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Due to their high abundance, polymeric character, and chemical tunability, polysaccharides are perfect candidates for the stabilization of photoactive nanoscale objects, which are of great interest in modern science but can be unstable in aqueous media. In this work, we have demonstrated the relevance of oxidized dextran polysaccharide, obtained via a simple reaction with H 2 O 2 , towards the stabilization of photoactive octahedral molybdenum and tungsten iodide cluster complexes [M 6 I 8 }(DMSO) 6 ](NO 3 ) 4 in aqueous and culture media. The cluster-containing materials were obtained by co-precipitation of the starting reagents in DMSO solution. According to the data obtained, the amount and ratio of functional carbonyl and carboxylic groups as well as the molecular weight of oxidized dextran strongly affect the extent of stabilization, i.e., high loading of aldehyde groups and high molecular weight increase the stability, while acidic groups have some negative impact on the stability. The most stable material based on the tungsten cluster complex exhibited low dark and moderate photoinduced cytotoxicity, which together with high cellular uptake makes these polymers promising for the fields of bioimaging and PDT.

This article gives an overview of the research activity of the LAC2 team at LCC developed at Castres in the field of sustainable chemistry with an emphasis on the collaboration with a research team from the University of Zagreb, Faculty of Science, Croatia. The work is situated within the context of sustainable chemistry for the development of catalytic processes. Those processes imply molecular complexes containing oxido-molybdenum, -vanadium, -tungsten or simple polyoxometalates (POMs) as catalysts for organic solvent-free epoxidation. The studies considered first the influence of the nature of complexes (and related ligands) on the reactivity (assessing mechanisms through DFT calculations) with model substrates. From those model processes, the work has been enlarged to the valorization of biomass resources. A part concerns the activity on vanadium chemistry and the final part concerns the use of POMs as catalysts, from molecular to grafted catalysts, (ep)oxidizing substrates from fossil and biomass resources.

Close monitoring of vital physiological parameters is often key in following the evolution of certain medical conditions (e.g., diabetes, infections, post-operative status or post-traumatic injury). The allocation of trained medical staff and specialized equipment is, therefore, necessary and often translates into a clinical and economic burden on modern healthcare systems. As a growing field, transient electronics may establish fully bioresorbable medical devices capable of remote real-time monitoring of therapeutically relevant parameters. These devices could alert remote medical personnel in case of any anomaly and fully disintegrate in the body without a trace. Unfortunately, the need for a multitude of biodegradable electronic components (power supplies, wires, circuitry) in addition to the electrochemical biosensing interface has halted the arrival of fully bioresorbable electronically active medical devices. In recent years molybdenum (Mo) and tungsten (W) have drawn increasing attention as promising candidates for the fabrication of both energy-powered active (e.g., transistors and integrated circuits) and passive (e.g., resistors and capacitors) biodegradable electronic components. In this review, we discuss the latest Mo and W-based dissolvable devices for potential biomedical applications and how these soluble metals could pave the way towards next-generation fully transient implantable electronic systems.

Compounds based on new cyanide cluster anions [{Mo 6 I 8 }(CN) 6 ] 2- , trans -[{Mo 6 I 8 }(CN) 4 (MeO) 2 ] 2- and trans -[{W 6 I 8 }(CN) 2 (MeO) 4 ] 2- were synthesized using mechanochemical or solvothermal synthesis. The crystal and electronic structures as well as spectroscopic properties of the anions were investigated. It was found that the new compounds exhibit red luminescence upon excitation by UV light in the solid state and solutions, as other cluster complexes based on {Mo 6 I 8 } 4+ and {W 6 I 8 } 4+ cores do. The compounds can be recrystallized from aqueous methanol solutions; besides this, it was shown using NMR and UV-Vis spectroscopy that anions did not undergo hydrolysis in the solutions for a long time. These facts indicate that hydrolytic stabilization of {Mo 6 I 8 } and {W 6 I 8 } cluster cores can be achieved by coordination of cyanide ligands.

Raman spectroscopy was used for the quantitative determination of Mo and W in Mo- and W-supported mesoporous silica (Mo/SBA-15 and W/SBA-15, respectively) and Mo-supported beta zeolite (Mo-BEA). Three Raman quantitative models were developed and optimized for the metal contents of Mo/SBA-15, W/SBA-15, and Mo/BEA. Subsequently, the models were characterized using the root mean square error of calibration (RMSEC), root mean square error of cross-validation (RMSECV), root mean square error of prediction (RMSEP), correlation coefficient, and predicted residual error sum of squares (PRESS) diagnostic function. The calibration range of the models were in the range of approximately 2-40 wt% for the SBA-15 support and 1-21 wt% for the BEA support because the BEA support presented lower Mo absorption than the SBA-15 support. The RMSEC, RMSECV, and RMSEP values were below 1.80% for all developed models. The highest and lowest correlation coefficients corresponded to the W/SBA-15 (0.9984) and Mo/BEA (0.9777) models, respectively. The change in catalyst support affected the mentioned chemometric parameters (Mo/SBA-15 vs. Mo/BEA). Subsequently, Raman spectroscopy combined with the temperature control stage was used to study the calcination of Mo/BEA, Mo/SBA-15, and W/SBA-15 using three-dimensional diagrams, in which the changes in catalyst structure were analyzed as functions of the temperature and time. Raman spectroscopy was determined to be a suitable analytical tool for the quantitative analysis of the metal contents of the catalyst and optimization of the calcination process. Therefore, Raman spectroscopy can be used during catalyst manufacturing.

Tungsten (W) is a valuable element with considerable industrial and economic importance that belongs to the European Union list of critical metals with a high supply risk. Therefore, the development of effective and new methods for W recovery is essential to ensure a sustainable supply. In the present study, the Sulfitobacter dubius W transport system TupABC was explored in order to demonstrate both its functionality in Escherichia coli cells and to construct a bioaccumulator (EcotupW). The complete gene cluster tupBCA or partial gene cluster tupBC were cloned in an expression vector and transformed into E. coli. Metal accumulation was evaluated when each construct strain was grown with three separate metal oxyanions (tungstate, molybdate or chromate). The specificity of the bioaccumulator was determined by competition assays using cells grown with mixed solutions of metal oxyanions (W/Mo and W/Cr). The results showed the relevance of the TupA protein in the TupABC transporter system to W-uptake and also allowed Mo and Cr accumulations, although with amounts 1.7 and 2.9-fold lower than W, respectively. To identify the importance of the valine residue in the accumulation efficiency of the VTTS motif, site-directed mutagenesis of tupA was performed. A mutant with a threonine residue, instead of the respective valine, confirmed that W was internalized by nearly double the amount compared to the native form. The findings indicated that cells carrying the native S. dubius TupABC system were great W-bioaccumulators and could be promising tools for W recovery., (Copyright © 2019 Elsevier GmbH. All rights reserved.)

Grafting a molybdenum oxo alkylidene on silica (partially dehydroxylated at 700 °C) affords the first example of a well-defined silica-supported Mo oxo alkylidene, which is an analogue of the putative active sites in heterogeneous Mo-based metathesis catalysts. In contrast to its tungsten analogue, which shows poor activity towards terminal olefins because of the formation of a stable off-cycle metallacyclobutane intermediate, the Mo catalyst shows high metathesis activity for both terminal and internal olefins that is consistent with the lower stability of Mo metallacyclobutane intermediates. This Mo oxo metathesis catalyst also outperforms its corresponding neutral silica-supported Mo and W imido analogues., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An overview is provided of the molybdenum- and tungsten-containing enzymes that catalyze the interconversion of formate and CO 2 , focusing on common structural and mechanistic themes, as well as a consideration of the manner in which the mature Mo- or W-containing cofactor is inserted into apoprotein., (© 2018 The Protein Society.)

Octahedral molybdenum and tungsten clusters have potential biological applications in photodynamic therapy and bioimaging. However, poor solubility and hydrolysis stability of these compounds hinder their application. The first water-soluble photoluminescent octahedral tungsten cluster [{W 6 I 8 }(DMSO) 6 ](NO 3 ) 4 was synthesised and demonstrated to be at least one order of magnitude more stable towards hydrolysis than its molybdenum analogue. Biological studies of the compound on larynx carcinoma cells suggest that it has a significant photoinduced toxicity, while the dark toxicity increases with the increase of the degree of hydrolysis. The increase of the dark toxicity is associated with the in situ generation of nanoparticles that clog up the cisternae of rough endoplasmic reticulum., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Background: Tungsten (W) interferes with molybdenum (Mo) binding sites and has been associated with prevalent cardiovascular disease (CVD). We evaluated if (1) W exposure is prospectively associated with incident CVD and (2) the association between urinary W levels and incident CVD is modified by urinary Mo levels., Methods: We estimated multi-adjusted hazard ratios (HRs) for incident CVD outcomes by increasing W levels for 2726 American Indian participants in the Strong Heart Study with urinary metal levels measured at baseline (1989-1991) and CVD events ascertained through 2008., Results: Increasing levels of baseline urinary W were not associated with incident CVD. Fully-adjusted HRs (95% CIs) of incident CVD comparing a change in the IQR of W levels for those in the lowest and highest tertile of urinary Mo were 1.05 (0.90, 1.22) and 0.80 (0.70, 0.92), respectively (p-interaction = 0.02); for CVD mortality, the corresponding HRs were 1.05 (0.82, 1.33) and 0.73 (0.58, 0.93), respectively (p-interaction = 0.03)., Conclusions: The association between W and CVD incidence and mortality was positive although non-significant at lower urinary Mo levels and significant and inverse at higher urinary Mo levels. Although prior cross-sectional epidemiologic studies in the general US population found positive associations between urinary tungsten and prevalent cardiovascular disease, our prospective analysis in the Strong Heart Study indicates this association may be modified by molybdenum exposure., (Copyright © 2018. Published by Elsevier Inc.)

The influence of molybdenum, tungsten on germination and growth of barley Hordeum vulgare L. was studied. Results of this study revealed the differential effect of heavy metals on seedlings growth. Exogenous molybdenum treatment stimulated the growth of seedlings. The addition of the metal significantly stimulated root elongation. Contrastingly, the addition of tungsten resulted in increased seed germination and inhibits the growth of seedlings. The negative effect of tungsten on the growth of barley was more profound for roots of plants. In addition, the influence of metals on the growth of plants was also tested in saline conditions. It is shown that under salinity stress plant growth drastically decreased in presence of tungsten. Results of this study showed that activity of molybdenum-containing aldehyde oxidase (AO; EC 1.2.3.1) was also significantly affected by metals. The activity of AO in leaves and roots enhanced with increasing concentrations of molybdate, while tungstate treatment inhibited the enzyme activity. Perhaps, the differential influence of molybdenum and tungsten on the growth of barley is a direct effect of metals on aldehyde oxidase activity in plants. Moreover, the intense negative effect of tungsten treatment on barley growth under salinity conditions emphasizes an important role of aldehyde oxidase in plant resistance to stress factors., (Copyright © 2018 Elsevier GmbH. All rights reserved.)

Adverse health effects related to accumulative cadmium (Cd) exposure have aroused widespread attention from the public in China. Knowledge on the relationships between Cd exposure and early renal effects is particularly limited for children, who are more susceptible to absorbing metals than adults. A typical Cd-polluted area of South China was selected to determine the Cd exposure and related early renal effects of the general population, including children. In total, 211 children and 806 adults were enrolled in the study. The urinary levels of Cd (U-Cd), β 2 -microglobulin (U-BMG), retinol binding protein (U-RBP), and N-acetyl-β-D-glucosaminidase (U-NAG) were measured. The relationship between U-Cd and ranked indicators of early renal effects was examined by multiple regression analysis. The average U-Cd ranged from 7.01 μg/g creatinine (boys) to 13.55 μg/g creatinine (women) in the Cd-polluted areas. These values are much higher than those of the control group and those that have been reported by other countries. In agreement with previous studies, environmental Cd pollution resulted in elevated Cd accumulation in the bodies of children, and it increased the concentration of NAG in their urine. Similarly, environmental Cd pollution increased NAG and BMG in the urine of adults. Multivariate models showed that the urinary excretion of BMG, RBP, and NAG was positively associated with Cd levels in the urine of both children and adults. The reference thresholds of U-Cd in relation to elevated U-BMG, U-RBP, and U-NAG were higher in children than adults after standardization for other covariates. These results reinforce the need to control and regulate the sources of environmental Cd contamination and to promote more effective risk management measures, especially for vulnerable groups.

We have examined the kinetic and spectroscopic properties of a tungsten-substituted form of DMSO reductase from Rhodobacter sphaeroides, an enzyme that normally possesses molybdenum. Partial reduction with sodium dithionite yields a well-resolved W(V) EPR signal of the so-called "high-g split" type that exhibits markedly greater g-anisotropy than the corresponding Mo(V) signal of the native form of the enzyme, with the g values shifted to higher magnetic field by as much as Δg ave  = 0.056. Deuteration of the enzyme confirms that the coupled proton is solvent-exchangeable, allowing us to accurately simulate the tungsten hyperfine coupling. Global curve-fitting analysis of UV/vis absorption spectra observed in the course of the reaction of the tungsten-substituted enzyme with sodium dithionite affords a well-defined absorption spectrum for the W(V) species. Surprisingly, the absorption spectrum for this species exhibits significantly larger molar extinction coefficients than either the reduced or the oxidized spectrum. This spectrum, in conjunction with those for fully oxidized W(VI) and fully reduced W(IV) enzyme, has been used to deconvolute the absorption spectra seen in the course of turnover, in the which enzyme is reacted with sodium dithionite and DMSO, demonstrating that the W(V) is an authentic catalytic intermediate that accumulates to approximately 50% of the total enzyme in the steady state.

Due to the similarities of molybdenum (Mo) with tungsten (W) in the physical structure and chemical properties, studies involving the two elements have mainly examined their competitive relationships. The objectives of this study were to assess the effects of equimolar W on Mo accumulation, transport and subcellular distribution in oilseed rape at two Mo levels with four treatments: Mo 1 (1μmol/L Mo, Low Mo), Mo 1 +W 1 (1μmol/L Mo+1μmol/LW, Low Mo with Low W), Mo 200 (200μmol/L Mo, High Mo) and Mo 200 +W 200 (200μmol/L Mo+200μmol/L Mo, High Mo with high W). The fresh weight and root growth were inhibited by equimolar W at both low and high Mo levels. The Mo concentration and accumulation in root was increased by equimolar W at the low Mo level, but that in the root and shoot was decreased at the high Mo level. Additionally, equimolar W increased the Mo concentrations of xylem and phloem sap at low Mo level, but decreased that of xylem and increased that of phloem sap at the high Mo level. Furthermore, equimolar W decreased the expression of BnMOT1 in roots and leaves at the low Mo level, and only decreased its expression in leaves at the high Mo level. The expression of BnMOT2 was also decreased in root for equimolar W compared with the low Mo level, but increased compared with high Mo level. Moreover, equimolar W increased the proportion of Mo in cell wall fraction in root and that of soluble fraction in leaves when compared with the low Mo level. The results suggest that cell wall and soluble fractions might be responsible for the adaptation of oilseed rape to W stress., (Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.)

Molybdenum and tungsten enzymes which contain the pyranopterin cofactor are ubiquitous in Nature and perform a wide variety of biological functions. They catalyze a diversity of mostly two-electron oxidation-reduction reactions crucial in the metabolism of nitrogen, sulfur and carbon. These enzymes share common structural features, but reveal different polypeptide folding topologies and different active site coordination geometries, which, in part, dictate their function and specificity. On the basis of structural, spectroscopic and biochemical characteristics, they have been classified into three broad families named according to well-studied enzymes of each family: xanthine oxidase, sulfite oxidase and DMSO reductase. An overview of the X-ray crystallography data for representative members of the three enzyme families is given here, focusing on the mechanistic implications drawn from the structural data.

Purpose: To investigate the average glandular dose (AGD) applied for clinical digital mammograms acquired with the anode/filter combinations molybdenum/molybdenum (Mo/Mo), molybdenum/rhodium (Mo/Rh), and tungsten/rhodium (W/Rh)., Materials and Methods: Using the method of Dance, the AGD was evaluated from the exposure data of 4867 digital mammograms at two sites equipped with a full-field digital mammography (FFDM) system based on an amorphous selenium detector. 1793 images were acquired and analyzed with Mo/Mo, 643 with Mo/Rh, and 2431 with W/Rh., Results: In the Mo/Mo cases the mean compressed breast thickness was 46 +/- 10 mm with an average AGD of 2.29 +/- 1.31 mGy. For the Mo/Rh cases with a mean compressed thickness of 64 +/- 9 mm, we obtained 2.76 +/- 1.31 mGy. The W/Rh cases with a mean compressed thickness of 52 +/- 13 mm resulted in 1.26 +/- 0.44 mGy. The image quality was assessed as normal and adequate for diagnostic purposes in all cases., Conclusion: Applying a W/Rh beam quality permits the reduction of the patient dose by approximately 50 % when using an FFDM system based on amorphous selenium. The dose reduction becomes larger as the breast thickness increases. The results are in agreement with simulations and phantom studies known from the literature.

In this study, scattered x-ray distributions were produced by irradiating a tissue equivalent phantom under clinical mammographic conditions by using Mo/Mo, Mo/Rh and W/Rh anode/filter combinations, for 25 and 30 kV tube voltages. Energy spectra of the scattered x-rays have been measured with a Cd(0.9)Zn(0.1)Te (CZT) detector for scattering angles between 30 degrees and 165 degrees . Measurement and correction processes have been evaluated through the comparison between the values of the half-value layer (HVL) and air kerma calculated from the corrected spectra and measured with an ionization chamber in a nonclinical x-ray system with a W/Mo anode/filter combination. The shape of the corrected x-ray spectra measured in the nonclinical system was also compared with those calculated using semi-empirical models published in the literature. Scattered x-ray spectra measured in the clinical x-ray system have been characterized through the calculation of HVL and mean photon energy. Values of the air kerma, ambient dose equivalent and effective dose have been evaluated through the corrected x-ray spectra. Mean conversion coefficients relating the air kerma to the ambient dose equivalent and to the effective dose from the scattered beams for Mo/Mo, Mo/Rh and W/Rh anode/filter combinations were also evaluated. Results show that for the scattered radiation beams the ambient dose equivalent provides an overestimate of the effective dose by a factor of about 5 in the mammography energy range. These results can be used in the control of the dose limits around a clinical unit and in the calculation of more realistic protective shielding barriers in mammography.

Three compounds containing two quadruply bonded Mo(2)(DAniF)(3) (DAniF = N,N'-di-p-anisylformamidinate) units linked by tetrahedral EO(4)(2-) anions (E = S, Mo, W) have been prepared and characterized by crystallography and NMR. The linkers in these [Mo(2)(DAniF)(3)](2)(mu-EO(4)) compounds hold the Mo(2) units in an approximately perpendicular orientation and mediate strong electrochemical communication between them. Each of the three compounds shows two quasireversible (mu-SO(4)) or fully reversible (mu-MoO(4), mu-WO(4)) features in its cyclic voltammogram corresponding to successive oxidation of each of its Mo(2) units. The DeltaE(1/2) values are the largest thus far measured for Mo(2)-X-Mo(2) bridged complexes and may be sufficiently large to permit isolation of the singly oxidized species.

The comparative performance of mammographic X-ray systems that use different anode/filter combinations has been assessed for screen-film and digital imaging. Monte Carlo techniques have been used to calculate average glandular dose as well as contrast and signal-to-noise ratio for imaging two test details. Five anode/filter combinations have been studied to establish the potential for dose saving or image quality improvement. For screen-film mammography, it was found that little benefit is gained by changing from a standard 28 kV molybdenum/molybdenum spectrum for breasts up to 6 cm thick. For thicker breasts, where the tube potential for the standard technique might be increased, 20% improvement in contrast can be achieved without dose penalty using molybdenum/rhodium or rhodium/rhodium spectra, whereas dose savings of more than 50% can be attained whilst maintaining contrast using tungsten/rhodium or rhodium/aluminium spectra. In digital mammography, a molybdenum/molybdenum spectrum delivers the lowest dose for a 2 cm breast, but gives the highest dose for thicker breasts. Tungsten/rhodium or rhodium/aluminium spectra provide the lowest doses at greater thicknesses. It is concluded that for screen-film mammography, molybdenum/molybdenum is the spectrum of choice for all but the thickest or most glandular breasts. In digital mammography, an alternative spectrum is preferable for breasts thicker than 2 cm.

Computer simulation is a convenient and frequently used tool in the study of x-ray mammography, for the design of novel detector systems, the evaluation of dose deposition, x-ray technique optimization, and other applications. An important component in the simulation process is the accurate computer-generation of x-ray spectra. A computer model for the generation of x-ray spectra in the mammographic energy range from 18 kV to 40 kV has been developed. The proposed model requires no assumptions concerning the physics of x-ray production in an x-ray tube, but rather makes use of x-ray spectra recently measured experimentally in the laboratories of the Center for Devices and Radiological Health. Using x-ray spectra measured for molybdenum, rhodium, and tungsten anode x-ray tubes at 13 different kV's (18, 20, 22, ..., 42 kV), a spectral model using interpolating polynomials was developed. At each energy in the spectrum, the x-ray photon fluence was fit using 2, 3, or 4 term (depending on the energy) polynomials as a function of the applied tube voltage (kV). Using the polynomial fit coefficients determined at each 0.5 keV interval in the x-ray spectrum, accurate x-ray spectra can be generated for any arbitrary kV between 18 and 40 kV. Each anode material (Mo, Rh, W) uses a different set of polynomial coefficients. The molybdenum anode spectral model using interpolating polynomials is given the acronym MASMIP, and the rhodium and tungsten spectral models are called RASMIP and TASMIP, respectively. It is shown that the mean differences in photon fluence calculated over the energy channels and over the kV range from 20 to 40 kV were -0.073% (sigma = 1.58%) for MASMIP, -0.145% (sigma = 1.263%) for RASMIP, and 0.611% (sigma = 2.07%) for TASMIP. The polynomial coefficients for all three models are given in an Appendix. A short C subroutine which uses the polynomial coefficients and generates x-ray spectra based on the proposed model is available on the World Wide Web at http:/(/)www.aip.org/epaps/epaps.html.

Purpose: The impact of different anode materials (tungsten and rhodium) on spatial resolution, image contrast and radiation exposure was studied., Materials and Methods: Two mammographic systems providing bimetal x-ray tubes (Mo/W and Mo/Rh) were compared by imaging a breast radiography phantom with additional acrylic plates from 3 to 8 cm thickness. Spatial resolution was evaluated using a line bar pattern. Image contrast was assessed by measuring the ratio of optical densities in a acrylic step-wedge. The entrance dose was measured with a low energy ionisation chamber., Results: The spatial resolution was about 13 lp/mm regardless of the beam quality. The image contrast depended substantially on the thickness. A similar image contrast was found with Mo/Mo, Mo/Rh and Rh/Rh for simulated breast thicknesses of 4 to 6 cm and with Rh/Rh and W/Rh for 7 cm. In comparison to Mo/Mo the dose reduction was significant for Mo/Rh (35%), Rh/Rh (50%) and W/Rh (60%)., Conclusions: Bimetal x-ray tubes provide optimal conditions for screen film mammography of both normal and dense breasts, allowing good contrast and dose reduction by using the adequate anode/filter-combination.

Workers of Kabardino-Balkarian coal-extracting enterprise were examined hy the one-step standardized epidemiologic study. Incidence of ischemic heart disease, arterial hypertension, smoking, obesity, medium levels of arterial pressure, smoking intensity, weight index in individuals of different ages and age-standardized parameters among 20-59 years old people are represented. Higher incidence of ischemic heart disease in comparison with the other male population of this region and higher incidence of arterial hypertension in comparison with the workers of similar enterprises are shown.

A modified Lowry protein assay which contains sodium dodecyl sulfate (Markwell et al., 1978, Anal. Biochem. 87, 207-210) has been adapted for use in 96-well microtiter plates. A spectrophotometer interfaced with a computer is used to plot the standard curve and calculate the protein content of each sample. The method is suitable for measuring 4-40 micrograms of protein/assay in a volume of 50 microliters. There was no need for prior solubilization of proteins which had been extracted from brain tissue. Test samples, up to 21 in triplicate, can be tested on a single microtiter plate plus standards. Alternatively, further samples can be tested separately on extra plates using the standard curve from the original plate for calculations.

The treatment of neuromuscular junctions with phosphomolybdic acid (PMA) and silicotungstic acid (STA) heteropolyanions permits the visualization of electron dense precipitates in the synaptic vesicles of the cholinergic motor nerve terminals. At the light microscopic level, the uncolored molybdenum salt is visualized after reduction to molybdenum blue. The blue coloration is confined to the nerve terminals. Since PMA and STA are known as strong precipitating agents of quaternary ammonium compounds (cations) it is supposed that they have insolubilized in situ the acetylcholine (Ach) of the synaptic vesicles by means of a rapid ionic interaction. Furthermore, in spite of the strong acidity of PMA and STA solutions, the ultrastructure of the treated tissue is not significantly altered but on the contrary seems to be well preserved. The ionic insolubilization of Ach, added to the good preservation of the ultrastructure prompted us to use the term "ionic fixation".

Gridless screen-film mammography at 23 kVp with a W anode (inherent filtration: 0.1 mm A1, added filtration: 0.025 mm Mo) can achieve contrast identical to that achieved with gridless film-screen mammography at 27 kVp with a Mo anode (inherent filtration: 1.0 mm Be, added filtration: 0.025-mm Mo). However, W-anode film-screen mammograms obtained at 23 kVp require more radiation than Mo-anode film-screen mammograms obtained at 27 kVp. The lack of contrast of W-anode film-screen images produced at the same kVp as Mo-anode images was verified clinically and with a low contrast test object imaged over a range of densities. A step wedge test object was then used to match contrast between Mo- and W-anode gridless film-screen images at various kVp. The low contrast test object images verified the contrast equivalence of images obtained at 23 kVp for a W anode and 27 kVp for a Mo anode. A comparison of the two kVp for different anode materials was tested clinically on ten patients. The clinical and low contrast test object experiments were reviewed by three radiologists specializing in mammography.

The relative merits of tungsten and molybdenum targets for mammography have been the subject of much discussion. Therefore the spectra and outputs (at constant potential) from molybdenum and tungsten targets, interchangeable in the same tube, have been measured with a Ge(Li) detector and ion chamber respectively. All conditions apart from the target material were unaltered. The spectra have been corrected for the distortions produced by the detector. The effects of filtration on spectra and exposure rates have been calculated and are in agreement with measured values. The spectra and outputs from molybdenum and tungsten targets filtered by aluminium and molybdenum have been investigated and the results are discussed with reference to mammography and the radiography of specimens.

The copper-catalyzed oxidation of peptides and proteins by phosphomolybdic/phosphotungstic acid (Folin phenol reagent) was studied with respect to redox stoichiometry of color formation and nature of the oxidation products. From peptides without reducing side chains two reducing equivalents were transferred under ideal conditions to Mo6+/W6+ for each unit of tetradentate copper complex with concomitant formation of an imino peptide. Tyrosine and tryptophan side chains contributed four additional reducing equivalents. Oxidation of proline-containing peptides was greatly impaired as judged from color formation due to the interference of the imino acid with complex formation. Reaction of the oxidized peptides with 2,4-dinitrophenyl (DNP)-hydrazine gave a peptide amine and the DNP-hydrazone of a 2-oxoacyl peptide. The oxidation products from tetraalanine were identified as dialanine amide and pyruvoylalanine DNP-hydrazone. From the time course of the development of the blue color on reduction of Folin reagent with tetraalanine it was inferred that the reaction consisted of an initial (less than 5 s) oxidation to a Cu3+ peptide complex followed by slow changes in absorbance, especially above 0.2 mM. Due to these complications the two-electron stoichiometry has to be considered only as a limiting case for peptide concentrations below 0.02 mM.

Methods of comparing mammograms produced by radiation derived from tungsten and molydenum anodes are described. In film mammography better images were obtained using molybdenum radiation. In xeromammography images of equal quality were produced by either technique. However, the dose required for good xeromammography using a molybdenum source was significantly higher than for tungsten.

Comparison of within-run and between-day imprecision of protein assays using CSF controls as well as 96 random CSF samples from the routine laboratory shows that the Cu-Folin differential test and the Coomassie-Brilliant-Blue method from Bio-Rad are equally suited to total protein determination in cerebrospinal fluid. Problems possibly arising with very low concentrations of CSF or urine protein and the influence of some drugs often used in the neurological clinic are presented and discussed.

A simple, sensitive, accurate, and rapid method for the quantitative determination of naproxen, oxyphenbutazone, mefenamic acid, indomethacin, and diclofenac sodium in pharmaceutical preparations is proposed. The method is based on the formation of blue complexes with Folin-Ciocalteu reagent.

Concentrations of manganese, considerably in excess of the quantity required for normal vegetative growth, are needed by Bacillus for (i) synthesis of such secondary metabolites and structures as antibiotics, D-glutamyl peptide, endospores, bacteriophage, and protective antigen; and (ii) longevity of vegetative cell cultures. No other biologically active element can substitute for manganese, and no secondary biosynthetic process of Bacillus has been found in which the requirement for manganese is absent. In the present study, manganese could induce sporulation of B. megaterium even when added to synthetic broth cultures as late as 100 hr after inoculation. When sub-bactericidal concentrations of various biologically active trace elements were supplied within 2 hr of manganese addition, suppression of spore formation occurred in cultures exposed to elements of group VI (chromium, molybdenum, tungsten, selenium, tellurium) and one of group VIII (nickel); of the six interfering elements, selenium and nickel were most potent.