Sodium Hypochlorite Reactions. III. The Catalytic Nakagawa and Related Systems

Mainly through the extensive investigations of Nakagawa and coworkers, nickel peroxide has emerged as a powerful oxidant for organic compounds. For example, it has been used for the oxidation of alcohols to aldehydes or carboxylic acids,^2,3 allylic hydroxyl (selectively) to the carbonyl group,⁴ α-ketols to α-diketones,⁵ α-glycols, α-ketols, α-hydroxyl and α-keto acids to cleavage products,⁶ aldehydes to amides or nitriles in the presence of ammonia,⁷ phenols to quinones,^8,9 certain Schiff bases to benzoxazoles,¹⁰ amines to azo compounds or nitriles,^11,12 diarylamines to hydrazines,¹³ carbazoles to dimers and trimers,¹⁴ hydrazones to diazo compounds,^15,16 1-aminobenzotriazole to benzyne,¹⁷ N-substituted hydroxylamines to azoxy compounds,¹⁸ phenylacetonitrile to dimeric products,¹⁹ a thiouracil to a uracil derivative,²⁰ thiols to disulfides and sulfides to sulfones,²¹ N-substituted phenothiazines to sulfoxides and sulfones,²¹ haloforms to hexahaloethanes.²³     

Radioactivity of coals and fly ashes

The level and the behavior of the naturally occurring primordial radionuclides ²³⁸U, ²²⁶Ra, ²¹⁰Pb, ²³²Th, ²²⁸Ra and ⁴⁰K in coals and fly ashes are described. The activity concentrations of the examined coals and originated from coal mines in Greece ranged from 117 to 435 Bq·kg⁻¹ for ²³⁸U, from 44 to 255 Bq·kg⁻¹ for ²²⁶Ra, from 59 to 205 Bq·kg⁻¹ for ²¹⁰Pb, from 9 to 41 Bq·kg⁻¹ for ²²⁸Ra and from 59 to 227 Bq·kg⁻¹ for ⁴⁰K. These levels are comparable to those appeared in coals of different countries worldwide. The activity concentrations of the examined fly ashes and produced in coal-fired power plants in Greece ranged from 263 to 950 Bq·kg⁻¹ for ²³⁸U, from 142 to 605 Bq·kg⁻¹ for ²²⁶Ra, from 133 to 428 Bq·kg⁻¹ for ²¹⁰Pb, from 27 to 68 Bq·kg⁻¹ for ²²⁸Ra and from 204 to 382 Bq·kg⁻¹ for ⁴⁰K. The results showed that there is an enrichment of the radionuclides in fly ash relative to the input coal during the combustion process. The enrichment factors (EF) ranged from 0.60 to 0.76 for ²³⁸U, from 0.69 to 1.07 for ²²⁶Ra, from 0.57 to 0.75 for ²¹⁰Pb, from 0.86 to 1.11 for ²²⁸Ra and from 0.95 to 1.10 for ⁴⁰K.     

Concentration factors for 226Ra in the mullet (Mugilidae) species Mugil cephalus from the South Adriatic Sea

²²⁶Ra activity concentration in the mullet (Mugilidae) species Mugil cephalus whole individuals, and some organs (gills, gastrointestinal system, fins, muscle and bones), was measured by the γ-coincidence spectrometer PRIPYAT-2M. ²²⁶Ra transfer parameters [concentration factors (CFs)] from seawater, sediment and mud with detritus to fish tissues, and annual intake by humans consuming this fish species, have been estimated. Minimum detected radium activity concentration in whole M. cephalus individuals was found to be 0.89 ± 0.42 to 3.09 ± 0.41 Bq kg⁻¹, with arithmetic mean of 1.65 ± 0.39 Bq kg⁻¹. An average concentration in muscles is found to be 2.28 ± 0.84 Bq kg⁻¹, in gills—5.02 ± 1.85 Bq kg⁻¹, in gastrointestinal system—12.88 ± 1.71 Bq kg⁻¹, and in bones—14.72 ± 3.75 Bq kg⁻¹. No one fins showed radium activity above minimum detectable one. Annual intake of ²²⁶Ra by human consumers of this fish species is estimated to provide an effective dose of 0.006 mSv year⁻¹. CFs for ²²⁶Ra indicating transfer from seawater to whole individuals ranged from 8.9 to 30.9, and those indicating transfer from the sediment and mud with detritus—from 0.11 to 0.39 and from 0.08 to 0.3, respectively. The seawater to bones CFs varied from 97.9 to 197.3, to gastrointestinal system—from 59 to 178.8, to gills—from 22.5 to 68.3, to muscles—from 17 to 30.8.     

Radiological characterization of phosphate fertilizers: Comparison between alpha and gamma spectrometry

The natural radioactivity in phosphate fertilizers used in central Italy has been measured by alpha and gamma spectrometry. The results show that the specific activities of ²³⁸U, ²³⁴U and ²³⁵U ranged within interval from < 0.5 to 2628.8, from < 0.5 to 2826.3 and from < 0.9 to 138.0 Bq kg^{− 1} respectively and those of ²¹⁰Pb and ²¹⁰Po ranged within interval from < 15.0 to 401.5 and < 0.5 to 351.6 Bq kg^{− 1} respectively. The ²²⁸Th, ²³⁰Th and ²³²Th concentrations found by alpha spectrometry ranged from < 0.5 to 50.2, from 0.9 to 2727.2 and from < 0.5 to 60.8 Bq kg^{− 1} respectively. ²²⁶Ra and ²²⁸Ra activity concentrations ranged from < 14.3 to 290.9 and from < 2.9 to 24.9 respectively. ⁴⁰K specific activities ranged from 39.2 to 8263.7 Bq kg^{− 1}. A very good correlation exists between the activity concentrations found by alpha spectrometry and those found by gamma spectrometry.     

Magnetic microsphere-based methods to study the interaction of teicoplanin with peptides and bacteria

Teicoplanin (teic) from Actinoplanes teichomyceticus is a glycopeptide antibiotic used to treat many Gram-positive bacterial infections. Glycopeptide antibiotics inhibit bacterial growth by binding to carboxy-terminal d-Ala-d-Ala intermediates in the peptidoglycan of the cell wall of Gram-positive bacteria. In this paper we report the derivatization of magnetic microspheres with teic (teic-microspheres). Fluorescence-based techniques have been developed to analyze the binding properties of the microspheres to two d-Ala-d-Ala terminus peptides. The dissociation constant for the binding of carboxyfluorescein-labeled d-Ala-d-Ala-d-Ala to teic on microspheres was established via fluorimetry and flow cytometry and was determined to be 0.5 × 10⁻⁶ and 3.0 × 10⁻⁶ mol L⁻¹, respectively. The feasibility of utilizing microparticles with fluorescence methods to detect low levels (the limit of bacterial detection was determined to be 30 colon-forming units; cfu) of Gram-positive bacteria has been demonstrated. A simple microfluidic experiment is reported to demonstrate the possibility of developing microsphere-based affinity assays to study peptide–antibiotic interaction.     

Reactive properties of trans-dichlorooxirane in relation to the contrasting carcinogenicities of vinyl chloride and trans-dichloroethylen

Our objective in this work is to gain insight into the contrasting carcinogenic activities of vinyl chloride (definitely carcinogenic) and trans-dichloroethylene (apparently inactive). The initial metabolic step for each molecule is believed to be epoxidation of the double bond, and there is evidence indicating that for vinyl chloride, this epoxide (chlorooxirane) is its ultimate (direct-acting) carcinogenic form. This article presents the findings of a computational study of the reactive properties of trans-dichlorooxirane (the epoxide of trans-dichloroethylene). An ab initio SCF -MO procedure was used to determine the energy requirements for stretching the C? O and C? Cl bonds (S_N1 reactivity) and to study the epoxide's S_N2 interactions with ammonia, taken as a model nucleophile. The starting points were the oxygen- and chlorine-protonated forms of the epoxide. The structure of the system was reoptimized at each step along the various reaction pathways. The results of this work are compared to an analogous earlier study of the reactive properties of chlorooxirane. The chlorineprotonated C? Cl bonds are found to have much lower energy barriers to stretching than do the oxygen-protonated C? O bonds. In the S_N2 processes, intermediate complexes are formed with ammonia by both the oxygen- and the chlorine-protonated epoxides; the latter complexes are the more stable. Based on our results, we propose two mechanisms (one S_N1 and the other S_N2) whereby trans-dichlorooxirane can interact with N₇ of guanine to produce an adduct analogous to one formed by chlorooxirane, which has been found to be the primary in vivo DNA alkylation product of vinyl chloride and to which has been attributed the carcinogenicity of the latter. Overall, trans-dichlorooxirane is found to be chemically more reactive than chlorooxirane; this may help to account for the much lesser carcinogenic and mutagenic activities of trans-dichloroethylene, since the epoxide may be reacting with other cellular nucleophiles before it reaches the key site(s) at which the carcinogenic or mutagenic interaction would occur. We also offer some speculations concerning other possible factors related to the differing carcinogenicities of vinyl chloride and trans-dichloroethylene, such as ease of epoxide formation and the likelihood of oxygen protonation.     

Optical fiber evanescent wave absorption spectrometry of nanocrystalline tin oxide thin films for selective hydrogen sensing in high temperature gas samples

SnO₂ nanocrystalline material was prepared with a sol-gel process and thin films of the nanocrystalline SnO₂ were coated on the surface of bent optical fiber cores for gas sensing. The UV/vis absorption spectrometry of the porous SnO₂ coating on the surface of the bent optical fiber core exposed to reducing gases was investigated with a fiber optical spectrometric method. The SnO₂ film causes optical absorption signal in UV region with peak absorption wavelength at around 320 nm when contacting H₂-N₂ samples at high temperatures. This SnO₂ thin film does not respond to other reducing gases, such as CO, CH₄ and other hydrocarbons, at high temperatures within the tested temperature range from 300 °C to 800 °C. The response of the sensing probe is fast (within seconds). Replenishing of the oxygen in tin oxide was demonstrated by switching the gas flow from H₂-N₂ mixture to pure nitrogen and compressed air. It takes about 20 min for the absorption signal to decrease to the baseline after the gas sample was switched to pure nitrogen, while the absorption signal decreased quickly (in 5 min) to the baseline after switching to compressed air. The adhesion of tin oxide thin films is found to be improved by pre-coating a thin layer of silica gel on the optical fiber. Adhesion increases due to increase interaction of optical fiber surface and the coated silica gel and tin oxide film. Optical absorption spectra of SnO₂ coating doped with 5 wt% MoO₃ were observed to change and red-shifted from 320 nm to 600 nm. SnO₂ thin film promoted with 1 wt% Pt was found to be sensitive to CH₄ containing gas.     

The role of doped Fe on the activity of alumina-supported Pt and Pd diesel exhaust catalysts

Supported Pt and Pd are most commonly used for oxidation catalysts. They have similar and different characteristics for deactivation factors. The catalytic activity of Pt and Pd catalysts supported on ??-Al₂O₃ was studied in the presence and absence of H₂O and SO₂ during CO oxidation under simulated conditions of diesel exhaust gas. Without the addition of H₂O and SO₂ to the feed gas, Pd/Al₂O₃ had a superior catalytic activity compared to Pt/Al₂O₃. The addition of H₂O to the feed gas strongly and negligibly affected the activity of Pd and Pt, respectively, while the addition of SO₂ to the feed gas had a strong poisoning effect on the catalytic activity of both Pt and Pd catalysts. Although being the most active, Pd catalysts exhibited a strong sensitivity to water and sulfur-containing compounds. Fe was added to the Pt and Pd catalysts to introduce sulfur resistance. The addition of Fe enhanced the activity of the catalysts by suppressing the phase transition of Al₂O₃ to Al₂(SO₄)₃ and by hindering metal sintering.     

Oxidation of Dimethyl Sulfide in Air Using Electron-Beam Irradiation,and Enhancement of its Oxidation Via an MnO<Subscript>2</Subscript> Catalyst

The decomposition of dimethyl sulfide (DMS) at initial concentrations of 4.5–18.0 ppmv in air was studied under electron-beam (EB) irradiation. Doses to decompose 90% of input DMS were 2.5 kGy for 4.5 ppmv, 3.4 kGy for 10.6 ppmv, and 3.9 kGy for 18.0 ppmv. HCOOH, (CH₃)₂SO, and trace CH₃OH and (CH₃)₂SO₂ were produced as irradiation products in addition to CO₂ and CO. Application of an O₃ decomposition catalyst to an irradiated sample gas led to an enhancement in the oxidation of DMS and its products into CO₂ and the decomposition of O₃. For 10.6 ppmv DMS/air, the mineralization ratio increased from 41% via only EB irradiation to 100% via the combination treatment at 6.3 kGy. The yield of CO₂ to CO_x increased from 5.3 to 87.6% by combination with catalytic oxidation. This combination treatment enables the irradiation energy used to deodorize gas streams containing DMS to be reduced.     

Kinetic investigation of propane oxidation on diluted Mo1–V0.3–Te0.23–Nb0.125–Ox mixed-oxide catalysts

Reaction kinetics and proposed mechanism for the oxidation of propane over diluted Mo₁–V_0.3–Te_0.23–Nb_0.125–O _x are described. The kinetic study allowed determination of the orders of propane disappearance, propene formation, CO _x formation, and acids formation. The results show that selective oxidation of propane to propylene over this catalyst follows the Langmuir-Hinshelwood mechanism. Deep oxidation of propane to carbon dioxide is first order with respect to hydrocarbon, and partial order (0.21) with respect to oxygen. The selective oxidation of propane to acrylic acid is half order with respect to hydrocarbon and partial order (0.11) with respect to oxygen, while water does not participate directly in propane transformation. The result also shows that the overall reaction consists of three parallel process channels. One main sequence of consecutive reactions leads to the desired product.     

Structural,torsional, vibrational and response electric properties of 2,2′-bitellurophene rotamers. An ab initio and density functional theory investigation

The molecular structure, conformational behaviour, vibrational spectra and electronic (hyper)polarizabilities of tellurophene and 2,2′-bitellurophene rotamers were determined in gas by correlated ab initio and density functional theory calculations. The torsional potential for the rotation around the C²–C^2′ inter-ring bond shows two minima corresponding to anti-gauche and syn-gauche structures and three maxima to planar anti and syn forms and to perpendicular conformation. The potential energy curve is rather flat over the entire 0°–180° twisting range and free rotation cannot be excluded. The IR and Raman spectra of the gauche structures are rather similar to each other, vibrational transitions being scarcely helpful for an unambiguous identification of the rotamers. The dipole moment and the first-order hyperpolarizability increase on passing from the anti-gauche to the syn-gauche conformation by a factor of five and four, respectively. The second harmonic generation nonlinear optical process can be useful to identify the 2,2′-bitellurophene rotamers. On the other hand, the electronic polarizabilities of these structures are much more closer to each other, being predicted to be within 2–13 %.     

Inactivation by Pulsed Light of Bacillus subtilis Spores with Impaired Protection Factors

The resistance to pulsed light (PL) of spores of Bacillus subtilis strain 168 and of strains with mutations increasing sensitivity to UV‐C or affecting spore structure was evaluated and compared to resistance to continuous UV‐C and moist heat, in order to reveal original mechanisms of inactivation by PL. Spores of B. subtilis strain 168 (1A1) and eight mutant strains (sspA, sspB, sspAB, cotA, gerE, cotE, uvrA and recA) were exposed to PL (up to 1.77 J cm^?2), continuous UV‐C (up to 147 mJ cm^?2) and moist heat at 90°C. Spores of the strains lacking proteins linked to coat formation or structure (cotA, gerE and cotE) were markedly more sensitive to PL than 1A1, while their sensitivity to continuous UV‐C or to moist heat was similar to the one of strain 1A1. Coat proteins had a major contribution to the resistance of B. subtilis spores to PL irradiation characterized by short‐time and high‐energy pulses of white light in the wavelengths 200–1100 nm. In contrast the role of coat proteins to UV‐C or to moist heat resistance was marginal or null.     

Sub-solidus Relations in the System KF—PbF2 to high Pressures

The phase β-K_0.25Pb_0.75F_1.75 previously found in the KF-PbF₂ system appears to be metastable at low temperatures relative to a mixture of orthorhombic PbF₂ and a new phase suspected to be KPbF₃ II. KPbF₃ II transforms to KPbF₃ I at 298.5°C at atmospheric pressure. The KPbF₃ II/I transition line rises with pressure, but the substance appears to reversibly disproportionate above ～360°C, 5 kbar, possibly to a mixture of PbF₂ and K₄PbF₆. Instead of β-K_0.25Pb_0.75F_1.75, a mixture with this composition yielded, in addition to weak heat events due to the KPbF₃ II/I transition, strong heat events at 254.5°C and atmospheric pressure (thermal hysteresis ～13°C) which were ascribed to the PbF₂ orthorhombic/cubic transition. This transition rises with pressure to 673°C at 37.8 kbar.     

Correlation of SiO x layer thickness and properties of BOPP/SiO x composite films with spin coating process parameters

The effects of the spin coating process parameters on the thickness of the SiOx layer of the BOPP/SiOx composite film were investigated. When the concentration of tetraethoxysilane (TEOS) increased from 12.5 vol% to 55% vol%, the SiOx thickness increased from about 80 nm to 470 nm. In the sol time range of 1.5 h to 5 h the SiOx layer thickness reached a maximum at about 4 h and the change of the thickness roughly matched the change of the silica colloidal sphere sizes in sol. When the spin-coating speed of the dispensing stage increased from 450 r/min to 500 r/min, the SiOx layer thickness drastically decreased from about 1.67 μm to 400 nm. While the spin-coating speed of the thinning and drying stage went up to 1200 r/min, the SiOx layer thickness was in the range of 330 nm to 390 nm. It was also found that the SiOx layer thickness was almost increased linearly from about 500 nm to 1.02 μm with the ratio of the commercial silica colloidal to the TEOS from 0.2 to 1.0. The water contact angles decreased to about 23.0° for the BOPP/Si-Sol composite film with 1.67 μm SiOx layer and about 4.0° for the BOPP/mixing Si-Sol composite film with 1.02 μm SiOx layer. Compared to BOPP, the light transparency of the BOPP/Si-Sol composite films decreased by about 5.5% with the SiOx layer from about 80 nm to 1.67 μm and by 7.0% for the BOPP/mixing Si-Sol composite film with the SiOx layer from about 350 nm to 1.02 μm respectively.     

Studies on thermal oxidation of chalcopyrite from Chitradurga,Karnataka State,India

When chalcopyrite is heated in air, up to 350? there is no marked change. Between 350 and 440?, surface material is oxidised to iron sulphate, CuSO₄ and Fe₂O₃, while in regions not accessible to oxygen the formation of Cu₅FeS₄, FeS and S takes place. From 440 to 500? oxidation and sulphation phenomena occur. Stable compounds between 500 and 650? are iron sulphate, CuSO₄ and Fe₄O₃, with a minor amount of 6CuO.Cu₂O indicated at 650?. After the decomposition of iron sulphate, CuSO₄ decomposes, first to CuO.CuSO₄ and then to CuO. By 750? the sulphur has been totally lost from all compounds, while the oxides of copper and iron partly react to form CuFe₂O₄. Final products of oxidation between 800 and 850? are CuO, CuFe₂O₄ and Fe₃O₄.     

Polymer drying. VI. EPR spin-probe studies on swelled poly(styrene-co-divinylbenzene)

The electron paramagnetic resonance (EPR) signal and the residual number (α_t) of volatile molecules per phenyl group of poly(styrene-co-divinylbenzene) in samples that had been swelled to saturation in a dilute solution of a nitroxide spin-probe (TEMPO or 4-oxo-TEMPO), dissolved in a volatile liquid, were monitored simultaneously as the system containing excess liquid was allowed to evaporate to dryness. The results showed that the characteristic motionally narrowed three-line EPR spectrum began to change when α_t became equal to α_g (the number of sorbed molecules per phenyl group of polymer at liquid-saturation). The ratio of the intensity of the low-field and high-field hyperfine peaks relative to the middle peak decreased monotonically to an asymptotic limit that was attained when α_t became equal to α_g (the number of residual adsorbed molecules per phenyl group of polymer at completion of the transition from the rubbery state to the glassy state). The EPR hyperfine pattern, from which the rotational correlation times were estimated, changed most significantly as α_t decreased from α_G to α_g while exhibiting inflections at about α′_s and α′_g the compositions that mark, respectively, incipient desorption of adsorbed molecules and incipient transition from the rubbery state to the glassy state. The pattern between these inflections points, however, varied with the affinity of the solvent for the polymer.     

Studies of the system TaS2−xSex

Single crystal and powder samples of the system TaS_2?xSe_x have been prepared and studied. The range of solubility was found to extend from x = 0 to x = 2.0. X-Ray analysis has shown that mixed anion samples exhibit a series of hexagonal layered polymorphs similar to those found in TaS₂ and TaSe₂, with the a and c lattice parameters increasing monotonically from TaS₂ to TaSe₂. Electrical transport properties were measured on single crystals and found to be similar to the end compositions. Organic molecules such as pyridine and collidine were found to intercalate TaS_2?xSe_x for x ≦ 1.4, and superconducting transition temperatures were measured for both intercalated and unintercalated samples. The highest T_c obtained was 4.1 K in the 4H(c) phase of the sample TaS_1.6Se_0.4.     

Glucose-induced heat production, insulin secretion and lactate production in isolated Wistar rat pancreatic islets

Transplantation of pancreatic islets is efficient in improving the metabolic control and quality of life and in preventing severe hypoglycemia in patients with brittle type 1 diabetes mellitus. More accurate methods to assess islet viability would be extremely useful in designing target interventions for islet cytoprotection and in reducing the number of islets required to achieve insulin independence. Here we report on an application of calorimetry to evaluate the metabolic response of pancreatic islets to glucose stimulation. A significant increase in metabolic heat was produced by islet samples when consecutively subjected to 2.8 and 16.3 mmol L⁻¹ glucose. Under these glucose concentrations, 1000 islets released average heat values of 9.16 ± 0.71 mJ and 14.90 ± 1.21 mJ over 50 min, respectively. Additionally, the glucose stimulation indexes were 1.67 ± 0.30 for insulin, 1.72 ± 0.13 for heat and 2.91 ± 0.50 for lactate, raising the important possibility of substituting the secreted insulin index/ratio by the index/ratio of the heat released in the evaluation of Langerhans islets viability for transplantation. Altogether, our results demonstrate the applicability of calorimetry to assess the quality of isolated pancreatic islets and to study vital islet functions.     

Sensitive and selective detection of aspartic acid and glutamic acid based on polythiophene-gold nanoparticles composite

In recent years, gold nanoparticles and water-soluble fluorescent conjugated polymers are promising materials in terms of their potential applications in a variety of fields, ranging from monitoring DNA hybridization to demonstrate the interaction between proteins, or detecting diseased cell, metal ions and small biomolecular. In order to exploit some new properties of the both, many attempts have been devoted to achieve nanoparticle-polymer composite via incorporating metal nanoparticle into polymer or vice versa, however, only few of them are put into practical application. In the present paper, we utilize the “superquenching” property of AuNPs to polythiophene derivatives for detecting aspartic acid (Asp) and glutamic acid (Glu) in pure water, and discuss the factors accounting for fluorescence quenching and recovery via modulating pH. Thus an exceptionally simple, rapid and sensitive method for detecting Asp and Glu is established with a limit of detection (LOD) is 32 nM for Asp and 57 nM for Glu, the linear range of determination for Asp is 7.5 × 10⁻⁸ M to 6 × 10⁻⁶ M and 9.0 × 10⁻⁸ M to 5 × 10⁻⁶ M for Glu. The system is applied to real sample detection and the results are satisfying. Otherwise the composite is very sensitive to pH change of solution, we expect it will be possible to use as pH sensor with wide range in the future.