An overview of analytical methodologies for the determination of antibiotics in environmental waters

The widespread occurrence of antibiotics as contaminants in the aquatic environment has increased attention in the last years. The concern over the release of antibiotics into the environment is related primarily to the potential for the development of antimicrobial resistance among microorganisms. This article presents an overview of analytical methodologies for the determination of quinolone (Qs) and fluoroquinolone (FQs), macrolide (MLs), tetracycline (TCs), sulfonamide (SAs) antibiotics and trimethoprim (TMP) in different environmental waters. The analysis of these antibiotics has usually been carried out by high-performance liquid chromatography (HPLC) coupled to mass spectrometry (MS) or tandem mass spectrometry (MS/MS) and to a lesser extent by ultraviolet (UV) or fluorescence detection (FD). A very important step before LC analysis is sample preparation and extraction leading to elimination of interferences and prevention of matrix effect and preconcentration of target analytes.     

Novel combination of non-aqueous capillary electrophoresis and multivariate curve resolution-alternating least squares to determine phenolic acids in virgin olive oil

This paper presents the development of a non-aqueous capillary electrophoresis method coupled to UV detection combined with multivariate curve resolution-alternating least-squares (MCR-ALS) to carry out the resolution and quantitation of a mixture of six phenolic acids in virgin olive oil samples. p-Coumaric, caffeic, ferulic, 3,4-dihydroxyphenylacetic, vanillic and 4-hydroxyphenilacetic acids have been the analytes under study. All of them present different absorption spectra and overlapped time profiles with the olive oil matrix interferences and between them. The modeling strategy involves the building of a single MCR-ALS model composed of matrices augmented in the temporal mode, namely spectra remain invariant while time profiles may change from sample to sample. So MCR-ALS was used to cope with the coeluting interferences, on accounting the second order advantage inherent to this algorithm which, in addition, is able to handle data sets deviating from trilinearity, like the data herein analyzed. The method was firstly applied to resolve standard mixtures of the analytes randomly prepared in 1-propanol and, secondly, in real virgin olive oil samples, getting recovery values near to 100% in all cases. The importance and novelty of this methodology relies on the combination of non-aqueous capillary electrophoresis second-order data and MCR-ALS algorithm which allows performing the resolution of these compounds simplifying the previous sample pretreatment stages.     

Advantages of using a modified orthogonal sampling configuration originally designed for LC-ESI-MS to couple CE and MS for the determination of antioxidant phenolic compounds found in virgin olive oil

A ThermoFinnigan sheath liquid flow capillary electrophoresis-mass spectrometry system designed for coupling via a co-axial interface was coupled through an adapted via an alternative, commercially available interface for orthogonal sampling. The affordable, reversible structural alterations made in the commercial LC-MS interface resulted in improved analytical performance.The results of a conventional capillary electrophoresis (CE) method using a commercial co-axial source to determine antioxidant phenolic acids present in virgin olive oil, were compared with those obtained by using a modified orthogonal sampling position. In both cases, separations were done using a 10 mM ammonium acetate/ammonium hydroxide buffer solution at pH 10.0 and a constant applied voltage of 25 kV. The operating variables for the mass spectrometry interface were re-optimized for the modified orthogonal orientation. This allowed the sheath liquid, sheath gas flow rates and capillary voltage to be lowered with respect to the co-axial coupling configuration. In addition, the orthogonal sampling position provided a higher selectivity by effect of ion sampling excluding larger droplets—with an increased momentum along the axis—which were drained through the sink at the bottom of the ion source. Also, the new configuration facilitated sample ionization, improved electrospray stability and led to stronger signals as a result.The new system was validated in terms of precision (repeatability), linearity, and limits of detection and quantification. A comparison of the validation data with the results previously obtained by using a commercial co-axial configuration revealed the adapted orthogonal sampling position to provide better repeatability in both migration times and relative peak areas (<1% and 7% respectively with n = 15 replicates), a good linear range (with levels in the microgram-per-litre region) and lower limits of detection—especially for the compounds detected with the lowest sensitivity when co-axial ESI was used, as HFA, GEN, FER and VAN finding LOD among 24-3.0 μg L⁻¹ respectively.     

丙烯腈与芳烃分子配位作用的研究

报导了用UV法和NMR法共同测量丙烯腈与某些芳烃的分子配合常数,以Rose-Drago方程处理数据.并比较了二种方法测定得到的配位常数.结果表明UV法和NMR法测量所得相关系数都很高,大都在0.99以上,认为体系以1:1形式配位的假设是合理的,两种方法得到的配位常数的误差也大体相当.     

液体混合物的推广Vander Waals理论

本文通过对Van der Waals模型中排斥体积的修正, 建立了一个液体状态方程式,并将它推广到了二元液体混合物, 预测和关联了液体混合物的过量性质, 计算结果表明, 可与Flory理论相比拟, 但所需提供的纯组分性质比Flory理论少, 计算也得到了简化.     

Growth and characterization of a new organic nonlinear optical crystal: Vanillylideneaniline

Vanillylideneaniline with chemical formula C₁₄H₁₃NO₂ (VAN), a second order nonlinear optical (SONLO) organic single crystal was synthesized and grown for the first time from dimethyl formamide (DMF) employing slow solvent evaporation technique. Single crystal X-ray diffraction data reveals that the crystal belongs to noncentrosymmetric orthorhombic space group C222₁. The high-resolution diffraction curve containing single peak with full width at half maximum (FWHM) of 62 arc s ascertains VAN was perfectly crystallized and free from structural grain boundaries. The formation of the material was confirmed quantitatively by FTIR, ₁H¹ and ¹³C NMR spectral analyses. The UV–vis–NIR spectrum reveals the percentage of the transmission of VAN crystal in the entire region. The variations of dielectric constant (?_r) and dielectric loss (D) with frequency at different temperatures were investigated. The SHG of VAN crystal is confirmed by Kurtz Powder technique. The mechanical strength of the crystal was estimated by Vickers hardness test. VAN has yield strength of 8.70 MPa. Thus the grown organic VAN single crystal can be recommended as a promising candidate for SONLO application and device fabrication technology.     

正离子的边界半径

本文建议和讨论了离子的边界半径, 给出了一价正离子的边界半径的周期表以及某些常见正离子的边界半径。正离子的边界半径与SP半径、Pauling离子半径、晶体离子半径等有一定的关联, 显示了其合理性和可应用性。由这些关联性质, 还可以预言某些元素的难以测定的电离能。     

原子的边界半径

本文建议和讨论2了原子大小的一种新量度-原子的边界半径, 经出了边界半径的周期表。对于惰性气体原子和汞原子, 有实验测得的有效半径, 它们与边界半径符合得相当好。原子的边界半径与实验的van der Waals半径有良好的线性关系。因此, 由边界半径可以预言某些原子的有效半径以及van der Waals半径。     

Electrochemical degradation of 2,4-Dinitrotoluene (DNT) from aqueous solutions using three-dimensional electrocatalytic reactor (3DER): Degradation pathway,evaluation of toxicity and optimization using RSM-CCD

2,4-Dinitrotoluene (2,4-DNT) has been found to be an important petrochemical compound, which is primarily employed for the synthesis of tolylene diisocyanate and the production of dyes, rubber, and explosives. Since this compound has high toxicity and carcinogenicity, the cautions should be considered when wastewater contaminated with DNTs and their derivatives is released into the environment. Thus, the object of the present study was the investigation of the 2,4-DNT degradation efficiency using the three-dimensional electrocatalytic reactor (3DER) with two different types of particle electrodes (granular activated carbon (GAC) and magnetized clinoptilolite zeolite (MCZ)@Fe₃O₄ nanoparticles)). Preparation of the graphite (G)/β-PbO₂ anode was done by electrochemically depositing PbO₂ layers on graphite sheets. The prepared graphite sheet and a stainless-steel 316 sheet (with the same dimensions) were employed as the anode and the cathode, respectively. Field emission scanning electron microscopy (FESEM), X-ray diffraction analysis (XRD), and energy-dispersive X-ray spectroscopy mapping (EDS-mapping) confirmed the successful preparation of G/β-PbO₂ anode. The surface morphology, chemical composition of MCZ@Fe₃O₄ nanoparticles as a particle electrode were determined by scanning electron microscope (SEM) and XRD pattern. To determine the optimal conditions, we employed the response surface methodology-based central composite design (RSM-CCD) method. According to observed results, higher efficiency of 3DER was obtained by increasing the reaction time and current density and decreasing pH and the pollutant concentration. Studies highlighted the initial 2,4-DNT concentration of 23.5 mg/L, current density 4.8 mA/cm², pH of 4.1, electrolysis time of 50 min, particle electrodes dose = 6 g/250 cc as optimum values of parameters. The 2,4-DNT degradation efficiencies using GAC and MCZ@Fe₃O₄ nanoparticles as particle electrodes under mentioned optimal conditions were 98.6% and 96.5%, respectively. Moreover, the chemical oxygen demand (COD) and total organic carbon (TOC) removal efficiencies were 88.5% and 80.9% at the end of 50 min, respectively. Furthermore, results were indicative of an enhancement in average oxidation state (AOS) (from 1.27 to 2.36) and carbon oxidation state (COS) (from 1.27 to 3.68) in the 3DER process and a reduction in the COD/TOC ratio (from 1.81 to 1.09); these signposts the effectiveness of 3DER system for providing the biodegradability of 2,4-DNT. Considering the results, the 3DER could lead to suitable results for the degradation of wastewater containing DNT and resistant contaminants as pretreatment and has remarkable applicability for enhancing the biodegradability of wastewater.     

^1^7O, ^3^3S NMR化学位移结构效应的分子力学研究

本文通过对环状磷酸酯和环状亚磷酸酯类化合物的分子力学计算,观察到^1^7ONMR化学位移的变化同时受到氧原子局部范德华相互综合利用(E~V~D~W~-~O)和局部偶极相互作用能(E~i~i~p-~O)的影响。此外,在上述两类化合物中,环外氧原子的δ-压缩效应极为明显,这主要是由于该氧原子局部范德华相互作用能起决定作用的缘故。同时,经对二烷基砜类化合物的分子力学计算,首次获得^3^3SNMR化学位移和硫原子局部范德华相互作用能E~V~D~W~-~S之间良好的线性关系。