Preparation of18F source for slow positron beam by proton bombardment of18O-water

Fluorine-18 produced by the¹⁸O(p,n)¹⁸F reaction on¹⁸O-water has proved to be highly useful as a source for a slow positron beam. About 70 GBq of¹⁸F is produced routinely by an ultra-compact cyclotron. The¹⁸F formed in H₂ ¹⁸O target is sent through a fine pipe to the site of positron slowing-down, fixed on a small spot by adsorption or drying, and then placed close to the moderator foil. An automatic apparatus has been set up for the entire process including the recovery of H₂ ¹⁸O.     

Tetrabrominated Lead Naphthalocyanine for Optical Power Limiting

The complex 2,(3)‐tetrabromo‐3,(2)‐tetra[(3,5‐di‐tert‐butyl)phenyloxy]‐naphthalocyaninato lead [Br₄(tBu₂C₆H₃O)₄NcPb, 1 ] has been prepared and its optical limiting properties for ns light pulses have been measured. Complex 1 behaves as a reverse saturable absorber within the spectral range 440–720 nm with a limiting threshold of 0.1 J cm^?2 at 532 nm. The lifetime of the absorbing triplet excited state has been evaluated as 3.8×10^?7 s and the quantum yield of triplet formation has been measured as 0.07 in toluene. The nonlinear optical transmission properties of complex 1 have also been determined in Plexiglas [naphthalocyanine content: 5.0×10^?4 M (0.1 % by weight)]. A reversible nonlinear absorption was again observed for a fluence above 0.4 J cm^?2, but through different excited‐state dynamics. This may be rationalized in terms of aggregation of the molecule in the polymer matrix.     

Study of the <Superscript>241</Superscript>Am(n,2n)<Superscript>240</Superscript>Am reaction cross section in the energy range of <Emphasis Type="Italic">E</Emphasis><Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> = 8.8−11.1 MeV

The measurement of the cross section of the reaction ²⁴¹Am(n,2n)²⁴⁰Am has been performed at neutron energies from 8.8 to 11.1 MeV, implementing the activation technique. The neutron beam was produced at the TANDEM accelerator of NCSR “Demokritos” by the ²H(d,n)³He reaction, using a deuterium gas target. During the 5-day long irradiation, the neutron beam fluctuations were monitored in 100 seconds intervals by a BF₃ counter connected with a multiscaling unit. The radioactive target consisted of a 37 GBq ²⁴¹Am source enclosed in a Pb container. A natural Au foil, a ²⁷Al foil and a ⁹³Nb foil were used as reference materials for the neutron flux determination. After the end of the irradiation the activity induced at the target and the reference foils, was measured off-line by a 56% HPGe detector.     

一种含咔唑基团的混配型钌(II)配合物的合成、表征和酸碱性质研究

合成了钌(II)配合物cis-[Ru(HL)(Hdcbpy)(NCS)₂]^－•[N(C₄H₉)₄]^＋ (HL＝2-(9-乙基-9H-3-咔唑基)-1H-咪唑[4,5-f] [1,10]邻菲啰啉, H₂dcbpy＝4,4'-二羧酸-2,2'-联吡啶). 采用元素分析、核磁共振氢谱、红外光谱、紫外-可见吸收光谱、质谱(MS)对配合物进行了表征. 通过紫外-可见吸收光谱和稳态荧光光谱, 研究了该配合物的基态和激发态酸碱性质. 结果表明该配合物在基态时能发生5步质子化/去质子化反应, 表现出基于光致发光强度和激发态能量转移途径的质子化/去质子化诱导的分子开关性质.     

Doubly charged ion mass spectra: III—N-alkanes

Doubly charged ion mass spectra have been obtained for 15 n-alkane hydrocarbons. Spectra were measured using a Nier-Johnson geometry Hitachi RMU-7L mass spectrometer operated at 1.6kV accelerating voltage. Fragment ions, which resulted from C? C bond rupture and extensive H loss, dominated the spectra. Molecular ions have not been observed. The most intense ions in the doubly charged ion mass spectra of n-alkanes were [C₂H₄]²⁺, [C₃H₂]²⁺, [C₄H₃]²⁺, [C₅H₂]²⁺, [C₆H₆]²⁺, [C₆H₈]²⁺, [C₇H₆]²⁺, [C₇H₈]²⁺, [C₈H₆]²⁺ and [C₈H₈]²⁺. Appearance energies for forming the prominent doubly charged fragment ions have been measured and range from 27.5 eV to energies greater than 60eV. A geometry optimized SCF approach has been used to compute the energies and structures of prominent ions in the doubly charged mass spectra.     

Ion pair generation rates near planar3H and63Ni electron capture detector foils

The ion-pair generation rate (ionization topography) in plasmas from⁶³Ni and particularly Ti³H₄ foils, as used in electron capture detectors, was measured at room temperature using large, parallel plates of low backscattering ability in nitrogen gas of varying density. For one atmosphere pressure, the fall-off of ion pair formation as calculated from the exponential region equalsN ₀·e ^–0.19d for⁶³Ni andN ₀·e ^–1.4d for³H (whereN ₀ is the initial ionization rate immediately adjacent to the foil andd is the distance from the foil in mm). The experimentally measured half ranges (distances from the foil within which 50% of all possible ion pairs are created) are 2.7 mm for⁶³Ni and 0.27 mm for³H. The half ranges calculated from the exponential region where there is less interference from electron backscattering, are 3.7 and 0.5 mm, respectively. The latter values are considered closer to the true, unimpeded ionization topography near planar⁶³Ni and³H foils.Material taken from doctoral thesis     

Chemical ionization mass spectra of mononitroarenes

The H₂ and CH₄ chemical ionization mass spectra of a selection of substituted nitrobenzenes have been determined. It is shown that reduction of the nitro group to the amine is favoured by high source temperatures and the presence of water in the ion source. The H₂ chemical ionization mass spectra are much more useful for distinguishing between isomeric compounds than the CH₄ CI mass spectra because of the more extensive fragmentation. For ortho substituents bearing a labile hydrogen abundant [MH ? H₂O]⁺ fragments are observed. When the substituent is electron-releasing both ortho and para substituted nitrobenzenes show abundant [MH? OH]⁺ fragment ions while meta substituted compounds show abundant loss of NO and NO₂ from [MH]⁺. The latter fragmentation is interpreted in terms of protonation para to the substituent or ortho to the vitro function, while the first two fragmentation routes arise from protonation at the nitro group. When the substituent is electron-attracting the chemical ionization mass spectra of isomers are very similar except for the H₂O loss reaction for ortho compounds.     

Assessment of the natural radioactivity using two techniques for the measurement of radionuclide concentration in building materials used in Japan

The specific activities of ²³⁸U, ²³²Th, and ⁴⁰K in selected building materials used in Japan were measured using a high-purity germanium detector. The uranium and thorium concentrations were determined from same samples using inductively coupled plasma mass spectrometry. There was a good agreement between the measurement of uranium and thorium with both methods (R ² = 0.94, and 0.97, respectively). Based on the specific activities, we have estimated some hazard indexes such as radium equivalent activities (Ra _eq), external hazard index (H _ex), internal hazard index (H _in), annual gonadal equivalent dose (AGED), internal alpha dose, mass exhalation rate and emanation coefficient of radon.     

Affinity of a new copper(II) complex to DNA/BSA and antioxidant/radical scavenging activities: crystal structure of [Cu(4,7-diphenyl-1,10-phenanthroline)(leucine)(NO3)(H2O)]

A new copper(II) complex, [Cu(Bphen)(Leu)(NO₃)(H₂O)] (Bphen = 4,7-diphenyl-1,10-phenanthroline, leu = L-leucine), has been synthesized and characterized by IR spectroscopy, CHN analysis, and single-crystal X-ray diffraction techniques. The CT-DNA binding properties of the complex have been investigated by both absorption and emission spectroscopy. The binding parameters for the fluorescence Scatchard plot were also determined. Further, the interaction of the complex with bovine serum albumin (BSA) has been investigated using absorption and emission spectroscopy. The thermodynamic parameters, free energy change (ΔG), enthalpy change (ΔH), and entropy change (ΔS), were calculated by the van’t Hoff equation and discussed. The distance between BSA and the complex has been obtained according to fluorescence resonance energy transfer. Conformational changes of BSA have been observed from synchronous fluorescence. Antioxidant and radical scavenging activities of the complex were determined by various in vitro assays such as 1,1-diphenyl-2-picryl-hydrazyl free radicals (DPPH˙), 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) radicals (ABTS˙⁺), and reducing ability determination by H₂O₂ scavenging methods.     

Laser induced photoacoustic spectroscopy in liquid samples: temperature and solvent effects

Summary Laser induced photoacoustic spectroscopy (LIPAS) has been confirmed as an analytical tool, suitable for the determination of inorganic and organic species in aqueous and organic solvents, reaching detection limits two orders of magnitude lower than those obtained with conventional spectrophotometry.A significant influence of the solvent on the enhancement of the magnitude of the LIPAS response waveform of the piezoelectric detector has been found experimentally for inorganic species (neodymium ions) and organic compounds (e.g. -carotene and the cytochrome c), when water was replaced by organic solvents. This is particularly true, when a laser excitation wavelength above 500 nm was used, where the absorption coefficient for H₂O increases drastically.Furthermore, the temperature dependence of the magnitude of the LIPAS signal has been measured, in the range between 20–70°C in samples containing Nd³⁺,-carotene and the macromolecule cytochrome c in various aqueous and organic (polar and non-polar) solvents (H₂O, HClO₄, acetone, ethanol and petrol ether). A very strong enhancement of the LIPAS response was observed with increasing temperature (a factor of two in an interval between 20 and 40°C) for all inorganic and organic substances in aqueous solution. On the other hand, in polar and non-polar organic solvents only a slight decline of the signals of about 20% was found over the same temperature range.     

Study of non-validity of mixture rule near K-absorption edges by X-ray spectrometric technique

X-ray spectrometric technique has been described to determine the X-ray mass attenuation coefficient, μ/ρ, of X-rays employing HPGe X-ray detector and radioactive sources. The photon intensity is measured by gating the channel of the spectrometer at FWHM/photo peak. Using the technique the “best value” values of μ/ρ were obtained for those thicknesses which lie in the transmission (T) range 0.5 ≥ T ≥ 0.02. Total attenuation cross sections for other elements and lead compounds were measured at photon energies from 17 to 88 keV to study the Bragg’s additivity law near the absorption edge of the lead. The measured values of mass attenuation coefficient values are compared with theoretical values obtained using Winxcom (programme). This study suggests that measured mass attenuation coefficient values at and near absorption edges differ from the theoretical value by about 17–23%.     

Laser photolysis studies of hydrazine vapor: 193 and 222-nm H-atom primary quantum yields at 296 K,and the kinetics of H + N2H4 reaction over the temperature range 222–657 K

The primary quantum yield of H-atom production in the pulsed-laser photolysis of hydrazine vapor, N₂H₄ + hν → H + N₂H₃, was measured to be (1.01 ± 0.12) at 193 nm relative to HBr photolysis, and (1.06 ± 0.16) at 222 nm relative to 248-nm N₂H₄ photolysis, in excess He buffer gas at 296 K. The H-atoms were directly monitored in the photolysis by cw-resonance fluorescence detection of H(²S) at 121.6 nm. The high H-atom yield observed in the photolysis is consistent with the continuous ultraviolet absorption spectrum of N₂H₄ involving unit dissociation of the diamine from repulsive excited singlet state(s). The laser photodissociation of N₂H₄ was thus used as a ‘clean’ source of H-atoms in excess N₂H₄ and He buffer gas to study the gas-phase reaction, H + N₂H₄ → products; (k₁), in a thermostated photolysis reactor made of quartz or Pyrex. The pseudo-first-order temporal profiles of [H] decay immediately after photolysis were determined for a range of different hydrazine concentrations employed in the experiments to calculate the absolute second-order reaction rate coefficient, k₁. The Arrhenius expression was determined to be k₁ = (11.7 ± 0.7) × 10^?12 exp[?(1260 ± 20)/T] cm³ molec^?1 s^?1 in the temperature range 222–657 K. The rate coefficient at room temperature was, within experimental errors, independent of the He buffer gas pressure in the range 24.5–603 torr. The above temperature dependence of k₁ is in excellent agreement to that we determine in our discharge flow-tube apparatus in the temperature range 372–252 K and in 9.5 torr of He pressure. The Arrhenius parameters we report are consistent with a metathesis reaction mechanism involving the abstraction of hydrogen from N₂H₄ by the H-atom. © 1995 John Wiley & Sons, Inc.     

Kinetics of the reaction between H atoms and allyl radicals

The reaction between H and C₃H₅ has been studied at 291 K. Exciplex laser flash photolysis at 193.3 nm of hexa-1,5-diene-He mixtures generated both H and C₃H₅ ([H] ? [C₃H₅]), which were detected in time-resolved mode by resonance fluorescence and absorption spectroscopy, respectively. Rate coefficients are presented at four pressures in the range 98 ? P/torr ? 400; no clear pressure-dependence is found in this range of pressures and the mean rate coefficient is (2.8 ± 1.0) × 10^?10 cm³ molecule^?1 s^?1. Calculations based on the Troe factorization method confirm that this reaction is near its high-pressure limit under the experimental conditions.     

INO thermodynamic properties and ultraviolet spectrum

The equilibrium I₂(g) + 2NO(g) = 2INO(g) has been studied at room temperature by ultraviolet absorption spectroscopy. The equilibrium constant has been measured as K_p = (2.7 ± 0.3) × 10^?6 atm^?1 at 298 K. Third-law calculations lead to ΔH°_f,298 (INO) = 120.0 ± 0.3 kJ/mol. The relative absorption spectrum of INO has been measured between 225 and 300 nm. Quantitative measurements gave ?(λ_max = 238 nm) = (1.79 ± 0.5) × 10⁴ L/mol·cm and ?(410 nm) = 234.7 ± 21 L/mol·cm.     

The negative ion mass spectra of methanol and deuterated methanol

The negative ion mass spectra of methanol, methanol-d and trideuteromethanol have been measured at 70 eV. Use of deuterated methanols has enabled the ion at m/e 31 to be identified as CH₃O^? and not CH₂OH^?. Isotope effects have been determined for H^? and D^? formation, and for OH^? and OD^? formation. It has been shown that OH^? formation occurs as a rearrangement reaction as well as by simple C? O bond fission.     

IR laser absorption diagnostic for C2H4 in shock tube kinetics studies

An IR laser absorption diagnostic has been further developed for accurate and sensitive time‐resolved measurements of ethylene in shock tube kinetic experiments. The diagnostic utilizes the P14 line of a tunable CO₂ gas laser at 10.532 μm (the (0 0 1) → (1 0 0) vibrational band) and achieves improved signal‐to‐noise ratio by using IR photovoltaic detectors and accurate identification of the P14 line via an MIR wavemeter. Ethylene absorption cross sections were measured over 643–1959 K and 0.3–18.6 atm behind both incident and reflected shock waves, showing evident exponential decay with temperature. Very weak pressure dependence was observed over the pressure range of 1.2–18.6 atm. By measuring ethylene decomposition time histories at high‐temperature conditions (1519–1895 K, 2.0–2.8 atm) behind reflected shocks, the rate coefficient of the dominant elementary reaction C₂H₄ + M → C₂H₂ + H₂ + M was determined to be k₁ = (2.6 ± 0.5) × 10¹⁶exp(?34,130/T, K) cm³ mol^?1 s^?1 with low data scatter. Ethylene concentration time histories were also measured during the oxidation of 0.5% C₂H₄/O₂/Ar mixtures varying in equivalence ratio from 0.25 to 2. Initial reflected shock conditions ranged from 1267 to 1440 K and 2.95 to 3.45 atm. The measured time histories were compared to the modeled predictions of four ethylene oxidation mechanisms, showing excellent agreement with the Ranzi et al. mechanism (updated in 2011). This diagnostic scheme provides a promising tool for the study and validation of detailed hydrocarbon pyrolysis and oxidation mechanisms of fuel surrogates and realistic fuels. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 423–432, 2012     

Shock tube study of monomethylamine thermal decomposition and NH2 high temperature absorption coefficient

CH₃NH₂ thermal decomposition is shown to provide a suitable NH₂ radical source for spectroscopic and kinetic shock tube studies. Using this precursor, the absorption coefficient of the NH₂ radical at a detection wavelength of 16739.90 cm⁻¹ has been determined. In the temperature range 1600–2000K the low‐pressure absorption coefficient is described by the polynominal equation: k_NH2=3.953×10¹⁰/T ³+7.295×10⁵/T ²−1.549×10³/T [atm⁻¹ cm⁻¹] The uncertainty of the determined absorption coefficient is estimated to be ±10%. The rate of the thermal decomposition reaction CH₃NH₂+M → CH₃+NH₂+M is determined over the temperature range 1550–1900 K and at pressures near 1.6 atm. The rate coefficient was found to be: k₁=2.51×10¹⁶ exp(−28430/T) [cm³ mol⁻¹ s⁻¹] The uncertainty of the determined rate coefficients is estimated to be ±20%. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 323–330, 1999     

Zum Mechanismus massenspektrometrischer Fragmentierungsreaktionen—IXSterische Effekte in den Massenspekten der Stereoisomeren von Decalin-2,3-diolen,Decalin-2,4-Diolen und Ihen Dimethyläthern

The mass spectra of all stereoisomers of decalin-2,3-diol, the corresponding dimethyl ethers and of some deuterated derivatives are discussed. The mass spectra of isomeric decalin-2,3-diols differ only slightly in ion intensities. The mass spectra of the stereoisomeric 2,3-dimethoxy-decalins are nearly identical within the series of transand cisderivatives. A mass spectrometric identification of the stereoisomers of these compounds is therefore diffucult. Stereoselective eliminations from the molecular ion are not observed. The mass spectra -of stereoisomeric decalin-1,4-diols show characteristic differences in the intensities of the[M ? H₂O]⁺˙-ions, which can be related to the geometry of the molecules in a similiar mode as was the case with cyclohexane-1,4-diols, The sterechemical control of the elimination of H₂O from the molecular ions has been confirmed by deuterium labelling. The mass spectra of stereoismeric 1,4-dimethoxy-decalins also differ characteristically in the intensities of the [M ? CH₃OH]⁺˙ ions. Furthermore peak due to the [M ? CH₂O]⁺˙ ions are only observed in the mass spectra of those stereoisomers, which have at least one conformation with a short distance between the two methoxy. The stereospecifity of the CH₃OH- and CH₂O-eliminationjs has also been determined by deuterium labelling.     

Real‐time measurement of peroxyacetyl nitrate using selected ion flow tube mass spectrometry

The on‐line detection of gaseous peroxyacetyl nitrate (PAN) using selected ion flow tube mass spectrometry (SIFT‐MS) has been investigated using a synthetic sample of PAN in air at a humidity of ～30%. Using the H₃O⁺ reagent ion, signals due to PAN at m/z 122, 77 and 95 have been identified. These correspond to protonated PAN, protonated peractetic acid and its water cluster, respectively. These products and their energetics have been probed through quantum mechanical calculations. The rate coefficient of H₃O⁺ has been estimated to be 4.5 × 10^?9 cm³ s^?1, leading to a PAN sensitivity of 138 cps/ppbv. This gives a limit of detection of 20 pptv in 10 s using the [M+H]⁺ ion of PAN at m/z 122. Copyright © 2010 John Wiley & Sons, Ltd.     

Rate constant and products of the BrO + BrO reaction at 298 K

The overall rate coefficient k of the self recombination of BrO radicals has been measured at 298 K with use of the discharge flow/mass spectrometry technique. The rate coefficient k₂ for the reaction channel forming Br₂ has been also determined. The results are: k = (3.2 ± 0.5) × 10^?12 and k₂ = (4.7 ± 1.5) × 10^?13 (in cm³ molecule^?1 s^?1). These results are discussed with respect to previous literature data.