Using porous iron composite (PIC) material to immobilize rhenium as an analogue for technetium.

Technetium (99Tc), a uranium-235 (235U) and plutonium-239 (239Pu) fission product, is a primary risk driver in low level radioactive liquid waste at U.S. Department of Energy sites. Previous studies have shown success in using Zero Valent Iron (ZVI) to chemically reduce and immobilize redox sensitive groundwater contaminants. Batch and column experiments were performed to assess the ability of a novel porous iron composite material (PIC) to immobilize Tc(VII) in comparison with two commercial Fe oxide sorbents and reagent grade ZVI in the presence and absence of NO3-, a competing oxidized species that is often found in high concentrations in liquid nuclear waste. Perrhenate (ReO4-) was used as a non-radioactive chemical analogue for pertechnetate (TcO4-) under both oxic and anoxic test conditions. The PIC powder was the most effective at immobilizing Re(VII) under all batch test conditions. The presence of nitrate (NO3-) slowed the removal of ReO4- from solution, presumably through chemical reduction and precipitation. Even so, the PIC and ZVI were effective at removing both Re(VII) and NO3- completely from solution. Nitrate was reduced to NH3 with very little nitrite (NO2-) buildup during equilibration. Significant Re immobilization was observed in the column tests containing PIC sorbent, even though inlet solutions were in equilibrium with O2. The presence of NO3- hastened Re breakthrough, while NO3- reduction to NH3 was observed. The results suggest that PIC and ZVI would be the most effective at the removal of TcO4- from contaminated groundwater sites.

Intracellular distribution and stability of a luminescent rhenium(i) tricarbonyl tetrazolato complex using epifluorescence microscopy in conjunction with X-ray fluorescence imaging.

Optical epifluorescence microscopy was used in conjunction with X-ray fluorescence imaging to monitor the stability and intracellular distribution of the luminescent rhenium(i) complex fac-[Re(CO)3(phen)L], where phen = 1,10-phenathroline and L = 5-(4-iodophenyl)tetrazolato, in 22Rv1 cells. The rhenium complex showed no signs of ancillary ligand dissociation, a conclusion based on data obtained via X-ray fluorescence imaging aligning iodine and rhenium distributions. A diffuse reticular localisation was detected for the complex in the nuclear/perinuclear region of cells, by either optical or X-ray fluorescence imaging techniques. X-ray fluorescence also showed that the rhenium complex disrupted the homeostasis of some biologically relevant elements, such as chlorine, potassium and zinc.

(99m)Tc-Cyclopentadienyl Tricarbonyl Chelate-Labeled Compounds as Selective Sigma-2 Receptor Ligands for Tumor Imaging.

We have designed and synthesized a series of cyclopentadienyl tricarbonyl rhenium complexes containing a 5,6-dimethoxyisoindoline or a 6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline pharmacophore as σ2 receptor ligands. Rhenium compound 20a possessed low nanomolar σ2 receptor affinity (K(i) = 2.97 nM) and moderate subtype selectivity (10-fold). Moreover, it showed high selectivity toward vesicular acetylcholine transporter (2374-fold), dopamine D2L receptor, NMDA receptor, opiate receptor, dopamine transporter, norepinephrine transporter, and serotonin transporter. Its corresponding radiotracer [(99m)Tc]20b showed high uptake in a time- and dose-dependent manner in DU145 prostate cells and C6 glioma cells. In addition, this tracer exhibited high tumor uptake (5.92% ID/g at 240 min) and high tumor/blood and tumor/muscle ratios (21 and 16 at 240 min, respectively) as well as specific binding to σ receptors in nude mice bearing C6 glioma xenografts. Small animal SPECT/CT imaging of [(99m)Tc]20b in the C6 glioma xenograft model demonstrated a clear visualization of the tumor at 180 min after injection.

Norharmane rhenium(I) polypyridyl complexes: synthesis, structural and spectroscopic characterization.

Two novel Re(i) complexes with the general formula fac-[Re(CO)3(L)(nHo)]CF3SO3, where L = 2,2'-bipyridine (bpy) or 1,10 phenanthroline (phen) and nHo (9H-pyrido[3,4-b]indole; norharmane) have been synthesized. The Re(i)-nHo complexes were characterized by structural X-ray diffraction, (1)H and (13)C NMR, UV-vis absorption and FT-IR spectroscopy, and by a combination of two mass spectrometry techniques, namely ESI-MS and UV-MALDI-MS. All characterizations showed that nHo is coordinated to the metal atom by the pyridine nitrogen of the molecule. X-ray structural analysis revealed that the crystal lattices for both complexes are further stabilized by a strong >N-HO bond between the pyrrole NH group of the pyridoindole ligand and one oxygen atom of the trifluoromethanesulfonate counter-ion. Ground state geometry optimization by DFT calculations showed that in fluid solution the nHo ligand may rotate freely. The nature of the electronic transitions of Re(CO)3(bpy)(nHo)(+) were established by TD-DFT calculations. The set of the most important electronic transitions present in this complex are comprised of π→π* electronic transitions centered on bpy and nHo moieties, LLCTnHo→COs, MLLCTRe(CO)3→bpy and LLCTnHo→bpy transitions. Additionally, TD-DFT calculations predict the existence of another two intense MLLCTRe(CO)3→nHo electronic transitions. Calculated UV-vis absorption spectra are in good agreement with the corresponding experimental data for the bpy-containing complex.

Re and (99m)Tc complexes of BodP3--multi-modality imaging probes.

A fluorescent tridentate phosphine, BodP3 (2), forms rhenium complexes which effectively image cancer cells. Related technetium analogues are also readily prepared and have potential as dual SPECT/fluorescent biological probes.

Study of the therapeutic effect of 188Re labeled folate targeting albumin nanoparticle coupled with cis-diamminedichloroplatinum cisplatin on human ovarian cancer.

This paper aimed to investigate the treatment efficiency of 188Re labeled folate targeting albumin nanoparticles with cis-Diamminedichloroplatinum Cisplatin (188Re-folate-CDDP/HAS MNP) on human ovarian cancer. SKOV3 cells or tumor-bearing mice were divided into different groups and treated as follow: (A) negative control; (B) chemotherapy; (C) radiotherapy; (D) hyperthermia; (E) chemotherapy and radiotherapy; (F) chemotherapy and hyperthermia; (G) radiotherapy and hyperthermia; (H) chemotherapy, radiotherapy and hyperthermia. Treatment of B to H inhibited proliferation of SKOV3 cells, with the greatest inhibition being observed in group H (P<0.05). Obvious apoptotic hypodiploid peak appeared beside G1 phase in groups of B to H. The apoptotic rates of SKOV3 cells in groups of A to H were 0.08%, 7.56%, 8.64%, 17.14%, 21.64%, 23.77%, 33.94% and 57.16%, respectively. Our findings in vivo study showed that the mass of tumor in each group of B to H was significantly lower than that in the negative control (p <0.05). In addition, compared with each group of B to G, group H showed highest inhibition of tumor growth (p<0.05). In conclusion, the combination of magnetic induced hyperthermia, chemotherapy and targeted radionuclide of radiation exposure can effectively inhibit the growth of ovarian cancer, which indicates a potential applications in ovarian cancer treatment.

Investigation of activation cross-section data of proton induced nuclear reactions on rhenium.

In the frame of systematic investigations of activation cross-section data for different applications the excitation functions of (nat)Re(p,x)(185)Os, (183m)Os, (183g)Os, (182)Os, (181m)Os, (186g)Re, (184m)Re, (184g)Re, (183)Re, (182m)Re, (182g)Re and (181g)Re reactions were measured up to 70MeV. The data for the (nat)Re(p,x) (183m)Os, (183g)Os, (182)Os, (181g)Os,(186g)Re, (184m)Re,(182m)Re, (182g)Re, and (181)Re reactions are reported for the first time. The activation method, the stacked foil irradiation technique and γ-spectroscopy for activity detection were used. The experimental data were compared with predictions of three theoretical codes. From the measured cross-section thick target integral yields were also calculated and presented.

Direct observation of ¹7O-¹85/¹87Re ¹J-coupling in perrhenates by solid-state ¹7O VT MAS NMR: temperature and self-decoupling effects.

(17)O MAS NMR spectra recorded at 14.1T and room temperature (RT) for (17)O-enriched samples of the two perrhenates, KReO4 and NH4ReO4, exhibit very similar overall appearances of the manifold of spinning sidebands (ssbs) for the satellite transitions (STs) and the central transition (CT). These overall appearances of the spectra are easily simulated in terms of the usual quadrupole coupling and chemical shift interaction parameters. However, a detailed inspection of the line shapes for the individual ssbs of the STs and, in particular, for the CT in the spectrum of KReO4 reveals line-shape features, which to our knowledge have not before been observed experimentally in 1D MAS NMR spectra for any quadrupolar nucleus, nor emerged from simulations for any combination of second-order quadrupolar interaction and chemical shift anisotropy. In contrast, such line-shape features are not observed for the corresponding ssbs (STs and CT) in the 14.1T RT (17)O MAS NMR spectrum of NH4ReO4. Considering the additional interaction of a combination of residual heteronuclear (17)O-(185/)(187)Re dipolar and scalar J coupling between this spin pair of two quadrupolar nuclei, spectral simulations for KReO4 show that these interactions are able to account for the observed line shapes, although the expected (1)J((17)O-(185/)(187)Re) six-line spin-spin splittings are not resolved. Low-temperature, high-field (21.1T) (17)O VT MAS NMR spectra of both KReO4 and NH4ReO4 show that full resolution into six-line multiplets for the centerbands are achieved at -90°C and -138°C, respectively. This allows determination of (1)J((17)O-(187)Re)=-268Hz and -278Hz for KReO4 and NH4ReO4, respectively, i.e., an isotropic (1)J coupling and its sign between two quadrupolar nuclei, observed for the first time directly from solid-state one-pulse 1D MAS NMR spectra, without resort to additional 1D or 2D experiments. Determination of T1((187)Re) spin-lattice relaxation times, observed indirectly through a 2D (17)O EXSY experiment for NH4ReO4 at several low temperatures, show that the dynamics observed for the ReO4(-) anion in the (17)O VT MAS NMR spectra at low temperatures are caused by self-decoupling of (1)J((17)O-(187)Re). The (1)J((17)O-(187)Re) values determined here for ReO4(-) from solid-state (17)O MAS NMR, along with literature (1)J((17)O-M) values for oxoanions (M being a quadrupolar nucleus) obtained from liquid-state NMR, have allowed correlations to be established between the reduced coupling constant (1)K((17)O-M)=2π(1)J((17)O-M)/(γ17OγMℏ) and the atomic number of M.

Trace element profiles in sediments as proxies of dead zone history; rhenium compared to molybdenum.

Warm-season dead zones-volumes of coastal water containing too little O(2) to support macrofauna-are a growing global menace. Trace elements that are deposited in sediments in response to reducing or sulfidic conditions can provide proxy records for reconstructing dead zone evolution. Based on relative enrichment in reduced vs oxidized marine sediments, Re seems promising as a dead zone proxy. Here, Re is determined by isotope dilution mass spectrometry in sediments underlying the summertime dead zone in Chesapeake Bay. Contrary to expectation, Re becomes only modestly (∼2-fold) elevated during the 20th century and fails to track the historic record of summertime O(2) depletion. Rhenium enrichments are watershed-specific and apparently controlled by anthropogenic sources, not by redox-linked authigenic processes. In contrast, Mo enrichments do track historic O(2) depletion. Three factors cause redox control to override anthropogenic control in the case of Mo: relative to weathering fluxes, anthropogenic Mo fluxes are weaker than Re fluxes; during anoxic periods, Mn refluxing amplifies Mo but not Re concentrations near the sediment surface; and high pore water sulfide-polysulfide promotes Mo fixation in pyrite while promoting formation of organo-Re adducts; the latter are too mobile and reactive to preserve a reliable historic record under seasonally fluctuating redox conditions.

Synchrotron radiation FTIR detection of a metal-carbonyl tamoxifen analog. Correlation with luminescence microscopy to study its subcellular distribution.

1,1-Di(4-hydroxyphenyl)-2-cyrhetrenylbut-1-ene 1 is an organometallic conjugate where a [(Cp)Re(CO)(3)] unit is linked to a hydroxytamoxifen-like structure. Its subcellular nuclear distribution was previously observed in a single cell using the near-field technique AFMIR. We show here that synchrotron radiation FTIR spectromicroscopy (SR-FTIR-SM) enabled the mapping of 1 based on its IR-signature (characteristic bands in the 1850-2200 cm(-1) range) and pointed out the colocalization of 1 with an area of high amide density. Fluorescence microscopy using DAPI staining performed on the same cells confirmed that this area corresponds to the cell nucleus.

Biological dosimetry after radiosynoviorthesis with rhenium-186 sulphide and erbium-169 citrate.

UNLABELLED: Radiosynoviorthesis (RSO) with the nuclides rhenium-186 sulphide (186Re) and erbium-169 citrate (169Er) is an established concept for the treatment of persistent synovitis of medium and small sized joints. THE AIM of the present studies was to investigate the biological radiation effect based on analysing chromosome aberrations. PATIENTS, METHODS: Immediately before and 17 to 19 days (186Re) or 45 to 50 (169Er) days after RSO with 186Re or 169Er colloid and subsequent immobilisation of the treated joint, blood samples of a total of 23 patients were collected. The yield of dicentric chromosomes in lymphocytes was determined exclusively in metaphases of the first cell cycle in vitro. In addition, for 186Re the activity leakage was measured three days after RSO by whole-body scintigraphy. RESULTS: No statistically significant increase in the number of dicentric chromosomes (40 and 88 before and 59 and 105 after treatment with 186Re and 169Er, respectively) in a total of 47017 cells analysed from 46 blood samples could be found as a result of RSO. For 186Re an activity leakage of 3.9%±7% with a maximum of 23.4% corresponding to an effective dose of 2.8±4.5 mSv , respectively 13.8 mSv, was determined. Also in the case of the maximum leakage no significant increase of dicentric chromosomes were detected. CONCLUSIONS: No significant biological radiation effect can be detected after RSO with 186Re and 169Er, also in cases of high leakage. Therefore, RSO can be classified as a save therapeutic procedure without a relevant radiation risk.

Development of a highly selective cell-permeable ratiometric fluorescent chemosensor for oxorhenium(V) ion.

A novel 6-(2-pyridinyl)-5,6-dihydrobenzimidazo[1,2-c]quinazoline (HL) serves as a first-time highly selective and sensitive ratiometric fluorescent chemosensor probe for oxorhenium (ReO(V)) ion in acetonitrile : water = 9 : 1 (v/v) at 25 °C. The decrease in fluorescence at 410 nm and increase in fluorescence at 478 nm with an isoemissive point at 444 nm in the presence of ReO(V) ion is accounted for by the formation of mononuclear [ReOL(2)Cl] complex, characterized by physico-chemical and spectroscopic tools. The fluorescence quantum yield of the chemosensor (HL) was only 0.198 at 410 nm, and it increased more than 3-fold in the presence of 2 equiv. of the ReO(V) ion at 478 nm. Interestingly, the introduction of other metal ions and relevant anions caused the fluorescence intensity at 478 nm to be either unchanged or weakened. The fluorescence-response fits a Hill coefficient of 2.088 indicates the formation of a 1 : 2 stoichiometry for the L-ReO(V) complex. In the concentration range of 0-20 µM of oxorhenium(V) species calibration graph was linear with correlation coefficient (R) of 0.99994 and the calibration sensitivity was found to be 4.0 × 10(-7) M. The cellular image in the confocal microscope clearly indicated the presence of ReO(V) in Candida albicans cells using this chemosensor (HL).

Luminescent conjugates between dinuclear rhenium(I) complexes and peptide nucleic acids (PNA) for cell imaging and DNA targeting.

New luminescent dinuclear rhenium(I) tricarbonyl complex-PNA conjugates have been synthesized through a reliable solid-phase synthetic methodology. Their photophysical properties have been measured. The most luminescent Re-PNA conjugate 7 showed interesting two-photon absorption (TPA) properties, that were exploited for imaging experiments, to demonstrate its easy uptake into living cells.

Determination of rhenium content in molybdenite by ICP-MS after separation of the major matrix by solvent extraction with N-benzoyl-N-phenylhydroxalamine.

A simple and rapid analytical method for determining the concentration of rhenium in molybdenite for Re-Os dating was developed. The method used isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS) after the removal of major matrix elements (e.g., Mo, Fe, and W) from Re by solvent extraction with N-benzoyl-N-phenylhydroxylamine (BPHA) in chloroform solution. The effect on extraction efficiency of parameters such as pH (HCl concentration), BPHA concentration, and extraction time were also assessed. Under the optimal experimental conditions, the validity of the separation method was accessed by measuring (187)Re/(185)Re values for a molybdenite reference material (JDC). The obtained values were in good agreement with previously measured values of the Re standard. The proposed method was applied to replicate Re-Os dating of JDC and seven samples of molybdenite from the Yuanzhuding large Cu-Mo porphyry deposit. The results demonstrate good precision and accuracy for the proposed method. The advantages of the method (i.e., simplicity, efficiency, short analysis time, and low cost) make it suitable for routine analysis.

Molecular recognition of pertechnetate and perrhenate.

This tutorial review covers the chemistry of artificial receptors designed to recognize the pertechnetate and perrhenate anions. It focuses on the molecular features that give rise to effective and selective complexation. Specific receptor classes are discussed in the context of available solution-phase and solid-state data with differences between pertechnetate and perrhenate binding behavior being highlighted where appropriate.

Determination of Pd, Pt and Rh in vehicles escape fumes by GF-AAS and ICP-OES.

Automotive exhaust gases from vehicles using catalytic converters were filtered through cellulose filter papers to collect suspended particles expulsed along with the engine's escape fumes. A specially designed sample collector was used for supporting the filter papers during collection. The collector was manufactured from a new car's exhaust pipe. A cellulose circular paper filter, 11 cm diameter, was attached to one end of the pipe and kept centered by pressing it against the borders of the pipe by means of a perforated aluminum cap, slightly wider than the pipe, used to cover this end of the collector. Filter papers loaded with the solid particles were acid-digested using a modified domestic microwave oven to bring the solid material into solution. The resulting solutions were analyzed for Pt by graphite furnace atomic absorption spectrometry (GF-AAS) and for Pd and Rh by inductively coupled plasma (ICP-OES). Results indicate that concentration of these analytes in the particulate is higher for new vehicles, having new catalytic converters, than for old ones. Maximum Pd, Pt and Rh in the samples analyzed were found to be 5.36, 12.60 and 1.03 microg g(-1), respectively.

Determination of bioavailable rhenium fraction in agricultural soils.

Rhenium (Re) mobility in agricultural soils was studied in order to obtain information relevant to (99)Tc mobility in soil-to-plant systems. Since water soluble Tc and Re are highly bioavailable, extraction of Re with water was carried out in addition to a total Re determination in the soils. The geometric means of total Re for paddy field, upland field and other soils were 0.34, 0.23, and 0.28 ng g(-1), respectively, while those of water soluble Re (<0.45 microm membrane filterable) were 0.053, 0.015 and 0.008 ng g(-1), respectively. There were no differences for total Re among soil uses; however, the water soluble Re/total Re ratio was significantly higher in paddy field soils (16%) than in other soil uses (6% for upland fields and 3% for other uses). Rhenium mobility and plant availability were higher in paddy fields than in other agricultural fields, and similar phenomena would be expected for (99)Tc.

Comparison of measured and calculated spatial dose distributions for a bench-mark 106Ru/106Rh hot particle source.

This study is a part of a programme of research to provide validated dose measurement and calculation techniques for beta emitting hot particles by the construction of well-defined model hot particle sources. This enables parallel measurements and calculations to be critically compared. This particular study concentrates on the high-energy beta emitter, (106)Ru/(106)Rh (Emax = 3.54 MeV). This source is a common constituent of failed nuclear fuel, particularly in accident situations. The depth dose distributions were measured using radiochromic dye film (RDF); an imaging photon detector coupled to an LiF thermoluminescent dosemeter (LiF-IPD) and an extrapolation ionisation chamber (ECH). Dose calculations were performed using the Monte Carlo radiation transport code MCNP4C. Doses were measured and calculated as average values over various areas and depths. Of particular interest are the doses at depths of 7 and 30-50 mg cm(-2), and averaged over an area of 1 cm2, as recommended by the International Commission on Radiological Protection for use in routine and accidental over-exposures of the skin. In this case, the average ratios (MCNP/measurement) for RDF, ECH and LiF-IPD were 1.07 +/- 0.02, 1.02 +/- 0.01 and 0.83 +/- 0.16, respectively. There are significantly greater discrepancies between the ECH and LiF-IPD measurement techniques and calculations-particularly for shallow depths and small averaging areas.

Very stable 188Re-S4 chelates for labelling biomolecules: preparation with highly concentrated perrhenate eluates.

AIM: The preparation and stability of a new (188)Re-S(4)-complex [S(4) = (1-aza-18-crown-6)(O)C-C(SH)-C(SH)-C(O)NH-(CH(2))(3)-NH-(CH(2))(3)-NHC(O)-C(SH)-C(SH)-C(O)(1-aza-18-crown-6] was studied at therapeutic relevant radioactive concentrations. The results were compared with (188)Re-MAG(3) (MAG(3): mercaptoacetyltriglycine) and (188)Re-DMSA preparations (DMSA: dimercaptosuccinic acid) performed with the same highly concentrated [(188)Re]perrhenate solution (12-15 GBq/ml). METHODS: The (188)Re complexes were prepared by direct reduction of perrhenate ((188)Re-S(4)-complex) as well as via the (188)Re-EDTA precursor complex ((188)Re-MAG(3), (188)Re-DMSA). The preparations were stabilised with 15 mg of ascorbic acid and analysed after 1, 2, and 24 hours by TLC and HPLC. Additionally, in vitro and in vivo stability studies were performed with the purified complexes. RESULTS: After stabilisation with 15 mg of ascorbic acid, all of the complexes were nearly stable under nitrogen for hours, and only 2-8% of perrhenate was observed after 24 h. In contrast, only the (188)Re-S(4) complex was completely stable in vitro and in all investigated in vivo samples after separation of ligand excess and reducing agent by HPLC. CONCLUSION: The bridging amine group or free carboxylic groups of the S(4)-ligand framework make available reactive positions for coupling biomolecules to the chelate. Thus it appears that the new (188)Re-S(4) complexes offer the possibility of stable and high specific activity labelling of biomolecules for therapeutic application.

A whiff of oxygen before the great oxidation event?

High-resolution chemostratigraphy reveals an episode of enrichment of the redox-sensitive transition metals molybdenum and rhenium in the late Archean Mount McRae Shale in Western Australia. Correlations with organic carbon indicate that these metals were derived from contemporaneous seawater. Rhenium/osmium geochronology demonstrates that the enrichment is a primary sedimentary feature dating to 2501 +/- 8 million years ago (Ma). Molybdenum and rhenium were probably supplied to Archean oceans by oxidative weathering of crustal sulfide minerals. These findings point to the presence of small amounts of O2 in the environment more than 50 million years before the start of the Great Oxidation Event.