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1.
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  相似文献   

2.
Radioactivity of coals and fly ashes   总被引:1,自引:0,他引:1  
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.  相似文献   

3.
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 (SN1 reactivity) and to study the epoxide's SN2 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 SN2 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 SN1 and the other SN2) 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.  相似文献   

4.
The electron paramagnetic resonance (EPR) signal and the residual number (αt) 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 αt became equal to αg (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 αt became equal to αg (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 αt decreased from αG to αg 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.  相似文献   

5.
6.
Infrared spectra of CO-treated platinum hydrosols subsequently treated with acetylene, hydrogen, and oxygen reveal that v(CO)ads decreases from 2070 cm−1 with increasing gas-treatment time. This has been attributed to a reduction in the coverage of adsorbed CO. In Pt sol/CO/C2H2 systems, v(CO)ads decreases to a limiting value of ca. 2060 cm−1 after exposure to acetylene. In the Pt sol/CO/H2 systems, v(CO)ads decreases to ca. 2050 cm−1 after exposure to hydrogen gas. The lower frequency in the Pt sol/CO/H2 system has been attributed to CO adsorption on more active metal sites formed from the reduction of surface platinum oxides. Exposure of the CO-treated platinum hydrosols to O2 gas was found to cause the eventual disappearance of the v(CO)ads band in infrared spectra, which was attributed to oxidation of adsorbed CO to CO2 by weakly bound surface layers of platinum oxides formed by the oxygen treatment.  相似文献   

7.
The conditions of thermal decomposition of Y, La, Ce(III), Pr, Nd, Sm, and Gd aconitates have been studied. On heating, the aconitate of Ce(III) loses crystallization water to yield anhydrous salt, which then is transformed in to oxide CeO2. The aconitates of Y, Pr, Nd, Sm, Eu and Gd decompose in three stages. First, aconitates undergo dehydration to form the anhydrous salts, which next decompose to Ln2O2CO3. In the last one the thermal decomposition of Ln2O2CO3 to Ln2O3 is accompanied by endothermic effect. Dehydration of aconitate of La undergoes in two stages. The anhydrous complex decomposes to La2O2CO3; this subsequently decomposes to La2O3.  相似文献   

8.
Reaction kinetics and proposed mechanism for the oxidation of propane over diluted Mo1–V0.3–Te0.23–Nb0.125–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.  相似文献   

9.
Abstract The negative side effects of chlorarnphenicol (CAP) mostly involve blood dyscrasias (e.g. irreversible nondose-dependent aplastic anemia), allergic skin reactions and eye damage. To learn the cause of these side effects, most research focuses on metabolically formed nitroso- and hydroxylamino derivatives in the predisposed patient. In previous investigations it was demonstrated that photochemical decomposition of CAP in vitro by UV-A leads to formation of p-nitrobenzaldehyde (pNB), p-nitrobenzoic acid (pNBA) and p-nitrosobenzoic acid (pNOBA); the latter comprises up to 45 mol% of the starting amount of CAP. Incubation of these photoproducts in rat blood showed that pNB and pNOBA rapidly react and that PNBA is stable under these conditions. Reaction products from pNB (half-life 1.7 min) proved to be pNBA and p-nitrobenzyl alcohol (pNBOH) while pNOBA (half-life 3.7 min) was converted into p-aminobenzoic acid (pABA). Exposure of CAP in rat blood to UV-A yielded the same end products: pNBA, PABA and pNBOH. To estimate the amount of oxidative stress generated in vivo by these compounds, the ability to form methemoglobin (MetHb) in erythrocytes was tested; only pNOBA and p-hydroxylaminobenzoic acid (pHABA), a possible intermediate in the decomposition of pNOBA, proved to be reactive. Ultraviolet-A exposure of rats, after intraperitoneal injection of CAP, led to 3.6 times the basic level of MetHb. In addition, covalent binding of 3H-labeled CAP photoproducts to the skin of the back and to the ears was found, which was 9.1 and 3.2 times higher, respectively, than the dark values. Toxicity toward bone marrow cells of all photoproducts was established in vitro. p-Nitrobenzaldehyde, pNOBA andpHABA were 20, 6 and 6 times more toxic than CAP, respectively. These results show that photodecomposition of CAP in vivo does occur. Its reactive photoproducts are able to cause damage that may lead to (systemic) side effects. The latter is supported by the fact that the nature of the reactive products, nitroso- and hydroxylamino derivatives, is the same as the expected metabolites.  相似文献   

10.
Electron-capture negative ion chemical ionization (EC-NICI) and field desorption (FD) mass spectrometric techniques were utilized to examine polyfluorinated C60. Two different samples from the same preparation, one prior to sublimation and the other sublimed material, were investigated. From the raw non-sublimed product in EC-NCI six series of ions corresponding to different numbers of attached oxygen atoms were obtained, which are represented by the formula [C60F2nOm]?, where n ranged from 0 to 30 and m from 0 to 5. The sublimed material in EC-NICI produced the same six series of ions with up to 48 fluorine atoms attached to C60. The field desorption of the same sample produced similar results, but the signal-to-noise ratios of the spectra were low. Both samples, in the two different techniques examined, yielded C60F60 ions with only an even number of fluorine atoms attached. The present investigation, for the first time, provides direct experimental evidence for the existence of higher fluorinated C60 up to C60F60 and multiple oxides of polyfluoro-C60 with up to five oxygen atoms attached.  相似文献   

11.
Childhood exposure to ultraviolet radiation (UVR) is a major risk factor for the development of melanoma later in life. However, it is challenging to accurately determine personal outdoor exposure to UVR, specifically erythemally weighted UVR (UVEry), due to technological constraints, variable time–activity patterns, and the influence of outdoor environmental design. To address this challenge, this study utilized mobile and stationary techniques to examine the UVEry exposures of 14 children in a schoolyard in Lubbock, TX, in spring 2016. The aims of the study were to examine the influence of artificial shade on personal UVEry exposures and to assess full sun exposure ratios (ERs) within the same playground microenvironment. On average, personal wrist dosimeters worn during play in the sun measured 18% of the total onsite UVEry measured by a stationary UV pyranometer. Shade was found to significantly reduce the personal UVEry exposures by 55%, UVB280–315 nm exposures by 91%, and the overall solar radiation by 84%. Substantial benefits can be garnered through focused design of children's recreational space to utilize shade—both natural and artificial—to reduce UVR exposures during play, and to extend safe outdoor stays. Finally, although the wrist is a practical location for a dosimeter, it often underestimates full exposures, particularly during physical activity.  相似文献   

12.
Ortho-phenylene-bridged phosphinoborane (2,6-Cl2Ph)2B-C6H4-PCy2 1 was synthesized in three steps from commercially available starting materials. 1 reacts with H2 or H2O under mild conditions to form corresponding zwitterionic phosphonium borates 1-H2 or 1-H2O . NMR studies revealed both reactions to be remarkably reversible. Thus, when exposed to H2, 1-H2O partially converts to 1-H2 even in the presence of multiple equivalents of water in the solution. The addition of parahydrogen to 1 leads to nuclear spin hyperpolarization both in dry and hydrous solvents, confirming the dissociation of 1-H2O to free 1 . These observations were supported by computational studies indicating that the formation of 1-H2 and 1-H2O from 1 are thermodynamically favored. Unexpectedly, 1-H2O can release molecular hydrogen to form phosphine oxide 1-O . Kinetic, mechanistic, and computational (DFT) studies were used to elucidate the unique “umpolung” water reduction mechanism.  相似文献   

13.
The racemic 7‐oxanorbornanyl and norbornanyl aminoalcohols 3, 4, 42, 45 , and 46 were synthesized and tested as snail β‐mannosidase inhibitors. The amino tetraol 3 was obtained from the known sulfonyl acrylate 9 and furan 10 . Esterification provided 11 that underwent an intramolecular Diels–Alder reaction to the 7‐oxanorbornene 12 . Reduction of 12 to 13 , desulfonylation, isopropylidenation, and cis‐dihydroxylation gave 16 . A second isopropylidenation to 17 , followed by debenzylation and a Mitsunobu–Gabriel reaction provided 19 that was deprotected via 20 to 3 . Diels–Alder cycloaddition of furfuryl acetate and maleic anhydride to 21 , followed by alcoholysis of the anhydride, cis‐dihydroxylation, isopropylidenation, and Barton decarboxylation gave the ester 25 . Deacetylation to 26 and a Mitsunobu–Gabriel reaction led to 27 that was transformed into the N‐Boc analogue 29 , reduced to the alcohol 30 , and deprotected to 4 . The 1‐aminonorbornane 5 was obtained from Thiele's Acid 31 . Diels–Alder cycloaddition of the cyclopentadiene obtained by thermolysis of the diester 32 , methanolysis of the resulting anhydride 33 , dihydroxylation, isopropylidenation, Barton decarboxylation, and Curtius degradation led to the benzyl carbamate 39 that was reduced to the alcohol 40 , transformed into the N‐Boc carbamate 41 , and deprotected to 5 . The alcohol 40 was also transformed into the benzylamine 42 , aniline 45 , and hydroxylamine 46 . Snail β‐mannosidase was hardly inhibited by 3, 4, 42, 45 , and 46 . Only the amino triol 5 proved a stronger inhibitor. The inhibition by 5 depends on the pH value (at pH 3.5: Ki = 1900 μM ; at pH 4.5: Ki = 340 μm; at pH 5.5: Ki = 110 μm). The results illustrate the strong dependence of the inhibition by bicyclic mimics upon the precise geometry and orientation of the amino group as determined by the scaffold. It is in keeping with the hypothesis that the reactive conformation imposed by snail β‐mannosidase is close to a 1,4B/1S3.  相似文献   

14.
In 2008, the first Proficiency Testing Scheme of Chemical Oxygen Demand (1stCOD-PTADG) was conducted to assess the results obtained for different research groups whose field work is mainly anaerobic digestion. This study was performed using four samples, two solid samples as raw materials and two solid samples to prepare high concentration suspended solid solutions. Invitations were sent to a large number of laboratories, mainly to anaerobic digestion research groups. Finally, thirty labs from sixteen countries agreed to participate, but for different reasons four participants could not send any data. In total, twenty-six results were reported to the COD-PT coordinator.This study showed the importance of continuous participation in proficiency testing (PT) schemes in order to compare the results obtained. Taking into account the lack of a general standard method and high quality certified reference materials (CRMs), the traceability of COD determination is not currently easy to check. In addition, the spread of participants’ results obtained was high and pointed to the advisability of using consensus values due to their unreliability. Therefore, the theoretical oxygen demand (ThOD) values were considered as assigned values for all the samples analysed. On the other hand, in this PT the established standard deviation (ESD) has been determined by the Horwitz modified function.Participants of this 1stCOD-PTADG were asked to give a short report on the analytical method used. Although all the participants used potassium dichromate as their oxidant reagent, their experimental procedures were very different. With the purpose of comparing the results obtained, the different experimental conditions used were classified into five methods, corresponding to two main categories, open and closed reflux. The performance of laboratories was expressed by the z-score, whose value is considered satisfactory when z-score ≤±2. The overall analytical data evaluation showed that 64% of z-scores obtained were outside the accepted limits.  相似文献   

15.
The synthesis of unsubstituted oligo-para-phenylenes ( OPP ) exceeding para-hexaphenylene—in the literature often referred to as p-sexiphenyl—has long remained elusive due to their insolubility. We report the first preparation of unsubstituted para-nonaphenylenes ( 9PP s) by extending our precursor route to poly-para-phenylenes ( PPP ) to a discrete oligomer. Two geometric isomers of methoxylated syn- and anti-cyclohexadienylenes were synthesized, from which 9PP was obtained via thermal aromatization in thin films. 9PP was characterized via optical, infrared and solid-state 13C NMR spectroscopy as well as atomic force microscopy and mass spectrometry, and compared to polymeric analogues. Due to the lack of substitution, para-nonaphenylene, irrespective of the precursor isomer employed, displays pronounced aggregation in the solid state. Intermolecular excitonic coupling leads to formation of H-type aggregates, red-shifting emission of the films to greenish. 9PP allows to study the structure–property relationship of para-phenylene oligomers and polymers, especially since the optical properties of PPP depend on the molecular shape of the precursor.  相似文献   

16.
Summary. The magnetic and microstructure properties of Fe2O3–0.4NiO–0.6ZnO–B2O3 glass system, which was subjected to heat treatment in order to induce a magnetic crystalline phase (Ni0.4Zn0.6-Fe2O4 crystals) within the glass matrix, were investigated. DSC measurement was performed to reveal the crystallization temperature of the prepared glass sample. The obtained samples, produced by heat treatment at 765°C for various times (1, 1.5, 2, and 3 h), were characterized by X-ray diffraction, IR spectra, transmission electron microscopy, and vibrating sample magnetometer. The results indicated the formation of spinel Ni–Zn ferrite in the glass matrix. Particles of the ferrite with sizes ranging from 28 to 120 nm depending on the sintering time were observed. The coercivity values for different heat-treatment samples were found to be in the range from 15.2 to 100 Oe. The combination of zinc content and sintering times leads to samples with saturation magnetization ranging from 12.25 to 17.82 emu/g.  相似文献   

17.
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.  相似文献   

18.

Ti–Ta and Ti–Ta–xSn shape memory alloys (SMAs) were produced successfully by microwave sintering. Tin element was added to Ti–Ta SMA with three different atomic percentages (0.37, 0.745 and 2.26 at.%). The influences of Sn addition on microstructure, transformation temperatures, mechanical properties, shape memory behaviours, corrosion resistance and bioactivity were investigated. It was found that the morphologies of the modified and unmodified Ti–Ta alloys contain a plate-like and needle-like structure, where the former structure is related to the β phase and the latter related to the α phase. The transformation temperatures of M s to M f with and without Sn additions were observed to be in the range of 389.65 to 355 K, while the transformation temperatures of A s to A f were found to be in the range of 250.42 to 365.8 K. By increasing the proportion of Sn, the compressive fracture strength and shape memory behaviour were enhanced; however, the corrosion resistance tended to be decreased. Based on the bioactivity results, antibacterial activity was improved with the addition of Sn. In conclusion, the existent results indicate that Ti–30 at.% Ta SMAs may be a convenient alternative to Ni–Ti for certain biomedical applications.

  相似文献   

19.
The mass spectra of a group of m- and p-substituted acetanilides were measured to determine the effect of the substituents, if any, on the rate of C2H2O expulsion (rearrangement) vs. the rate of [CH3CO]+ formation (simple cleavage). Our results agree with observations of others in that substituents which raise the ionization potential of the aromatic ring appear to localize, on the average, less charge density on this locus, and conversely. The atomic composition of the substituent, however, irrespective of its position, seems to determine the relative rates of the competing reaction. Although in several cases Zm/Zp values were close to unity, rearrangement of isomeric molecular ions to a common species is shown not to occur.  相似文献   

20.
Antimony (Sb) contamination has become a growing concern in recent years. Strategies for reducing Sb contamination and its related health risks are urgently desired. This study was conducted to explore the possibility of selenium (Se) detoxification on Sb toxicity in paddy rice in order to find a feasible method to reduce the health risk of Sb pollution. Seedlings of paddy rice were exposed to 5 mg L1 Sb (KSbC4H4 O7·1/2H2O), in the presence of Se (Na2SeO3) at 0.1, 1, 5 mg L1 in culture solution, with no Sb and Se addition as the control. Paddy rice took up Sb greatly and the highest Sb contents measured among all treatments in this experiment in the leaves, stems and roots were 65.5, 298.5 and 195.7 mg kg1, respectively. Without Sb addition in the solution, single exposure to 0.1 mg L1 Se remarkably reduced the malondialdehyde (MDA) formation in paddy rice,demonstrating the beneficial effect of Se at low dosages. The addition of 5 mg L1 Sb was found to generate toxicity to paddy rice, showing as decreased biomass and increased leaf MDA content in paddy rice, while addition of 1 mg L1 Se mitigated the toxicity of Sb, as seen with the decreased leaf MDA content and increased biomass, indicating antidotal role of Se to Sb. In addition, the presence of 0.1, 1, 5 mg L1 Se generally decreased the accumulation of Sb in the leaves, stems and roots in paddy rice. Toxicity was also seen when paddy rice was exposed to single Se at 1 and 5 mg L1 levels, however, 5 mg L1 Sb addition was found to decrease the contents of Se in the leaves/stems whereas increased them in roots, accompanied with decreased MDA contents and increased biomass in paddy rice, indicating a possible detoxification role of Sb to Se too. Therefore, Sb, although toxic, could also be an antitoxin to Se in paddy rice at certain condition. Our results showed that Se could alleviate Sb toxicity efficiently in paddy rice through two effects as antagonism and antioxidation.  相似文献   

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