Differentiation of red wines using an electronic nose based on surface acoustic wave devices

An electronic nose, utilizing the principle of surface acoustic waves (SAW), was used to differentiate among different wines of the same variety of grapes which come from the same cellar. The electronic nose is based on eight surface acoustic wave sensors, one is a reference sensor and the others are coated by different polymers by spray coating technique. Data analysis was performed by two pattern recognition methods; principal component analysis (PCA) and probabilistic neuronal network (PNN). The results showed that electronic nose was able to identify the tested wines.     

A novel approach for honey pollen profile assessment using an electronic tongue and chemometric tools

Nowadays the main honey producing countries require accurate labeling of honey before commercialization, including floral classification. Traditionally, this classification is made by melissopalynology analysis, an accurate but time-consuming task requiring laborious sample pre-treatment and high-skilled technicians. In this work the potential use of a potentiometric electronic tongue for pollinic assessment is evaluated, using monofloral and polyfloral honeys. The results showed that after splitting honeys according to color (white, amber and dark), the novel methodology enabled quantifying the relative percentage of the main pollens (Castanea sp., Echium sp., Erica sp., Eucaliptus sp., Lavandula sp., Prunus sp., Rubus sp. and Trifolium sp.). Multiple linear regression models were established for each type of pollen, based on the best sensors' sub-sets selected using the simulated annealing algorithm. To minimize the overfitting risk, a repeated K-fold cross-validation procedure was implemented, ensuring that at least 10–20% of the honeys were used for internal validation. With this approach, a minimum average determination coefficient of 0.91 ± 0.15 was obtained. Also, the proposed technique enabled the correct classification of 92% and 100% of monofloral and polyfloral honeys, respectively. The quite satisfactory performance of the novel procedure for quantifying the relative pollen frequency may envisage its applicability for honey labeling and geographical origin identification. Nevertheless, this approach is not a full alternative to the traditional melissopalynologic analysis; it may be seen as a practical complementary tool for preliminary honey floral classification, leaving only problematic cases for pollinic evaluation.     

Monitoring storage time and quality attribute of egg based on electronic nose

The objective of this study was to investigate the potential of an electronic nose (E-nose) technique for monitoring egg storage time and quality attributes. An electronic nose was used to distinguish eggs under cool and room-temperature storage by means of principal component analysis (PCA), linear discriminant analysis (LDA), BP neural network (BPNN) and the combination of a genetic algorithm and BP neural network (GANN). Results showed that the E-nose could distinguish eggs of different storage time under cool and room-temperature storage by LDA, PCA, BPNN and GANN; better prediction values were obtained by GANN than by BPNN. Relationships were established between the E-nose signal and egg quality indices (Haugh unit and yolk factor) by quadratic polynomial step regression (QPSR). The prediction models for Haugh unit and yolk factor indicated a good prediction performance. The Haugh unit model had a standard error of prediction of 3.74 and correlation coefficient 0.91; the yolk factor model had a 0.02 SEP and 0.93 correlation coefficient between predicted and measured values respectively.     

Rapid discrimination of slimming capsules based on illegal additives by electronic nose and flash gas chromatography

The discrimination of counterfeit and/or illegally manufactured medicines is an important task in the pharmaceutical industry for pharmaceutical safety. In this study, 22 slimming capsule samples with illegally added sibutramine and phenolphthalein were analyzed by electronic nose and flash gas chromatography. To reveal the difference among the different classes of samples, principal component analysis and linear discriminant analysis were employed to analyze the data acquired from electronic nose and flash gas chromatography, respectively. The samples without illegal additives can be discriminated from the ones with illegal additives by using electronic nose or flash gas chromatography data individually. To improve the performance of classification, a data fusion strategy was applied to integrate the data from electronic nose and flash gas chromatography data into a single model. The results show that the samples with phenolphthalein, sibutramine and both can be classified well by using fused data.     

Electronic nose based on metal oxide semiconductor sensors as a fast alternative for the detection of adulteration of virgin olive oils

An “electronic nose” has been used for the detection of adulterations of virgin olive oil. The system, comprising 12 metal oxide semiconductor sensors, was used to generate a pattern of the volatile compounds present in the samples. Prior to different supervised pattern recognition treatments, feature selection techniques were employed to choose a set of optimally discriminant variables. Linear discriminant analysis (LDA), quadratic discriminant analysis (QDA) and artificial neural networks (ANN) were applied. Excellent results were obtained in the differentiation of adulterated and non-adulterated olive oils and it was even possible to identify the type of oil used in the adulteration. Promising results were also obtained as regards quantification of the percentages of adulteration.     

A useful approach for the differentiation of wines according to geographical origin based on global volatile patterns

In this study, the feasibility of solid‐phase extraction combined with gas chromatography and mass spectrometry in tandem with partial least squares discriminant analysis was evaluated as a useful strategy to differentiate wines according to geographical origin (Azores, Canary and Madeira Islands) and types (white, red and fortified wine) based on their global volatile patterns. For this purpose, 34 monovarietal wines from these three wine grape‐growing regions were investigated, combining the high throughput extraction efficiency of the solid‐phase extraction procedure with the separation and identification ability. The partial least squares discriminant analysis results suggested that Madeira wines could be clearly discriminated from Azores and Canary wines. Madeira wines are mainly characterized by 2‐ethylhexan‐1‐ol, 3,5,5‐trimethylhexan‐1‐ol, ethyl 2‐methylbutanoate, ethyl dl ‐2‐hydroxycaproate, decanoic acid, 3‐methylbutanoic acid, and (E)‐whiskey lactone, whereas 3‐ethoxypropan‐1‐ol, 1‐octen‐3‐ol, (Z)‐3‐hexenyl butanoate, 4‐(methylthio)‐1‐butanol, ethyl 3‐hydroxybutanoate, isoamyl lactate, 4‐methylphenol, γ‐octalactone and 4‐(methylthio)‐1‐butanol, are mainly associated with Azores and Canary wines. The data obtained in this study revealed that solid‐phase extraction combined with gas chromatography and quadrupole mass spectrometry data and partial least squares discriminant analysis provides a suitable tool to discriminate wines, both in terms of geographical origin as well as wine type and vintage.     

A fluorescence ratiometric sensor for hypochlorite based on a novel dual-fluorophore response approach

A fluorescence ratiometric sensor for OCl⁻ has been developed based on a novel dual fluorophore response approach. The sensor molecule contains a coumarin fluorophore and a rhodamine fluorophore, and the two fluorophores are directly linked to an OCl⁻ recognition group. The structure of the sensor was characterized by ESI-MS, NMR, and X-ray crystallographic analysis. Upon treatment with OCl⁻, both fluorophores in the sensor responded simultaneously at two separate optical windows, with large enhancement of the fluorescence ratio (I₅₇₈/I₅₀₁) from 0.01 to 39.55. The fluorescence ratios for the sensor showed a good linearity with the concentration of OCl⁻ in the range of 0.2–40 μM and the detection limits is 0.024 μM (S N⁻¹ = 3). Investigation of reaction products indicated that the sensor reaction with OCl⁻ produced two new fluorescent molecules, which were responsible for the fluorescence changes in two optical windows. In addition, the sensor showed high selectivity to OCl⁻ over other reactive oxygen species, reactive nitrogen species, cations, and anions. The sensor has also been successfully applied to detection of OCl⁻ in natural water samples with satisfactory recovery.     

The influence of oxoG on the electronic properties of ds-DNA. Damage versus mismatch: A theoretical approach

The seed of life is concealed in the base sequence in DNA. This macromolecule is continuously exposed to harmful factors which can cause it damage. The stability of genetic information depends on the protein efficiency of repair systems. Glycosylases are the scouts which recognize and remove damaged bases. Their efficiency depends on how rapidly they recognize DNA lesions. One theory states that charge transfer is involved in protein cross talking through ds-DNA. For these reasons a comparative analysis of ds-oligo containing a mismatched base pair dA:::dG and a damaged dA::dG^OXO is proposed. Additionally, the electronic properties of the short ds-oligo in the context of non-equilibrated and equilibrated solvent modes were taken into theoretical consideration. All energetic calculations were performed at the M062x/6-31++G** level of theory, while for geometry optimized ONIOM methodology was used. The lowest adiabatic ionization potential was assigned for DNA containing a dA:dG^OXO pair. Moreover, the adiabatic electron affinity was assigned at the same level for the mismatched and lesioned ds-oligo. Surprisingly, in the non-equilibrated mode, a significantly higher vertical electro affinity was found for lesioned DNA. The higher VEA in a non-equilibrated solvent state supported faster recognition in the A:G^OXO base pair than A:G by MutY glycosylases under electron transfer mechanism.     

A simple model for predicting the electronic configuration of a dn ion in a tetragonally distorted octahedral environment

A simple, but general model which enables prediction of the electronic structure adopted by ad ⁿ ion in an axially distorted octahedron of ligands (D _4h) is described. The variousd ⁿ configurations (n = 1 to 9) are briefly reviewed with some recent results concerning the stabilization of unusual electronic configurations or oxidation states in oxides.     

On the influence of data noise and uncertainty on ordering of objects,described by a multi‐indicator system. A set of pesticides as an exemplary case

A priori in partial ordering methodology the input data are understood as exact and true values, which is denoted as the “original data matrix”. As such even minor differences between values are regarded as real. However, in real life data are typically associated with a certain portion of noise or uncertainty. Hence, introducing noise may cause changes in the overall ordering of objects. The present paper deals with the effects of data noise or uncertainties on the partial ordering of a series of objects, a series of obsolete pesticides being used as an illustrative example. The approach is fuzzy like, and partially ordered sets are obtained as function of noise. A main focus of the work is to identify the range in terms of noise, where the original partial order is retained. We call this range the “stability range”. It is demonstrated that by increasing data noise the range where the “original partial order” is obtained decreases. The original partial order is based on the original data matrix. Further, it is found that significant changes in the partial ordering appear outside of this stability range. The possible relation between data noise and the stability range is discussed on an empirical basis. Copyright © 2015 John Wiley & Sons, Ltd.     

A novel algorithm for linear multivariate calibration based on the mixed model of samples

We present a novel algorithm for linear multivariate calibration that can generate good prediction results. This is accomplished by the idea of that testing samples are mixed by the calibration samples in proper proportion. The algorithm is based on the mixed model of samples and is therefore called MMS algorithm. With both theoretical support and analysis of two data sets, it is demonstrated that MMS algorithm produces lower prediction errors than partial least squares (PLS2) model, has similar prediction performance to PLS1. In the anti-interference test of background, MMS algorithm performs better than PLS2. At the condition of the lack of some component information, MMS algorithm shows better robustness than PLS2.     

新的碲络合物的合成、性质与电子结构的研究

应用有机-水混合溶剂共热沉淀法,合成了一种新的白色固体细粉末Te2(OH)8(H2O)2Cl2,即[Te(OH)4(H2O)Cl]2双碲络合物,并用多种物理化学方法,对其组成和性质进行了测定.考察了温度、溶剂、反应时间等因素对其生成量及稳定性的影响,结果表明该络合物是很稳定的,具有许多有意义的性质.结合实验,在B3LYP/CEP-4G水平上对其几何构型进行了优化,得到了最佳稳定形态的电子结构,最低总能量为-5 553246×105kJ·mol-1,每个中心原子Te净电荷为1 998958e,表明是电子"授体",反馈给四个"受体"配位体HO上的O原子,分别为-0 221138e,-0 209388e,-0 221098e和-0 250985e,也表明该络合物是稳定的.比较合理地说明了实验结果.     

Mg助剂对Co/Mg/HZSM-5催化剂结构及其催化甲烷部分氧化制合成气性能的影响

采用XRD、TEM、H2-TPR、Raman、XPS和活性评价等方法, 研究了Mg助剂对Co/Mg/HZSM-5催化剂物理化学性质和甲烷部分氧化(POM)制合成气反应性能的影响. 研究发现, 在Co/HZSM-5催化剂中添加Mg助剂, 可有效地提高催化剂的催化活性和稳定性. 在750 ℃和空速1.0×10⁵ mL·h^-1·g^-1反应条件下, Co/Mg/HZSM-5在连续反应30 h的实验时间内催化活性稳定不变, 而Co/HZSM-5因其活性中心Co0转化生成CoAl2O4非活性相, 反应10 h后即迅速失活. 催化剂表征结果表明, 在Co/Mg/HZSM-5催化剂中钴物种除以Co3O4存在外, 一部分钴物种还与Mg助剂发生强相互作用生成较难还原的MgCo2O4, 由此导致还原后钴金属的分散度较高. 关联催化剂表征和活性评价结果, 讨论了催化剂结构与性能之间的关系.     

A novel approach for electromembrane extraction based on the use of silver nanometallic-decorated hollow fibers

A novel approach based on the use of nanometallic-decorated hollow fibers to assist electromembrane extraction is proposed. Microporous polypropylene hollow fibers, on which nanometallic silver was deposited, have been used for the first time as liquid membrane support in electromembrane extraction (EME). Different methods for the generation/deposition of silver nanoparticles (AgNPs) were studied. The best results were obtained with chemical reduction of silver nitrate using NaBH₄ in aqueous solution followed by direct deposition on the hollow fibers. The extraction performance of the new supports was compared with a previously developed EME procedure used for the extraction of selected non-steroidal anti-inflammatory drugs (NSAIDs), resulting in an increase in the extraction ratio by a factor of 1.2–2 with a 30% reduction in the extraction time. The new nanometallic-decorated supports open new possibilities for EME due to the singular properties of nanometallic particles, including chemical fiber functionalization.     

Syntheses and electronic properties of the nickel and palladium complexes of the octaethylporphyrin(M1)-(dihexylbithiophene)n-octaethylporphyrin(M2) system [OEP(M1)-(DHBTh)n-OEP(M2)] connected with the diacetylene linkage. A methodology for molecular design of the particular electronic structure

The palladium complexes of highly extended π-electronic conjugation system, octaethylporphyrin(Pd)-(dihexylbithiophene)_n-octaethylporphyrin(Pd) [OEP(Pd)-(DHBTh)_n-OEP(Pd), n=1-6], were synthesized, in which all the chromophores are connected with diacetylene linkage. The unsymmetrical derivatives of OEP(Ni)-DHBTh-OEP(Pd) were also successfully synthesized. Electronic properties of these symmetrical and unsymmetrical complexes were conclusively described, as compared with those of OEP(Ni)-(DHBTh)_n-OEP(Ni). Based on the structure elements, a methodical guiding principle for molecular design of the particular electronic structure will be proposed.     

Solvent effects on the electronic absorption spectrum of formamide studied by a sequential Monte Carlo/quantum mechanical approach

Sequential Monte Carlo/quantum mechanical calculations are performed to study the solvent effects on the electronic absorption spectrum of formamide (FMA) in aqueous solution, varying from hydrogen bonds to the outer solvation shells. Full quantum-mechanical intermediate neglect of differential overlap/singly excited configuration interaction calculations are performed in the supermolecular structures generated by the Monte Carlo simulation. The largest calculation involves the ensemble average of 75 statistically uncorrelated quantum mechanical results obtained with the FMA solute surrounded by 150 water solvent molecules. We find that the n → π* transition suffers a blueshift of 1,600 cm⁻¹ upon solvation and the π → π* transition undergoes a redshift of 800 cm⁻¹. On average, 1.5 hydrogen bonds are formed between FMA and water and these contribute with about 20% and about 30% of the total solvation shifts of the n → π* and π → π* transitions, respectively. The autocorrelation function of the energy is used to sample configurations from the Monte Carlo simulation, and the solvation shifts are shown to be converged values. Received: 14 March 2002 / Accepted: 3 April 2002 / Published online: 24 June 2002     

Validation and application of a novel LC/MS/MS method for the determination of isoginkgetin in rat plasma

Isoginkgetin is a biflavonoid compound isolated from the leaf extracts of Ginkgo biloba. In this study, an liquid chromatography–tandem mass spectrometry (LC/MS/MS) with liquid–liquid extraction was developed and validated for the analysis of isoginkgetin in rat plasma. In the process of chromatographic separation, selected reaction monitoring transitions for isoginkgetin and IS were m/z 566.8 → 134.7 and m/z 430.8 → 269.3, respectively. The validation parameters including selectivity, linearity, LLOQ, accuracy, precision, matrix effect, stability and recovery were satisfactory. The intra‐ and inter‐batch precision (RSD) were <12.1% in plasma, while the accuracy (RE) was within ±14.3%. This method was employed in a pharmacokinetic study on rats after the intravenous administration of isoginkgetin.     

Validation of a novel LC-MS/MS method for the quantitation of colistin A and B in human plasma

A liquid chromatography/tandem mass spectrometry (LC-MS/MS) method, characterized by complete automation and high-throughput, was developed for the determination of colistin A and B in human plasma. All sample preparation procedures were performed by using 2.2 mL 96-deep-well plates, whereas robotic liquid-handling workstations were utilized for all liquid transfer steps, including solid-phase extraction (SPE). The whole preparation procedure was very rapid, whereas the method had a very short chromatographic run time of just 2 min. Sample analysis was performed by reversed phase LC-MS/MS, with positive electrospray ionization, using multiple reaction monitoring. The absence of available purified colistin A and B standards led to the development of a novel LC method with evaporative light-scattering detector for the determination of their stoichiometries in the standard mixture, along with its purity. The proposed bioanalytical method was fully validated and it was proven to be selective, accurate, precise, reproducible and suitable for the determination of colistin A and B in human plasma. It was applied successfully to a pharmacokinetic study for the determination of both analytes in samples of patients.