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Boolean experimental designs 布尔实验设计
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000131
J. Goupy
Experimental designs are generally interpreted using a polynomial mathematical model. But this mathematical model is not always appropriate and may sometimes not describe the phenomenon studied. Boolean experimental designs can conceived if the factors and the response can be treated as boolean variables. The results provided are then intrepreted using Boolean algebra. We have treated a real example, the setting of an instrument for analytical chemistry using both classical and boolean interpretations. The classical treatment give surprising results, with one strong interaction between two non-influent factors and interactions of order 3 and 4. The boolean interpretation gives comprehensive results and provides simple rules for the instrument settings. Boolean modelling for the responses of an experimental design opens a new and complementary approach to the classical method that uses generally mathematical polynoms. In some cases it can provide a better interpretation of the phenomenon than the ordinary methodology.
实验设计通常用多项式数学模型来解释。但这种数学模型并不总是合适的,有时可能无法描述所研究的现象。如果因子和响应可以被视为布尔变量,则可以设想布尔实验设计。然后使用布尔代数解释所提供的结果。我们已经处理了一个真实的例子,即使用经典和布尔解释设置分析化学仪器。经典处理给出了令人惊讶的结果,两个非影响因素之间有一个强相互作用,3阶和4阶相互作用。布尔解释给出了全面的结果,并为仪器设置提供了简单的规则。布尔模型的反应实验设计打开了一个新的和补充的方法,经典方法,一般使用数学多项式。在某些情况下,它可以提供比普通方法更好的解释现象。
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引用次数: 1
Desirability approach for optimisation of electrothermal atomic absorption spectrometry factors in iron determinations 电热原子吸收光谱法测定铁的最佳化方法
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000133
S. Salomon, P. Giamarchi, A. Bihan
We report here on from determination in sea matrix by electrothermal atomic absorption spectrometry. We optimised the experimental conditions of the spectroscopic factors, i.e. entrance monochromator slit height, slit width and lamp current, and of the electrothermal factors, i.e. calcination temperature, calcination duration, atomisation temperature and injected volume, since these two groups are independent. Because of the technical constraints occuring on our experimental domain of study we built a D-optimal experimental design to conduct these optimisations. We monitored three experimental responses, i.e. the standard deviation of the instantaneous specific absorbance, the specific integrated absorbance and the non-specific integrated absorbance. The three of them clearly showed an optimum in three opposed experimental conditions. Consequently, a desirability transformation of the experimental responses permitted us to obtain a better compromise. We, finally, computed a new experimental response which took the raw measurements into account to directly estimate the limits of detection. The optimisation of this computed response showed us that the lowest detection limit was obtained under the same experimental compromise than the one suggested by the desirability study. This result allowed us to validate the computed response as an interesting optimisation criterion in electrothermal atomic absorption spectrometry.
本文报道了电热原子吸收光谱法测定海洋基质中的硫化氢。我们优化了光谱因素,即入口单色器狭缝高度、狭缝宽度和灯电流,以及电热因素,即煅烧温度、煅烧时间、雾化温度和注入体积的实验条件,因为这两组是独立的。由于我们的实验研究领域存在技术限制,我们建立了一个d -最优实验设计来进行这些优化。我们监测了瞬时比吸光度、比积分吸光度和非比积分吸光度的标准差三种实验响应。在三种相反的实验条件下,它们都清楚地显示出最优。因此,实验反应的可取性转换使我们能够获得更好的折衷方案。最后,我们计算了一个新的实验响应,该响应考虑了原始测量值,以直接估计检测限。该计算响应的优化表明,在相同的实验妥协下获得的最低检测限比可取性研究建议的最低检测限。这一结果使我们能够验证计算响应作为电热原子吸收光谱的一个有趣的优化准则。
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引用次数: 7
Prediction of odours of aliphatic alcohols and carbonylated compounds using fuzzy partition and self organising maps (SOM) 用模糊划分和自组织图(SOM)预测脂肪族醇和羰基化合物的气味
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000139
K. Audouze, F. Ros, M. Pintore, J. Chrétien
A set of 114 olfactory molecules divided into fruity, ethereal and camphoraceous compounds, was submitted to an analysis by Kohonen Neural Networks, also known as Self Organising Map (SOM). The compounds are represented in a hyperspace derived from their molecular descriptors and SOM gives a useful projection of this hyperspace onto a 2D map. Owing to the complexity of the olfaction mechanism, evidenced by the fact that one compound can exhibit simultaneously different properties, SOM alone is unable to take into account the olfaction diversity of the original 114 compounds, Then, a Fuzzy Partition method was applied on the Kohonen map previously developed. The obtained results allowed delineating different representative zones for the three odours, expressing more closely the olfactory richness. The ability of the Hybrid System combining SO and Fuzzy Partition to model the three odours was validated by dividing the 114 compounds into a training set and a test set, including 86 and 28 molecules, respectively. The most important olfactory characteristics were reproduced satisfactorily for the entire test set compounds.
一组114种嗅觉分子被分为果味、空灵和樟脑化合物,提交给Kohonen神经网络(也称为自组织图(SOM))进行分析。这些化合物在由其分子描述符派生的超空间中表示,SOM给出了该超空间在二维地图上的有用投影。由于嗅觉机制的复杂性,一种化合物可以同时表现出不同的性质,单独的SOM无法考虑原始114种化合物的嗅觉多样性,因此,将模糊划分方法应用于先前开发的Kohonen图。所获得的结果可以划定三种气味的不同代表区域,更接近地表达嗅觉丰富度。通过将114种化合物划分为训练集和测试集(分别包含86和28个分子),验证了混合系统结合SO和模糊划分对三种气味建模的能力。最重要的嗅觉特征在整个测试组化合物中都得到了令人满意的再现。
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引用次数: 10
For unitary "theory" of Chemometrics 对于化学计量学的统一“理论”
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000130
J. Chrétien
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引用次数: 0
Characterisation of the staphylococcal enterotoxin research method in a dairy product 乳制品中葡萄球菌肠毒素研究方法的特点
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000137
L. Macaluso, C. Lapeyre
The staphylococcal enterotoxin research method is a quantitative method, involving a sample preparation and an imunoenzymatic detection. In order to estimate its performance characteristics, a method characterisation is carried out with a single dairy product and for staphyloccal enterotoxin A. Statistical analysis shows that the method is linear over a contamination interval between 0 - 1 ng SEA per gram of cheese. The limit of detection is about 0.01 ng SEA per gram of cheese and the limit of quantification is about 0.04 ng SEA per gram of cheese. The intra laboratory repeatability and intermediate precision are estimated on two levels of contamination. The repeatability coefficient of variation is included between 3.1 % and 6.2 %, the intermediate precision coefficient of variation is included between 4.7 % and 11.0 %.
葡萄球菌肠毒素研究方法是一种定量方法,涉及样品制备和免疫酶检测。为了估计其性能特征,对单一乳制品和葡萄球菌肠毒素a进行了方法表征。统计分析表明,该方法在每克奶酪0 - 1 ng SEA的污染区间内是线性的。检测限约为0.01 ng SEA / g奶酪,定量限约为0.04 ng SEA / g奶酪。实验室内的可重复性和中间精度是在两个污染水平上估计的。重复性变异系数在3.1% ~ 6.2%之间,中间精密度变异系数在4.7% ~ 11.0%之间。
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引用次数: 7
■ Development of an HPLC method for the determination of phenolic by-products: optimisation of the separation by means of the experimental designs methodology ■开发测定酚类副产物的高效液相色谱方法:通过实验设计方法优化分离
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000135
B. Motamed, J. Böhm, D. Hennequin, H. Texier, R. Mosrati, D. Barillier
The separation of nine phenolic by-products was realized by Reverse Phase HPLC using a binary gradient water-acetic acid/acetonitrile whose elution program was optimized by means of the experimental design methodology. Significant factors are: the initial isocratic elution time, the gradient running time and the gradient curvature. Modelization was made by using a central composite plane in 17 experiments. Responses were measured by the resolution between four couples of components: p-hydroxybenzaldehyde, acetovanilone - acetosyringone and acetosyringone - benzoic acid. According to the resulting quatraic model, an optimized program of gradient elution was set up and successfully tested as it gives satisfactory separations (isocratic elution time: 8 min; gradient running time from 1 % to 25 % acetonitrile: 40 min; linear gradient; room temperature).
采用水-乙酸/乙腈二元梯度反相高效液相色谱法对9种酚类副产物进行了分离,并通过实验设计方法优化了洗脱程序。影响因素有:初始等压洗脱时间、梯度运行时间和梯度曲率。17次试验采用中心复合平面进行建模。采用对羟基苯甲醛、乙酰香草酮-乙酰丁香酮和乙酰丁香酮-苯甲酸四对组分的分辨法测定了反应。根据所得的二次模型,建立了优化的梯度洗脱程序,并成功地进行了测试,获得了满意的分离效果(等压洗脱时间:8 min;从1%乙腈到25%乙腈梯度运行时间:40 min;线性梯度;室温)。
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引用次数: 3
Experimental design optimization of chromatographic separation for polycyclic aromatic hydrocarbons in vegetable oils 植物油中多环芳烃色谱分离的实验设计优化
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000134
A. Dorthe, J.-L. Ramberti, A. Thienpont
HPLC with an electron acceptor stationary phase called tetrachlorophtalimidopropyl (TCP) was used to separate Polycyclic Aromatic Hydrocarbons (PAHs) in vegetable oil without any preparation of the samples being studied. Using an hexane/methylterbutylether mobile phase then an hexane/dichloromethane one, it was possible to separate triglycerids and tocopherols from PAH fraction. A fractional factorial design 2 7-4 was used to perform the fractionating then the separation of the PAH fraction with the minimum of experiments. Seven factors were examined and the chromatography quality was evaluated through four answers. Finally, the predictions of the models and the characteristics of the separation were compared: the agreement was very good.
采用电子受体固定相四氯酞酰丙基(TCP)高效液相色谱(HPLC)分离植物油中的多环芳烃(PAHs),而无需对被研究样品进行任何制备。采用正己烷/甲基叔丁醚流动相和正己烷/二氯甲烷流动相,可以从多环芳烃馏分中分离出甘油三酯和生育酚。采用分数析因设计2 7-4进行分馏,以最小的实验次数分离多环芳烃馏分。考察了7个因素,通过4个答案评价色谱质量。最后,将模型的预测结果与分离特性进行了比较,结果吻合较好。
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引用次数: 7
Central composite design and optimization by multiresponse analysis of octacalcium phosphate synthesis 八磷酸钙合成中心复合设计及多响应分析优化
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000132
J. Heughebaert, A. Lebugle, F. Vu, R. Phan-tan-luu
Synthesis of octacalcium phosphate (OCP) by hydrolysis of brushite was studied using a 3 block central composite design including 4 factors and 6 responses. Analysis of the responses allowed the definition of one set of experimental conditions in which OCP was obtained with the highest overall desirability (87.6 %).
采用4因素6响应的3块中心复合设计研究了水解法合成磷酸八钙(OCP)的工艺条件。对反应的分析允许定义一组实验条件,在这些条件下,OCP获得了最高的总体可取性(87.6%)。
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引用次数: 4
Chemometrics applied to the optimization of the preparation of hydrotropes for detergents starting from BTX fraction of natural gas 化学计量学应用于以天然气BTX馏分为原料制备洗涤剂用亲水物的优化
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000138
A. Kamoun, M. Chaâbouni
Manufacturers of cleaning products use hydrotopes to increase the solubility of surfactants in concentrated liquid detergents. In contrast to benzenesulfonate, alkylbenzenesulfonates with short chains (n < 4) are used as hydrotopes. In this paper, we present the results obtained from the preparation of toluenesulfonic and xylenesulfonic acids by selective sulfonation of toluene and xylenes present in the BTX fraction (benzene, toluene, xylenes) of the Tunisian natural gas MISKAR deposit. Chemometrics were applied to determine the optimal experimental conditions for the selective sulfonation of toluene and xylenes, we use a 2 IV 6-2 fractional factorial design in addition to several analytical methods (GC, HPLC, FTIR...). These conditions were found to be: the use of concentrated sulfuric acid as sulfonating agent, the azeotropic elimination of water during the reaction, a temperature of 110 °C, a duration of 9 hours and a molar ratio of sulfuric acid to toluene plus xylenes of 0.8. The application of all of these experimental conditions gives an aqueous phase with a composition that can be used very effectively as hydrotope agent in liquid detergents. This conclusion was the outcome from comparing the effect of our product on the clear point of a typical premium formulation of a liquid detergent to that of sodium xylenesulfonates, the most important hydrotope for light duty liquids.
清洁产品制造商使用水合物来增加表面活性剂在浓缩液体洗涤剂中的溶解度。与苯磺酸盐相反,短链(n < 4)的烷基苯磺酸盐被用作氢基。本文介绍了突尼斯MISKAR天然气矿床BTX馏分(苯、甲苯、二甲苯)中甲苯和二甲苯选择性磺化制备甲苯磺酸和二甲苯磺酸的结果。采用化学计量学方法确定了甲苯和二甲苯选择性磺化反应的最佳实验条件,并采用了2 IV 6-2分数析因设计和多种分析方法(GC、HPLC、FTIR等)。得到的条件为:以浓硫酸为磺化剂,反应时共沸消水,反应温度110℃,反应时间9小时,硫酸与甲苯加二甲苯的摩尔比为0.8。所有这些实验条件的应用给出了一种水相组合物,该组合物可以非常有效地用作液体洗涤剂中的水基剂。这一结论是通过比较我们的产品对液体洗涤剂的典型优质配方的澄清点的影响与二甲苯磺酸钠的效果的结果,二甲苯磺酸钠是轻质液体最重要的水相。
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引用次数: 4
■ Modeling properties of water-based paints dried by microwaves from the design and analysis of a mixture-process experiment ■通过混合工艺实验的设计和分析,对微波干燥水性涂料的特性进行建模
Pub Date : 2000-09-01 DOI: 10.1051/ANALUSIS:2000136
S. Barra, F. Boulanger, A. Trapani, D. Cabrol-Bass
Heightened environmental awareness has lead major paint companies to develop environmentally friendly waterborne coatings. Recently, microwave radiation has been used to accelerate the drying of industrial waterborne coatings. The aim of this study was to develop statistical models to optimise the performance of microwave radiation dried paints. This paper explores the effects and interactions between the major components of the paints and examines how these interactions affect the properties of the paints. A combined mixture with a double factorial design, including several types of components, has been used in this work. Eight paint properties and three microwave energy levels have been considered on each point of the experimental design. A computer simulation consisting of 12 separate models has been developed that accurately predicts the performance of paint.
环保意识的增强促使各大涂料公司开发环保型水性涂料。近年来,微波辐射已被用于加速工业水性涂料的干燥。本研究的目的是建立统计模型来优化微波辐射干燥涂料的性能。本文探讨了涂料的主要成分之间的作用和相互作用,并研究了这些相互作用如何影响涂料的性能。在这项工作中使用了双因子设计的组合混合物,包括几种类型的成分。在实验设计的每个点上考虑了8种涂料性能和3种微波能级。一个由12个独立模型组成的计算机模拟已经被开发出来,可以准确地预测油漆的性能。
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引用次数: 0
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Analusis
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