The application of different detection methods for irradiated dried anchovy and shrimp

Three different techniques, photostimulated luminescence (PSL), electron spin resonance (ESR) and thermoluminescence (TL) were applied for the detection of dried anchovy and shrimp exposed to electron beam at 0–10 kGy. PSL values for irradiated samples were more than 5000 photon counts/60 s, upper threshold (T₂), whereas those of non-irradiated samples were <700 counts (lower threshold, T₁) in anchovy and intermediate values of T₁–T₂ in shrimp. ESR measurements using both the whole samples did not show any signals specific to irradiation. However, in the case of anchovy it was possible to use bone for ESR detection, showing typical signals (g=2.002, 1.998). Minerals separated from both the samples for TL measurement showed that non-irradiated samples were characterised by glow curves situated at about 300°C with low intensity, while all irradiated samples showed glow peaked at about 200°C and its intensity was high enough to be discriminated from the non-irradiated ones. Furthermore, normalization by a re-irradiation enhanced the reliability of detection results of TL. In conclusion, a multi-step detection using different methods enhances confidence in the detection of irradiated food.     

Syntheses and structural determination of nine-coordinate K3[Nd(nta)2(H2O)]·6H2O and K3[Er(nta)2(H2O)]·5H2O

The syntheses and structural determination of Nd^III and Er^III complexes with nitrilotriacetic acid (nta) were reported in this paper. Their crystal and molecular structures and compositions were determined by single-crystal X-ray structure analyses and elemental analyses, respectively. The crystal of K₃[Nd^III(nta)₂(H₂O)]·6H₂O complex belongs to monoclinic crystal system and C2/c space group. The crystal data are as follows: a=1.5490(11) nm, b=1.3028(9) nm, c=2.6237(18) nm, β=96.803(10)°, V=5.257(6) nm³, Z=8, M=763.89, D_c=1.930 g cm⁻³, μ=2.535 mm⁻¹ and F(000)=3048. The final R₁ and wR₁ are 0.0390 and 0.0703 for 4501 (I>2σ(I)) unique reflections, R₂ and wR₂ are 0.0758 and 0.0783 for all 10474 reflections, respectively. The Nd^IIIN₂O₇ part in the [Nd^III(nta)₂(H₂O)]³⁻ complex anion has a pseudo-monocapped square antiprismatic nine-coordinate structure in which the eight coordinate atoms (two N and six O) are from the two nta ligands and a water molecule coordinate to the central Nd^III ion directly. The crystal of the K₃[Er^III(nta)₂(H₂O)]·5H₂O complex also belongs to monoclinic crystal system and C2/c space group. The crystal data are as follows: a=1.5343(5) nm, b=1.2880(4) nm, c=2.6154(8) nm, b=96.033(5)°, V=5.140(3) nm³, Z=8, M=768.89, D_c=1.987 g cm⁻³, μ=3.833 mm⁻¹ and F(000)=3032. The final R₁ and wR₁ are 0.0321 and 0.0671 for 4445 (I>2σ(I)) unique reflections, R₂ and wR₂ are 0.0432 and 0.0699 for all 10207 reflections, respectively. The Er^IIIN₂O₇ part in the [Er^III(nta)₂(H₂O)]³⁻ complex anion has the same structure as Nd^IIIN₂O₇ part in which the eight coordinate atoms (two N and six O) are from the two nta ligands and a water molecule coordinate to the central Nd^III ion directly.     

Guest and host deuterium effects of the large ZFS parameters D of dimethylbenzaldehydes in durene single crystals

The ZFS parameters D of 2,4-, 2,5- and 3,4-dimethylbenzaldehyde-1h₁ and -1d₁ guests in perhydrogenated and perdeuterated durene single crystals are determined by comparing the experimental and calculated resonance curves. It is found that the deuterium substitution of the guest aldehydic group in a given host leads to the decrease of the D values and to the increase of the energy gaps ΔE_T between the zero-point levels of the ³nπ* and ³ππ* states of the guests. On the other hand, the perdeuteration of the host results in the decrease of ΔE_T with a corresponding increase of the D value of a given guest. The D value of 1 cm⁻¹ determined for 2,5-dimethylbenzaldehyde-1h₁ in perdeuterated durene is the lategest ever found for an aromatic carbonyl compound. Correlations between D and ΔE_T indicate that the ZFS parameters D of the guests are determined by contributions from both spin-spin and spin-orbit interactions between the ³nπ* and ³ππ* states. The large guest and host deuterium effects observed on the D values are attributed to the changes of the gaps ΔE_T of the guests.     

The geometry, vibrational frequencies, thermochemistry, quadrupole moments and electronic structure of C2Na2: Comparison with C2Li2, C2H2, C2F2 and C2Cl2

The electronic structure of Na₂C₂ is studied using ab initio electronic structure methods and is compared to the companion molecule Li₂C₂. Both the linear D_∞h and planar structures are minima on the ground state potential surface with the planar D_2h conformation being the lowest energy form, similar to Li₂C₂. At the CCSD(t) level the planar form is more stable that the linear by 11.2 kcal/mol as compared with 7.34 kcal/mol for Li₂C₂. Both molecules are significantly ionic. The vibrational frequencies, atomization energy at 0 K, D₀, and the standard enthalpy of formation, are calculated and compared to those of Li₂C₂ as well as HCCH, FCCF and ClCCCl. We find D₀ and to be 331.1 and 84.92 kcal/mol for Li₂C₂ and 298.3 and 93.25 kcal/mol for Na₂C₂. We calibrate these by calculating the same quantities for HCCH, FCCF and ClCCCl.     

Measurement of binary diffusion coefficient from impulse response curve having extremely low absorbance intensity under supercritical condition by noise elimination technique

A noise elimination technique was applied to the determination of binary diffusion coefficients D₁₂ from the response curves having extremely low absorbance intensities in impulse response methods under supercritical conditions of carbon dioxide. The effectiveness of this technique was experimentally examined for the analyses of response curves through both the curve-fitting and the moment methods in two cases: the chromatographic impulse response method for phenol and β-carotene with a polymer-coated capillary column, and the Taylor dispersion method for acetone with an uncoated capillary column. Unreliable D₁₂ values were obtained from the moment method of the response curves at lower absorbance intensities, even treated with noise elimination. The curve-fitting method with the noise elimination treatment was quite effective for determining the D₁₂ values accurately, and was valid at the lowest absorbance intensities, on the order of 10⁻⁴ absorbance unit of UV-Vis multi-detector, corresponding to the smallest quantity of the solute, i.e. 6×10⁻⁵, 6×10⁻⁶, and 5×10⁻² μ mol for phenol, β-carotene, and acetone, respectively, under conditions studied. Infinite dilution regions for binary diffusion coefficients were obtained by injecting various amounts: the binary diffusion coefficients showed constant values at concentrations less than 0.6, 0.004, and 0.08 mol m⁻³ for phenol, β-carotene, and acetone, respectively, in supercritical carbon dioxide at 313.2 K and 16–18 MPa.     

DNA analysis of a radiotolerant bacterium Pantoea agglomerans by FT-IR spectroscopy

A radiation tolerance strain, Pantoea agglomerans was isolated from γ-irradiated carrot samples (Daucus carota). D₁₀ determination showed that the radioresistance of this bacterium is five-fold higher than Escherichia coli, both belonging to the family of Enterobacteriaceae. DNA isolated from untreated and irradiated bacterial cells was analyzed by FT-IR spectroscopy to investigate the radiotolerance of this bacterium. At doses <5 kGy, an alteration of the interbase hydrogen networks was observed and characterized mainly by an increase of bands assigned to the carbonyl non-pairing and the free amine groups. Moderate breakage of the DNA backbone and damage of the osidic structure were also observed. Similar spectral profiles were noticed at doses ≥5 kGy, but additional increase of the band intensity of CC and CN suggests damages of nucleobases. High number of asymmetric PO₂⁻ and upper shift of symmetric PO₂⁻ are indicative of DNA strand breaks. Osidic damages were evidenced by decrease of the absorption bands ascribed to deoxyribosyl moieties and by appearance of C–OH band. DNA degradation at high irradiation doses was also noticed by electrophoresis using agarose gel. It appeared that DNA underwent covalent cross-linking, as revealed by agglomeration of DNA in the wells of agarose gel.     

Preparation and crystal structure of a 1:1 inclusion compound of 1,4,11,14-tetramethoxy-dibenzo[b,n]tetraphenylene with pyridine

The new host 1,4,11,14-tetramethoxy-dibenzo[b,n]tetraphenylene forms a 1:1 inclusion compound with pyridine, in which a pair of centrosymmetrically-related guest species are enclosed in the cage surrounded by six host molecules. C₃₆H₂₈O₄·C₅H₅N, F_W=603.68, triclinic, space group P-1, a=11.796(2), b=16.075(3), c=9.004(2) Å; =98.39(3)°, β=90.01(3)°, γ=108.19(3)°, V=1602.8(5) Å³, Z=2, F(000)=636, D_c=1.251 g/cm³, μ=0.080 mm⁻¹. The final R indices [I>2σ(I)] R₁=0.0759, wR₂=0.1970 for 5623 MoK observed data.     

The use of ESR spectroscopy for the investigation of dosimetric properties of egg shells

Electron spin resonance (ESR) spectroscopy was used to investigate the dosimetric properties of chicken egg shells. The ESR spectra of the irradiated egg shell were found to have an asymmetric absorption characterized by a major resonance at g=2.0019 and a minor resonance at g_||=1.9980. The study was carried out on g=2.0019 signal because of the accuracy of measurements and the possibility of using it as ESR dosimeter. The activation energy (E), frequency factor (k₀) and mean-life (τ) were calculated to be 1.50±0.10 eV, 2×10¹³ s⁻¹ and (4.4±0.4)×10⁴ year respectively. Dose–response was investigated between dose ranges of 1 Gy and 10 kGy for ⁶⁰Co γ-rays. Dose–response was found to be appropriate for dosimetry in the range 3 Gy to 10 kGy. The lower limit of observable doses for egg shell sample was about 3 Gy. The other ESR dosimetric parameters of egg shell samples, fading characteristic, light effect, dose-rate dependence and energy dependence, have also been studied in detail. Apart from its non-tissue equivalence, egg shell has very good dosimetric properties with insignificant fading, light independence, linearity in dose–response (3 Gy–10 kGy), dose-rate independence and independence from energy above 500 keV. It suggests that egg shell may be used as a retrospective γ radiation dosimetry after nuclear accidents or other short accidental radiation events.     

Tautomeric properties, conformations and structure of N-(2-hydroxy-5-chlorophenyl) salicylaldimine

The crystal structure of N-(2-hydroxy-5-chlorophenyl) salicylaldimine (C₁₃H₁₀NO₂Cl) was determined by X-ray analysis. It crystallizes orthorhombic space group P2₁2₁2₁ with a=12.967(2) Å, b=14.438(3) Å, c=6.231(3) Å, V=1166.5(6) Å³, Z=4, D_c=1.41 g cm⁻³ and μ(MoK)=0.315 mm⁻¹. The title compound is thermochromic and the molecule is nearly planar. Both tautomeric forms (keto and enol forms in 68(3) and 32(3)%, respectively) are present in the solid state. The molecules contain strong intramolecular hydrogen bonds, N1–H1O1/O2 (2.515(1) and 2.581(2) Å) for the keto form and O1–H01N1 for the enol one. There is also strong intermolecular O2–HO1 hydrogen bonding (2.599(2) Å) between neighbouring molecules. Minimum energy conformations AM1 were calculated as a function of the three torsion angles, θ₁(N1–C7–C6–C5), θ₂(C8–N1–C7–C6) and θ₃(C9–C8–N1–C7), varied every 10°. Although the molecule is nearly planar, the AM1 optimized geometry of the title compound is not planar. The non-planar conformation of the title compound corresponding to the optimized X-ray structure is the most stable conformation in all calculations.     

Theoretical investigations on the SO2 + HO2 reaction and the SO2–HO2 radical complex

The mechanism of the SO₂ + HO₂ reaction was studied theoretically for the first time. Three product channels were revealed, namely, O₂ + HOSO, O₂ + HSO₂, and OH + SO₃. The O₂ + HOSO channel dominates the reaction under combustion conditions. A five-member-ring complex [SO₂–HO₂] exists at the entrance of the reaction. The structure and binding energy (D_e and D₀) of the SO₂–HO₂ complex have been calculated. In view of D₀ = 21.2 ± 2.0 kJ mol⁻¹, the SO₂–HO₂ complex should be stable at low temperature. The infrared spectra and frequency shifts were calculated for both SO₂–HO₂ and SO₂–DO₂, and compared with the available experimental data.     

高浓度乳液稳定性评价方法及其应用

分散相液滴的粒径及其分布是影响乳液性质的重要因素,其随时间及环境的变化可用于评价乳液的稳定性。动态光散射等方法难以用于准确测量高浓度乳液液滴粒径。本文报道了一种可用于准确、高效测量乳液液滴粒径的成像表征方法。该方法采用荧光染料标记乳液液滴,利用激光扫描共聚焦荧光显微成像技术获取三张焦平面间距确定的乳液光学切片,由光学切片给出的乳液液滴表观直径计算进而确定所测量乳液液滴的粒径。我们将上述方法用于表征高浓度原油模拟物-水乳液的稳定性,结果表明本文提出的方法可以准确、高效地测量乳液液滴的抗凝聚稳定性,而目前广泛采用的"瓶试法"则难以反映乳液液滴的抗凝聚稳定性。     

Structural and theoretical studies of Xe(OChF5)2 and [XeOChF5][AsF6] (Ch = Se, Te)

The XeOSeF₅⁺ cation has been synthesized for the first time and characterized in solution by ¹⁹F, ⁷⁷Se and ¹²⁹Xe NMR spectroscopy and in the solid state by X-ray crystallography and Raman spectroscopy with AsF₆⁻ as its counter anion. The X-ray crystal structures of the tellurium analogue and of the Xe(OChF₅)₂ derivatives have also been determined: [XeOChF₅][AsF₆] crystallize in tetragonal systems, P4/n, a=6.1356(1) Å, c=13.8232(2) Å, V=520.383(14) Å³, Z=2 and R₁=0.0453 at −60°C (Te) and a=6.1195(7) Å, c=13.0315(2) Å, V=488.01(8) Å³, Z=2 and R₁=0.0730 at −113°C (Se); Xe(OTeF₅)₂ crystallizes in a monoclinic system, P2₁/c, a=10.289(2) Å, b=9.605(2) Å, c=10.478(2) Å, β=106.599(4)°, V=992.3(3) Å³, Z=4 and R₁=0.0680 at −127°C; Xe(OSeF₅)₂ crystallizes in a triclinic system, , a=8.3859(6) Å, c=12.0355(13) Å, V=732.98(11) Å³, Z=3 and R₁=0.0504 at −45°C. The energy minimized geometries and vibrational frequencies of the XeOChF₅⁺ cations and Xe(OChF₅)₂ were calculated using density functional theory, allowing for definitive assignments of their experimental vibrational spectra.     

Sensitizing effect of polyfunctional monomers on radiation crosslinking of polychloroprene

Radiation-induced crosslinking of polychloroprene containing nine different polyfunctional monomers (PFM) has been investigated. The PFMs were kneaded into polychloroprene on a Labo Plastomill at 80°C, and then the mixtures were irradiated using an electron beam accelerator, to initiate the crosslinking reaction. The results showed that the crosslinking density (1/M_c) of the product is linearly proportional to the absorbed dose (D) and the initial PFM content (C₀), i.e. 1/M_c=(A+KC₀)D, where A and K are constants. The values of K increased quickly with the specific unsaturation (moles of double bonds per 100 g of the monomer) of the PFMs. The tensile strength of crosslinked polychloroprene with 4G (Polyethyleneglycol 200 dimethylacrylate) or UA101H (Urethane prepolymer) was found to be the best.     

Strong antiferromagnetism in the dinuclear 2-pyridone complex with N–C–O bridges: A paddle-wheel analogue of the dinuclear tetracarboxylates

A novel dinuclear complex [Cu₂(μ-L)₄(HL)₂] (1) was isolated from starting 2-pyridone (HL) via a resonance and a tautomeric transformation. Each copper centre is in a square-pyramidal coordination sphere, defined by two oxygen atoms (Cu–O4 1.978(5), Cu–O11 1.964(4) Å) and two nitrogen atoms (Cu–N2 2.003(5), Cu–N3 2.007(5) Å) of four bridging deprotonated pyridin-2-olates and an oxygen atom on the top from a neutral 2-pyridone (Cu–O2 2.227(5) Å), analogous to tetracarboxylate paddle-wheel complexes. Compound 1 was compared with mixed pyridin-2-olato/methanoato analogues [Cu₂(μ-HCO₂)₂(μ-L)₂(HL)₂] · 2CH₃CN (2) and [Cu₂(μ-HCO₂)₂(μ-L)₂(HL)₂] (2a) (2a is an air stable form obtained from 2 outside mother-liquid). The EPR spectra of air stable 1 and 2a show three signals H_z1, H₂ and H_z2, typical for the binuclear systems with spin S = 1, both revealing strong antiferromagnetism 2J = −334 (1) and −324 cm⁻¹ (2a). Interestingly, only for 1 additional H₁ signal at 100 mT is noticed (D(1) = 0.293 cm⁻¹ < hν = 0.320 cm⁻¹ < D(2a) = 0.347 cm⁻¹). On the other hand, several broad signals in the 100–450 mT region, only in the high temperature spectrum for 2a are observed. These results are in agreement with the magnetic susceptibility analysis.     

Flow injection analysis methods for determination of diffusion coefficients

Two flow injection analyses (FIA) methods for the determination of diffusion coefficients in a straight single tube FIA system were developed. Based on the analytical solution of the convection-diffusion equation, linear relationships of the logarithmic values of the dispersion coefficient (D) and the half-peak width (W_1/2) with the diffusion coefficient (D_m) were obtained. Experiments were designed to verify these methods. For example, for potassium hexacyanoferrate (III) a D_m value of 0.72 × 10⁵ cm² s⁻¹ was found versus a literature value of 0.76 × 10⁵ cm² s⁻¹ (error, 5%). For potassium hexacyanoferrate (II) a D_m value of 0.67 × 10⁵ cm² s⁻¹ was obtained versus a literature value of 0.63 × 10⁵ cm² s⁻¹ (error, 6%). The diffusion coefficients of some important biomedical compounds, such as dopamine, epinephrine, norepinephrine and ascorbic acid, were then determined. The values of 10⁵ D_m/cm² s⁻¹ are 0.60 ± 0.03, 0.44 ± 0.02, 0.60 ± 0.01 and 0.68 ± 0.06, respectively.     

Kinetics study of the gas-phase reactions of C2F5OC(O)H and n-C3F7OC(O)H with OH radicals at 253–328 K

The rate constants, k₁ and k₂ for the reactions of C₂F₅OC(O)H and n-C₃F₇OC(O)H with OH radicals were measured using an FT-IR technique at 253–328 K. k₁ and k₂ were determined as (9.24 ± 1.33) × 10⁻¹³ exp[−(1230 ± 40)/T] and (1.41 ± 0.26) × 10⁻¹² exp[−(1260 ± 50)/T] cm³ molecule⁻¹ s⁻¹. The random errors reported are ±2 σ, and potential systematic errors of 10% could add to the k₁ and k₂. The atmospheric lifetimes of C₂F₅OC(O)H and n-C₃F₇OC(O)H with respect to reaction with OH radicals were estimated at 3.6 and 2.6 years, respectively.     

Transport phenomenon as a function of counter and co-ions in solution: chronopotentiometric behavior of anion exchange membrane in different aqueous electrolyte solutions

Anion exchange membrane has been investigated in different electrolyte solutions by chronopotentiometry to explore the influence of co-ion and counterion of the exchange group of the membrane, on the transport phenomena. Chloride, nitrate, sulfate and acetate in sodium salts were used as counterions and sodium, potassium, calcium and ammonium in chloride salts were used as co-ions. The membrane showed a potential drop (E₀) in all these electrolytes when a constant current was applied across it, which remained constant for a period less than τ, called the transition time and rose gradually to a maximum (E_max) value. The parameters such as τ, E₀ and E_max and the potential jump (ΔE) and τ and the inflection zone (Δt) along the time axis have been measured and compared at an applied current density (I) of 10 mA cm⁻² in 10 mM solutions. The values of τ^1/2/z_A[A₀] or τ^1/2/z_C[C₀], with or , E₀ and ΔE with or (where r_A and r_C are the ionic radii of counter and co-ions, respectively) have been correlated. Permselectivity (P) and transference number of the membrane with respect to each one of the above electrolytes have been evaluated and discussed.     

Stretched exponential survival statistics for microorganisms in radiation field

The so-called concave or tailed survival curves are reported both for multi and single species bacterial populations. Taking as an example Bacillus pumilus, frequently encountered in decontamination studies, it is shown that the tailed survival curves are adequately described by stretched (0<<1) exponential SF=exp[−(D/D₀)], where SF denotes the fraction of species surviving the irradiation dose D, D₀ is the effective dose, and is the dispersion parameter interpreted phenomenologically in terms of radiation sensivity distribution for single species population under the given experimental conditions.     

Relationships between oxygen diffusion characteristics of polycrystalline and single crystal 2MgO · TiO2

Self-diffusion coefficients of oxygen in both polycrystalline and single crystal 2MgO·TiO₂ have been measured at an ambient oxygen pressure of about 40 mm Hg over the temperature range 1080–1450°C. A convenient method to estimate the volume diffusion coefficient, D₁, of this polycrystal in which the relative magnitude in D_g (grain boundary diffusion coefficient) with respect to D₁ falls between two extremes, i.e., D_g = D₁ and D_g D₁, is newly proposed, and its plausibility is examined by comparing the resultant D₁ with that of single crystal 2MgO·TiO₂. Not only the magnitude but also the temperature dependence of the “apparent” diffusivity of these polycrystalline particles considerably varied with their particle size. The reason for this semiquantitatively interpreted in terms of the relative magnitude of D_g with respect to D₁.     

Concerning the crystal structure of BrF3·AuF3

Crystals of the adduct, BrF₃·AuF₃, are monoclinic, with: a=5.356(4) Å, b=5.766(4) Å, c=8.649(3) Å, β=101.39(4)°, V=261.8(5) Å³, z=2, D_c=4.96 g/cm³. An ordered structure in P2₁ was found, but is of low precision (R₁=0.082) because of crystal deformation. The structure has planar BrF₄ units sharing F ligands cis with planar AuF₄ groups, each AuF₄ being similarly linked to two BrF₄. This generates a ribbon, creased at the bridging F along y, the gold on one side of the crease, the bromine on the other. Such ribbons are stacked parallel along y, with nearest neighbors related by twofold screw axes. This sandwiches each AuF₄ strip of a ribbon symmetrically between like strips. These contacts between the Au-strips bring up, to each Au-atom, two “non-bridging Au–F ligands” of each of the two neighboring strips, to give eight coordination in F. The bromine side of the creased ribbon is unsymmetrically sandwiched between a screw-axis related relative, and the edge of a Au-containing strip oriented almost perpendicular to it. This brings two non-bridging F of the nearest-strip BrF₄ and two non-bridging F of the AuF₄ strip into the secondary cordination sphere of the Br atom. Raman spectra of the BrF₃·AuF₃, molecular BrF₃, and polymeric AuF₃ suggest that the Br–F and Au–F stretching vibrations of BrF₃·AuF₃ are shifted slightly from those of the parent BrF₃ and AuF₃, and indicate some BrF₂⁺AuF₄⁻ character.