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PubMed1995

Non-radioactive detection of oligonucleotide probes by photochemical amplification of dioxetanes.

We describe a new method of non-radioactive labelling and detection of oligonucleotide probes. The approach is based on a simple chemical principle. Oligonucleotides labelled with methylene blue (a photosensitizer) are hybridized on a membrane to immobilized DNA target sequences. After hybridization and stringency washing 2(-)[3-(hydroxyphenyl)methoxymethylene] adamantane is added to the membrane and the membrane is irradiated with a tungsten lamp light source through a cut-off filter. Thermally stable dioxetanes are amplified during irradiation at the positions of the labelled probe. These amplified dioxetanes are detected using chemically triggered chemiluminescent decay. Signals are recorded on commercial X-ray film. Detection is possible immediately after the last washing step and a hard copy of the blot is obtained within 1 h. Dependent on the level of the target sequences, the sensitivity of the method allows detection of 0.3 pg single-stranded M13mp18(+) plasmid DNA in dot blots and 75 pg in Southern blots. Additional immunological reaction steps and washing steps with blocking reagents and buffers are avoided. Furthermore, expensive reagents and equipment for physical detection are not necessary. The method might be particularly useful for fast routine analysis in forensic and medical applications. The synthesis of the olefin, conditions of hybridization and the protocol of detection are described in detail.

Adamantane↗
PubMed2005

An investigation of microleakage from root-end fillings in ultrasonic retrograde cavities with or without finishing: a quantitative analysis.

OBJECTIVE: The aim of this study was to make a quantitative assessment of the sealing ability of Super-EBA, IRM, and Pro Root MTA root-end fillings subjected to 3 different finishing techniques. STUDY DESIGN: Eighty-one ultrasonically prepared root-end cavities in human canines were separated randomly into 3 test groups of 27 roots each. The cavities were filled with Super-EBA, IRM, or Pro Root MTA and finished by ball burnishing. Sequentially, 18 roots from each group received a final smoothing with either a 30-fluted tungsten carbide finishing bur or a Zekrya carbide 28-mm bur. Samples were prepared and immersed in 2% methylene blue dye neutral solution for 12 hours. Roots were ground into a powder and prepared for analysis in an absorbency spectrophotometer. RESULTS: The results revealed that Pro Root MTA displayed significantly less mean dye microleakage ( P < .05) than Super-EBA and IRM root-end fillings. The Super-EBA root-end fillings, although presenting a greater mean dye microleakage, did not differ significantly from IRM ( P > .05). The finishing technique did not significantly ( P > .05) affect the incidence of microleakage among the materials tested. CONCLUSIONS: The favorable results obtained with MTA in leakage studies may be related to its good marginal adaptation. Spectrophotometric analysis may provide valuable information about the sealing capacity of root-end fillings. None of the procedures tested were able to avoid leakage, a finding that stresses the importance of the eradication of irritants within the root canal system.

Aluminum Compounds↗
PubMed2000

Direct determination of lead in biological samples by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) after furnace-fusion in the sample cuvette-tungsten boat furnace.

The newly conceived electrothermal vaporization (ETV) system using a tungsten boat furnace (TBF) sample cuvette was designed for the direct analysis of solid samples with detection by inductively coupled plasma mass spectrometry (ICP-MS). Into this small sample cuvette, a solid mixture of the biological samples and diammonium hydrogenphosphate powder as a fusion flux was placed and situated on a TBF. Tetramethylammonium hydroxide solution was added to the mixture. After the on-furnace digestion had been completed, the analyte in the cuvette was vaporized and introduced into the ICP mass spectrometer. The solid samples were analyzed by using a calibration curve prepared from the aqueous standard solutions. The detection limit was estimated to be 5.1 pg of lead, which corresponds to 10.2 ng g(-1) of lead in solid samples when a prepared sample amount of 1.0 mg was applied. The relative standard deviation for 8 replicate measurements obtained with 100 pg of lead was calculated to be 6.5%. The analytical results for various biological samples are described.

Animals↗
PubMed1982

Construction of a composite thin-element TLD using an optical-heating method.

A composite thermoluminescent dosimeter (TLD), composed of four, thin TL elements with a high-speed reader, has been developed by employing an optical-heating method. Each TL element, which is 15 mg/cm2 thick with a 3 mm dia., is prepared by applying Li2B4O7:Cu or CaSO4:Tm to a plastic substrate 14 mg/cm2 thick. Each element can be heated to 350 degree C within 0.8 sec. by IR radiation from a tungsten lamp. The characteristics of this TLD system include the following: (1) the detection limit of the Li2B4O7:Cu is 3 mR and the limit for CaSO4:Tm is 0.1 mR; (2) the energy-dependence curves are similar to the dose-equivalent curve, showing slight under-responses by 15% near 70 KeV for Li2B4O7:Cu and over-responses by 50% at high energies for CaSO4:Tm; (3) despite quick heating, the residual dose is as low as 0.1% of the last exposure signal; (4) responses are very stable for more than 1,000 cycles of repeated exposure readings; (5) no false signal could be detected, even in the cases of sweat or soil contamination; (6) the thin Li2B4O7;Cu element can be used for skin dose monitoring; and (7) the processing time of the automatic reader for the composite dosimeter is 3 hr/500 dosimeters. This TLD system can be applied to personnel dosimetry, gate monitoring and environmental monitoring.

Borates↗
PubMed2001

The elusive 16-electron Cp*M(NO)Me(2)(M = Mo, W) complexes and their spontaneous conversions to Cp*M(NMe)(O)Me isomers.

Treatment of [Cp*Mo(NO)Cl(mu-Cl)](2) with magnesium (Me(2)Mg.dioxane, MeMgCl) or aluminum (Me(3)Al) methylating reagents affords the known compound [Cp*Mo(NO)Me(mu-Cl)](2) (1). Similar treatment of the dichloro precursor with MeLi in ethereal solvents generates an equimolar mixture of 1 and the trimethyl "ate" complex, Cp*MoMe(3)(NO-Li(OEt(2)(n)), (2-Et(2)O). Reaction of 2-Et(2)O with a source of [Me](+) forms Cp*MoMe(3)(=N-OMe)(3), a rare terminal alkoxylimido complex. Metathesis of the chloro ligands of [Cp*Mo(NO)Cl(mu-Cl)](2) by MeLi in toluene at low temperatures produces the target dimethyl complex, Cp*Mo(NO)Me(2) (4), in 75% isolated yield. In solution, 4 is predominantly a monomeric species, whereas in the solid state it adopts a dimeric or oligomeric structure containing isonitrosyl bridges as indicated by IR and (15)N/(13)C NMR spectroscopies. Hydrolysis of 4 affords meso- and rac-[Cp*Mo(NO)Me](2)(mu-O) (5), and the reactions of 4 with a range of Lewis bases, L, to form the 18e adducts Cp*Mo(NO)(L)Me(2) (e.g., Cp*Mo(NO)(PMe(3))Me(2) (7)), have established it to be the most electrophilic complex of its family. Acidolysis of the methyl groups of 4 is also facile. Most notably, 4 is thermally unstable in solution and undergoes isomerization via nitrosyl N-O bond cleavage to its oxo(imido) form, Cp*Mo(NMe)(O)Me (11), which is isolable from the final reaction mixture as the mu-oxo-bridged adduct formed by 4 and 11, i.e., Cp*Mo(NO)Me(2)(mu-O)Cp*Mo(NMe)Me (4 <-- 11). The rate of this isomerization is significantly faster for the tungsten dimethyl complex; hence, Cp*W(NO)Me(2) (12) is not isolable free of a supporting donor interaction and can only be isolated as Cp*W(NO)Me(2)(mu-O)Cp*W(NMe)Me (12 <-- 13) or Cp*W(NO)Me(2)(PMe(3)) (14) adducts.

Journal Article↗
PubMed2000

A selenopyrylium photosensitizer for photodynamic therapy related in structure to the antitumor agent AA1 with potent in vivo activity and no long-term skin photosensitization.

Cationic chalcogenopyrylium dyes 5 were synthesized in six steps from p-aminophenylacetylene (9), have absorption maxima in methanol of 623, 654, and 680 nm for thio-, seleno-, and telluropyrylium dyes, respectively, and generate singlet oxygen with quantum yields [Phi((1)O(2))] of 0.013, 0.029, and 0.030, respectively. Selenopyrylium dye 5-Se was phototoxic to cultured murine Colo-26 and Molt-4 cells. Initial acute toxicity studies in vivo demonstrate that, at 29 mg (62 micromol)/kg, no toxicity was observed with 5-Se in animals followed for 90 days under normal vivarium conditions. In animals given 10 mg/kg of 5-Se via intravenous injection, 2-8 nmol of 5-Se/g of tumor was found at 3, 6, and 24 h postinjection. Animals bearing R3230AC rat mammary adenocarcinomas were treated with 10 mg/kg of 5-Se via tail-vein injection and with 720 J cm(-2) of 570-750-nm light from a filtered tungsten lamp at 200 mW cm(-2) (24 h postinjection of 5-Se). Treated animals gave a tumor-doubling time of 9 +/- 4 days, which is a 300% increase in tumor-doubling time relative to the 3 +/- 2 days for untreated dark controls. Mechanistically, the mitochondria appear to be a target. In cultured R3230AC rat mammary adenocarcinoma cells treated with 0.1 and 1.0 microM 5-Se and light, mitochondrial cytochrome c oxidase activity was inhibited relative to cytochrome c oxidase activity in untreated cells. Irradiation of isolated mitochondrial suspensions treated with 10 microM dye 5-Se inhibited cytochrome c oxidase activity. The degree of enzyme inhibition was abated in a reduced oxygen environment. Superoxide dismutase, at a final concentration of 30 U, did not alter the photosensitized inhibition of mitochondrial cytochrome c oxidase by dye 5-Se. The data suggest that singlet oxygen may play a major role in the photosensitized inhibition of mitochondrial cytochrome c oxidase.

Adenocarcinoma↗
PubMed1972

Effects of molybdate, tungstate, and selenium compounds on formate dehydrogenase and other enzyme systems in Escherichia coli.

The role of selenium and molybdenum in the metabolism of Escherichia coli was explored by growing cells in a simple salts medium and examining the metabolic consequences of altering the concentration of molybdenum and selenium compounds in the medium. The addition of tungstate increased the molybdate deficiency of this medium, as reflected by lowered levels of enzyme systems previously recognized to require compounds of molybdenum and selenium for their formation [formate-dependent oxygen reduction, formate dehydrogenase (FDH) (EC 1.2.2.1), and nitrate reductase (EC 1.9.6.1)]. The requirement for selenium and molybdenum appears to be unique to the enzymes of formate and nitrate metabolism since molybdate- and selenite-deficient medium had no effect on the level of several dehydrogenase and oxidase systems, for which the electron donors were reduced nicotinamide adenine dinucleotide, succinate, d- or l-lactate, and glycerol. In addition, no effect was observed on the growth rate or cell yield with any carbon source tested (glucose, glycerol, dl-lactate, acetate, succinate, and l-malate) when the medium was deficient in molybdenum and selenium. dl-Selenocystine was about as effective as selenite in stimulating the formation of formate dehydrogenase, whereas dl-selenomethionine was only 1% as effective. In aerobic cells, an amount of FDH was formed such that 3,200 or 3,800 moles of formate were oxidized per min per mole of added selenium (added as dl-selenocystine or selenite, respectively).

Aerobiosis↗
PubMed2003

A prototype small CdTe gamma camera for radioguided surgery and other imaging applications.

Gamma probes have been used for sentinel lymph node biopsy in melanoma and breast cancer. However, these probes can provide only radioactivity counts and variable pitch audio output based on the intensity of the detected radioactivity. We have developed a small semiconductor gamma camera (SSGC) that allows visualisation of the size, shape and location of the target tissues. This study is designed to characterise the performance of the SSGC for radioguided surgery of metastatic lesions and for other imaging applications amenable to the smaller format of this prototype imaging system. The detector head had 32 cadmium telluride semiconductor arrays with a total of 1,024 pixels, and with application-specific integrated circuits (ASICs) and a tungsten collimator. The entire assembly was encased in a lead housing measuring 152 mmx166 mmx65 mm. The effective visual field was 44.8 mmx44.8 mm. The energy resolution and imaging aspects were tested. Two spherical 5-mm- and 15-mm-diameter technetium-99m radioactive sources that had activities of 0.15 MBq and 100 MBq, respectively, were used to simulate a sentinel lymph node and an injection site. The relative detectability of these foci by the new detector and a conventional scintillation camera was studied. The prototype was also examined in a variety of clinical applications. Energy resolution [full-width at half-maximum (FWHM)] for a single element at the centre of the field of view was 4.2% at 140 keV (99mTc), and the mean energy resolution of the CdTe detector arrays was approximately 7.8%. The spatial resolution, represented by FWHM, had a mean value of 1.56 +/- 0.05 mm. Simulated node foci could be visualised clearly by the SSGC using a 15-s acquisition time. In preliminary clinical tests, the SSGC successfully imaged diseases in a variety of tissues, including salivary and thyroid glands, temporomandibular joints and sentinel lymph nodes. The SSGC has significant potential for diagnosing diseases and facilitating subsequent radioguided surgery.

Aged↗
PubMed2003

Lead and lead toxicity in domestic and free living birds.

At present, domestic and wild fauna are being exposed to aspects and factors which are foreign to the habitat in which they live. One that stands out is the enormous amount and variety of chemical compounds which, in many cases, are highly complex and which are constantly being released into the atmosphere, mainly from agricultural and industrial activity. All these substances affect some species more than others, whether they be plants or animals, from the most insignificant micro-organism to the most evolved species, among them birds. Finally, another cause of mortality in many birds is plumbism, namely death caused by the ingestion of lead. Lead has been one of the main causes of poisoning in man since ancient times due to its use in many activities although it is only recently that this toxicity has been recognized. Moreover, the use of lead pellets for shooting has resulted in the release into the environment of millions of these over many years, with serious repercussions for many bird species populations, which have ingested them either directly or indirectly. Added to this use of lead in cynegetic activities is the fate of the lead weights (sinkers or ballast) used by rod fishers, which sink to the bottom or accumulate on the banks of rivers, lakes, lagoons or reservoirs. The problem arises when these pellets or weights are ingested by birds, mainly Anatidae, which mistake them for the small stones or grit they use to triturate food in their gizzards. Small particles of lead enter the digestive tract, start dissolving in the form of lead salts, are incorporated into the bloodstream and the rest of the body, accumulate in organs like the liver or kidneys, and cause physiological or behavioural changes. When certain concentrations of lead are reached, the birds then die. If lead-poisoned birds are consumed by carrions or predators, the latter also ingest the lead so that they may also be affected or die from plumbism since, being a heavy metal, its degradation and/or elimination is very difficult. There is, therefore, no doubt that millions of birds die annually worldwide from lead poisoning (in the U.S.A., around 3,000,000), this problem being most acute in marshland. The solutions could include the introduction of legislation regulating or banning shooting, in the use of non-toxic ammunition in marshes and protected areas, the substitution of lead pellets for other non-toxic ones, such as steel, bismuth, tungsten or other suitable metals, and to go on studying other possible alternatives to end such a dramatic situation for birds all over the world.

Animals↗
PubMed2003

Mammotomography with pinhole incomplete circular orbit SPECT.

UNLABELLED: Dedicated mammotomography with pinhole incomplete circular orbit (PICO) SPECT imaging of an uncompressed pendant breast was evaluated with small, very-high-stopping-power pinhole apertures. Comparisons were made with planar pinhole scintimammography. Enhanced 3-dimensional imaging performance with very-high-stopping-power apertures is thought to ultimately yield improved sensitivities for lesion detection and identification in breast disease. METHODS: Pinhole collimators made of high-density and high atomic number (184)W or depleted (238)U, with aperture diameters from 1 to 4 mm, were used to image 0.6- and 1.0-cm-diameter spherical lesions in a pendulous, uncompressed breast phantom in planar and PICO-SPECT modes. The breast was centered on the horizontal axis of rotation of an incomplete circular orbit. Lesion, breast and body, and myocardial activities (L:B:M) were included in the phantoms to simulate clinical imaging conditions with (99m)Tc (140 keV). Lesion contrasts and signal-to-noise ratios (SNRs) for all apertures were determined for near clinical acquisition times for L:B:M ratios of 12:1:20 and 7:1:25. A set of minidisks inserted in the breast phantom was scanned to determine sampling limitations at depth from the nipple. In an initial study, a patient with biopsy-confirmed breast carcinoma was injected with 960 MBq (99m)Tc-tetrofosmin and scanned 2 h later with planar pinhole and PICO-SPECT techniques. RESULTS: Overall, for PICO-SPECT imaging there were small differences in measured counting rate sensitivity (4.9%) and lesion contrast (8.8%) with larger SNR differences (20.8%) between tungsten and depleted uranium pinhole materials at this energy and these lesion sizes. Backgrounds from simulated myocardial uptake had minor contributions in all reconstructed image volumes because of the rapid sensitivity fall-off for pinhole apertures. An optimal aperture diameter between 2 and 3 mm was determined from peak SNR, indicating that these aperture sizes may have the best performance for lesions as small as 0.6 cm in diameter with activity concentration ratios of (99m)Tc similar to those currently seen in patients. Both lesions were visualized with PICO-SPECT better than with planar pinhole imaging, with respective contrast improvements >20 times the values obtained from planar imaging for the same pinholes. In the patient study, higher contrast (>6) visualization of the active tumor periphery was obtained with PICO-SPECT than with planar imaging. CONCLUSION: These results indicate that the enhanced spatial resolution of smaller apertures outweighs the loss in sensitivity in small lesion identification with PICO-SPECT. Although the imaging differences between investigated aperture types are small and some limitations to this imaging approach exist, dedicated PICO-SPECT of the breast appears to be an improved technique compared with conventional planar pinhole scintimammography. This technique provides enhanced contrast and SNR for imaging small lesions with the high-resolution pinhole apertures along with 3-dimensional localization of the lesions.

Breast↗
PubMed1997

The emergence of life from iron monosulphide bubbles at a submarine hydrothermal redox and pH front.

Here we argue that life emerged on Earth from a redox and pH front at c. 4.2 Ga. This front occurred where hot (c. 150 degrees C), extremely reduced, alkaline, bisulphide-bearing, submarine seepage waters interfaced with the acid, warm (c. 90 degrees C), iron-hearing Hadean ocean. The low pH of the ocean was imparted by the ten bars of CO2 considered to dominate the Hadean atmosphere/hydrosphere. Disequilibrium between the two solutions was maintained by the spontaneous precipitation of a colloidal FeS membrane. Iron monosulphide bubbles comprising this membrane were inflated by the hydrothermal solution upon sulphide mounds at the seepage sites. Our hypothesis is that the FeS membrane, laced with nickel, acted as a semipermeable catalytic boundary between the two fluids, encouraging synthesis of organic anions by hydrogenation and carboxylation of hydrothermal organic primers. The ocean provided carbonate, phosphate, iron, nickel and protons; the hydrothermal solution was the source of ammonia, acetate, HS-, H2 and tungsten, as well as minor concentrations of organic sulphides and perhaps cyanide and acetaldehyde. The mean redox potential (delta Eh) across the membrane, with the energy to drive synthesis, would have approximated to 300 millivolts. The generation of organic anions would have led to an increase in osmotic pressure within the FeS bubbles. Thus osmotic pressure could take over from hydraulic pressure as the driving force for distension, budding and reproduction of the bubbles. Condensation of the organic molecules to polymers, particularly organic sulphides, was driven by pyrophosphate hydrolysis. Regeneration of pyrophosphate from the monophosphate in the membrane was facilitated by protons contributed from the Hadean ocean. This was the first use by a metabolizing system of protonmotive force (driven by natural delta pH) which also would have amounted to c. 300 millivolts. Protonmotive force is the universal energy transduction mechanism of life. Taken together with the redox potential across the membrane, the total electrochemical and chemical energy available for protometabolism amounted to a continuous supply at more than half a volt. The role of the iron sulphide membrane in keeping the two solutions separated was appropriated by the newly synthesized organic sulphide polymers. This organic take-over of the membrane material led to the miniaturization of the metabolizing system. Information systems to govern replication could have developed penecontemporaneously in this same milieu. But iron, sulphur and phosphate, inorganic components of earliest life, continued to be involved in metabolism.

Bacteria↗
PubMed2004

Curing depths of a universal hybrid and a flowable resin composite cured with quartz tungsten halogen and light-emitting diode units.

This in vitro study evaluated curing depths of a universal hybrid resin composite with two viscosities (Tetric Ceram and Tetric Flow) after curing with 6 different quartz tungsten halogen and light-emitting diode curing units. Irradiance (light intensity) of the curing units varied between 200 and 700 mW/cm2. The curing units were used for standard, soft-start, or pulse curing. Curing times were 20 and 40 s for standard curing, 3 + 10 s and 3 + 30 s for pulse curing, and 40 s for soft-start. Resin composite specimens, 5 in each group, with a diameter of 4 mm and a height of 6 mm, were made in brass molds and cured from one side at a distance of 6 mm. After 2 weeks, the specimens were ground longitudinally half through the specimen. Curing depth was then determined by measurement of Wallace hardness for each half millimeter starting at 0.5 mm from the top surface. For all curing units and for both resin composites an increased curing time led to statistically significantly higher depth of cure (P < 0.0005). Tetric Flow showed a statistically significantly higher depth of cure than Tetric Ceram (P < 0.0005). All curing units cured more than 2.0 mm of both composites from a distance of 6 mm at 20 s curing time. The value for 40 s was 3.0 mm. The composite closer to the surface than the depth of cure value was equally well cured with all curing units investigated. There was a significant linear correlation between the determined irradiance of the curing units and the depths of cure obtained (20s: r = 0.89, P < 0.025; 40 s: r = 0.91, P < 0.01).

Aluminum Compounds↗
PubMed2005

In vitro toxicity of nanoparticles in BRL 3A rat liver cells.

This study was undertaken to address the current deficient knowledge of cellular response to nanosized particle exposure. The study evaluated the acute toxic effects of metal/metal oxide nanoparticles proposed for future use in industrial production methods using the in vitro rat liver derived cell line (BRL 3A). Different sizes of nanoparticles such as silver (Ag; 15, 100 nm), molybdenum (MoO(3); 30, 150 nm), aluminum (Al; 30, 103 nm), iron oxide (Fe(3)O(4); 30, 47 nm), and titanium dioxide (TiO(2); 40 nm) were evaluated for their potential toxicity. We also assessed the toxicity of relatively larger particles of cadmium oxide (CdO; 1 microm), manganese oxide (MnO(2); 1-2 microm), and tungsten (W; 27 microm), to compare the cellular toxic responses with respect to the different sizes of nanoparticles with different core chemical compositions. For toxicity evaluations, cellular morphology, mitochondrial function (MTT assay), membrane leakage of lactate dehydrogenase (LDH assay), reduced glutathione (GSH) levels, reactive oxygen species (ROS), and mitochondrial membrane potential (MMP) were assessed under control and exposed conditions (24h of exposure). Results showed that mitochondrial function decreased significantly in cells exposed to Ag nanoparticles at 5-50 microg/ml. However, Fe(3)O(4), Al, MoO(3) and TiO(2) had no measurable effect at lower doses (10-50 microg/ml), while there was a significant effect at higher levels (100-250 microg/ml). LDH leakage significantly increased in cells exposed to Ag nanoparticles (10-50 microg/ml), while the other nanoparticles tested displayed LDH leakage only at higher doses (100-250 microg/ml). In summary the Ag was highly toxic whereas, MoO(3) moderately toxic and Fe(3)O(4), Al, MnO(2) and W displayed less or no toxicity at the doses tested. The microscopic studies demonstrated that nanoparticle-exposed cells at higher doses became abnormal in size, displaying cellular shrinkage, and an acquisition of an irregular shape. Due to toxicity of silver, further study conducted with reference to its oxidative stress. The results exhibited significant depletion of GSH level, reduced mitochondrial membrane potential and increase in ROS levels, which suggested that cytotoxicity of Ag (15, 100 nm) in liver cells is likely to be mediated through oxidative stress.

Animals↗
PubMedDate not supplied

Sulfhydryl-selective, covalent labeling of biomolecules with transition metallocarbonyl complexes. Synthesis of (eta5-C5H5)M(CO)3(eta1-N-maleimidato) (M = Mo, W), X-ray structure, and reactivity studies.

The photochemical reaction of (eta5-C5H5)Mo(CO)3I with maleimide in the presence of diisopropylamine yielded complex (eta5-C5H5)Mo(CO)3(eta1-N-maleimidato) 4 in 52% yield. The single-crystal X-ray structure of this complex was determined and shows unusual interactions between oxygen atoms of the maleimidato ligand and carbon atoms of the cis-CO ligands. The tungsten analogue of 4, (eta5-C5H5)W(CO)3(eta1-N-maleimidato) 5, was synthesized in 37% yield by the reaction of (eta5-C5H5)W(CO)3I with the thallium(I) salt of maleimide. Complexes 4 and 5 reacted with cysteine ethyl ester and glutathione to afford products of the addition of the sulfhydryl group to the ethylenic bond of the maleimidato ligand. The reaction of 4 and 5 with glutathione proceeded faster than the reaction of the analogous complex (eta5-C5H5)Fe(CO)2(eta1-N-maleimidato) (3). However, all these complexes react with glutathione more slowly than N-ethylmaleimide. Complexes 4 and 5 were used for labeling of bovine serum albumin (BSA), enriched in thiol groups by reaction with Traut's reagent. Reaction of thiolated BSA containing 7.4 SH groups with 4 and 5 gave bioconjugates bearing 6.9 and 6.4 metallocarbonyl moieties, respectively. Under the same conditions, reaction with 3 afforded a BSA conjugate containing 7.6 metallocarbonyl moieties. Labeling was presumed to be site-specific, as the number of metallocarbonyl entities matched very well with the initial number of SH groups measured for the thiolated BSA sample. IR spectra of BSA labeled with 4 and 5 show intense nu(C[triple bond]O)) bands (2042 and 1948 cm(-1) in the latter case), enabling sensitive detection of the bioconjugates in biological samples. Complexes 4 and 5 (especially the latter) should be of interest as heavy atom phasing reagents for protein X-ray crystallography.

Alkylation↗
PubMed2005

Characterization of steric and electronic properties of NiN2S2 complexes as S-donor metallodithiolate ligands.

The physical properties and structures of a series of six complexes of the type (NiN(2)S(2))W(CO)(4) have been used to establish electronic and steric parameters for square planar NiN(2)S(2) complexes as bidentate, S-donor ligands. According to the nu(CO) stretching frequencies and associated computed Cotton-Kraihanzel force constants of the tungsten carbonyl adducts, there is little difference in donor abilities of the five neutral NiN(2)S(2) metallodithiolate ligands in the series. The dianionic Ni(ema)(2)(-) (ema = N,N'-ethylenebis(2-mercaptoacetamide)) complex transfers more electron density onto the W(CO)(4) moiety. A ranking of donor abilities and a comparison with classical bidentate ligands is as follows: Ni(ema)(=) > {[NiN(2)S(2)](0)} > bipy approximately phen > Ph(2)PCH(2)CH(2)PPh(2) > Ph(2)PCH(2)PPh(2). Electrochemical data from cyclic voltammetry find that the reduction event in the (NiN(2)S(2))W(CO)(4) derivatives is shifted to more positive potentials by ca. 0.5 V compared to the ca. -2 V Ni(II/I) redox event in the free NiN(2)S(2) ligand, consistent with the electron drain from the nickel-dithiolate ligands by the W(CO)(4) acceptor. Differences in Ni(II/I) DeltaE(1/2) values appear to have a ligand dependence which is related to a structural feature of the hinge angle imposed by the (mu-SR)(2) bridges. Thus the angle formed by the intersection of NiN(2)S(2)/WS(2)C(2) planes has been established by X-ray diffraction analyses as a unique orientational feature of the nickel-dithiolate ligands in contrast to classical diphosphine or diimine ligands and ranges in value from 136 to 107 degrees . Variable-temperature (13)C NMR studies show that the spatial orientations of the ligands remained fixed with respect to the W(CO)(4) moiety to temperatures of 100 degrees C.

Binding Sites↗
PubMed2000

X-ray spectroscopy of enzyme active site analogues and related molecules: bis(dithiolene)molybdenum(IV) and -tungsten(IV,VI) complexes with variant terminal ligands.

The X-ray absorption spectra at the molybdenum and selenium K-edges and the tungsten L2,3-edges are acquired for a set of 14 Mo(IV) and W(IV,VI) bis(dithiolene) complexes related to the active sites of molybdo- and tungstoenzymes. The set includes square pyramidal [MoIVL(S2C2Me2)2]- (L = O2-, R3SiO-, RO-, RS-, RSe-) and [WIV(OR)(S2C2Me2)2]-, distorted trigonal prismatic [MoIV(CO)(SeR)(S2C2Me2)2]- and [WIV(CO)L(S2C2Me2)2]- (L = RS-, RSe-), and distorted octahedral [WVIO(OR)(S2C2Me2)2]-. The dithiolene simulates the pterin-dithiolene cofactor ligand, and L represents a protein ligand. Bond lengths are determined by EXAFS analysis using the GNXAS protocol. Normalized edge spectra, non-phase-shift-corrected Fourier transforms, and EXAFS data and fits are presented. Bond lengths determined by EXAFS and X-ray crystallography agree to < or = 0.02 A as do the M-Se distances determined by both metal and selenium EXAFS. The complexes [MoIV(QR)(S2C2Me2)2]- simulate protein ligation by the DMSO reductase family of enzymes, including DMSO reductase itself (Q = O), dissimilatory nitrate reductase (Q = S), and formate dehydrogenase (Q = Se). Edge shifts of these complexes correlate with the ligand electronegativities. Terminal ligand binding is clearly distinguished in the presence of four Mo-S(dithiolene) interactions. Similarly, five-coordinate [ML(S2C2Me2)2]- and six-coordinate [M(CO)L(S2C2Me2)2]- are distinguishable by edge and EXAFS spectra. This study expands a previous XAS investigation of bis(dithiolene)metal(IV,V,VI) complexes (Musgrave, K. B.; Donahue, J. P.; Lorber, C.; Holm, R. H.; Hedman, B.; Hodgson, K. O. J. Am. Chem. Soc. 1999, 121, 10297) by including a larger inventory of molecules with variant physiologically relevant terminal ligation. The previous and present XAS results should prove useful in characterizing and refining metric features and structures of enzyme sites.

Binding Sites↗
PubMed1997

GABAA-mediated IPSCs in piriform cortex have fast and slow components with different properties and locations on pyramidal cells.

GABAA-mediated IPSCs in piriform cortex have fast and slow components with different properties and locations on pyramidal cells. J. Neurophysiol. 78: 2531-2545, 1997. A recent study in piriform (olfactory) cortex provided evidence that, as in hippocampus and neocortex, gamma-aminobutyric acid-A (GABAA)-mediated inhibition is generated in dendrites of pyramidal cells, not just in the somatic region as previously believed. This study examines selected properties of GABAA inhibitory postsynaptic currents (IPSCs) in dendritic and somatic regions that could provide insight into their functional roles. Pharmacologically isolated GABAA-mediated IPSCs were studied by whole cell patch recording in slices. To compare properties of IPSCs in distal dendritic and somatic regions, local stimulation was carried out with tungsten microelectrodes, and spatially restricted blockade of GABAA-mediated inhibition was achieved by pressure-ejection of bicuculline from micropipettes. The results revealed that largely independent circuits generate GABAA inhibition in distal apical dendritic and somatic regions. With such independence, a selective decrease in dendritic-region inhibition could enhance integrative or plastic processes in dendrites while allowing feedback inhibition in the somatic region to restrain system excitability. This could allow modulatory fiber systems from the basal forebrain or brain stem, for example, to change the functional state of the cortex by altering the excitability of interneurons that mediate dendritic inhibition without increasing the propensity for regenerative bursting in this highly epileptogenic system. As in hippocampus, GABAA-mediated IPSCs were found to have fast and slow components with time constants of decay on the order of 10 and 40 ms, respectively, at 29 degrees C. Modeling analysis supported physiological evidence that the slow time constant represents a true IPSC component rather than an artifactual slowing of the fast component from voltage clamp of a dendritic current. The results indicated that, whereas both dendritic and somatic-region IPSCs have both fast and slow GABAA components, there is a greater proportion of the slow component in dendrites. In a companion paper, the hypothesis is explored that the resulting slower time course of the dendritic IPSC increases its capacity to regulate the N-methyl--aspartate component of EPSPs. Finally, evidence is presented that the slow GABAA-mediated IPSC component is regulated by presynaptic GABAB inhibition whereas the fast is not. Based on the requirement for presynaptic GABAB-mediated block of inhibition for expression of long-term potentiation, this finding is consistent with participation of the slow GABAA component in regulation of synaptic plasticity. The lack of susceptibility of the fast GABAA component to the long-lasting, activity-induced suppression mediated by presynaptic GABAB receptors is consistent with a protective role for this process in preventing seizure activity.

Animals↗
PubMed2006

Hardness and wear resistance of two resin composites cured with equivalent radiant exposure from a low irradiance LED and QTH light-curing units.

PURPOSE: To measure and compare three-body wear and Vickers hardness at depths of 0 mm and 2 mm in two composite resin materials cured with either a low irradiance light emitting diode (LED) or a quartz tungsten halogen (QTH) light-curing unit (LCU) in which exposure duration with the LED was increased to deliver equivalent radiant exposure in the 450-490 nm wavelength range. METHODS: The VIP QTH and Freelight LED LCU's were obtained and the emission spectrum of each was determined using a Spectra Pro 750 spectrograph. Irradiance in the 450-490 nm range for each LCU was determined by calculating the area under the spectral curve. Curing of two composite resins (Z100 and Esthet-X) with equivalent radiant exposure within this prescribed wavelength range was achieved by increasing the irradiation time of the LED 33% from 30-40 seconds to compensate for its lower irradiance (Table 1). The resulting radiant exposure of 8.40 J/cm2 was roughly equivalent to the radiant exposure produced in 30 seconds by the QTH LCU (8.67 J/cm2). The cured specimens were polished with progressively fine wet silicon carbide papers to 600 grit and stored in distilled water at 37 degrees C for 24 hours prior to evaluating hardness and wear. Indentations for Vickers hardness testing were produced by applying a 0.5 kg load with a 15-second dwell time. Equivalent degree of cure was established indirectly through Vickers hardness numbers for the top and bottom surface of 2 mm thick disks of each material cured with each light (N = 3/group). Hardness ratios were computed by dividing mean bottom hardness by mean top hardness within each group. Three-body wear testing (N = 10/group) was performed on similarly fabricated specimens with a mechanical wear device using 44 microm unpolymerized PMMA beads as a simulated food bolus. The composite resin samples opposed spherical, stainless steel styli. A 75 N contact force was applied at 1.2 Hz for 100,000 cycles. Profilometry was used to quantify localized wear of the resin. Multivariate ANOVA and the Tukey-Kramer post hoc test (alpha = 0.05) were used to assess differences in hardness and wear of the materials. RESULTS: With respect to hardness, no difference was noted between top and bottom specimen sides based on material or curing method. Specimens cured using the LED exhibited hardness ratios approaching unity. No significant difference in hardness was found for the main effect of light used, but the main effect of material was highly significant. This was primarily because Z100 cured with the LED demonstrated statistically higher hardness than the other three groups, which were statistically similar. No significant difference in wear was found based on the light used, with the lowest mean wear seen in Z100 cured with the LED. Overall, Z100 exhibited significantly greater surface hardness (P < 0.001) and significantly less wear (P < 0.01) compared to Esthet-X

Carbon Compounds, Inorganic↗