UV/TiO2 photodegradation of metronidazole,ciprofloxacin and sulfamethoxazole in aqueous solution: An optimization and kinetic study

Emerging pharmaceutical ingredients (APIs) like sulfamethoxazole (SMX), metronidazole (MNZ) and ciprofloxacin (CIP) are biopersistent and toxic to the environment and public health. In this study, UV/TiO₂ photodegradation was applied in the degradation of SMX, MNZ and CIP individually and in a mixture. For a 5 mg/L SMX solution, about 97% of SMX was degraded within 360 min, which was reduced to 80% for 80 mg/L of SMX solution at the same TiO₂ dosage and photodegradation time. The maximum removals of MNZ and CIP as individual components were 100% and 89%, respectively at 600 min of photodegradation reaction time. For binary mixtures, the highest removal (100%) was achieved for MNZ and CIP ([MNZ] = [CIP] = 40 mg/L) mixture at 120 min whereas the degradations were 97% and 96% for SMX and MNZ, and SMX and CIP binary mixtures, respectively, even after 600 min of experimental time at the same concentrations. For tertiary mixture, the maximum degradation 99% was observed for (SMX = CIP] = 20 mg/L and [MNZ] = [40 mg/L) at 600 min. The observed reaction rate was 0.01085 min^?1 when SMX concentration was 5 mg/L, which decreased to 0.00501 min^?1 for SMX concentration of 80 mg/L, indicating decreasing of reaction rate at higher concentration. The results indicate that the UV/TiO₂ process is promising to apply for the treatment of pharmaceutical wastewaters.     

THERMODYNAMIC STUDY OF ADSORPTION OF PHENOLIC COMPOUNDS FROM AQUEOUS SOLUTION BY A WATER-COMPATIBLE HYPERCROSSLINKED POLYMERIC ADSORBENT

Equilibrium data for the adsorption of phenolic compounds, i.e., phenol, p-cresol, p-chlorophenol and p-nitrophenol from aqueous solutions by a water-compatible hypercrosslinked polymeric adsorbent (NJ-8) within temperature range of 283-323 K were obtained and correlated with a Freundlich-type of isotherm equation, so that equilibrium constants KF and n were obtained. The capacities of equilibrium adsorption for all the four phenolic compounds on the NJ-8 from aqueous solutions are around 2 times as high as those of Amberlite XAD-4, which may be attributed to the unusual micropore structure and the partial polarity on the network. The values of the enthalpy (always negative) are indicative of an exothermic process, which manifests the adsorption of all the four phenolic compounds on the two polymeric adsorbents to be a process of physical adsorption. The negative values of free energy change show that the solute is more concentrated on the adsorbent than in the bulk solution. The absolute free energy values of adsorption for NJ-8 are always higher than those for Amberlite XAD-4, which indicates that phenolic compounds are preferentially adsorbed on NJ-8. The negative values of the adsorption entropy are consistent with the restricted mobilities of adsorbed molecules of phenolic compounds as compared with the molecules in solution. The adsorption entropy values of phenolic compounds for NJ-8 are lower than those for Amberlite XAD-4, which means the micropores of NJ-8 require more orderly arranged adsorbate.     

Determination of diethanolamine or <Emphasis Type="Italic">N</Emphasis>-methyldiethanolamine in high ammonium concentration matrices by capillary electrophoresis with indirect UV detection: application to the analysis of refinery process waters

Alkanolamines such as diethanolamine (DEA) and N-methyldiethanolamine (MDEA) are used in desulfurization processes in crude oil refineries. These compounds may be found in process waters following an accidental contamination. The analysis of alkanolamines in refinery process waters is very difficult due to the high ammonium concentration of the samples. This paper describes a method for the determination of DEA in high ammonium concentration refinery process waters by using capillary electrophoresis (CE) with indirect UV detection. The same method can be used for the determination of MDEA. Best results were achieved with a background electrolyte (BGE) comprising 10 mM histidine adjusted to pH 5.0 with acetic acid. The development of this electrolyte and the analytical performances are discussed. The quantification was performed by using internal standardization, by which triethanolamine (TEA) was used as internal standard. A matrix effect due to the high ammonium content has been highlighted and standard addition was therefore used. The developed method was characterized in terms of repeatability of migration times and corrected peak areas, linearity, and accuracy. Limits of detection (LODs) and quantification (LOQs) obtained were 0.2 and 0.7 ppm, respectively. The CE method was applied to the determination of DEA or MDEA in refinery process waters spiked with known amounts of analytes and it gave excellent results, since uncertainties obtained were 8 and 5%, respectively.     

Initiation of polymer degradation via transfer of infectious species

A novel dual stage chemiluminescence detection system incorporating individually controlled hot stages has been developed and applied to probe for material interaction effects during polymer degradation. Utilization of this system has resulted in experimental confirmation for the first time that in an oxidizing environment a degrading polymer A (in this case polypropylene, PP) is capable of infecting a different polymer B (in this case polybutadiene, HTPB) over a relatively large distance. In the presence of the infectious degrading polymer A, the thermal degradation of polymer B is observed over a significantly shorter time period. Consistent with infectious volatiles from material A initiating the degradation process in material B it was demonstrated that traces (micrograms) of a thermally sensitive peroxide in the vicinity of PP could induce degradation remotely. This observation documents cross-infectious phenomena between different polymers and has major consequences for polymer interactions, understanding fundamental degradation processes and long-term aging effects under combined material exposures.     

1,4-双(4''''-溴苯酰基)苯的合成工艺改进

以对苯二甲酰氯和溴苯为原料,无水氯化铝粉末为催化剂,合成了1,4-双(4'-溴苯酰基)苯,其结构经1H NMR,IR和DSC表征.     

Gas–liquid partition coefficients and Henry's law constants of methyl mercaptan in aqueous solutions of Fe(II)–CDTA chelate complex

Utilization of ferric chelate complex of trans-1,2-cyclohexanediaminetetraacetic acid (CDTA) for the oxidative scrubbing of H₂S and CH₃SH in Kraft mill streams can be beneficial from the standpoints of iron protection against precipitation and oxygen-mediated regenerative oxidation of the ferrous chelate CDTA. The physical solubility of methyl mercaptan in CDTA–Fe(III) complex cannot be measured directly because of oxidation of the sulfur-bearing gaseous species with the ferric chelate. Therefore, this investigation was carried out to determine the gas–liquid partition coefficients and Henry's law constants of methyl mercaptan in aqueous iron-free CDTA solutions and non-reacting ferrous chelate solutions (CDTA–Fe(II) complex), using the static headspace method with an estimated accuracy of about 2%. Experiments with aqueous solutions of chelate concentrations varying between 38 and 300 mol m⁻³ were carried out at temperatures between 298 and 333 K and atmospheric pressure. It was shown that the methyl mercaptan solubility decreases with increasing temperature for all systems but was not much influenced, in the studied conditions, by the chelate concentration especially at larger temperatures.     

无溶剂研磨条件下四氢苯并吡喃衍生物的一锅法合成

四氢苯并吡喃衍生物在药物和农药研究中有着广泛的用途. 基于合成这类化合物的传统方法所用溶剂多为对环境不利的极性溶剂, 且合成需分步进行, 在提倡绿色化学和发展节约型经济的今天, 如何改良这类反应已成为一个热点. 本工作通过选择不同的碱尝试反应最佳条件, 发现用价廉易得的碳酸钾为碱, 对不同官能团取代的底物芳醛采用研磨的手段, 在无溶剂条件下, 一锅法可成功合成四氢苯并吡喃衍生物. 该法条件温和, 收率高, 易于操作, 对环境影响小.     

Novel Gel—like Process for Synthesizing Submicron LiaNi0.8Co0.2O2 Powders Used in Lithium Ion Batteries

A novel gel-like process has been developed for synthesizing LiaNi0.8Co0.2O2 powders,using citric acid as a chelating agent. This process improves the homogeneity of constituent cation and enhances their reactivity in the obtained precursor. The results of electrochemical test demonstrated that these materials exhibited excellent electrochemical properties. Its initial capacity reached 181.6 mAh/g and reversible efficiency at the first cycle is about 88.6%.     

酚酞型聚芳醚砜(Ⅶ):K_2C0_3存在下PP/DCDPS体系聚合反应机理的研究

利用~(13)C-NMR方法研究了弱碱K_2CO_3存在下酚酞成盐反应及其与活性双卤砜亲核缩聚反应过程中的结构特征。对一系列碱性条件下酚酞(PP)与4,4'-二氯二苯砜(DCDPS)的缩聚反应的研究表明任何影响内酯结构酚酞盐生成的因素都会严重阻碍聚合反应的进行。对模型化合物存在下K_2CO_3在极性非质子溶剂中的溶解/解离行为的研究结果表明酚酞类Card。双酚与固体K_2CO_3之间可能存在着一种特殊的络合作用。基于我们系列研究结果,本文中总结提出了弱碱K_2CO_3存在下酚酞的反应机理。     

The non-isothermal devitrification of lithium germanate glasses

The non-isothermal devitrification of lithium germanate glasses, examined by DTA and XRD, is reported and discussed. The glass compositions are expressed by the general formula:xLi₂O(1?x)GeO₂ withx=0.050, 0.125, 0.167, 0.200 and 0.250. All the glasses studied, unlike GeO₂ glass, exhibit internal crystal nucleation without the addition of any nucleating agent. The devitrification processes occur in one or more steps. Phases which crystallized at each step are identified and crystallization mechanisms proposed. These crystallization mechanisms are related to structures of the crystallizing phases. Activation energy values as well as those for glass transition temperatures, do not vary linearly with increase in Li₂O content but pass through a maximum atx=0.200.