title: Indenols, indenones and (arylcyclohexadienyl)Mn(CO)3 π-complexes from the thermally promoted reactions of alkynes with ortho-Mn(CO)4 aryl ketone, amide, ester and aldehyde derivatives

authors: Robinson, Nicholas P.

subjects: Manganese

abstract: Thermally promoted reactions of a range of alkynes with the orthomanganated acetophenone (η2-2-acetylphenyl)Mn(CO)4 generally give 1H-inden-1-ols in good yield; effects of substituents and solvent on these reactions are reported, along with the crystal structure of 1-methyl-2,3-diphenyl-1H-inden-1-ol. The corresponding orthomanganated benzophenone similarly gives the indenol with diphenylacetylene but by exception, orthomanganated 3-acetylthiophene with phenylacetylene reacts via triple alkyne insertion and cyclisation, shown by crystal structure determination of the π-complex product [(1,2,3,4,5-η)-2-(3-acetylthien-2-yl)-1,3,5-triphenylcyclohexadienyl]tricarbonylmanganese. Corresponding orthomanganated derivatives of N,N-dimethylbenzamide, methyl 3,4,5-trimethoxybenzoate and 4-dimethylaminobenzaldehyde all give indenones with diphenylacetylene, but with (excess) acetylene only the aldehyde gives an indenone, the amide and ester giving instead [(1,2,3,4,5-η)-6-arylcyclohexadienyl]Mn(CO)3 complexes. 1H NMR analysis of these complexes shows H at C6 to be on the same face of the cyclohexadienyl ring as Mn(CO)3 (endo-6-H; exo 6-aryl) as expected from three successive syn additions of alkyne at metallated carbon followed by intramolecular syn addition of alkene in the final cyclisation stage.

text: Indenols, indenones and (arylcyclohexadienyl)Mn(CO)3 π-complexes from the thermally promoted reactions of alkynes with ortho-Mn(CO)4 aryl ketone, amide, ester and aldehyde derivatives Thermally promoted reactions of a range of alkynes with the orthomanganated acetophenone (η2-2-acetylphenyl)Mn(CO)4 generally give 1H-inden-1-ols in good yield; effects of substituents and solvent on these reactions are reported, along with the crystal structure of 1-methyl-2,3-diphenyl-1H-inden-1-ol. The corresponding orthomanganated benzophenone similarly gives the indenol with diphenylacetylene but by exception, orthomanganated 3-acetylthiophene with phenylacetylene reacts via triple alkyne insertion and cyclisation, shown by crystal structure determination of the π-complex product [(1,2,3,4,5-η)-2-(3-acetylthien-2-yl)-1,3,5-triphenylcyclohexadienyl]tricarbonylmanganese. Corresponding orthomanganated derivatives of N,N-dimethylbenzamide, methyl 3,4,5-trimethoxybenzoate and 4-dimethylaminobenzaldehyde all give indenones with diphenylacetylene, but with (excess) acetylene only the aldehyde gives an indenone, the amide and ester giving instead [(1,2,3,4,5-η)-6-arylcyclohexadienyl]Mn(CO)3 complexes. 1H NMR analysis of these complexes shows H at C6 to be on the same face of the cyclohexadienyl ring as Mn(CO)3 (endo-6-H; exo 6-aryl) as expected from three successive syn additions of alkyne at metallated carbon followed by intramolecular syn addition of alkene in the final cyclisation stage.

year: 2005-08-01

title: Stimulation of TNF-α release in monocytes by honey

authors: Tonks, A.

subjects: honey

abstract: Although evidence exists for the antibacterial effects of honey there is limited objective evidence for direct promotion of healing. We investigated the effect of manuka, pasture and an artificial honey on macrophage function. Reactive oxygen intermediate (ROI) production was assessed by luminol enhanced chemoluminescence and tumour necrosis factor-alpha (TNF-α) release was determined by immunoassay. ROI production was significantly (P<0.001) decreased by pasture honey and manuka honey. TNF-α release was significantly enhanced (P<0.001) in unprimed MM6 cells by manuka and pasture honey but was not altered in primed cells. These results could explain the suggested therapeutic properties of honey in promoting wound healing.

text: Stimulation of TNF-α release in monocytes by honey Although evidence exists for the antibacterial effects of honey there is limited objective evidence for direct promotion of healing. We investigated the effect of manuka, pasture and an artificial honey on macrophage function. Reactive oxygen intermediate (ROI) production was assessed by luminol enhanced chemoluminescence and tumour necrosis factor-alpha (TNF-α) release was determined by immunoassay. ROI production was significantly (P<0.001) decreased by pasture honey and manuka honey. TNF-α release was significantly enhanced (P<0.001) in unprimed MM6 cells by manuka and pasture honey but was not altered in primed cells. These results could explain the suggested therapeutic properties of honey in promoting wound healing.

year: 2001

title: Patient-reported diagnostic intervals to colorectal cancer diagnosis in the Midland region of New Zealand: a prospective cohort study

authors: Blackmore, Tania Louise

subjects: Science & Technology

abstract: Background and objectives
New Zealand (NZ) has high rates of colorectal cancer (CRC) but low rates of early detection. The majority of CRC is diagnosed through general practice, where lengthy diagnostic intervals are common. We investigated factors contributing to diagnostic delay in a cohort of patients newly diagnosed with CRC.

Methods
Patients were recruited from the Midland region and interviewed about their diagnostic experience using a questionnaire based on a modified Model of Pathways to Treatment framework and SYMPTOM questionnaire. Descriptive statistics were used to describe the population characteristics. Chi-square analysis and logistic regression were used to analyse factors influencing diagnostic intervals.

Results
Data from 176 patients were analysed, of which 65 (36.9%) experienced a general practitioner (GP) diagnostic interval of >120 days and 96 (54.5%) experienced a total diagnostic interval (TDI) > 120 days. Patients reporting rectal bleeding were less likely to experience a long TDI (odds ratio [OR] 0.34, 95% confidence interval [CI]: 0.14–0.78) and appraisal/help-seeking interval (OR, 0.19, 95% CI: 0.06–0.59). Patients <60 were more likely to report a longer appraisal/help-seeking interval (OR, 3.32, 95% CI: 1.17–9.46). Female (OR, 2.19, 95% CI: 1.08–4.44) and Māori patients (OR, 3.18, 95% CI: 1.04–9.78) were more likely to experience a long GP diagnostic interval.

Conclusion
NZ patients with CRC can experience long diagnostic intervals, attributed to patient and health system factors. Young patients, Māori, females, and patients experiencing change of bowel habit may be at particular risk. We need to increase symptom awareness of CRC for patients and GPs. Concentrated efforts are needed to ensure equity for Māori in access to screening, diagnostics, and treatment.

text: Patient-reported diagnostic intervals to colorectal cancer diagnosis in the Midland region of New Zealand: a prospective cohort study Background and objectives
New Zealand (NZ) has high rates of colorectal cancer (CRC) but low rates of early detection. The majority of CRC is diagnosed through general practice, where lengthy diagnostic intervals are common. We investigated factors contributing to diagnostic delay in a cohort of patients newly diagnosed with CRC.

Methods
Patients were recruited from the Midland region and interviewed about their diagnostic experience using a questionnaire based on a modified Model of Pathways to Treatment framework and SYMPTOM questionnaire. Descriptive statistics were used to describe the population characteristics. Chi-square analysis and logistic regression were used to analyse factors influencing diagnostic intervals.

Results
Data from 176 patients were analysed, of which 65 (36.9%) experienced a general practitioner (GP) diagnostic interval of >120 days and 96 (54.5%) experienced a total diagnostic interval (TDI) > 120 days. Patients reporting rectal bleeding were less likely to experience a long TDI (odds ratio [OR] 0.34, 95% confidence interval [CI]: 0.14–0.78) and appraisal/help-seeking interval (OR, 0.19, 95% CI: 0.06–0.59). Patients <60 were more likely to report a longer appraisal/help-seeking interval (OR, 3.32, 95% CI: 1.17–9.46). Female (OR, 2.19, 95% CI: 1.08–4.44) and Māori patients (OR, 3.18, 95% CI: 1.04–9.78) were more likely to experience a long GP diagnostic interval.

Conclusion
NZ patients with CRC can experience long diagnostic intervals, attributed to patient and health system factors. Young patients, Māori, females, and patients experiencing change of bowel habit may be at particular risk. We need to increase symptom awareness of CRC for patients and GPs. Concentrated efforts are needed to ensure equity for Māori in access to screening, diagnostics, and treatment.

year: 2021