非晶态镍硼酸盐结构的EXAFS研究

由摩尔比分别为1:2和1:8的NiCl₂·6H₂O和Na₂B₄O₇·10H₂O作为反应物, 合成两种非晶态镍硼酸盐, 同时通过水热法合成β-Ni(OH)₂. 化学分析和热重-微商热重法(TG-DTG)分析结果确定两种非晶态镍硼酸盐的分子组成分别为NiO·0.8B₂O₃·4.5H₂O和NiO·B₂O₃·3H₂O. 激光拉曼(Raman)实验结果表明镍硼酸盐样品中主要存在的硼氧阴离子为B₃O₃(OH)₅^2-和B₂O(OH)₆^2-. 同步辐射扩展X射线吸收精细结构(EXAFS)方法对样品进行结构解析, 通过数据拟合给出样品中Ni 原子周围近邻配位原子种类、配位数以及原子间距离. 用不同晶体结构作为标准对两种非晶态镍硼酸盐进行拟合的结果表明, 样品中Ni 原子周围局域结构与Ni₃B₂O₆晶体(ICSD No.31387)中的吻合较好. Ni 原子周围配位原子为O、B和Ni, 对于NiO·0.8B₂O₃·4.5H₂O, 配位数分别为5.7、3.8和3.8, 配位距离分别为0.208、0.263 和0.311 nm; 对于NiO·B₂O₃·3H₂O, 配位数分别为6.0、4.0 和4.0, 配位距离分别为0.207、0.262和0.310 nm.     

Surface and internal modification of composite ion exchange membranes for removal of molybdate,phosphate, and nitrate from polluted groundwater

Al₂O₃/chitosan-multiwall carbon nanotubes (MWCNTs) were created to increase the exchange capacity of polyvinylidene fluoride (PVDF) ion-exchange membranes. The composite membranes were made by mixing Al₂O₃ nanoparticles into the PVDF cast solution, then applying a thin coating of chitosan functionalized carbon nano tubes (Cs-MWCNTs) to the PVDF membrane surface. The structure and characteristics of the hybrid membranes were described using XRD, SEM, IR, and TG-DTA. The Al₂O₃-PVDF/Cs-MWCNTs membrane beat the other Al₂O₃-PVDF/Cs, Al₂O₃-PVDF, and PVDF membranes in terms of molybdate, phosphate, and nitrate adsorption. The removal efficiency, pH solution, adsorption capacity, and desorption process of molybdate, phosphate, and nitrate anions by Al₂O₃-PVDF and PVDF membranes were investigated. The removal effectiveness of molybdate, phosphate, and nitrate, according to the testing findings, was 94.3, 65.6, and 85.78 %, respectively. The adsorption of MoO₄^2?, PO₄^3?, and NO₃^? increased as the pH increased initially until the best adsorption was achieved, and then decreased significantly as the pH increased further. The total adsorption capabilities of MoO₄^2?, PO₄^3?, and NO₃^?for the Al₂O₃-PVDF/Cs-MWCNTs membrane were 65.50, 61.22, and 59.77 mg/g, respectively. Using regeneration and reuse experiments for the simultaneous adsorption of molybdate, phosphate, and nitrate during three consecutive cycles, the adsorption/desorption of Al₂O₃-PVDF/Cs-MWCNTs was assessed. Al₂O₃-PVDF/Cs-MWCNTs offer a lot of promise when it comes to eliminating MoO₄^2?, PO₄^3?, and NO₃^?from actual wastewater samples.     

Changes in the composition of volatile monoterpenes and sesquiterpenes of Pinus armandi, P. tabulaeformis, and P. bungeana in Northwest China

The volatile mono-and sesquiterpenes obtained from the needles and resin of Pinus armandi, P. tabulaeformis, and P. bungeana growing in the Qinling, Taibai, and Huanglong Mountain forest ecosystem were analyzed by means of GC-MS. Forty-eight constituents were identified, and α-pinene, β-pinene, 1R-α-pinene, β-caryophyllene, cadindiene, α-caryophyllene, D-limonene, and 1S-β-pinene were the major components of the mono-and sesquiterpenes in the needles and resin. The components of the volatile mono-and sesquiterpenes from the needles and resin at Qinling, Taibai, and Huanglong Mountains had remarkable differences in three pine species, whereas the monopertene content such as α-pinene, β-pinene, D-limonene, and camphene were mostly changed in the growing stage. The intraspecies variation in the different ecosystems can be attributed to the species’ geography and genetic variation, and even the adaptation of the pine species to different ecological environments. Moreover, monoterpenes and sesquiterpenes can be induced by the attack of bark beetles, of which the α-pinene, β-pinene, 1R-α-pinene, 1S-α-pinene, b-myrecene, and β-caryophyllene contents had positive relations with the attacking Dendroctonus armandi and D. valens. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 430–433, September–October, 2006.     

Anti-pathogenic,anti-diabetic,anti-inflammatory,antioxidant, and wound healing efficacy of Datura metel L. leaves

Datura metel L. is an important medicinal plant of Solanaceae family which has extensive pharmacological properties. The present investigation was aimed to identify the presence of phytoconstituents and assess in vitro antibacterial, anti-biofilm, anti-diabetic, anti-inflammatory, antioxidant, cytotoxicity, and wound healing efficacy of D. metel leaves extract. Among different solvent extracts, methanolic extract showed higher amount of phenolic (124.61 ± 0.68 mg GAE/g), alkaloid (88.77 ± 1.01 mg AE/g), flavonoids (42.24 ± 0.18 mg QE/g), and tannins contents (38.72 ± 0.51 mg GAE/g). The extract exhibited not only significantly (P < 0.05) different antibacterial activities against pathogens tested but also showed maximum biofilm inhibition of 94, 88, and 92% against B. subtilis, MRSA, and E. coli, respectively. Anti-diabetic assay depicted 22.55 ± 0.62–79.41 ± 1.13% and 24.31 ± 1.47–72.59 ± 0.22% of α-amylase and α-glucosidase inhibition abilities of methanolic extract, respectively at varied concentrations. The methanolic extract showed potential anti-inflammatory effect (P < 0.05) by showing 28.11 ± 0.13, 34.94 ± 1.11, 55.73 ± 0.42, 73.28 ± 0.72, and 92.62 ± 1.33% of inhibition of protein denaturation at different concentrations with an IC₅₀ value of 52.45 µg/mL. The extract revealed significant (P < 0.05) rate of ABTS scavenging, DPPH degradation, and reducing power assay in a concentration dependent manner. The cytotoxicity assay was demonstrated on L929 mouse fibroblast cell line and found > 90% of cell viability in the presence of methanolic extract, thereby indicating its non-toxicity effect. Wound healing assay indicated that methanolic extract at 50 µg/mL closed 100% of wound gap after 24 h with high rate of migration and proliferation. Furthermore, GC–MS chromatogram revealed the presence of several components in methanolic extract, including neophytadiene, hexadecanoic acid, and hentriacontane as principal phytoconstituents. In conclusion, methanolic extract of D. metel leaves could be used as potent therapeutic agent not only for treating metabolic diseases but also superficial chronic diabetic wounds.     

Determination of As, Sb, Se, Te and Bi in milk by slurry sampling hydride generation atomic fluorescence spectrometry

A simple and fast analytical procedure has been developed for the determination of As, Sb, Se, Te and Bi in milk samples by hydride generation atomic fluorescence spectrometry (HG-AFS). Samples were treated with aqua regia for 10 min in an ultrasound water bath and pre-reduced with KBr for total Se and Te determination or with KI and ascorbic acid for total As and Sb, the determination of Bi being possible in all with or without pre-reduction. Slurries of samples, in the presence of antifoam A, were treated with NaBH₄ in HCl medium to obtain the corresponding hydrides, and AFS measurements were processed in front of external calibrations prepared and measured in the same way as samples. Results obtained by the developed procedure compare well with those found after microwave-assisted complete digestion of samples. The proposed method is simple and fast, and only 1 ml of milk is needed. The values obtained for detection limit are 2.5, 1.6, 3, 6 and 7 ng l⁻¹ for As, Sb, Se, Te and Bi respectively in the diluted samples, with average relative standard deviation values of 3.8, 3.1, 1.9, 6.4 and 1.2% for three independent analysis of a series of commercially available samples of different origin. Data found in Spanish market samples varied from 3.2±0.3 to 11.3±0.2 ng g⁻¹ As, from 3.1±0.2 to 11.6±0.4 ng g⁻¹ Sb, from 10.7±0.5 to 25.5±0.4 ng g⁻¹ Se, from 0.9±0.2 to 9.4±0.6 ng g⁻¹ Te and from 11.5±0.1 to 27.7±0.4 ng g⁻¹ Bi.     

Excess molar volumes and viscosities of binary mixtures of cyclohexane and n-alkane at 298.15 K

Awwad, A.M. and Salman, M.A., 1986. Excess molar volumes and viscosities of binary mixtures of cyclohexane and n-alkane at 298.15 K. Fluid Phase Equilibria, 25: 195-208.Excess molar volumes, viscosities, excess molar viscosities, and excess molar activation energies of viscous flow were determined for binary mixtures of cyclohexane + n-pentane, + n-hexane, + n-heptane, + n-octane, + n-nonane, + n-decane, + n-dodecane, + n-tetradecane and + n-hexadecane at 298.15 K. The effect of orientational order of n-alkane on solution molar volumes and viscosities is investigated as well as the adequacy of the Flory theory and free volume theories used to predict solution molar volumes and viscosities. For longer n-alkanes V^E, η^E and ΔG*^E are positive and associated with the orientational order.     

Improvement of HS-SPME for analysis of volatile organic compounds (VOC) in water samples by simultaneous direct fiber cooling and freezing of analyte solution

The sensitivity and precision of headspace solid-phase micro extraction (HS-SPME) at an analyte solution temperature (T _as) of +35 °C and a fiber temperature (T _fiber) of +5 °C were compared with those for HS-SPME at T _as and T _fiber of −20 °C for analysis of the volatile organic compounds benzene, 1,1,1-trichloroethane, trichloroethylene, toluene, o-xylene, ethylbenzene, m/p-xylene, and tetrachloroethylene in water samples. The effect of simultaneous fiber cooling and analyte solution freezing during extraction was studied. The compounds are of different hydrophobicity, with octanol/water partition coefficients (Kow) ranging from 126 and 2511. During a first set of experiments the polydimethylsiloxane (PDMS) SPME fiber was cooled to +5 °C with simultaneous heating of the aqueous analyte solution to +35 °C. During a second set of experiments, both SPME fiber holder and samples were placed in a deep freezer maintained at −20 °C for a total extraction time of 30 min. After approximately 2 min the analyte solution in the vial began to freeze from the side inwards and from the bottom upwards. After approximately 30 min the solution was completely frozen. Analysis of VOC was performed by coupling HS-SPME to gas chromatography-mass spectrometry (GC-MS). In general, i.e. except for tetrachloroethylene, the sensitivity of HS-SPME increased with increasing compound hydrophobicity at both analyte solution and fiber temperatures. At T _as of +35 °C and T _fiber of +5 °C detection limits of HS-SPME were 0.5 μg L⁻¹ for benzene, 1,1,1-trichloroethane, trichloroethylene, and tetrachloroethylene, 0.125 μg L⁻¹ for toluene, and 0.025 μg L⁻¹ for ethylbenzene, m/p-xylene, and o-xylene. In the experiments with T _as and T _fiber of −20 °C, detection limits were reduced for compounds of low hydrophobicity (Kow<501), for example benzene, toluene, 1,1,1-trichloroethane, and trichloroethylene. In the concentration range 0.5–62.5 μg L⁻¹, the sensitivity of HS-SPME was enhanced by a factor of approximately two for all compounds by performing the extraction at −20 °C. A possible explanation is that freezing of the water sample results in higher concentration of the target compounds in the residual liquid phase and gas phase (freezing-out), combined with enhanced adsorption of the compounds by the cooled fiber. The precision of HS-SPME, expressed as the relative standard deviation and the linearity of the regression lines, is increased for more hydrophobic compounds (Kow>501) by simultaneous direct fiber cooling and freezing of analyte solution. Background contamination during analysis is reduced significantly by avoiding the use of organic solvents.     

Nonlinear relaxation of stress and birefringence in simple extension of 1,2-polybutadiene

Relaxation of stress and birefringence in simple extension has been studied for two samples of 1,2-polybutadiene with 95% and 88% vinyl content and weight-average molecular weight 1.9 and 2.9 × 10⁵, respectively. The extension ratio, λ, ranged from 1.14 to 2.08, temperatures from 0 to 15°C, and times, reduced to 0°C, up to 3 × 10⁵ sec. The stress-optical coefficient C was negative and positive, respectively, for the two samples, the difference being attributable to opposite signs and very different magnitudes of the contributions of the 1,2 and 1,4 moieties to the birefringence. For each polymer, C was independent of time but increased (algebraically) with temperature. For one polymer a very minor dependence of C on λ was observed. At any instant of time, the dependence of both stress and birefringence on λ could be described by equations of the Mooney–Rivlin form with coefficients C₁,C₂ and B₁,B₂, respectively. At short times the contributions of the C₁ and C₂ terms to the stress and of the B₁ and B₂ terms to the birefringence are roughly equal. With increasing time, C₁ and B₁ decrease gradually while C₂ and B₂ remain constant over several decades in time. Finally, C₂ and B₂ decrease rather rapidly. A tentative interpretation of these phenomena in terms of motions of entanglements is given.     

Development of a method for nuclide leaching from glass fiber in HEPA filter

For the disposal of the high efficiency particulate air (HEPA) glass filter to environment, the glass fiber should be leached to lower its radioactive concentration. To derive the optimum method for removal of Co and Cs from HEPA glass fiber, four methods were applied in this study. Results of electrochemical leaching of glass fiber by 4.0 M HNO₃–0.1 M Ce(IV) solution showed that the removal efficiency of ¹³⁴Cs, ¹³⁷Cs, and ⁶⁰Cs from glass fiber after 5 h was 96.4, 93.6, and 93.8%, respectively. Results by 5 wt% NaOH solution showed that the removal efficiency of ¹³⁴Cs, ¹³⁷Cs, and ⁶⁰Cs after 30 h was 81.7, 82.1, and 10.0%, respectively. Results by repeat 2.0 M HNO₃ solution showed that the removal efficiencies of ¹³⁴Cs, ¹³⁷Cs, and ⁶⁰Cs after 2 h of three repetitions were 96.2, 99.4, and 99.1%, respectively. Finally, results by repeat 4.0 M HNO₃ solution showed that the removal efficiencies of ¹³⁴Cs, ¹³⁷Cs, and ⁶⁰Cs after 4 h of three repetitions were 100, 99.9, and 99.9%, respectively, and their radioactivities were below 0.1 Bq/g. Therefore, the chemical leaching method by 4.0 M HNO₃ solution was considered as an optimum one for removal of cesium and cobalt from HEPA glass fiber for self disposal. Also the removal efficiencies of ⁶⁰Co, ¹³⁴Cs, and ¹³⁷Cs from the waste-solution after its precipitation-filtration treatment for reuse of 4.0 M HNO₃ waste-solution were 88.0, 95.0, and 99.8%.     

Substituent effects on the redox potentials of dihydroxybenzenes: theoretical and experimental study

The redox reactions of p-hydroquinone and pyrocatechol undergo a two-proton-two-electron process in aqueous solution. We calculated their redox potentials at the B3LYP/6-311+G(d,p) level, and verified the values by employing cyclic voltammetry experiments. Then we selected seven substituent groups (–F, –Cl, –OH, –COOH, –CN, –NH₂, and –NO₂ groups) to systematically investigate the substituent effect, including the sort, position, and number of the substituent, on the redox potentials of p-hydroquinone and pyrocatechol. The calculated results show that –NH₂ and –OH groups can decrease the redox potentials, while –F, –Cl, –COOH, –CN, and –NO₂ groups increase the potential values of p-hydroquinone and pyrocatechol. The calculations can accurately predict the substituent effects on the redox potentials of pyrocatechol and p-hydroquinone. We would expect that the accurate calculation results for the model systems could be applied in the prediction of electrode potentials of other molecules.     

A pilot study for the production of a certified reference material for trace elements in honey

In the context of the general mandate of the European Union Community Reference Laboratory (CRL) for residues in living animals and their products established at the Istituto Superiore di Sanità, a pilot study was undertaken to assess the possibility of producing a new certified reference material (CRM) for trace elements in a matrix of honey. The elements considered were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sn, V and Zn. Their determination was performed by inductively coupled plasma (ICP)-based techniques. Data obtained with different ICP techniques were generally in good agreement. In light of these results, the next step was the effective production of a candidate CRM in a honey matrix. In the preliminary phase, two different types of honey, i.e., Eucalyptus (solid and sticky) and Robinia (viscous and sticky), were pretreated at the Institute for Reference Materials and Measurements, Joint Research Centre, European Commission (EC-JRC-IRMM) in order to produce the materials candidate for the certification process. Approximately 600 ampoules were thus produced for the Robinia honey and 450 ampoules for the Eucalyptus honey, each ampoule containing 5 g of an aqueous solution of honey (with 20% and 30% high purity water, respectively) and sealed under inert gas (Ar). A ring test to determine the levels of the chemical elements and a long-term study to evaluate the stability of the samples is in progress. Tentative figures for the analytes of interest are (in ng g⁻¹): Robinia, As, 1.28±0.09; Cd, 0.59±0.08; Cr, 2.36±0.21; Cu, 57.6±3.2; Fe, 209±9; Mn, 90.8±3; Ni, 18.1±0.6; Pb, 23±1.5; Sn, 8.10±0.35; V, 1.19±0.37; and Zn, 178±4; Eucalyptus, As, 3.18±0.21; Cd, 0.70±0.08; Cr, 2.73±0.22; Cu, 141±6; Fe, 926±16; Mn, 1905±81; Ni, 7.77±0.4; Pb, 138±4; Sn, 7.97±0.16; V, 3.47±0.15; and Zn, 405±9.     

Effect of a metal ion on intramolecular spin exchange in spin-labeled complexes

The characteristic features of intramolecular spin exchange in 14 complexes of Ag^I, Hg^II, Ni^II, Pd^II, Pt^II, Au^III, and Pt^IV with spin-labeled ligands were studied by ESR spectroscopy. The measured values of the exchange integral ‖J‖ and the differences between the enthalpies of the efficient conformations (ΔH) were compared with the electronic polarization (refraction)R _f of the Ni^II, Pd^II, and Pt^II ions and Klopman's rigidity parameters σ_K, which characterize the total polarazibility of the ions and the degree of covalence of the bond between the metal atom and the donor atom of the ligand, respectively. Delocalization of the electron spin density and the efficiency of spin exchange are determined by the relative contributions of the s, p, and d orbitals, which produce the overlap integral of wave functions, ‖J‖, and by the geometric features of the coordination polyhedron, which affect the mutual orientation of the N−O fragments. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2005–2009, October, 1999.     

CoMFA,CoMSIA, Topomer CoMFA,HQSAR, molecular docking and molecular dynamics simulations study of triazine morpholino derivatives as mTOR inhibitors for the treatment of breast cancer

mTOR has become a promising target for many types of cancer like breast, lung and renal cell carcinoma. CoMFA, CoMSIA, Topomer CoMFA and HQSAR were performed on the series of 39 triazine morpholino derivatives. CoMFA analysis showed q² value of 0.735, r²_cv value of 0.722 and r²_pred value of 0.769. CoMSIA analysis (SEHD) showed q² value of 0.761, r²_cv value of 0.775 and r²_pred value of 0.651. Topomer CoMFA analysis showed q² value of 0.693, r² (conventional correlation coefficient) value of 0.940 and r²_pred value of 0.720. HQSAR analysis showed q²,r²and r²_pred values of 0.694, 0.920 and 0.750, respectively. HQSAR analysis with the combination of atomic number (A), bond type (B) and atomic connections showed q² and r² values of 0.655 and 0.891, respectively. Contour maps from all studies provided significant insights. Molecular docking studies with molecular dynamics simulations were carried out on the highly potent compound 36. Furthermore, four acridine derivatives were designed and docking results of these designed compounds showed the same interactions as that of the standard PI-103 which proved the efficiency of 3D-QSAR and MD/MS study. In future, this study might be useful prior to synthesis for the designing of novel mTOR inhibitors.     

The Correlations Between TCA-Glyoxalate Metabolite and Antibiotic Production of <Emphasis Type="Italic">Streptomyces</Emphasis> sp. M4018 Grown in Glycerol,Glucose, and Starch Mediums

The alterations of organic acids citrate, α-ketoglutarate, succinate, fumarate, malate production together with isocitrate lyase activity as a glyoxalate shunt enzyme, and antibiotic production of Streptomyces sp M4018 were investigated in relation to changes in the glucose, glycerol and starch concentrations (5–20 g/L) after identification as a strain of Streptomyces hiroshimensis based on phenotypic and genotypic characteristics. The highest intracellular citrate and α-ketoglutarate levels in 20 g/l of glucose, glycerol, and starch mediums were 399.47 ± 4.78, 426.93 ± 6.40, 355.84 ± 5.38 ppm and 444.81 ± 5.12, 192.96 ± 2.26, 115.20 ± 2.87 ppm, respectively. The highest succinate, malate, and fumarate levels were also determined in 20 g/l of glucose medium as 548.9 ± 11.21, 596.15 ± 8.26, and 406.42 ± 6.59 ppm and the levels were significantly higher than the levels in glycerol and starch. Extracellular organic acid levels measured also showed significant correlation with carbon source concentrations by showing negative correlation with pH levels of the growth medium. The antibiotic production of Streptomyces sp. M4018 was also higher in glucose medium as was the case also for organic acids when compared with glycerol. On the other hand, there is no production in starch.     

Fast sequential multi-element determination of Ca,Mg, K,Cu, Fe,Mn and Zn for foliar diagnosis using high-resolution continuum source flame atomic absorption spectrometry: Feasibility of secondary lines,side pixel registration and least-squares background correction

The fast sequential multi-element determination of Ca, Mg, K, Cu, Fe, Mn and Zn in plant tissues by high-resolution continuum source flame atomic absorption spectrometry is proposed. For this, the main lines for Cu (324.754 nm), Fe (248.327 nm), Mn (279.482 nm) and Zn (213.857 nm) were selected, and the secondary lines for Ca (239.856 nm), Mg (202.582 nm) and K (404.414 nm) were evaluated. The side pixel registration approach was studied to reduce sensitivity and extend the linear working range for Mg by measuring at wings (202.576 nm; 202.577 nm; 202.578 nm; 202.580 nm; 202.585 nm; 202.586 nm; 202.587 nm; 202.588 nm) of the secondary line. The interference caused by NO bands on Zn at 213.857 nm was removed using the least-squares background correction. Using the main lines for Cu, Fe, Mn and Zn, secondary lines for Ca and K, and line wing at 202.588 nm for Mg, and 5 mL min^− 1 sample flow-rate, calibration curves in the 0.1–0.5 mg L^− 1 Cu, 0.5–4.0 mg L^− 1 Fe, 0.5–4.0 mg L^− 1 Mn, 0.2–1.0 mg L^− 1 Zn, 10.0–100.0 mg L^− 1 Ca, 5.0–40.0 mg L^− 1 Mg and 50.0–250.0 mg L^− 1 K ranges were consistently obtained. Accuracy and precision were evaluated after analysis of five plant standard reference materials. Results were in agreement at a 95% confidence level (paired t-test) with certified values. The proposed method was applied to digests of sugar-cane leaves and results were close to those obtained by line-source flame atomic absorption spectrometry. Recoveries of Ca, Mg, K, Cu, Fe, Mn and Zn in the 89–103%, 84–107%, 87–103%, 85–105%, 92–106%, 91–114%, 96–114% intervals, respectively, were obtained. The limits of detection were 0.6 mg L^− 1 Ca, 0.4 mg L^− 1 Mg, 0.4 mg L^− 1 K, 7.7 µg L^− 1 Cu, 7.7 µg L^− 1 Fe, 1.5 µg L^− 1 Mn and 5.9 µg L^− 1 Zn.     

Investigation of Zn<Subscript>m</Subscript>Cd<Subscript>n</Subscript>X<Subscript>y</Subscript> (y = m + n; X = Te,Se and S) Clusters with TDDFT Method

Based on zinc blende and wurtzite structures of experimental ZnTe and CdTe nanocrystals, Zn_mCd_nX_y (X = Te, Se and S) clusters were investigated using DFT/B3LYP/LANL2DZ. From analyses of their characters of conformations, HOMO–LUMO gaps, Raman and absorption spectra, Mulliken charges and WBI (Wiberg Bond Index) values, we have discovered that Zn_mCd_nTe_y, Zn_mCd_nSe_y and Zn_mCd_nS_y molecules had similar characters. In this paper, characters of Zn_mCd_nTe_y were investigated in detail. First, we have found that HOMO–LUMO gaps, Raman spectra, absorption spectra, bond lengths and Mulliken charges of doping Zn₂CdTe₃, ZnCd₂Te₃, Zn₃CdTe₄, Zn₂Cd₂Te₄ and ZnCd₃Te₄ structures were in the scope of corresponding naked ZnTe and CdTe clusters. These characters of doping Zn_mCd_nTe_y molecules show that their stabilities are good. Second, comparing with ZnTe structures, the wavelengths of the absorption peaks of doping Zn_mCd_nTe_y clusters shift to red in water environment. Moreover, with increasing of the number of Cd atom, their wavelengths of the absorption peaks gradually shift to red. This conclusion is consistent with the experimental fact. Third, Raman spectra of pure ZnTe clusters have higher frequencies than corresponding naked CdTe structures. As for doping molecules, the frequencies of their Raman spectra gradually shift to low frequencies with increasing of Cd atoms’ number.     

NMR and X-ray diffraction studies of the influence of adsorbed molecule nature on phase transitions in a ZSM-5 silicalite

Pulsed NMR and X-ray diffraction analysis are employed to study the influence of adsorbed toluene, p-xylene, acetone, and di(ethylene glycol) (DEG) molecules on phase transitions in a ZSM-5 silicalite. In the region of phase transitions, times T₁ and T₂ of longitudinal and transverse magnetic relaxation of apolar molecules adsorbed in silicalite micropores increase and decrease in a jumpwise manner, respectively, with a rise in the total content of the liquid. Such changes in T₁ and T₂ occur for hexane, decane, toluene, and p-xylene molecules. Qualitatively different concentration dependences of T₁ and T₂ are observed for polar acetone and DEG molecules, because these liquids do not cause a earrangement in the crystal lattice of silicalite; this is confirmed by the X-ray diffraction data.Translated from Kolloidnyi Zhurnal, Vol. 66, No. 6, 2004, pp. 802–806.Original Russian Text Copyright © 2004 by Pimenov, Skirda, Maksimenko, Morozov, Opanasyuk.     

Spatial distribution and risk assessment of radioactivity and heavy metal levels of sediment,surface water and fish samples from Lake Van,Turkey

In this study, radioactivity levels of 228 lake water samples, 63 upper and depth sediment samples and 12 fish samples from Lake Van were investigated from 2005 to 2008 and the distribution patterns of the radionuclides were presented. Analysis included gross alpha–beta and total radium isotopes activities and uranium concentrations of the water, and gross alpha and gross beta activities and relevant ²³⁸U, ²³²Th and ⁴⁰K activity of the sediment and fish samples of the lake. Mean gross alpha, gross beta and radium isotopes activities of lake water were found 0.74 ± 0.46, 0.02 ± 0.01 and 0.06 ± 0.04 Bq/L, respectively. Mean gross alpha and beta activities in upper and depth sediments were found to be 41 ± 6 and 1,514 ± 74 Bq/kg; 77 ± 5 and 394 ± 24 Bq/kg at a 95 % confidence level, respectively. Mean activities of ²³⁸U, ²³²Th and ⁴⁰K activity concentrations in upper and depth sediments were determined to be 225 ± 22, 70 ± 7 and 486 ± 39 Bq/kg; 174 ± 4, 63 ± 3 and 263 ± 25 Bq/kg, respectively. The mean gross alpha and beta, ²³⁸U, ²³²Th and ⁴⁰K aktivities in fish samples were established as 47 ± 18, 470 ± 12, 0.57 ± 0.220, 0.022 ± 0.006, 319 ± 11 Bq/kg, respectively. The transfer factor from lake water to fish tissues, annual intake by humans consuming fish, and annual committed effective doses were estimated and evaluated.     

Physicochemical and catalytic properties of systems based on CeO<Subscript>2</Subscript>

The effect of synthesis conditions, the nature of components, and the ratio between the components on the phase composition, the texture, and the redox and catalytic properties of the Ce-Zr-O, Ce-Zr-M₁-O (M₁ = Mn, Ni, Cu, Y, La, Pr, or Nd), N/Ce-Zr-O (N = Rh, Pd, or Pt), and Pd/Ce-Zr-M₂-O/Al₂O₃ (M₂ = Mg, Ca, Sr, Ba, Y, La, Pr, Nd, or Sm) was considered. A cubic solid solution with the fluorite structure was formed on the introduction of <50 mol % zirconium into CeO₂, and the stability of this solid solution depended on preparation procedure and treatment conditions. The presence of transition or rare earth elements in certain concentrations extended the range of compositions with the retained fluorite structure. The texture of the Ce-Zr-O system mainly depended on treatment temperature. An increase in this temperature resulted in a decrease in the specific surface area of the samples. The total pore volume varied over the range of 0.2–0.3 cm³/g and depended on the Ce/Zr ratio. The presence of transition or rare earth elements either increased the specific surface area of the system or made it more stable to thermal treatment. The introduction of the isovalent cation Zr⁴⁺ into CeO₂ increased the number of lattice defects both on the surface and in the bulk to increase the mobility of oxygen and facilitate its diffusion in the Ce_{1 − x} Zr _x O₂ lattice. The catalytic properties of the Ce-Zr-M₁-O or N/Ce-Zr-M₂-O systems were due to the presence of anion vacancies and the easy transitions Ce⁴⁺ ai Ce³⁺, M₁²ⁿ⁺ ai M₁ ⁿ⁺, and N ^δ+ → N ⁰ in the case of noble metals.