飞秒激光诱导Li2O-Nb2O5-SiO2玻璃析晶拉曼谱研究

通过使用波长 800nm、重复频率 250kHz的飞秒激光脉冲聚焦进Li2O-Nb2O5-SiO2组分的玻璃内部,空间选择性诱导出铌酸锂微晶.为了进一步地研究辐照区域晶体的生长机制,使用显微拉曼光谱仪分析了玻璃样品辐照区域不同位置的结构变化.研究表明,在飞秒激光辐照一段时间后的聚焦区域,由于非线性效应和热累积效应形成了一个高温辐射梯度场,在激光辐照中心区域超过玻璃的析晶温度而促使玻璃熔融析晶.     

Release and speciation of uranium in low-ionic-strength groundwaters at an abandoned uranium mine in Val Vedello (Orobic Alp—Italy) by adsorptive cathodic stripping voltammetry

Adsorptive cathodic stripping voltammetry (AdCSV) with HDME and a chloranilic acid ligand was used in the trace analysis of uranyl ions at pH?=?2 in low-ionic-strength groundwaters around mining areas. Upon optimization, the limit of detection around 0.10?µg?L^?1 was found with linearity up to 10?µg?L^?1. In the abandoned mining area of Val Vedello (Orobic Alps, Italy), measured uranium concentrations in water ranged from 0.3?µg?L^?1 above the uranium mineralization levels to 145?µg?L^?1 in groundwaters percolating from mine galleries. Such uranium concentrations are related to natural weathering effects of CO₂ and/or hydrogen carbonate ion on uranium mineralizations under oxic conditions. A marked seasonal dependence was then found, in agreement with literature data on a pre-operational survey dating back to 1980–1981. No significant chemical impact of the abandoned mining activity on groundwater quality could be found. Accordingly, no significant increase in contaminants derived from the heat-burn of explosives, such as chloride and nitrate, in groundwaters from mine galleries was found.     

The Effect of Simulated In Vitro Digestion on Biological Activity of Viburnum opulus Fruit Juices

In the present study, an in vitro digestion method has been used to assay the influence of the physiological conditions in the mouth, stomach, and intestine on the stability and activity in different cell models of the main phenolic compounds from Viburnum opulus fresh juice (FJ), phenolic-rich juice (PJ), and the bioavailable fractions (DFJ and DPJ). The data obtained indicate that the V. opulus samples achieved after in vitro digestion had an influence on cellular glucose and lipid metabolism. The bioavailable fraction of both digested juices stimulated glucose uptake and decreased lipid accumulation by L6 myoblasts and HepG2 hepatocytes. Both DFJ and DPJ reduced the secretion of inflammatory cytokines by 3T3-L1 adipocytes: interleukin-6 (IL-6) and tumor necrosis factor-α (TNF-α). Simultaneously, DFJ and DPJ enhanced oxidative stress in MIN6 cells and decreased glucose-stimulated insulin secretion (GSIS). UPLC–MS analysis revealed qualitative and quantitative changes in hydroxycinnamic acids. In particular, the content of chlorogenic acid decreased drastically; its content in the bioavailable fraction was almost 7 times and 30 times lower than in the FJ and PJ, respectively. Our results suggested that although the phenolic compounds of V. opulus juices undergo transformation during digestion, they are still potent antioxidant agents with biological activity.     

Lead Film Electrode Prepared with the Use of a Reversibly Deposited Mediator Metal in Adsorptive Stripping Voltammetry of Nickel

The paper presents the first report on application of a “hybrid” lead film electrode for the adsorptive stripping voltammetric determination of Ni(II) in the presence of nioxime as a complexing agent. The strategy to create a “hybrid” electrode is based on the combination of ex situ and in situ plating methods and the use of a reversibly deposited mediator metal (Zn) for the lead film formation. The surface morphology of a new sensor was characterized by atomic force microscopy. The detection limit for Ni(II) obtained at 120 s of accumulation time was 3.9×10^?11 mol L^?1. The proposed method was validated for the determination of nickel in water certified reference materials with good results.     

Adsorptive Cathodic Stripping Voltammetric Determination of Uranium(VI) in Presence of N‐Phenylanthranilic Acid

N‐Phenylanthranilic acid was used as a complexing agent for determination of uranium(VI) by adsorptive cathodic stripping voltammetry. Under the optimal experimental conditions of the experimental parameters, the peak current was proportional to the concentration of U(VI) in the range 0.75–30 ng mL^?1 and the detection limit was 0.036 ng mL^?1. The influence of possible interferences was investigated. The method was applied for determination of uranium in waste water from uranium conversion facility and natural water samples. Application of the method for simultaneous determination of U(VI) and Cu(II) showed that these ions could be simultaneously determined in a single scan at relatively wide concentration range.     

基于灰作用量优化的分数阶灰色预测模型研究

针对小样本振荡型数据序列的灰建模预测问题,提出基于灰作用量优化的分数阶GM(1,1|sin+cos)预测模型.在已有经典GM(1,1|sin)的基础上,一方面,将一阶累加灰生成拓展为分数阶累加灰生成,使得构建的模型更加符合新信息优先原理.另一方面,将灰作用量b_1 sin pk+b_2改进为b_1 sin pk+b_2 cos qk+b_3,其作用是通过增加余弦函数项cos qk,使得具有两个不同周期的运动项cos qk与b_1 sin pk+b_2叠加复合之后,能够生成更加贴近于振荡原始序列趋势和特征的时间响应序列,从而得到拟合精度较高的灰色模型.其次,对建模过程的时间响应式、模型参数p和q的最优估计问题进行了研究,构造了最优累加阶数r、参数p和q的粒子群优化算法,得到的优化模型实现了某些类型振荡序列较高精度的预测.实际数据例子结果表明,所建立的模型能够较好地模拟常见振荡型数据序列的波动趋势和特征,具有较强的适用性和拟合性能.     

焙烧温度对TiO2柱撑膨润土结构、吸附及光催化性能的影响

采用酸性溶胶法合成了TiO2柱撑膨润土(Ti-Na-MMT), 采用XRD, FTIR, TG-DTA, BET和DRS等技术, 研究了焙烧温度对Ti-Na-MMT结构和处理偶氮染料废水性能的影响. 结果表明, 所制备的Ti-Na-MMT具有较好的热稳定性, 经773 K热处理后, 其结构仍基本保持不变. 随着焙烧温度的升高, 晶面间距逐渐减少. Ti-Na-MMT的比表面积、孔体积、孔径分布等特征以及TiO2晶粒粒径与煅烧温度有关; 在473 K下, 焙烧制备的Ti-Na-MMT BET的比表面积和最大孔容最大, 平均孔径和TiO2粒径最小; 随着焙烧温度的进一步升高, TiO2粒子发生团聚, 粒径变大, 从而Ti-Na-MMT的比表面积和最大孔容减小, 而其平均孔径呈增大趋势. DRS结果表明, 在473 K下焙烧制备的Ti-Na-MMT对光的吸收能力最强. 焙烧温度对Ti-Na-MMT的吸附性能和光催化活性的影响规律一致, 这表明吸附和光催化过程存在一定的协同作用. 473 K时制备的Ti-Na-MMT表现出的吸附和光催化活性均最强.     

Novel Studies about the Electrooxidation of a Deoxynivalenol (DON) Mycotoxin Reduction Product Adsorbed on Glassy Carbon and Carbon Paste Electrodes

A novel and fast square‐wave adsorptive anodic stripping voltammetric procedure on glassy carbon and carbon paste electrodes is described for the indirect trace quantitation of deoxynivalenol (DON) mycotoxin that frequently contaminates soya and foodstuff. The in situ homogeneous reduction of the toxin by product/s of dissolved oxygen electroreduction in pH 8 buffer solution makes the quantitation of DON possible through a simple electroanalytical technique. Moreover, its potential use for the analysis of real samples was demonstrated using a soya flour sample spiked with DON without previous separating procedures. The DON detection limits were 3.6 and about 6 ppb from standard solutions and soya flour matrix, respectively.     

Al(III) and Fe(III) Balance in Hemodialysis Treatment Assessed via Fluid Analysis by Adsorptive Stripping Voltammetry and UV Sample Digestion

Simultaneous determination of Al(III) and Fe(III) in posthemodialysis fluids was investigated by the Adsorptive stripping voltammetry of solochrome violet metal complexes. The adsorption of the complexes on the mercury electrode (HMDE) was investigated by out of phase altenating current voltammetry in presence of the main matrix interfering species. Sample digestion by UV irradiation was investigated to overcome the matrix interference. The proposed method was valid for real posthemodialysis samples containing or not Desferrioxamine B. Detection limits of 1.4 and 1.8 μg L^?1 were calculated for Al(III) and Fe(III), respectively. Recoveries ranging from 88.1 to 106.3% were obtained from spiking experiments.     

Redox Speciation of Inorganic Arsenic in Water and Saline Samples by Adsorptive Cathodic Stripping Voltammetry in the Presence of Sodium Diethyl Dithiocarbamate

This paper describes a new voltammetric procedure for the inorganic speciation of As(III) and As(V) in water samples. The procedure is based on the chemical reduction of arsenate [As(V)] to arsenite [As(III)] followed by the voltammetric determination of total arsenic as As(III) at the hanging mercury drop electrode (HMDE) by adsorptive cathodic stripping voltammetry (AdCSV) in the presence of sodium diethyl dithiocarbamate (SDDC). The reduction step involved the reaction with a mixture of Na₂S₂O₅ and Na₂S₂O₃ in the concentrations 2.5 and 0.5 mg mL^?1, respectively, and the sample heating at 80 °C for 45 min. The linear range for the determination of total arsenic as As(III) in the presence of SDDC was between 5 and 150 μg L^?1 for a deposition time of 60 s (r=0.992). A detection limit of 1.05 μg L^?1 for total As was calculated for the method in water samples using a deposition time of 60 s. The detection limits of 4.2 μg L^?1 and 15.0 μg L^?1 for total As in seawater and dialysis concentrates, respectively, were calculated using a deposition time of 60 s. The relative standard deviations calculated were 2.5 and 4.0% for five measurements of 20 μg L^?1 As(V) as As(III) in water and dialysis concentrates, respectively, after chemical reduction under optimized conditions. The method was applied for the determination of As(III) and total As in samples of dialysis water, mineral water, seawater and dialysis concentrates. Recovery values between 86.0 and 104.0% for As(III) and As(V) added to the samples prove the satisfactory accuracy and applicability of the procedure for the arsenic monitoring.