On-line HPLC combined with multivariate statistical process control for the monitoring of reactions

On-line high performance liquid chromatography is used to monitor a steady state reaction over 35.2 h, with 197 chromatograms recorded as the reaction progresses. For each chromatogram, peaks are detected, baseline corrected, aligned and integrated to provide a peak table consisting of the intensities of 19 peaks, two corresponding to the reactants, one to the product and one to the solvent, the remaining being impurities, by-products or intermediates. D-charts and Q-charts from multivariate statistical process control are applied to the data to determine which samples are out of control and also provide diagnostic insight into why these samples are problematic. The D-chart is best at looking at overall performance issues such as problems with mixing or difficulties with instrument operation, whereas the Q-charts are best at detecting impurities during the reaction.     

On-line purge and trap gas chromatography for monitoring of trihalomethanes in drinking water distribution systems

A method using an automated on-line purge and trap gas chromatograph with a dry electrolytic conductivity detector (DELCD) has been developed for monitoring four regulated trihalomethanes in drinking water distribution systems. This analyzer samples trihalomethanes from drinking water by pervaporation through a silicone capillary membrane contained within a gas extraction cell (GEC) followed by preconcentration using an adsorbent trap. Trihalomethanes are subsequently desorbed from the trap onto a capillary column, separated and detected. The analyzer operates in real-time, samples directly from the drinking water distribution system and is fully automated. The optimization, operation, and evaluation of the analyzer and method are discussed. Method detection limits (MDL) are less than 1.0 μg L⁻¹ with acceptable estimates for accuracy, and precision. The results from two on-line monitoring studies in chlorinated and chloraminated distribution systems are presented. The performance of the method is compared directly to United Stated Environmental Protection Agency Method 502.2 and shows a very slight, but acceptable bias.     

Determination of reducing ends with flow injection analysis with amperometric detection: application to enzyme-hydrolysed methyl cellulose

A novel method for detection of reducing ends of sugars is proposed, based on the use of as the oxidant in combination with amperometric detection and flow injection analysis (FIA). The method is very sensitive, giving values of <10 μM for the limit of detection for a series of mono- and oligosaccharides. Samples can be analysed every 30 s, and injection can be made fully automated, making it possible to perform on-line analysis of polysaccharide samples subjected to hydrolysis. Three methylcelluloses (MC) of different qualities were hydrolysed with three different glucanases, and the concentrations of reducing ends prior to, during and after hydrolysis were determined. Differences were observed between the results obtained using different combinations of enzymes and MCs, which revealed different selectivities of the various enzymes for the different substrates. One MC was also hydrolysed and analysed in real-time for three hours. The method proposed is superior to many of the standard methods used today, which require manual labour and have a lower sensitivity. Figure Set-up used for the instrumentation in the FIA system with automated injection. A pump delivers the reaction solution to the autosampler, where the samples are injected; the sample and solution react in a temperature-controlled random coil and the response is detected using an amperometric detection cell     

Multi-analyte SPR immunoassays for environmental biosensing of pesticides

Multi-analyte detection of environmentally relevant pesticides is performed by using a two-channelled surface plasmon resonance (SPR) biosensor. The special design of the SPR instrument allows the determination of several analytes (DDT, chlorpyrifos and carbaryl) via different immobilization formats. First, simultaneous pesticide monitoring is possible by flowing chlorpyrifos, carbaryl or DDT samples separately over each channel of the SPR system, wherein their corresponding recognition element was previously immobilized. The second approach is based on the multiple and combined immobilization of several analyte recognition elements on the sensing surface of one individual flow cell. In this format, the analysis time for all three pesticides varied from 40 to 60 min depending on the number of regeneration cycles. In most cases, similar detection limits were attained for the target analyte irrespective of the assay format, with sensitivity values at the nanogram per litre level (18–50 ng L⁻¹). The assay reproducibility was proved through the repeated use of the same sensor surface for over more than 200 assay cycles, whereas the absence of biosensor response to non-related analytes showed the specificity and reliability of the analysis. The SPR instrument, including optics, electronics and microfluidics, is already commercialised by the company SENSIA, SL.     

Determination of human erythropoietin by on-line immunoaffinity capillary electrophoresis: a preliminary report

Several CE methodologies have been described for the analysis of rHuEPO in concentrated solutions, but the inherently limited concentration sensitivity of CE precludes the detection of EPO at the levels found in biological fluids. In this work, we have investigated an on-line immunoaffinity solid-phase extraction capillary electrophoresis (IA-CE) methodology for the selective preconcentration of EPO in diluted solutions. The preliminary results obtained using a custom-made immunoaffinity sorbent prepared from an anti-human EPO polyclonal antibody and glutaraldehyde–glass beads show the potential of this novel approach. The summarized findings are discussed in detail as a starting point for our ongoing investigations.     

Flow injection for the determination of Se(IV) and Se(VI) by hydride generation atomic absorption spectrometry with microwave oven on-line prereduction of Se(VI) to Se(IV)

An on-line flow injection system has been developed for the selective determination of Se(IV) and Se(VI) in citric fruit juices and geothermal waters by hydride generation atomic absorption spectrometry with microwave-aided heating prereduction of Se(VI) to Se(IV). The samples and the prereductant solutions (4 mol l⁻¹ HCl for Se(IV) and 12 mol l⁻¹ HCl for Se(VI)) which circulated in a closed-flow circuit were injected by means of a time-based injector. This mixture was displaced by a carrier solution of 1% v/v of hydrochloric acid through a PTFE coil located inside the focused microwave oven and mixed downstream with a borohydride solution to generate the hydride. The linear ranges were 0–120 and 0–100 μg l⁻¹ of Se(IV) and Se(VI), respectively. The detection limits were 1.0 μg l⁻¹ for Se(IV) and 1.5 μg l⁻¹ for Se(VI). The precision (about 2.0–2.5% RSD) and recoveries (96–98% for Se(IV) and 94–98% for Se(VI)) were good. Total selenium values were also obtained by electrothermal atomic absorption spectrometry which agreed with the content of both selenium species. The sample throughput was about 50 measurements per hour. The main advantage of the method is that the selective determination of Se(IV) and Se(VI) in citric fruit juices and geothermal waters is performed in a closed system with a minimum sample manipulation, exposure to the environment, minimum sample waste and operator attention.     

在线螯合树脂富集火焰原子吸收光谱法测定天然水体中铜和锌

对螯合树脂富集——火焰原子吸收光谱法测定天然水体中痕量铜和锌的在线富集条件、干扰因素等进行研究,在线富集倍数达到两个数量级,在灵敏度与石墨炉原子吸收光谱法相当情况下,提高了测定准确度。     

碳纤维复合材料的激光清洗等离子体光谱在线检测研究

近年来碳纤维复合材料（CFRP）由于性能优异,受到工业领域广泛关注。采用激光清洗技术预处理碳纤维复合材料表面的污染物和环氧树脂等杂质,有利于改善碳纤维复合材料表面性能,提高碳纤维复合材料胶接界面的结合强度。在线检测激光清洗过程,实时判断碳纤维复合材料的表面清洗质量,是保证激光清洗效果的关键环节,也是激光清洗装置自动化、集成化的核心技术。激光诱导等离子体光谱技术可以快速分析材料表面元素变化,实现在线检测激光清洗表面状态,在激光清洗领域有很广的应用前景。采用Nd∶YAG高能量脉冲激光器产生的1 064 nm激光在空气环境中诱导产生等离子体,利用改进型光栅光谱仪(ME5000)获取等离子体光谱,在线检测激光清洗碳纤维复合材料。研究外界空气环境对等离子体光谱检测结果的影响,发现350~700 nm波段的元素谱线可用于碳纤维复合材料表面物质成分分析;采用电子扫描显微镜观测的激光清洗表面形貌和X射线电子能谱仪测得的元素变化共同表征等离子体光谱检测的有效性,通过采集不同激光能量以及不同作用次数的等离子体光谱图,获得碳纤维复合材料表层树脂物质通过激光单次清洗干净的阈值,研究激光清洗质量与激光诱导等离子体谱线成分及其强度变化的关系。结果表明：在获取的激光诱导等离子体光谱中,光谱图中谱线波长在393.3 nm的S(Ⅱ)和589.5 nm的S(Ⅱ)谱线可有效在线表征碳纤维复合材料表面清洗质量;激光单次去除干净表面环氧树脂的阈值为10.68 mJ;低激光能量时需要清洗多次可以去除干净表面树脂;高激光能量时清洗单次可使表面树脂去除干净,多次清洗易造成基体损伤。实验结果为激光清洗碳纤维复合材料的智能集成化应用提供工艺依据和技术支持。     

基于辐射光谱法的高温颗粒辐射传热参数在线测量方法研究

针对在高温燃烧环境中的颗粒辐射传热问题,基于普朗克辐射定律,提出了用于高温颗粒辐射传热参数在线测量的辐射光谱法,根据高温颗粒可见波段辐射光谱随波长变化情况,通过参数拟合方法直接获得颗粒温度及辐射强度等辐射传热参数。为验证该方法测量准确性,搭建了高温黑体炉辐射测量系统,实验测量结果显示：温度测量值与设定温度相对偏差小于3%;辐射强度测量值与理论计算值相对偏差小于5%。以此为基础,设计了应用于高温燃烧环境下的颗粒辐射传热参数测量的水冷结构探针,并利用该探针开展了高温燃烧环境气固两相流200～1 100 nm波段辐射光谱测量,基于上述方法,直接获得了高温颗粒温度、辐射强度等辐射传热参数沿截面分布情况,有效剥离了高温气体对流传热的影响,为高温颗粒辐射传热研究提供数据支撑。     

番茄碰伤和可溶性固形物近红外光谱同时在线检测

可溶性固形物和碰伤是影响番茄品质的两个主要因素。研究的目的是探索可见近红外漫透射光谱同时在线检测番茄碰伤和可溶性固形物的可行性。在单通道送果速度5个每秒条件下,采集番茄近红外漫透射光谱。对比分析碰伤与正常番茄样品的近红外漫透射光谱特性,结果表明,碰伤与正常番茄样品的近红外漫透射光谱在光强上存在明显差异,碰伤果光强要强于正常果,其原因可能是碰伤后果肉变软,透光性变强;在650和675 nm处碰伤果比正常果要多两个吸收峰,可能是碰伤后,番茄表皮颜色发生变化所致。选取贡献率占比最多的前三个主成数,对正常果与碰伤果近红外漫透射光谱主成分定性分析,正常果与碰伤果不能有效聚类,故近红外漫透射光谱主成分定性分析效果不明显,需选择建立高维近红外漫透射光谱定性判别模型。故建立了碰伤番茄样品的近红外漫透射光谱偏最小二乘定性判别模型,误判率为0%,能正确判别碰伤果,故选用碰伤番茄样品的近红外漫透射光谱偏最小二乘定性判别模型作为番茄碰伤果在线剔除分选模型。通过对未参与建模的样品进行验证,能正确识别出碰伤果。经近红外漫透射光谱偏最小二乘定性判别模型剔除碰伤果后,按照可溶性固形物指标进行分级。分别使用全部波段和606～850 nm的波段进行建模预处理,且对全部波段和606～850 nm波段光谱进行2阶导数预处理,前后平滑设为9,利用连续投影算法与遗传算法优选可溶性固形物的光谱建模变量,对比发现,利用未经算法筛选过的606～850 nm波段光谱变量进行建模,效果最好,建立了可溶性固形物在线检测模型,预测集均方根误差为0.43 Brix°。采用未参与建模的样品进行碰伤和可溶性固形物同时在线检测验证,碰伤样品的分选准确率达96%,可溶性固形物样品的分选准确率达91%。表明：番茄碰伤和可溶性固形物近红外漫透射光谱同时在线检测是可行的。