Simultaneous determination of eight components in Angelica sinensis based on UHPLC‐ESI‐MS/MS method for quality evaluation

A method employing ultra‐high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) for determination of eight components including ferulic acid, senkyunolide A, butylphthalide, ligustilide, butylidenephalide, senkyunolide I, senkyunolide H and levistolide A in Angelica sinensis was established. The separation was carried out using a Waters ACQUITY UHPLC BEH C₁₈ column with gradient elution with 0.1% formic acid aqueous and acetonitrile at a flow rate of 0.4 mL/min. Good linearity was attained with R² of 0.9983–0.9998 in wide concentration ranges. The method had limit of detection (LOD) and quantitation (LOQ) in the range of 0.42–6.98 ng/mL and 1.39–23.28 ng/mL, respectively. Intra‐ and inter‐day precisions varied with relative standard deviations (RSDs) from 0.33% to 0.88% and 0.37% to 1.04%, respectively. Moreover, the average recoveries were in a satisfactory range of 92.7%–102.1% with RSDs of less than 3.60%. Finally, the method was successfully applied to analyze 19 batches of A. sinensis samples grown in Min County, Gansu province, China, as well as that collected in other regions. The findings indicated that the established method is reliable and may thus be applied as a powerful tool for qualitative and quantitative analysis of components in A. sinensis, which has its implications in quality control of A. sinensis.     

Internal inspection of semi-transparent objects by digital holographic micro-tomography

The combined use of digital holographic microscopy and computer tomography, here named digital holographic micro-tomography, is used to examine the interior of transparent channels. The proposed method is used to identify internal obstacles inside of transparent troughs having slightly different refractive index. The method is based in the acquisition of a set of digital holograms of the specimen whereas it is axially rotated from 0° to 180°. The phase differences retrieved from the obtained holograms are the inputs to a computerised axial tomography procedure. The technique has been numerically modelled in order to find the optimal tomographic conditions and also to realise the minimum difference of refractive index the method could detect. The obtained results show the feasibility of the proposed method for the non-destructive evaluation of transparent micro-objects.     

改进Vague集评价方法在IT项目经理评价中的应用

针对Vague集评价过程中信息容易遗失的问题,提出采用Vague综合评价的思想进行计算.通过定义Vague基本运算法则,以及建立加权综合评价函数构建了新的评价方法.方法体现了Vague集理论描述不确定性问题的优点,反映了项目经理评价的一般特点.最后,通过案例计算,得到了公平公正的评价结果,并验证了计算结果的可靠性.     

Effects of high-energy ultrasound on the functional properties of proteins

In recent years, high-energy ultrasound has been used as an alternative to improve the functional properties of various proteins, such as from milk, eggs, soy and poultry. The benefits of implementing this technology depend on the inherent characteristics of the protein source and the intensity and amplitude of the ultrasound, as well as on the pH, temperature, ionic strength, time, and all of the variables that have an effect on the physicochemical properties of proteins. Therefore, it is necessary to establish the optimal conditions for each type of food. The use of ultrasound is a promising technique in food technology with a low impact on the environment, and it has thus become known as a green technology. Therefore, this review focuses on the application of high-energy ultrasound to food; its effects on the functional properties of proteins; and how different conditions such as the frequency, time, amplitude, temperature, and protein concentration affect the functional properties.     

Ranking ranges in cross-efficiency evaluations

The existence of alternate optima for the DEA weights may reduce the usefulness of the cross-efficiency evaluation, since the ranking provided depends on the choice of weights that the different DMUs make. In this paper, we develop a procedure to carry out the cross-efficiency evaluation without the need to make any specific choice of DEA weights. The proposed procedure takes into consideration all the possible choices of weights that all the DMUs can make, and yields for each unit a range for its possible rankings instead of a single ranking. This range is determined by the best and the worst rankings that would result in the best and the worst scenarios of each unit across all the DEA weights of all the DMUs. This approach might identify good/bad performers, as those that rank at the top/bottom irrespective of the weights that are chosen, or units that outperform others in all the scenarios. In addition, it may be used to analyze the stability of the ranking provided by the standard cross-efficiency evaluation.     

Front face synchronous fluorescence as a tool for the quality assurance of Greek milk

This research focuses on implementing the low cost and rapid front face synchronous fluorescence (SyFS) in order to ensure the quality assurance of Greek milk. Specifically, samples originated from the Greek domestic production of goat, sheep, cow, as well as foreign cow milk samples and adulterated cow milk samples. SyFS spectra were acquired in the excitation area of 250–500 nm with (Δλ)= 100 nm. Greek and foreign cow milk samples were differentiated based on intensity variations at wavelengths 350–515 nm, 540–579 nm, and 580–600 nm. The emissions at these wavelength positions correspond to tryptophan, vitamin A, and riboflavin. The supervised model with 94 samples exhibited p-value = 7,98E-11, RMSEE= 0,29171, RMSEcv= 0,29284 and RMSEP= 0,98013, AUROC for Greek samples= 0,61 and AUROC for foreign= 0,85. We differentiated milk samples according to the animal type with PCA and OPLS-DA models of 107 samples exhibiting RMSEE= 0,225842, RMSEcv= 0,228054 and RMSEP= 0,518635, AUROC for sheep samples= 0,99, AUROC for goat samples= 0,98 and AUROC for cow samples= 0,96. In fact, the emission band 350–591 nm characterized sheep milk and corresponds to aminoacids and fatty acids, cow milk was related to the 350–600 nm emission band related to the b-carotene and to the goat milk the emission bands 350–505 nm and 520–600 nm were attributed to tryptophan, NADH and Rivoflabin. Finally, we investigated whether SyFS coupled with chemometrics may provide preliminary evidence on adulterated cow milk samples. All models were validated with permutation testing, p-values and ROC curves.     

Semiclassical transition state theory/master equation kinetics of HO + CO: Performance evaluation

Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty.     

基于荧光光谱技术的菜籽油氧化状态智能评价

菜籽油在加工及贮藏过程中，易受氧气、温度、光照等因素的影响，产生氧化酸败现象。为准确判断油脂氧化程度，实现不同氧化模式下菜籽油品质的快速判别，采用三维同步荧光光谱技术结合平行因子分析法及BP神经网络法建立菜籽油氧化状态的智能评价模型。以冷榨菜籽油为原料，将样品分别置于常温、Schaal烘箱、高温模式中氧化处理，期间采集菜籽油的三维同步荧光光谱数据及理化指标，当理化指标超出国标限定范围时，停止采集数据。结果表明，菜籽油中荧光物质在不同氧化模式中的演变规律呈显著差异，氧化温度对菜籽油荧光光谱有明显影响。常温氧化350 d与第1 d相比，菜籽油的特征荧光峰位置无变化，仅在激发波长Ex为620和660 nm附近荧光峰强度发生微弱变化；Schaal烘箱氧化26 d后，在激发波长Ex为620和660 nm附近荧光峰强度显著减弱，且在激发波长Ex为350～450 nm之间有新的荧光峰生成；高温氧化48 h后，Ex为620和660 nm处荧光峰消失，在Ex为400～550 nm处产生显著荧光峰，相对Schaal烘箱氧化，荧光波长发生一定程度红移，这是由于高温氧化过程中油脂氧化生成的物质稳定性较差引起的。利用平行因子分析法对三维同步荧光光谱数据进行分解获取有效的二维荧光光谱数据，当组分数为6，Δλ=60 nm时激发波长的载荷值最大，不同样品间差异最显著。选定Δλ=60 nm波段的二维荧光光谱数据用于智能评价，作为BP神经网络模型的输入值，以极性组分作为模型输出值，分别对菜籽油三种氧化模式数据建模训练。实验结果表明，三种氧化模式对应的训练集、验证集、测试集模型相关系数r均能达到0.9以上，其中常温氧化模式中验证集及测试集模型的相关系数r为1，输出值与目标值较接近，模型的预测效果较好；综合三种氧化模式数据建模，对应训练集、验证集、测试集模型的相关系数分别为0.999，0.913和0.988，均方误差均较小，说明该模型能准确判断菜籽油的不同氧化状态。因此，三维同步荧光光谱技术结合平行因子分析法、BP神经网络法建立快速检测模型能实现菜籽油不同氧化状态的判别，为菜籽油的氧化程度的评价提供新方法，同时为其他食用油的品质评价提供参考。     

In vitro biomolecular interaction studies and cytotoxic activities of copper(II) and zinc(II) complexes bearing ONS donor thiosemicarbazones

Among all the bio‐metals, zinc and copper derivatives of ONS donor thiosemicarbazone have aroused great interest because of their potential biological applications. Multisubstituted thiosemicarbazone ligand H₂dspt (3,5‐dichlorosalicylaldehyde‐N⁴‐phenylthiosemicarbazone) derived new ternary complexes like [Zn(dspt)(phen)]?DMF ( 1 ) and [Cu(dspt)(phen)]?DMF ( 2 ), and another thiosemicarbazone, H₂dsct (3,5‐dichlorosalicylaldehyde‐N⁴‐cyclohexylthiosemicarbazone), derived [Cu(dsct)(bipy)]?DMF ( 3 ). These complexes have been characterized by elemental analysis (CHNS), Fourier transform infrared (FT‐IR), ultraviolet–visible (UV–Vis) and proton nuclear magnetic resonance (¹H‐NMR) spectra. The structures of the complexes were obtained by single‐crystal X‐ray diffraction analysis. Compounds 1 and 2 got crystallized in the monoclinic P2₁/c space group. The complexes showed interesting supramolecular interaction, which in turn stabilizes the complexes. The ground state electronic configurations of the complexes were studied using the B3LYP/LANL2DZ basis set, and ESP plots of complexes were investigated. The interaction of the complexes with calf thymus DNA (CT‐DNA) was studied using absorption and fluorescence spectroscopic methods. A UV study of the interaction of the complexes with calf thymus DNA (CT‐DNA) has shown that the complexes can effectively bind to CT‐DNA, and [Cu(dspt)(phen)]·DMF ( 2 ) exhibited the highest binding constant to CT‐DNA (K_b = 3.7 × 10⁴). Fluorescence spectral studies also indicated that Complex 2 binds relatively stronger with CT DNA through intercalative mode, exhibiting higher binding constant (K_q = 4.7 × 10⁵). The DNA cleavage result showed that the complexes are capable of cleaving the DNA without the help of any external agent. Molecular docking studies were carried out to understand the binding of complexes with the molecular target DNA. Complex 2 exhibited the highest cytotoxicity against human breast cancer cell line MD‐MBA‐231 (IC₅₀ = 23.93 μg/mL) as compared to Complex 1 (IC₅₀ = 44.40 μg/mL) .