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ABSTRACT: Ruthenium complexes containing 2-(2-nitrosoaryl)pyridine (ON(^)N) and tetradentate thioether 1,4,8,11-tetrathiacyclotetradecane ([14]aneS4), [Ru(ON(^)N)([14]aneS4)](2+) [ON(^)N = 2-(2-nitrosophenyl)pyridine (2a), 10-nitrosobenzo[h]quinoline (2b), 2-(2-nitroso-4-methylphenyl)pyridine, (2c), 2-(2-nitrosophenyl)-5-(trifluoromethyl)pyridine (2d)] and analogues with the 1,4,7-trithiacyclononane ([9]aneS3)/tert-butylisocyanide ligand set, [Ru(ON(^)N)([9]aneS3)(C≡N(t)Bu)](2+) (4a and 4b), have been prepared by insertion of a nitrosonium ion (NO(+)) into the Ru-aryl bond of cyclometalated ruthenium(II) complexes. The molecular structures of the ON(^)N-ligated complexes 2a and 2b reveal that (i) the ON(^)N ligands behave as bidentate chelates via the two N atoms and the bite angles are 86.84(18)-87.83(16)° and (ii) the Ru-N(NO) and N-O distances are 1.942(5)-1.948(4) and 1.235(6)-1.244(5) Å, respectively. The Ru-N(NO) and N-O distances, together with ν(N═O), suggest that the coordinated ON(^)N ligands in this work are neutral moiety (ArNO)(0) rather than monoanionic radical (ArNO)(•-) or dianion (ArNO)(2-) species. The nitrosated complexes 2a-2d show moderately intense absorptions centered at 463-484 nm [ε(max) = (5-6) × 10(3) dm(3) mol(-1) cm(-1)] and a clearly discriminable absorption shoulder around 620 nm (ε(max) = (6-9) × 10(2) dm(3) mol(-1) cm(-1)), which tails up to 800 nm. These visible absorptions are assigned as a mixing of d(Ru) → ON(^)N metal-to-ligand charge-transfer and ON(^)N intraligand transitions on the basis of time-dependent density functional theory (TD-DFT) calculations. The first reduction couples of the nitrosated complexes range from -0.53 to -0.62 V vs Cp(2)Fe(+/0), which are 1.1-1.2 V less negative than that for [Ru(bpy)([14]aneS4)](2+) (bpy = 2,2'-bipyridine). Both electrochemical data and DFT calculations suggest that the lowest unoccupied molecular orbitals of the nitrosated complexes are ON(^)N-centered. Natural population analysis shows that the amount of positive charge on the Ru centers and the [Ru([14]aneS4)] moieties in 2a and 2b is larger than that in [Ru(bpy)([14]aneS4)](2+). According to the results of the structural, spectroscopic, electrochemical, and theoretical investigations, the ON(^)N ligands in this work have considerable π-acidic character and behave as better electron acceptors than bpy.
Inorganic Chemistry 11/2011; 50(22):11636-43. · 4.60 Impact Factor
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ABSTRACT: A case series of inverted papilloma of the urinary bladder and urethra is presented, together with a review of the literature with respect to multiplicity, recurrence rate and association with transitional cell carcinoma, and a discussion on surveillance of the lesion.
Cases of inverted papilloma of the lower urinary tract in a single centre were reviewed. Patient and tumour characteristics, recurrence and associated transitional cell carcinoma are reported.
Twenty patients were included (18 male, two female). The mean age was 60.8 years (range 35-78 years). All had solitary tumours ranging from 3 mm to 30 mm in size. Median cystoscopic follow up was 30 months (range 2-140 months). There was no recurrence. One patient was associated with subsequent transitional cell carcinoma 44 and 76 months later. Together with the present 20 cases, review of the English literature with respect to inverted papilloma of the lower urinary tract identified a total of 322 cases reported, with a recurrence rate of 3.85%. Moreover, 1.55%, 5.90% and 1.54% were associated with previous, simultaneous and subsequent transitional cell carcinoma, respectively.
Recurrence is not uncommon and risk of subsequent transitional cell carcinoma is not rare, such that non-invasive surveillance with flexible cystoscopy is recommended for inverted papilloma of the lower urinary tract.
ANZ Journal of Surgery 05/2005; 75(4):213-7. · 1.25 Impact Factor
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Chi Wai Cheng,
Siu Foon Peter Chan,
Lung Wai Chan,
Chi Kwok Chan,
Chi Fai Ng, Ho Yuen Cheung,
Shu Yin Eddie Chan,
Wai Sang Wong,
Fernand Mac-Moune Lai,
Ka Fai To,
Miu Ling Li
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ABSTRACT: To compare bacillus Calmette-Guerin (BCG) with epirubicin in adjuvant therapy of superficial bladder transitional cell carcinoma, with respect to recurrence, progression and survival. Prognostic factors are also evaluated.
Between October 1991 and September 1999, all patients harboring superficial bladder cancers (Ta or T1) with any of the relevant criteria (stage>a, grade>1, size>1 cm, multiple or recurrent tumors), after complete transurethral resection were randomized to receive either 81 mg Connaught strain BCG or 50 mg epirubicin. Patients with recurrences were eligible to crossover, even repeatedly, until progression. Recurrence, progression and survival were analyzed in relation to initial treatment, patient characteristics and tumor characteristics.
There were 209 patients included in the study, 149 men and 60 women. The mean age was 69.9 years (range, 24-92). The BCG group consisted of 102 patients and the epirubicin group contained 107 patients. Final analysis was made at a median follow up of 23, 47 and 61 months for recurrence, progression and survival, respectively. The 10-year Kaplan-Meier estimates for recurrence-free, progression-free and disease-specific survival were 61%, 78% and 80%, respectively, for the BCG group. The corresponding figures were 32%, 74% and 92%, respectively, for the epirubicin group. Time to recurrence differed significantly between two treatment groups (P=0.0004). Multiplicity increased the risk of recurrence, while grading influenced recurrence, progression and disease specific survival.
Bacillus Calmette-Guerin prolonged time to recurrence when compared with epirubicin. Grading was shown to be a universal prognostic factor for recurrence, progression and disease specific survival.
International Journal of Urology 05/2005; 12(5):449-55. · 1.75 Impact Factor
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ABSTRACT: We report a carcinosarcoma within a bladder diverticulum together with a review of 18 previously reported cases of intradiverticular sarcomas and carcinosarcomas with respect to their clinical features, treatments and outcomes. Frequent deaths with intra-abdominal recurrences suggest the need for total cystectomy, rather than diverticulectomy.
International Journal of Urology 01/2005; 11(12):1136-8. · 1.75 Impact Factor
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ABSTRACT: To report the recurrence, progression and survival in patients with T1G3 transitional cell carcinoma (TCC) of the urinary bladder treated with sequential intravesical bacillus Calmette-Guérin (BCG) and chemotherapeutic agents (doxorubicin or epirubicin) on long-term follow up.
Between July 1988 and September 1999, all patients in a single center with T1G3 bladder TCC, after complete transurethral resection (TURBT), received either 81 mg of Connaught strain BCG or 50 mg of doxorubicin or epirubicin as adjuvant therapy. A conservative approach was adopted whereby those with superficial recurrences were eligible to crossover, even repeatedly, until progression to muscle invasion. Recurrence, progression and disease-specific survival were analyzed.
There were 36 patients included, with 26 males and 10 females. The mean age was 71.6 years (range 53-85 years). Final analysis was made at a median follow-up of 23.5 months (range 0-125 months) for recurrence, 33 months (range 0-125 months) for progression and 45.5 months (range 3-125 months) for survival. Sixteen (44.4%) patients showed recurrence. Nine (25%) of these 16 patients progressed. Five (13.9%) of those who progressed died of TCC. The 10 year Kaplan-Meier estimates for recurrence-free survival, progression-free survival and disease-specific survival were 48, 68 and 81%, respectively. Figures with this conservative approach were comparable to those with more aggressive approaches reported in the literature.
Adjuvant intravesical therapy with either BCG or a chemotherapeutic agent (doxorubicin or epirubicin) and crossover on recurrence was an effective conservative treatment for T1G3 bladder TCC.
Japanese Journal of Clinical Oncology 05/2004; 34(4):202-5. · 1.78 Impact Factor
