C-14 and H-3 contents in the groundwater around radioactive repository site in Korea

The contents of H-3 and C-14 in groundwater and surface waters around low and medium-level atomic waste repository site in Korea were determined. The concentrations of C-14 were in the range 0.186–0.287 Bq/L. The H-3 concentration of the groundwaters and surface waters were <0.06–5.75 and 1.22–4.74 Bq/L. The average H-3 contents of west, north and south direction were 1.18 ± 0.12, 1.11 ± 0.78 and 2.85 ± 2.66. H-3 and C-14 concentrations in the south direction were relatively higher than west and north direction samples. The surface waters sampled from catchment were four times higher than average H-3 concentration in precipitation. The concentrations of H-3 and C-14 within 5 km area samples were much higher than other samples.     

Magnetic solid-phase extraction of warfarin and gemfibrozil in biological samples using polydopamine-coated magnetic nanoparticles via core-shell nanostructure

Herein, polydopamine-coated Fe₃O₄ spheres were synthesized using a very simple, easy, cost-effective, efficient, and fast method. First, magnetic nanoparticles (Fe₃O₄) were synthesized and were followed by accommodating polydopamine on the surface of the prepared Fe₃O₄. The prepared polydopamine-coated Fe₃O₄ spheres were utilized as a sorbent in magnetic solid phase extraction of gemfibrozil and warfarin (as the model analytes). The extracted model analytes were desorbed by a suitable organic solvent and were analyzed by high-performance liquid chromatography. Under optimized condition, the linearity of the method was in the range of 0.1–200.0 μg/L for the selected analytes in water. The limits of detection were calculated to be in the range of 0.026–0.055 μg/L for warfarin and gemfibrozil, respectively. The limits of quantification were calculated to be in the range of 0.089–0.185 μg/L. The inter-day and intra-day relative standard deviations were determined to be in the range of 1.4%–3.3% in three concentrations in order to calculate the method precision. Furthermore, the enrichment factors were found to be 78 and 81 for warfarin and gemfibrozil, respectively. Moreover, the calculated absolute recoveries were between 78% and 81%. The obtained recoveries indicated that the method was useful and applicable in complicated real samples.     

Preparation and properties of cellulose/silver nanoparticle composites with in situ-generated silver nanoparticles using Ocimum sanctum leaf extract

In the present work, silver nanoparticles were in situ-generated in cellulose matrix using Ocimum sanctum leaf extract as a reducing agent. Regenerated wet cellulose films were first immersed in O. sanctum leaf extract and then it was allowed to diffuse into the films. The leaf extract–diffused wet films were dipped in different concentrated aq.AgNO₃ solutions. The leaf extract inside the wet films reduced AgNO₃ into nanosilver. The dry composite films were black in color. Some of the nanoparticles were also formed outside the film in the solution. The nanoparticles were viewed by transmission electron microscopy and scanning electronic microscopy techniques. The composite films showed good antibacterial activity. The cellulose, matrix, and the composite films were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis techniques. The tensile properties of the composite films were higher than those of the matrix. These biodegradable films can be used for packaging and medical purposes.     

Preparation and application of sol–gel acrylate and methacrylate solid-phase microextraction fibres for gas chromatographic analysis of organoarsenic compounds

Novel solid-phase microextraction (SPME) fibres containing methyl, ethyl, butyl acrylate and methacrylate were first prepared by a sol–gel technique and investigated for determination of selected organoarsenic compounds (lewisite, methyldichloroarsine, phenyldichloroarsine, diphenylchloroarsine and triphenylarsine) from water samples. The influence of sorption and desorption temperature and time for extraction efficiency were examined. The best new fibre coatings (methyl acrylate (MA), methyl methacrylate (MMA) and combination of methyl acrylate and methacrylate (MA/MMA)) for analysis of organoarsenic compounds were selected and compared with commercial fibres. The distribution coefficients K_fs were determined for the best novel fibres and for absorption commercial fibres. The highest K_fs value were obtained for MA/MMA and MMA fibres and were respectively 9458 and 6561 for lewisite and 6458 and 5884 for triphenylarsine. The limit of detection and quantification were determined for the three laboratory obtained fibres (MA, MMA and MA/MMA). LODs for tested fibres, at a signal-to-noise of 3, were 0.03–0.3 ng mL⁻¹. LOQs for selected coatings, at signal-to-noise of 10, were 0.1–0.8 ng mL⁻¹. The relative standard deviations (RSD) for all measurements were 4.3–6.5% (n = 9) and relative errors were 2.5–5%. The laboratory obtained fibres were used for environmental analysis of pore water samples from the Baltic Sea.     

Optically active copolyamides by melt and solution condensation polymerization

The melt and solution condensation copolymerization of nylon salts which were prepared from d-camphoric acid and adipic acid with hexamethylenediamine were carried out, and optically active copolyamides were obtained. The copolyamides obtained had a positive specific rotation. The specific rotations for the copolyamides increased with increasing content of d-camphoryl units in the copolymers. The optical rotatory dispersion of the copolyamides had positive curves and were found to fit the simple Drude equation. The λ_c values of the polymers obtained by the melt and solution condensation polymerization were 241 mμ and 245 mμ, respectively.     

PHOTOPOLYMERS: SYNTHESIS AND CHARACTERIZATION OF POLY(4-CINNA-MOYLPHENYL METHACRYLATE) WITH GLYCIDYL METHACRYLATE

Copolymers of 4-cinnmoylphenyl methacrylate (CPMA) with glycidyl methacrylate were synthesized in methyl ethyl ketone solution using benzoyl peroxide as initiator at 70 ± 1°C. They were characterized by UV, IR, ¹H-NMR, and ¹³C-NMR spectra. Their compositions were determined by ¹H-NMR technique. The monomer reactivity ratios were determined by the Fineman-Ross and Kelen-Tüdös methods. The molecular weights ([Mbar]_w and [Mbar]_n) of the polymers were determined by GPC technique. Thermogravimetric analysis of the copolymers were carried out in air. The T_g of the polymers were determined by differential scanning calorimetry. The photocrosslinking properties of the homo and copolymers were also discussed.     

Temperature and Concentration Dependence of the Electrical Conductance,Diffusion, and Kinetics Parameters of the Ions in Aqueous Solutions of Sulfuric Acid,Selenic Acid,and Potassium Tellurate

The temperature and concentration dependences of the electrical conductance of aqueous solutions of sulfuric acid, selenic acid, and potassium tellurate were studied. The coefficients of the corresponding empirical equations were determined, and the values of equivalent conductances of the anions were evaluated at infinite dilution at the experimental temperatures. The values of the coefficients in the Fuoss and Onsager equation were evaluated for the three electrolytes at 298 K. The values of the molecular and ionic coefficients of self-diffusion at infinite dilution were calculated in the temperature range 288–318 K. The change of the translational energy Δ E∘_tr. of water molecules in the ionic hydration sphere was determined. The number of water molecules participating in the ionic hydration sphere at 298 K and the changes of Gibbs free energy, enthalpy, and entropy of activation of ionic conductance were calculated. The results obtained were interpreted according to the Samoylov’s theory of positive and negative hydration of ions. The differences observed in the temperature dependences of the mentioned parameters were explained in terms of the different radii and hydration numbers of the ions.     

Soluble aromatic polyamide and polyimides derived from di(aminophenyl) acetylenediurea

New aromatic polyamide and polyimides were prepared from di(aminophenyl)acetylenediurea. In addition, model compounds were synthesized and their IR spectra were in agreement with those of the corresponding polymers. The polymers were amorphous and readily soluble in polar aprotic solvents (DMF, NMP, DMSO) and certain acids (H₂SO₄, CCl₃COOH). The hydrophilicity of polyamide was estimated by measuring the isothermal water absorption. The polyamide softened at 260°C but no softening was observed for polyimides. The glass transition temperatures of polymers were determined by the TMA method and they were in the range of 235–310°C. The polymers were stable up to 359–404°C in N₂ or air and afforded char yields of 53–65% at 800°C in N₂. © 1996 John Wiley & Sons, Inc.     

Relationships observed in the structure and spectra of uracil and its 5-substituted derivatives

The effects on the geometry structure, atomic charges and vibrational wavenumbers of the main different substituents in the 5th position of the uracil ring were analysed, and relationships were established. The 5-monosubstituted derivatives studied were 5-XU (X = F, Cl, Br, I, CH₃, NH₂, NO₂). The geometry and vibrational wavenumbers were determined in these molecules. The FT-IR and Raman spectra were studied with the support of B3LYP calculations using several basis sets. Several general conclusions were underlined.     

Synthesis and physicochemical properties of 9,10-phenanthrenequinone monoxime and its nitro derivatives

Phenanthrenequinone monoxime and its mono-, di-, and trinitro derivatives were synthesized. The acidity constants and their variation with the number and position of nitro groups were determined. The electronic and IR spectra of the nitro compounds were studied. The bands in the electronic spectra were assigned based on quantum-chemical calculations in the Pariser—Parr—Pople approximation. Correlations between the pK _a values and some calculated characteristics of the compounds under study were found. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1106–1110, June, 1999.     

Phase complex of the Li,K,Ba‖F,Br quaternary reciprocal system

The partition of the Li,K,Ba??F,Br quaternary reciprocal system into simplexes was performed and confirmed by X-ray powder diffraction. Internal partitioning elements, LiF-2KBr · BaBr₂ and KBr-LiF · BaF₂, were identified; the tree of phases forms two cycles. Simplexes involving phase separation were determined. The stable partitioning triangles LiF-KBr-BaBr₂ and LiF-KBr-BaF₂ · BaBr₂ were experimentally studied by differential thermal and X-ray powder diffraction analyses. The T-x diagrams of explored sections and the liquidi of the systems were constructed. Phase separation regions within the systems under investigations were delimited. The characteristics of alloys corresponding to invariant compositions were determined.     

基于中空纤维液相微萃取的麻黄碱和伪麻黄碱优势构象的确定及含量测定

利用中空纤维液相微萃取方法(HF-LPME)分析麻黄碱和伪麻黄碱在不同基质中的优势构象,阐明了麻黄碱和伪麻黄碱的萃取机理;结合高效液相色谱(HPLC)建立了微量麻黄碱和伪麻黄碱的分离测定方法。以聚偏氟乙烯中空纤维为有机溶剂载体,正己醇为萃取溶剂,麻黄碱和伪麻黄碱的NaOH(5 mol/L)溶液为样品相,0.01 mol/L H2SO4溶液为接收相,在1200 r/min转速下萃取35 min,收集萃取液直接进行HPLC分析。麻黄碱和伪麻黄碱在水溶液中的线性范围为5～100 μg/L,检出限分别为1.9 μg/L和1.2 μg/L,富集倍数分别为38和61倍,平均回收率分别为100.6%±1.2%和103.2%±3.5%;在鼠尿液中的线性范围为100～5×104 μg/L,检出限分别为30 μg/L和42 μg/L,富集倍数分别为20和17倍,平均回收率分别为108.4%±4.4%和106.1%±5.4%。研究表明该方法操作简单,选择性高,适用于微量麻黄碱的含量测定和分析。     

Comparison of Methods for the Preconcentration of Cadmium (II) Using Amberlite XAD-16 Resin Modified with Anoxybacillus caldiproteolyticus and Geobacillus stearothermophilus as Novel Biosorbents

Abstract

The isolation, identification and characterization of bacteria obtained from soil of Ergani Makam Mountain were performed and the results revealed that the bacteria were thermophilic Anoxybacillus caldiproteolyticus. The characterized bacteria and purchased Geobacillus stearothermophilus were immobilized on Amberlite XAD-16 in order to prepare two biosorbents for preconcentration experiments for the determination of cadmium (II) ions. The produced biosorbents were enriched separately using mini-columns and the analyte was determined by flame atomic absorption spectrometry. The effects of solution parameters were investigated for the separation and preconcentration yields. The recovery efficiencies of Amberlite XAD-16 immobilized separately with A. caldiproteolyticus and G. stearothermophilus were determined to be 98.23?±?2.40 and 98.93?±?1.3 (n?=?5) for the optimum working conditions, respectively. Moreover, the Cd (II) ion was recovered with 10?mL of 1?mol L^?1 of HCl and 2?mL of 0.5?mol L^?1 HNO₃ solutions. The optimum working conditions were determined to be at pH 6.0 and a flow rate of 2?mL min^?1 for both biosorbents. The recovery efficiencies of matrix ions were characterized to investigate the feasibility of the developed preconcentration methods. The accuracy of the proposed methods were controlled by analyzing a SCP Science EnviroMAT Waste Water, Low (EU-L-2) certified reference material. The obtained results were comparable to the certified values. These methods were also applied to the analysis of water samples from Dicle River, Hazar Lake and Diyarbak?r tap water for Cd (II).     

Band shapes and moment analysis of the far-infrared absorptions of dipolar molecules in solutions

The moment analyses were performed on the far-infrared absorption bands of CH₃CN, CHCl₃, CH₂Cl₂, and their deuterated compounds dissolved in nonpolar solvents. The values of torque acting on the solute molecules were estimated from the fourth moments. The band profiles were simulated by means of the continued-fraction representation of the time correlation function by Mori, using the moment values obtained. The third order long-time approximation of the correlation function yields essentially good simulations. The effective rotation angles of molecules between collisions were estimated from the first positive-to-negative turning points of the memory functions. The solvent effects on the torque and the rotation angle were consistent with each other.     

邻-甲氧基苯酚和α-,β-环糊精包合现象的理论与实验研究

通过紫外可见光谱法考察了水溶液中邻-甲氧基苯酚(o-Mop)和α-与β-环糊精(CD)的分子间相互作用, 利用Hildebrand-Benesi方程给出了两个包合物的稳定常数(K_s). 采用半经验PM3方法研究了α-,β-CD和o-Mop及其类似物苯酚(Phe)、丁香酚(Eug)之间的包络作用, 阐述了这些主客体包合作用过程中体系能量随主客体相对位置改变而变化的细节, 据此推断出主-客体包合物可能的分子结构, 计算了包合物的稳定化能(ΔE_s). 研究结果表明, 本文所选主客体体系而言, 当客体和同一种主体分子作用时, 超分子包合物的ΔE_s随着客体分子苯环上取代基团数目的增多而增加. 基于PM3方法优化得到的主-客体包合物在真空中的分子结构和通过实验方法在水溶液中测定的结构一致.     

Synthesis,molecular conformation,vibrational, electronic transition,and chemical shift assignments of 4-(thiophene-3-ylmethoxy)phthalonitrile: a combined experimental and theoretical analysis

This work presents the synthesis and characterization of a novel compound, 4-(thiophene-3-ylmethoxy)phthalonitrile (TMP). The spectroscopic properties of the compound were examined by FT-IR, FT-Raman, NMR, and UV techniques. FT-IR and FT-Raman spectra in solid state were observed in the region 4000–400 cm⁻¹ and 3500–50 cm⁻¹, respectively. The ¹H and ¹³C NMR spectra were recorded in CDCl₃ solution. The UV absorption spectrum of the compound that dissolved in THF was recorded in the range of 200–800 nm. The structural and spectroscopic data of the molecule in the ground state were calculated using density functional theory (DFT) employing B3LYP exchange correlation and the 6-311++G(d,p) basis set. The vibrational wavenumbers were calculated and scaled values were compared with experimental FT-IR and FT-Raman spectra. The complete assignments were performed on the basis of the experimental results and total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Isotropic chemical shifts (¹³C NMR and ¹H NMR) were calculated using the gauge-invariant atomic orbital (GIAO) method. A study on the electronic properties, such as HOMO and LUMO energies, were performed by time-dependent DFT (TD-DFT) approach. The HOMO and LUMO analyses have been used to elucidate information regarding charge transfer within the molecule. Comparison of the calculated frequencies, NMR chemical shifts, absorption wavelengths with the experimental values revealed that DFT method produces good results.     

Comparison of separation performances of amylose- and cellulose-based stationary phases in the high-performance liquid chromatographic enantioseparation of stereoisomers of β-lactams

High-performance liquid chromatographic methods were developed for the separation of the enantiomers of 19 β-lactams. The direct separations were performed on chiral stationary phases containing either amylose tris(3,5-dimethylphenylcarbamate), (Kromasil® AmyCoat? column) or cellulose tris(3,5-dimethylphenylcarbamate), (Kromasil® CelluCoat? column) as chiral selector. The different methods were compared in systematic chromatographic examinations. The separations were carried out with good selectivity and resolution. The AmyCoat? and CelluCoat? columns appear to be highly complementary. The best separations of bi- and tricyclic β-lactam stereoisomers were obtained with the AmyCoat? column, while the 4-aryl-substituted β-lactams were better separated on the CelluCoat? column. The elution sequence was determined in all cases; no general rule could be established.     

Study of the interactions between fluoroquinolones and human serum albumin by affinity capillary electrophoresis and fluorescence method

The interactions between fluoroquinolones and human serum albumin (HSA) were investigated by affinity capillary electrophoresis (ACE) and fluorescence quenching technique. Based on the efficient separation of several fluoroquinolones using a simple phosphate buffer, the binding constants of fluoroquinolones with HSA were determined simultaneously during one set of electrophoresis by ACE method. The thermodynamic parameters were obtained from data at different temperatures, and the negative ΔH and ΔS values showed that both hydrogen bonds and van der Waals interaction played major roles in the binding of fluoroquinolones to HSA. The interactions were also studied by fluorescence quenching technique. The results of fluorescence titration revealed that fluoroquinolones had the strong ability to quenching the intrinsic fluorescence of HSA through the static quenching procedure. The binding site number n, apparent binding constant K_b and the Stern-Volmer quenching constant K_sv were determined. The thermodynamic parameters were also studied by fluorescence method, and the results were consonant with that of ACE.     

Experimental Study of the Effect of Temperature,Pressure, and Concentration on the Viscosity of Aqueous KBr Solutions

The viscosity of five (0.1240, 0.2378, 0.4645, 0.9440, and 2.2310 mol⋅kg⁻¹) binary aqueous KBr solutions have been measured with a capillary flow technique. Measurements were made at pressures up to 30 MPa for the temperature range 298 to 577 K. The total uncertainties of the viscosity, pressure, temperature, and composition measurements were estimated to be less than 1.6%, 0.05%, 15 mK, and 0.02%, respectively. The temperature and pressure coefficients of the viscosity of KBr(aq) were studied as a function of molality and temperature. The measured viscosities were compared with data, predictions and correlations previously reported in the literature. The viscosity data were used to accurately calculate the physical-meaningful parameters (viscosity A- and B-coefficients) of the extended Jones-Dole equation for the relative viscosity (η/η ₀). Various theoretical models {absolute rate theory, Tammann-Tait-Gibson (TTG) model, and extended Einstein model} were used to accurately represent the measured viscosities. Values of hydrodynamic molar volume V _k (effective rigid molar volume of the salt) were calculated using the present experimental data. The high-pressure viscosity measurements were used to test the predictive capability of the TTG model.     

Synthesis and characterization of soluble polyimides from 2,2-bis(4-aminophenyl)cycloalkane derivatives

New aromatic diamines [(1) and (2)] containing polycycloalkane structures between two benzene rings were synthesized by HCl-catalyzed condensation reaction of aniline hydrochloride and corresponding polycycloalkanone derivatives. The structures of diamines were identified by ¹H-NMR, ¹³C-NMR, FTIR spectroscopy, and elemental analysis. The polyimides were synthesized from the obtained diamines with various aromatic dianhydrides by one-step polymerization in m-cresol. The inherent viscosities of the resulting polyimides were in the range of 0.34–1.02 dL/g. The polyimides showed good thermal stabilities and solubility. All the polymers were readily soluble in N-methyl-2-pyrrolidone, m-cresol, tetrachloroethane, etc. Some of them were soluble even in chloroform at room temperature. The glass transition temperatures were observed in the range of 323–363°C, and all of the polymers were stable up to 400°C under nitrogen atmosphere. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3449–3454, 1999