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PubMed1991

Intravaginal iridium-192 in the management of embryonal rhabdomyosarcoma.

Three patients with vaginal rhabdomyosarcoma and residual vaginal disease following surgery and chemotherapy have been treated using high dose irradiation with vaginal moulds loaded with iridium-192. These patients remain well and disease-free seven years, 30 months and 18 months after their initial presentations. This paper describes a technique for local vaginal irradiation with individualized vaginal moulds made using a rapid-setting silastic foam impression and loaded with a single plane of iridium wires. Details of the dosimetry are also included.

Antineoplastic Combined Chemotherapy Protocols↗
PubMed2002

Fabrication of anodically electrodeposited iridium oxide film pH microelectrodes for microenvironmental studies.

A new method for fabrication of anodically electrodeposited iridium oxide film pH microelectrodes has been developed in this study. Novel for its tip size (3-10-microm tip diameter), the microelectrode is fabricated in a tapered glass micropipet filled with a low melting point alloy. The tapered end is recessed and platinized. Thereafter, iridium oxide is electrodeposited over the platinized end in the recessed part. The microelectrode has a very short response time (t80 < 5 s) in the pH range of 0-12 with an accuracy of 0.05 pH unit. The pH microelectrode is not affected by most ions and complexing agents of relevance in environmental and biological studies; it can be used in fluids over wide ranges of stirring speeds (0-55 rpm) and temperatures (approximately 5-40 degrees C). Redox agents such as dissolved oxygen and hydrogen peroxide have no effect on the pH response while quinhydrone, ferro- and ferricyanide, and sodium sulfide have marked effects. However, the microelectrode can still be used in any sample when calibration is done in standards having similar redox characteristics.

Electrodes↗
PubMed2005

Hydrogenation of two-electron mixed-valence iridium alkyl complexes.

Two-electron mixed-valence complexes of the general formula (tfepma)(3)Ir(2)(0,II)RBr [tfepma = bis(bis(trifluoroethoxy)phosphino)methylamine, MeN[P(OCH(2)CF(3))(2)](2), and R = CH(3) (2), CH(2)C(CH(3))(3) (3)] have been synthesized and structurally characterized and their reactivity with H(2) investigated. Hydrogenation of 2 and 3 proceeds in a cascade reaction to produce alkane upon initial H(2) addition, followed by the formation of the Ir(2)(I,III) binuclear trihydride-bromide complex (tfepma)(3)Ir(2)(I,III)H(3)Br (4) upon the incorporation of a second molecule of H(2). Hydrogenation of two-electron mixed-valence di-iridium alkyl complexes is examined with nonlocal density-functional calculations. H(2) attacks the Ir(II) metal center prior to alkyl protonation to produce an eta(2)-H(2) complex. Transition states link all intermediates to a complex that has the same regiochemistry as the crystallographically determined final product. Calculated atomic charges suggest that the second H(2) molecule is homolytically cleaved within the di-iridium coordination sphere and that a hydrogen atom migrates across the intact Ir-Ir metal bond. These results are consistent with the emerging trend that two-electron mixed-valence cores manage the two-electron chemistry of substrates with facility when hydrogen is the atom that migrates between metal centers.

Algorithms↗
PubMed2003

Regio- and enantioselective iridium-catalyzed intermolecular allylic etherification of achiral allylic carbonates with phenoxides.

An enantioselective and regioselective iridium-catalyzed allylic etherification is described. The reaction of sodium and lithium aryloxides with achiral (E)-cinnamyl and terminal aliphatic allylic electrophiles in the presence of 2 mol % of an iridium-phosphoramidite complex provides chiral allylic aryl ethers in high yields and excellent levels of regio- and enantioselectivity. Lithium aryloxides containing a single substituent at an ortho, meta, or para position as well as sterically hindered phenoxides were tolerated. Reactions in THF displayed the most suitable balance of rate, regio-, and enantioselectivity. High ee's were also observed for the products from the reaction of alkyl (E)-allylic carbonates.

Allyl Compounds↗
PubMed2005

Inter-ligand energy transfer and related emission change in the cyclometalated heteroleptic iridium complex: facile and efficient color tuning over the whole visible range by the ancillary ligand structure.

We report a novel color tuning methodology in the electrophosphorescent iridium complex by substituting one cyclometalating ligand to an ancillary ligand as an emitting center. Highly efficient exothermic inter-ligand energy transfer (ILET) from the MLCT3 state produced between iridium and cyclometalating 2-(2,4-difluorophenyl)pyridine to LX3 state of the ancillary ligand offers a chance to access a wider range of color from sky blue (478 nm) to red (666 nm). Characteristic shapes of photoluminescence spectra, strong solvatochromic phenomena as well as DFT calculations gave evidences for this exothermic ILET.

Color↗
PubMed2005

Iridium-catalyzed regio- and enantioselective allylation of ketone enolates.

The regio- and enantioselective alpha-allylation of unstabilized ketone enolates with unsymmetrical allylic carbonates to form the branched substitution products in the presence of metallacyclic iridium catalysts is reported. The products, branched gamma,delta-unsaturated ketones, were obtained from readily available silyl enol ethers and achiral Boc-protected allylic alcohols in high regioselectivities and enantioselectivities (91-96% ee). The combination of CsF and ZnF2 was shown to promote this reaction and suppress the formation of diallylation byproducts. In addition, iridium complexes derived from simple phosphoramidite ligands were shown to catalyze this reaction with excellent selectivities, and spectroscopic data show that a cyclometalated Ir precatalyst is formed in situ. This process provides an enantioselective access to synthetically important bifunctional compounds, which are generally accessible, but in racemic form, through Claisen rearrangements. Ten examples of the reactions of aromatic, as well as aliphatic, substrates are reported.

Catalysis↗
PubMed2004

Cross-couplings in the elaboration of luminescent bis-terpyridyl iridium complexes: the effect of extended or inhibited conjugation on emission.

The utility of Suzuki cross-coupling methodology for the in situ elaboration of bromo-functionalised bis-terpyridyl iridium(III) complexes has been explored. The complex [Ir(tpy)(tpy-phi-Br)]3+ [tpy-phi-Br = 4'-(4-bromophenyl)-2,2':6',2''-terpyridine] undergoes palladium-catalysed cross-coupling with aryl boronic acids to yield biaryl-substituted complexes directly. The biphenyl and 4-cyanobiphenyl-substituted products display relatively intense, long-lived (tau > 100 mus) yellow emission in degassed aqueous solution at room temperature, assigned to a 3pi-pi* state. A 4-aminobiphenyl-substituted analogue displays an additional low energy absorbance band, attributed to an intraligand charge-transfer (ILCT) excited state, and is scarcely emissive under the same conditions. The iridium(III) complex of 4'-mesityl-terpyridine is also reported. Its emission is much shorter-lived, with a spectral profile resembling that of unsubstituted [Ir(tpy)2]3+, confirming the need for the attainment of a roughly coplanar geometry for stabilisation of the 3pi-pi* excited state.

Absorption↗
PubMed2005

Light-emitting iridium(III) and ruthenium(II) polypyridyl complexes containing quadruple hydrogen-bonding moieties.

A novel compound containing both a 2,2'-bipyridine as well as a 2-ureido-4[1H]-ureidopyrimidinone supramolecular moiety (3) has been synthesised and fully characterized by 1H-NMR, MALDI-TOFMS, UV-vis and IR spectroscopy. Subsequent coordination to iridium and ruthenium polypyridyl precursors allowed the formation of iridium(III) and ruthenium(II) polypyridyl dimers (5 and 7) assembled via quadruple hydrogen-bonding as well as metal coordination interactions. The syntheses and complete characterization of these materials by means of two-dimensional NMR techniques (1H-1H COSY and 1H-1H DOSY) as well as IR and MALDI-TOFMS are described in detail. Comparative studies of the optical properties of the luminescent model complexes (5' and '7) and the dimer species (5 and 7) are also illustrated. In addition, good processability of the materials has been demonstrated by inkjet printing leading to thin films revealing their potential for light-emitting devices.

2,2'-Dipyridyl↗
PubMed2001

Attitudes and treatment outcome of breast conservation therapy for stage I & II breast cancer using peroperative iridium-192 implant boost to the tumour bed.

Breast conservation therapy for early breast cancer is an established but grossly under-utilized treatment option in India for various reasons. Breast conservation therapy was offered to 200 suitable breast cancer patients between June 1993 and June 1998. Fifty-one patients (25%) opted for breast conservation and the remaining preferred mastectomy. In patients agreeing to conservation therapy, surgery was performed first along with peroperative implantation of iridium-192 to deliver a boost. Whole breast irradiation of 45 Gy was delivered 3-4 weeks after the boost. Cosmesis was assessed at the end of 6 months from completion of therapy. The main reason for refusal of breast conservation therapy was fear of recurrence in the remaining breast (60%). There were no locoregional failures in our study at a median follow up of 42 months; one patient experienced a systemic relapse. Cosmesis was good to excellent in 80% of patients. Breast conservation therapy using peroperative iridium-192 implant provides excellent locoregional disease control and cosmesis. The results of our study indicate that patient preference for mastectomy is an important reason for the under-utilization of breast conservation therapy in India.

Adult↗
PubMed1987

Laser and endoluminal 192-iridium radiation.

The combination of laser and endoluminal 192-iridium irradiation for the palliation of malignancies of the esophagus and the cardia was introduced to overcome the short-term effect of laser treatment alone. On the basis of early experience, this method would seem to prolong the effect of laser treatment alone, and is associated with a low risk of complications. However, the initial optimistic results, claiming permanent relief of dysphagia in 80% of the patients, cannot be reproduced under prospective conditions. The combination of laser and 192-iridium irradiation with other palliative methods, such as external radiation treatment and/or chemotherapy is feasible, and remains to be studied in a comparative way.

Brachytherapy↗
PubMed1986

[New methods in the radiotherapy of bronchial carcinoma. Endobronchial small-field irradiation using the iridium-129 high-dose afterloading technic in combination with the neodymium-YAG laser].

106 patients with inoperable malignant tumours constricting the central bronchial tree underwent endobronchial small-field radiotherapy with iridium-192 at high dose between June 1983 and September 1985. Treatment was performed using the computer-guided after-loading technique and a flexible bronchoscope under local anaesthesia. In complete occlusion of a bronchus by the tumour, a neodymium YAG-laser was applied (57 patients) to allow insertion of the after-loading probe. Endoscopy showed tumour regression in 75% of the patients, accompanied by clinical improvement. Pulmonary function tests, arterial blood gas analyses and pulmonary perfusion scans yielded a highly significant improvement of data after treatment. The procedure also proved effective upon exhaustion of external radiation. Apart from its positive palliation, endobronchial small-field radiotherapy using high doses of iridium-192 also has a curative effect, thus opening up a new approach to the therapy of advanced bronchial carcinoma.

Aged↗
PubMed2004

Long-term clearance kinetics of inhaled ultrafine insoluble iridium particles from the rat lung, including transient translocation into secondary organs.

Recently it was speculated that ultrafine particles (UFP) may translocate from deposition sites in the lungs to systemic circulation and whether long-term clearance differs between ultrafine and micrometer-sized particles. We have studied lung retention and clearance kinetics in 12 healthy male adult WKY rats up to 6 mo after an inhalation of (192)Ir-radiolabeled, insoluble, ultrafine 15- to 20-nm iridium particles. Whole-body retention was followed by external gamma counting, and particle clearance kinetics were determined by excretion radioanalysis. Four rats each were sacrificed after 3 wk and 2 and 6 mo; all organs as well as tissues and the carcass were radioanalyzed to balance the entire deposited radioactivity of the particles. The most prominent fraction was retained in the lungs at each time point of sacrifice (26%, 15%, 6%, respectively), and clearance out of the body was solely via excretion. Extrapulmonary particle uptake did not continue to increase but decreased with time in liver, spleen, heart, and brain when compared to previous data obtained during the first 7 days after inhalation (Kreyling et al., 2002). UFP long-term lung retention derived from whole-body measurements was comparable to previously reported data using insoluble micrometer-sized particles (Bellmann et al., 1994; Lehnert et al., 1989). In addition, differential analysis including daily excretion data revealed a pattern of fractional particle clearance rate of the ultrafine iridium particles similar to that of micrometer-sized particles reported by Snipes et al. (1983) and Bailey et al. (1985).

Administration, Inhalation↗
PubMed1999

A MAD experiment performed at the white line of the iridium LIII absorption edge in lysozyme.

A multiple-wavelength anomalous diffraction (MAD) experiment was performed on an iridium derivative of hen egg-white lysozyme. Diffraction data were measured at five wavelengths on the X31 EMBL beamline on the DORIS III storage ring and at two further wavelengths on the X11 beamline. Four iridium-binding sites were located from the dispersive anomalous differences between two wavelengths at the rising and falling inflection points of the Ir LIII-edge white line using direct methods. All other attempts to determine the heavy-atom positions failed. The results demonstrate an experimental method whereby systematic error in MAD data due to sample absorption can be reduced where a white line is present in the absorption spectrum of a heavy atom.

Animals↗
PubMed2004

High-dose rate iridium-192 brachytherapy and external beam radiation therapy for prostate cancer with or without androgen ablation.

AIM: To report the results of our feasibility study incorporating iridium-192 high-dose-rate (HDR) afterloading brachytherapy and external beam radiation therapy (EBRT) for the treatment of prostate carcinoma and to assess the role of androgen ablation in conjunction with this treatment option. METHODS: From July 2000 to June 2002, 42 patients with clinically localized or locally extensive prostate carcinoma were treated with HDR iridium-192 brachytherapy and EBRT with or without androgen ablation. The median follow up was 16.5 months. RESULTS: The technique of HDR brachytherapy and EBRT proved to be feasible with acceptable morbidities. Continuous prostate-specific antigen (PSA) reduction was noted in all patients and no PSA failure was noted during follow up. Within 1 year, the decline of PSA nadir values less than 1 ng/mL was faster in patients with the addition of androgen blockade (P = 0.001). However, within 1 year, PSA nadir values less than 1.0 ng/mL can be achieved in all patients whose initial PSA is less than 20 ng/mL, with or without hormone blockade. CONCLUSIONS: The need for hormonal therapy in favorable-risk brachytherapy patients (PSA < 20 ng/mL) might be less than the need for intermediate- or high-risk patients. The use of hormonal therapy in intermediate-risk patients (PSA >/= 20 ng/mL) treated with HDR brachytherapy and pelvic EBRT is appealing, considering the favorable results. High dose rate brachytherapy appears to be an effective treatment for clinically localized and locally extensive prostate cancer, with minimal morbidity.

Aged↗
PubMed2003

Iridium-192 implantation for T1 and T2a carcinoma of the tongue and floor of mouth: retrospective study of the results of treatment at the Royal Berkshire Hospital.

Carcinomas of the tongue and floor of mouth are relatively rare tumours, which may be treated using several modalities. We reviewed the results of iridium wire implants performed at the Royal Berkshire Hospital between 1994 and 2000. 24 patients had iridium wire implants as primary treatment for tongue and floor of mouth cancers. Four patients were treated after excision biopsy with close or involved margins. One patient was treated for a recurrence after surgery. The median age at treatment was 61 years. There were 18 men and 11 women. 21 patients had tumours of the tongue and eight of the floor of mouth. 13 had T1 tumours and 11 had T2a tumours. The median follow up was 42 months. The primary tumour was controlled in 22 of the 29 patients by the implant alone. Of the seven patients with local recurrence four were successfully salvaged with surgery. The acturarial 2 year survival rates were: overall survival 81%, disease specific survival 91%, local recurrence free survival 85% and nodal relapse free survival 76%. The recorded complication rate was low, one patient developing radionecrosis of the mandible at 7 years post implant. We believe these results show that brachytherapy remains a treatment option for patients with early tongue carcinoma with a high rate of local control and low toxicity.

Adult↗
PubMed1997

New method for the evaluation of the response of cultured cell lines to continuous low-dose-rate irradiation from encapsulated iridium-192 seeds with hyperthermia.

A new method was designed to investigate and evaluate the biological effectiveness of hyperthermia combined with continuous low-dose-rate irradiation (CLDRI) from encapsulated iridium-192 seed sources on glioma cells in vitro using the MTT assay. The system consists of 10 iridium seeds contained in a catheter bent into a circle, which is placed on a culture plate containing the cells. The effects of CLDRI and CLDRI combined with hyperthermia on a cultured rat glioma cell line (C-6) were studied. The number of surviving cells decreased as the total radiation dose increased. There was no significant difference in survival rates at dose rates of 0.1 Gy/hr and of 0.2 Gy/hr (p = 0.2811). An additive effect was observed in the cells treated with hyperthermia at 41 degrees C and 42 degrees C, combined with CLDRI, and synergistic effect between the two treatment modalities was observed at 43 degrees C. This new device is less expensive, easily reproducible, and can also be performed easily enough to examine a large number of samples in a short time period for sensitivity testing.

Animals↗
PubMed1997

Effect of adjuvant iridium-192 brachytherapy on the survival of patients with malignant gliomas.

The effect of iridium-192 brachytherapy (BRTX) on the survival of patients with malignant gliomas was evaluated in 83 patients with malignant gliomas (42 astrocytoma grade III, 41 glioblastoma multiforme) over a period of 8.5 years. Fifty patients (Group 1) received only standard external beam radiotherapy (EBRT) (mean dose 51.5 +/- 12.4 Gy in 2.0 Gy fractions), and 33 patients (Group 2) received EBRT (mean dose 51.0 +/- 10.8 Gy) combined with BRTX (mean dose 50.2 +/- 13.2 Gy, dose rate of 0.3-0.4 Gy/hr). The median survival periods for patients in Groups 1 and 2 were 12.2 and 23.7 months, respectively (p = 0.0145). The median survival for 17 patients in Group 2 with glioblastoma multiforme was 21.9 months. Using BRTX as an adjuvant to EBRT appeared to confer survival benefits compared to only EBRT (p = 0.0284). Univariate and multivariate analysis identified the variables of histological diagnosis, location, Karnofsky performance status, and BRTX as relevant risk factors for survival time (p < 0.05 for each factor). Among these factors, BRTX was the most important for prolonging survival (p = 0.0015). Adjuvant iridium-192 BRTX and conventional EBRT appears to greatly improve the survival time of patients with malignant gliomas compared to only EBRT and may be the treatment of choice in selected patients with tumors located in deep-seated or eloquent areas.

Adult↗