Revealing the Effect of Heat Treatment on the Spectral Pattern of Unifloral Honeys Using Aquaphotomics

In this study we aimed to investigate the effect of heat treatment on the spectral pattern of honey using near infrared spectroscopy (NIRS). For the research, sunflower, bastard indigo, and acacia honeys were collected from entrusted beekeepers. The honeys were not subject to any treatment before. Samples were treated at 40 °C, 60 °C, 80 °C, and 100 °C for 60, 120, 180, and 240 min. This resulted in 17 levels, including the untreated control samples. The 5-hydroxymethylfurfural (HMF) content of the honeys was determined using the Winkler method. NIRS spectra were recorded using a handheld instrument. Data analysis was performed using ANOVA for the HMF content and multivariate analysis for the NIRS data. For the latter, PCA, PCA-LDA, and PLSR models were built (using the 1300–1600 nm spectral range) and the wavelengths presenting the greatest change induced by the perturbations of temperature and time intervals were collected systematically, based on the difference spectra and the weights of the models. The most contributing wavelengths were used to visualize the spectral pattern changes on the aquagrams in the specific water matrix coordinates. Our results showed that the heat treatment highly contributed to the formation of free or less bonded water, however, the changes in the spectral pattern highly depended on the crystallization phase and the honey type.     

Development of a Wine Metabolomics Approach for the Authenticity Assessment of Selected Greek Red Wines

Wine metabolomics constitutes a powerful discipline towards wine authenticity assessment through the simultaneous exploration of multiple classes of compounds in the wine matrix. Over the last decades, wines from autochthonous Greek grape varieties have become increasingly popular among wine connoisseurs, attracting great interest for their authentication and chemical characterization. In this work, 46 red wine samples from Agiorgitiko and Xinomavro grape varieties were collected from wineries in two important winemaking regions of Greece during two consecutive vintages and analyzed using ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (UHPLC-QToF-MS). A targeted metabolomics methodology was developed, including the determination and quantification of 28 phenolic compounds from different classes (hydroxycinnamic acids, hydroxybenzoic acids, stilbenes and flavonoids). Moreover, 86 compounds were detected and tentatively identified via a robust suspect screening workflow using an in-house database of 420 wine related compounds. Supervised chemometric techniques were employed to build an accurate and robust model to discriminate between two varieties.     

Multi-Elemental Analysis of Wine Samples in Relation to Their Type,Origin, and Grape Variety

Wine is one of the most popular alcoholic beverages. Therefore, the control of the elemental composition is necessary throughout the entire production process from the grapes to the final product. The content of some elements in wine is very important from the organoleptic and nutritional points of view. Nowadays, wine studies have also been undertaken in order to perform wine categorization and/or to verify the authenticity of products. The main objective of this research was to evaluate the influence of the chosen factors (type of wine, producer, origin) on the levels of 28 elements in 180 wine samples. The concentration of studied elements was determined by ICP-MS (Ag, B, Ba, Be, Bi, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Rb, Sb, Sn, Sr, Te, Tl, U, Zn), ICP-OES (Ca, Fe, K, Mg, Ti), and CVAAS (Hg) techniques in 79 red, 75 white, and 26 rose wine samples. In general, red wines contained higher values of mean and median of B, Ba, Cr, Cu, Mn, Sr and Zn in contrast to other wine types (white and rose). In white wines (when compared to red and rose wines) higher levels of elements such as Ag, Be, Bi, Cd, Co, Li, K and Ti were determined. In contrast, rose wines were characterized by a higher concentration of Fe and U. The study also revealed that in the case of 18 samples, the maximum levels of some metals (Cd—8 samples, Pb—9 samples, Cu—1 sample) were slightly exceeded according to the OIV standards, while for Zn and Ti in any wine sample the measured concentrations of these metals were above the permissible levels. Thus, it can be stated that the studied wines contained, in general, lower levels of heavy metals, suggesting that they should have no effect on the safety of consumption. The results also showed higher pH level for red wines as a consequence of the second fermentation process which is typically carried out for this type of wine (malolactic fermentation). The highest median value of pH was reported for Merlot-based wines, while the lowest was for Riesling. It is assumed that dry Riesling has a higher content of tartaric and malic acid than dry Chardonnay grown in the same climate. From all of the studied countries, wines from Poland seemed to present one of the most characteristic elemental fingerprints since for many elements relatively low levels were recorded. Moreover, this study revealed that also wine samples from USA and Australia can be potentially discriminated from the rest of studied wines. For USA the most characteristic metal for positive identification of the country of origin seems to be uranium, whereases for Australia – strontium and manganese. Based on the highly reduced set of samples, it was not possible to differentiate the studied wine products according to the grape variety other than Syrah, and partially Chardonnay. Since all the Syrah-based samples originated from the same country (Australia) thus, the observed grouping should be more related with the country of origin than the grape variety.     

Molecular Recognition of the Fungicide Carbendazim by a Molecular Imprinted Polymer Obtained through a Mimic Template Approach

Abstract

A molecularly imprinted polymer recognizing the fungicide carbendazim was prepared using a mimicking template approach. Methyl-3-propylcarbamoyl-1H-benzimidazol-2-ylcarbamate was synthesized and used as a mimic template for polymer preparation. Selectivity of this polymer for carbendazim and structurally related substances (the template, fluberidazole, rabenzazole, thiabendazole, and benomyl and its two degradation products) was evaluated by liquid chromatography. Results demonstrate that imprinted polymer shows significant recognition properties for carbendazim, whereas the mimic and other carbendazim-related molecules are not recognized. This peculiar selectivity pattern can be explained as an imprinting effect due to the in situ formation of carbendazim from mimic degradation during the polymerization process.     

Potential Value of Wood Tar as a Natural Fungicide against Valsa mali

The Valsa canker caused by Valsa mali seriously harmed the production of East Asian apples and caused very significant economic losses. Considering the chemical residues and the improvement of people’s awareness of environmental protection, there is a need for screening new green pesticides for the control of Valsa canker. Therefore, we conducted systematic evaluations on the antifungal activity of wood tar. In this research, the effective concentration (EC₅₀) of six strains of V. mali to wood tar was determined, and the EC₅₀ ranged from 69.54 to 92.81 μg/mL. After treatment with wood tar, the hyphae of V. mali broke, swelled, and deformed; the permeability of the cell membrane increased; and the activity of pectinase reduced. Moreover, the expression levels of five genes related to pectinase also decreased significantly. In addition, the activities of phenylalanine ammonia lyase (PAL) and peroxidase (POD) of apple leaves treated with wood tar also increased. On detached apple branches, wood tar also showed therapeutic and protective activities. In the 2016–2019 field experiments, wood tar also showed good efficacy against Valsa canker and promoted the formation of callus. (In the experiments from 2016 to 2019, it can be seen that the control effect of 50% wood tar and 100% wood tar in the field is above 75% and promoted the formation of callus.) This study is the first to report the bidirectional efficacy of wood tar against Valsa mali and for trunk wound healing. The above results evidenced that wood tar has great potential to be developed as a natural alternative to commercial fungicides for the management of apple Valsa canker.     

Understanding the Impact of Key Wine Components on the Use of a Non-Swelling Ion-Exchange Resin for Wine Protein Fining Treatment

The impact of key classes of compounds found in wine on protein removal by the ion-exchange resin, Macro-Prep^® High S, was examined by adsorption isotherm experiments. A model wine system, which contained a prototypical protein Bovine Serum Albumin (BSA), was used. We systematically changed concentrations of individual chemical components to generate and compare adsorption isotherm plots and to quantify adsorption affinity or capacity parameters of Macro-Prep^® High S ion-exchange resin. The pH (hydronium ion concentration), ethanol concentration, and prototypical phenolics and polysaccharide compounds are known to impact interactions with proteins and thus could alter the adsorption affinity and capacity of Macro-Prep^® High S ion-exchange resin. At low equilibrium protein concentrations (< ~0.3 (g BSA)/L) and at high equilibrium protein concentrations in model wines at various pH, the adsorption behavior followed the Langmuir isotherm, most likely due to the resin acting as a monolayer adsorbent. The resulting range of BSA capacity was between 0.15–0.18 (g BSA)/(g Macro-Prep^® High S resin). With the addition of ethanol, catechin, caffeic acid, and polysaccharides, the protein adsorption behavior was observed to differ at higher equilibrium protein concentrations (> ~0.3 (g BSA)/L), likely as a result of Macro-Prep^® acting as an unrestricted multilayer adsorbent at these conditions. These data can be used to inform the design and scale-up of ion-exchange columns for removing proteins from wines.     

Techniques for Mitigating the Effects of Smoke Taint While Maintaining Quality in Wine Production: A Review

Smoke taint has become a prominent issue for the global wine industry as climate change continues to impact the length and extremity of fire seasons around the world. Although the issue has prompted a surge in research on the subject in recent years, no singular solution has yet been identified that is capable of maintaining the quality of wine made from smoke-affected grapes. In this review, we summarize the main research on smoke taint, the key discoveries, as well as the prevailing uncertainties. We also examine methods for mitigating smoke taint in the vineyard, in the winery, and post production. We assess the effectiveness of remediation methods (proposed and actual) based on available research. Our findings are in agreement with previous studies, suggesting that the most viable remedies for smoke taint are still the commercially available activated carbon fining and reverse osmosis treatments, but that the quality of the final treated wines is fundamentally dependent on the initial severity of the taint. In this review, suggestions for future studies are introduced for improving our understanding of methods that have thus far only been preliminarily investigated. We select regions that have already been subjected to severe wildfires, and therefore subjected to smoke taint (particularly Australia and California) as a case study to inform other wine-producing countries that will likely be impacted in the future and suggest specific data collection and policy implementation actions that should be taken, even in countries that have not yet been impacted by smoke taint. Ultimately, we streamline the available information on the topic of smoke taint, apply it to a global perspective that considers the various stakeholders involved, and provide a launching point for further research on the topic.     

基于子空间重合判断的混合醇组分光谱识别方法

针对光谱分析中传统的特征峰比对法对物质定性检测存在的不足,采用基于子空间重合判断的混合光谱模式识别方法对9种混合醇组分进行定性检测。此法将测量到的待定性混合醇光谱信息视为向量,通过计算混合醇组分拉曼光谱与标准样品数据库拉曼光谱的子空间夹角,并依据子空间夹角变化,排列筛选出含有最少标准样品数目的子空间,该子空间所包含的标准样品组成即为待定性混合醇组分组成,从而成功实现了9种混合醇组分的定性识别,识别率100%。该法具有测试时间短、测试结果准确、与被测物含量无关、操作简便等优点,适用于多组分混合体系的定性识别。     

Hybrid Electronic Tongue as a Tool for the Monitoring of Wine Fermentation and Storage Process

Hybrid electronic tongue based on potentiometric and voltammetric sensors was applied for the monitoring of wine production process. The sensor array formed by miniaturized ion‐selective electrodes and glassy carbon electrodes provided the analysis of the progress and correctness of wine fermentation and storage process, detection of the presence of disturbing factors and evaluation of the quality of final product. The efficiency of the proposed approach was compared with the monitoring of wine production carried out using standard reference methods. The results indicated that hybrid electronic tongue could be used as simple and reliable analytical tool dedicated to qualitative and quantitative assessment of wine production.     

Chemometric analysis of gas chromatographic data—investigation of enological parameters of a bag‐in‐box white wine as affected by storage time and temperature

In this study, a bag‐in‐box white wine was stored at 22, 35, and 45 °C for up to 48 days to produce a series of samples that exhibited different enological parameters (absorbance at 420 nm, free SO₂, total SO₂, total phenol, and total aldehyde). Wine samples were extracted with dichloromethane and analyzed using gas chromatography (GC) to generate volatile fingerprints. Principal component analysis (PCA) score plots of the first three principal components showed grouping trends that were influenced by storage time and temperature. PCA loading plots revealed that changes in chemical profiles were different for wines held at different storage temperatures. Storage time could be predicted accurately by partial least squares (PLS) regression of the GC data. Coefficients of determination (R²) were >0.99, and the standard error of prediction values were 0.4, 0.5, and 1.9 days over the test period of 15, 30, and 48 days, respectively. Using the same GC data with PLS analyses, the enological parameters could be accurately predicted from GC fingerprints, except for the predictions of SO₂ in a wine stored at 22 °C and total phenol in a wine stored at 45 °C. Copyright © 2011 John Wiley & Sons, Ltd.     

老年Colles骨折X线Frykman分型在治疗方案选择中的应用价值探究

该回顾性研究旨在探究老年Colles骨折X线Frykman分型在治疗方案选择中的应用价值。2015年1月～2018年1月期间收治的120例老年Colles骨折患者纳入研究对象,完善X线检查并进行Frykman分型,比较不同Frykman分型的Colles骨折患者X线掌倾角、尺偏角、桡骨短缩等指标。依据Frykman分型将患者分为关节内、外型骨折,比较两种骨折类型患者治疗方式及X线指标的变化情况,并采用Lidstrom治疗效果分级评估不同分组患者不同治疗方式的治疗效果。结果显示,120例Colles骨折患者根据Frykman分型：Ⅰ型26例（21.67%）、Ⅱ型29例（24.17%）、Ⅲ型14例（11.67%）、Ⅳ型16例（13.33%）、Ⅴ型12例（10.00%）、Ⅵ型11例（9.17%）、Ⅶ型8例（6.67%）、Ⅷ型4例（3.33%）。120例患者中共有关节外型骨折患者55例,其中30例行保守治疗,25例接受手术治疗;关节内型骨折患者65例,其中29例行保守治疗,36例接受手术治疗。两组骨折类型患者治疗后手术治疗的掌倾角、尺偏角、桡骨短缩值均明显优于保守治疗的患者,比较差异均有统计学意义（P<0.05）。关节外型Colles骨折患者治疗总可接受率（72.73%）与关节内型治疗总接受率（75.38%）（χ²=0.11,P=0.74）相当;关节外型组手术治疗总可接受率（88.00%）高于保守治疗（73.33%）（χ²=1.83,P=0.18）;关节内型组手术治疗总可接受率（91.67%）明显高于保守治疗（55.17%）（χ²=11.53,P=0.00）。本研究证实老年Colles骨折X线Frykman分型在治疗方案选择中具有应用价值,关节外型骨折患者手术和保守治疗效果相当,关节内型患者优先选择手术治疗。     

Probably counterfeit in Roman Imperial Age: Pattern recognition helps diagnostic performed with inductive coupled plasma spectrometry and thermogravimetry analysis of a torso and a head of Roman Age marble statue

This work deals with the attempt to classify marbles, coupling chemometry and two different instrumental techniques, such as inductive coupled plasma atomic emission spectroscopy (ICP-AES) and thermogravimetry analysis (TGA). Chemometrics have been hyphenated, firstly to obtain variables selection on weight loss vs temperature in TGA and after for unsupervised classification of 22 samples (5 ancient marble and 17 single samples from quarries) obtaining a well recognisable classification. The objects in “test set” are the body and the head of one statue and a Torso Virile statue; the “evaluation set” are two well-known ancient finds; the “training set” is constituted by 17 samples coming from marble assigned to Italian, Greek and Turkish quarries.22 elements (Ca, Si, Na, K, Mg Ti, Al, Fe, Pb, Zn, Sr, Zr, Cu, Mn, Rb, Y) are taken into consideration; with TGA 951 values of mass-residual vs temperature are considered. After selection 8 variables from ICP-AES and 4 from TG compose the matrix.We obtain a separation of Italian marbles cluster from marbles of other countries and recognise the different provenience of the body and head and classify the unknown one. This methodology can be applied to classification study of similar ancient artefacts as pottery, ceramics, glass and stones.Counterfeit, or substitution of parts such as head, legs, and hands was a current practice in the late Roman Age, and also in the Renaissance a lot of statues were “rebuilt” with spare parts, so this word describes an historical restoration practice and not just depreciative.     

Magnetic Stirring-Assisted Dispersive Suspended Microextraction with Solidification of a Floating Organic Droplet for the Determination of Trace Fungicides in Water and Wine

For the first time, a simple method for magnetic stirring-assisted dispersive suspended microextraction has been developed for the determination of three fungicides (azoxystrobin, diethofencarb, and pyrimethanil) in water and wine samples. The method is based on the solidification of a floating organic droplet coupled with high performance liquid chromatography. In the proposed method, the low toxicity solvent 1-dodecanol was used as the extractant. Both the extraction and phase separation process were performed with magnetic stirring. No centrifugation step was involved. After separating the two phases, the extraction solvent droplet was easily collected through solidification at lower temperature. Important parameters such as the kind and volume of organic extraction solvent, extraction and restoration speed, extraction and restoration time, and salt concentration were optimized. Under the optimal conditions, the limits of detection for the analytes varied from 0.14 to 0.26 µg L^?1. The enrichment factors ranged from 125–200. The linearity ranges were 1–2000 µg L^?1, yielding correlation coefficients (r) higher than 0.9990. The relative standard deviation (n = 6) at two spiked level of 0.2 µg mL^?1 and 4 µg L^?1 varied between 2.2% and 7.8%. Finally, the developed technique was successfully applied to determine target fungicides in real water and wine samples, where the obtained recoveries ranged from 83.8–105.3%     

The Limit of Detection of a Reactant,in the Presence of Another,by Kinetic Analysis and Deviation-Pattern Recognition

Abstract

When a solution containing a single reactant is subjected to kinetic analysis with a reagent giving rise to a pseudo-first-order reaction, non-linear regression analysis of the concentrationtime data yields a random scatter of the residuals around the best fit to the pseudo-first-order equation. If the same equation is used when a second reactant is also present, systematic errors arise and yield a deviation plot having a characteristic shape. If the amplitude of that plot is substantially larger than the random error of measurement, the presence of the reactant can be detected, and its concentration can then be evaluated by non-linear regression onto the equation that takes its presence into account. The amplitude passes through a maximum as the relative concentration of the second reactant increases, or as the ratio of the rate constants increases. For any given ratio of concentrations, detection of the second reactant is impossible unless the ratio of the rate constants lies within a certain range, which will be governed by the data-acquisition schedule employed. For the particular schedule assumed here, examination of these dependences shows, for example, that it should be possible to detect the second reactant if its concentration is 2.5 per cent of that of the first reactant and if the ratio of the rate constants is between 7.1 and 21.7.     

Metabonomics Study of the Hematopoietic Effect of Medicinal Wine Maoji Jiu on a Blood Deficiency Rat Model by Ultra-High-Performance Liquid Chromatography Coupled to Quadrupole Time-of-Flight Mass Spectrometry and a Pattern Recognition Approach

Maoji Jiu (MJ) is a kind of medicinal wine that has been widely used by Chinese people for many years to nourish and promote blood circulation. The purpose of this study was to investigate the hematopoietic effect of MJ on the metabolism of blood deficient rats and to explore the underlying hematopoietic regulation mechanisms. Blood deficiency model rats were induced by subcutaneous injection of N-acetylphenylhydrazine (APH) and intraperitoneal injection of cyclophosphamide (CTX). The plasma metabolic fingerprints of blood deficiency model rats with and without MJ treatment were obtained by using metabonomics based on ultra-high-performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry (UHPLC–QTOF/MS). Orthogonal partial least squares-discriminant analysis (OPLS–DA) was used to evaluate the hematopoietic effect of MJ and identify potential biomarkers in the plasma of blood deficiency model rats. The levels of white blood cells (WBC), red blood cells (RBC) and hemoglobin (HGB) and the activity of antioxidant capacity showed a recovery trend to the control group after MJ treatment, while the dose of 10 mL/kg showed the best effect. In this study, thirteen potential biomarkers were identified, which were mainly related to seven metabolic pathways, including linoleic acid metabolism, d-glutamine and d-glutamate metabolism, alanine, aspartate and glutamate metabolism, tryptophan metabolism, pyrimidine metabolism, porphyrin and chlorophyll metabolism and arginine biosynthesis. Metabolomics was applied frequently to reflect the physiological and metabolic state of organisms comprehensively, indicating that the rapid plasma metabonomics may be a potentially powerful tool to reveal the efficacy and enriching blood mechanism of MJ.     

The Limit of Detection of a Weak Acid,in the Presence of Another,by Potentiometric Acid-Base Titrimetry and Deviation-Pattern Recognition

Abstract

When a solution containing a single monobasic weak acid is titrated potentiometrically with a strong base, non-linear regression analysis of the data yields a random scatter of the residuals around the best fit to the appropriate equation. If the same equation is used when a second weak acid is also present, systematic errors arise and yield a deviation plot having a characteristic shape. If the amplitude of that plot is substantially larger than the random error of measurement, the presence of the second acid can be detected, and its concentration can then be evaluated by non-linear regression onto the equation that takes its presence into account. The amplitude increases as the relative concentration of the second acid increases, and as the difference between the values of pK_a for the two acids increases. Examination of these dependences shows, for example, that it should be possible to detect 1 per cent of an impurity for which pK_a differs by 0.57 unit from that of the major component.     

Automation of sample preparation as a preliminary stage in the high-performance liquid chromatographic determination of polyphenolic compounds in sherry wines

The procedure for automating the method of sample preparation by solid-phase extraction prior to the HPLC analysis of polyphenolic compounds in sherry wine is described. This method consists of two stages, the first being sample preconcentration and cleaning using a C₁₈ cartridge and the second fractionation using a SAX anion exchanger. The first direct application of the method, using a semi-flexible robot system, did not produce satisfactory results, thus requiring a series of modifications and optimization of the variables inherent in the device itself. The automated method as modified produced considerable improvements over the manual method with respect to the recovery and repeatability values obtained with the different polyphenolic species used in its optimization. Subsequent testing of the method with real samples of sherry wine proved its applicability for tracking the evolution of polyphenolic species in wine.     

Copper Dissolution Rate as a Function of the Corroding-Surface Tilt

Measurements of the copper corrosion rate in 0.5 M H₂SO₄ as a function of the tilt angle of the corroding electrode surface in the gravitational field show that the downward flux of natural convection (NC), which arises during corrosion, effects the process similarly to NC that arises when electrochemical reactions proceed in a diffusion kinetics mode. The corrosion rate of a horizontal face-down electrode is 2.3 times that when facing up. Without NC, when a horizontal face-up copper electrode is in a recess, its corrosion rate is defined by the oxygen diffusion current and is 12–28 times as small as that with NC next to its surface.__________Translated from Elektrokhimiya, Vol. 41, No. 7, 2005, pp. 823–828.Original Russian Text Copyright © 2005 by Miecinskas.     

Molecular Imprinting-Chemiluminescence Determination of Norfloxacin Using a Norfloxacin-Imprinted Polymer as the Recognition Material

A selective molecular imprinting-chemiluminescence method was developed for the determination of norfloxacin by using a norfloxacin-imprinted polymer as recognition material and the Ce(IV)-sodium sulfite-norfloxacin chemiluminescence reaction as the detection system. The chemiluminescence intensity responded linearly to the concentration of norfloxacin within 1.0×10^–71.0×10^–5molL^–1 with a detection limit of 3×10^–8molL^–1. The relative standard deviation for 5.0×10^–7molL^–1 norfloxacin solution was 2.4% (n = 7). This method was applied to the determination of norfloxacin in urine samples, and the results obtained were satisfactory.