinic ion, 1-amino-2-naphthol, and 1-nitroso-2-naphthol.

ReCAP: Pharmacists' Impact in Hematopoietic Stem-Cell Transplantation: Economic and Humanistic Outcomes.

PURPOSE: This study seeks to evaluate the impact of pharmacists' involvement in the care of patients undergoing bone marrow transplantation (BMT). METHODS: This was a three-phase study. In phase 1, inpatient and outpatient pharmacist encounters were totaled and services provided were translated to revenue generated from prescription revenue and billing charges. In phase 2, pharmacists' activities and interventions were associated with time savings estimated by providers. In phase 3, patients and providers were surveyed to assess their expectations, experiences, and value perceptions of pharmacists.A positive response rate of 80%for each survey item was set as the threshold for high expectations and successful service delivery. RESULTS: In phase 1, after 6 months of data collection, clinical services were provided to 170 inpatients and 290 outpatients. For inpatients, there was an average discharge prescription revenue of $990 per patient through the outpatient pharmacy. In the outpatient clinic, pharmacist visits generated an additional $23,000 in charges (approximately $80 per patient) and an annual prescription revenue of approximately $840,000 through the outpatient pharmacy. In phase 2, pharmacists' activities led to a total time savings of 122 hours. In phase 3, patients and providers met the predetermined 80% positive response rate for most survey items. The item for which patient and provider responses consistently did not meet this threshold related to pharmacists educating patients about their BMT. CONCLUSION: Pharmacists are valuable resources in the care of patients undergoing BMT, as their care translates to increased revenue, provider time savings, and positive perceptions from patients and providers.

Crystal structure of bromido-nitro-syl-bis(tri-phenyl-phosphane-κP)nickel(II).

The asymmetric unit of the title complex, [NiBr(NO){P(C6H5)3}2], comprises two independent mol-ecules each with a similar configuration. The Ni(II) cation is coordinated by one bromide anion, one nitrosyl anion and two tri-phenyl-phosphane mol-ecules in a distorted BrNP2 tetra-hedral coordination geometry. The coordination of the nitrosyl group is non-linear, the Ni-N-O angles being 150.2 (5) and 151.2 (5)° in the two independent mol-ecules. In the crystal, mol-ecules are linked by weak C-H⋯Br hydrogen bonds and weak C-H⋯π inter-actions into a three-dimensional supra-molecular architecture.

The expression of laminin-5 in severe dysplasia/carcinoma in situ and early invasive squamous cell carcinoma: an immunohistochemical study.

AIM: The objective of the present study was to detect the immunohistochemical localization of laminin-5 in the subepithelial basement membrane and to investigate the integrity of the basement membrane in cases of severe dysplasia/carcinoma in situ and early invasive squamous cell carcinoma. METHODS: Tissue samples of 55 filed (25-early invasive squamous cell carcinoma; 25-severe dysplasia/carcinoma in situ;5-normal buccal mucosa as controls) cases were collected from the archives of Oral Pathology Department. Routine staining and Immunostaining for laminin-5 (Biogenex) was carried out on the sections. The immunohistochemical localization and integrity of the basement membrane protein isoform laminin-5 was studied in formalin fixed paraffin embedded sections of severe dysplasia/CIS and early invasive squamous cell carcinoma (EISCC). Chi square test was used for statistical analysis. P values <0.05 were considered statistically significant. RESULTS: The immunostaining of laminin-5 as observed under light microscope ranged from continuous to complete absence. The laminin-5 staining pattern was more often continuous in severe dysplasia/CIS and discontinuous or absent in EISCC. A statistical comparison between different scores of laminin-5 staining in severe dysplasia/CIS and early invasive squamous cell carcinoma showed a highly significant 'P' value (0.0001). CONCLUSION: The status of basal lamina, laminin-5 may provide additional and relevant information about invasive potential of dysplasias. Hence the study of laminin-5 immunohistologically can be regarded as an adjunct to distinguish severe dysplastic lesions from early oral invasive carcinoma.

Kinetics and mechanism of the manganese(II) catalysed Calmagite dye oxidation using in situ generated hydrogen peroxide.

The kinetics and mechanism for the bleaching of Calmagite (H3CAL, 3-hydroxy-4-(2-hydroxy-5-methylphenylazo)naphthalene-1-sulfonic acid) in aqueous solution at pH 8.00 and 23 ± 1 °C using in situ generated H2O2 is described. Complete mineralisation of H3CAL results with turnover frequencies (TOF = moles of H3CAL bleached per mole of manganese per hour) of 40 h(-1). The monohydroxy azo dyes Me-H2CAL, Orange G and Orange II are not bleached which indicates that a requirement of dye bleaching is the coordination of the dye to the Mn centre. Spectroscopic studies show the formation of Mn(CAL)2 and Mn(CAL) species but in the presence of Tiron (1,2-dihydroxybenzene-3,5-disulfonate, disodium salt, monohydrate, Na2TH2·H2O), [Mn(CAL)(T)] is formed. It is proposed that a Mn(III)-hydroperoxide species is generated, [Mn(O2H)(CAL)(TQ)] from the in situ generated H2O2, where TQ represents the o-quinone form of Tiron, and this is the active species in the bleaching of coordinated CAL; the formation of this hydroperoxide species is supported by UV/VIS and ESI-MS data. The formation of a Mn(III) species is supported by EPR studies which also show some evidence for the presence of a labile d(5) Mn(II) species in the presence of the reducing substrate hydroxylamine (NH2OH). This would enable rapid ligand exchange for both in situ H2O2 generation and dye bleaching to occur; there is no evidence for the presence of Mn(IV)=O species. The virtue of low local concentrations of in situ generated H2O2 is shown to be important in preventing over oxidation of the catalyst and thus contributing to a robust catalytic system.

The role of mast cells on angiogenesis in oral squamous cell carcinoma.

OBJECTIVE: Angiogenesis or neovascularization has long been known to aid in progression and metastasis of malignant tumors. Tumor angiogenesis is a complex event mediated by angiogenic factors released from cancer cells and or by host immune cells. Mast cells may induce tumor progression and potentiate metastasis by stimulating angiogenesis. The purpose of the present study was to validate topographic distribution of micro vessel density (MVD) and mast cell density (MCD) and help to elucidate the possible role of mast cells in tumor angiogenesis and correlating this with advanced disease parameters. . STUDY DESIGN: MVD and MCD were investigated in tumor specimens from 30 patients diagnosed with different histologic grades of oral squamous cell carcinoma (OSCC). Intratumor vessels were stained with collagen Type IV antibody and mast cells with Toluidine blue before being measured by light microscopy. RESULTS: There was a significant correlation between MVD and disease progression and number of blood vessels increased from well to poorly differentiated OSCC where as MCD decreased. CONCLUSIONS: These findings suggest that angiogenesis indeed occur in OSCC and might be used as an index to inflect the aggression of the disease however mast cells make up only a part of complex process of angiogenesis along with other factors secreted by tumor.

Unexpected formation of a novel pyridinium-containing catecholate ligand and its manganese(III) complex.

Nucleophilic aromatic substitution of tetrachloro-o-benzoquinone by pyridine and reduction of the o-quinone to the catechol by hydroxylamine forms 1,2-dihydroxy-3,5,6-trichlorobenzene-4-pyridinium chloride. This compound reacts with manganese(II) acetate in air to form chlorobis(3,5,6-trichlorobenzene 4-pyridinium catecholate)manganese(III), which represents the first complex of this ligand class to be structurally characterized by X-ray diffraction; this complex is active in the catalytic reduction of dioxygen to hydrogen peroxide under ambient conditions and turnover frequencies (TOFs) >10,000 h(-1) can be obtained.

Calmagite dye oxidation using in situ generated hydrogen peroxide catalysed by manganese(II) ions.

Hydrogen peroxide (H(2)O(2)) generated from the manganese(II) catalysed reduction of dioxygen has been shown to efficiently oxidize Calmagite (3-hydroxy-4-(2-hydroxy-5-methylphenylazo)naphthalene-1-sulfonic acid) in aqueous solution at pH 8.0 and 20 +/- 1 degrees C with de-protonated Tiron (1,2-dihydroxybenzene-3,5-disulfonate, disodium salt) acting as an essential co-ligand.