Exploration of Global and Specialized Near-Infrared Calibrations for the Quantification of Nutritional Content in Grapevine Organs, Berry Phenological Stages, and Shoot Lignification.

Current infrared spectroscopy applications in the field of viticulture are moving toward direct in-field measuring techniques. However, limited research is available on quantitative applications using direct measurement of fresh tissue. The few studies conducted have combined the spectral data from various cultivars, growing regions, grapevine organs, and phenological stages during model development. The spectral data from these heterogeneous samples are combined into a single data set and analyzed jointly during quantitative analysis. Combining the spectral information of these diverse samples into a global data set could be an unsuitable approach and could yield less accurate prediction results. Spectral differences among samples could be overlooked during model development and quantitative analysis. The development of specialized calibrations should be considered and could lead to more accurate quantitative analyses. This study explored a model optimization strategy attempting global and specialized calibrations. Global calibrations, containing data from multiple organs, berry phenological, and shoot lignification stages, were compared to specialized calibrations per organ or stage. The global calibration for organs contained data from shoots, leaves, and berries and produced moderately accurate prediction results for nitrogen, carbon, and hydrogen. The specialized calibrations per organ yielded more accurate calibrations with a coefficient of determination in validation (R2val) at 90.65% and a root mean square error of prediction (RMSEP) at 0.32% dry matter (DM) for the berries' carbon calibrations. The leaves and shoots carbon calibrations had R2val and RMSEP at 84.99%, 0.34% DM, and 90.06%, 0.37% DM, respectively. The specialized calibrations for nitrogen and hydrogen showed similar improvements in prediction accuracy per organ. Specialized calibrations per phenological and lignification stage were also explored. Not all stages showed improvement, however, most stages had comparable or improved results for the specialized calibrations compared to the global calibrations containing all phenological or lignification stages. The results indicated that both global and specialized calibrations should be considered during model development to optimize prediction accuracy.

Feasibility assessment of a low-cost visible spectroscopy-based prototype for monitoring polyphenol extraction in fermenting musts.

BACKGROUND: Polyphenols have long been used to evaluate grape and wine quality and it is necessary to measure them throughout various winemaking stages. They are currently assessed predominantly through analytical methods, which are characterized by time-consuming procedures and environmentally harmful practices. Non-destructive spectroscopy-based devices offer an alternative but they tend to be costly and not readily accessible for smaller wineries. This study introduces the initial steps in employing a portable, user-friendly, and cost-effective visible (VIS) spectrophotometer prototype for direct polyphenol measurement during winemaking. RESULTS: Grapes (cv Syrah, Bobal, and Cabernet Sauvignon) at different maturation stages were fermented with or without stems. Throughout fermentation, parameters such as color intensity, total polyphenol index, total anthocyanins, and tannins were monitored. Concurrently, VIS spectra were acquired using both the prototype and a commercial instrument. Chemometric approaches were then applied to establish correlation models between spectra and destructive analyses. The prototype models demonstrated an acceptable level of confidence for only a few parameters, indicating their lack of complete reliability at this stage. CONCLUSIONS: Visible spectroscopy is already utilized for polyphenol analysis in winemaking but the aspiration to automate the process in wineries, particularly with low-cost devices, remains unrealized. This study investigates the feasibility of a low-cost and user-friendly spectrophotometer. The results indicate that, in the early stages of prototype utilization, the goal is attainable but requires further development and in-depth assessments. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

White wine phenolics: current methods of analysis.

White wine phenolic analyses are less common in the literature than analyses of red wine phenolics. Analytical techniques for white wine phenolic analyses using spectrophotometric, chromatographic, spectroscopic, and electrochemical methods are reported. The interest of research in this area combined with the advances in technology aimed at the winemaking industry are promoting the establishment of novel approaches for identifying, quantifying, and classifying phenolic compounds in white wine. This review article provides an overview of the current research into white wine phenolics through a critical discussion of the analytical methods employed. © 2022 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Direct quantification of red wine phenolics using fluorescence spectroscopy with chemometrics.

Phenolic compounds are secondary metabolites known to play crucial roles in important chemical reactions impacting the mouthfeel, colour and ageing potential of red wine. Their complexity has resulted in a number of advanced analytical methods, which often prevent routine phenolic analysis in winemaking. Fluorescence spectroscopy could be an alternative to current spectrophotometric techniques and its combination with chemometrics was investigated for its suitability in directly quantifying phenolic content of unaltered red wine and fermenting samples. Front-face fluorescence was optimised and used to build predictive models for total phenols, total condensed tannins, total anthocyanins, colour density and polymeric pigments. Machine learning algorithms were used for model development. The most successful models were built for total phenols, total condensed tannins and total anthocyanins with coefficient of determination (R2cal) and RMSECV of 0.81, 0.89, 0.80 and 5.71, 104.03 mg/L, 60.67 mg/L, respectively. The validation results showed R2val values of 0.77, 0.8 and 0.77, and RMSEP values of 7.6, 172.37 mg/L and 76.57 mg/L, respectively. A novel approach for the classification of South African red wine cultivars based on unique fluorescent fingerprints was also successful with an overall cross validation score of 0.8. The best classification ability (validation score = 0.93) was shown for the data set containing only fermenting wines for the most widely represented cultivars (>20 samples). This approach may provide a useful tool for authentication and quality control by regulatory bodies.

Infrared Spectroscopy and Chemometric Applications for the Qualitative and Quantitative Investigation of Grapevine Organs.

The fourth agricultural revolution is leading us into a time of using data science as a tool to implement precision viticulture. Infrared spectroscopy provides the means for rapid and large-scale data collection to achieve this goal. The non-invasive applications of infrared spectroscopy in grapevines are still in its infancy, but recent studies have reported its feasibility. This review examines near infrared and mid infrared spectroscopy for the qualitative and quantitative investigation of intact grapevine organs. Qualitative applications, with the focus on using spectral data for categorization purposes, is discussed. The quantitative applications discussed in this review focuses on the methods associated with carbohydrates, nitrogen, and amino acids, using both invasive and non-invasive means of sample measurement. Few studies have investigated the use of infrared spectroscopy for the direct measurement of intact, fresh, and unfrozen grapevine organs such as berries or leaves, and these studies are examined in depth. The chemometric procedures associated with qualitative and quantitative infrared techniques are discussed, followed by the critical evaluation of the future prospects that could be expected in the field.

Trends in funding research and international collaboration on greenhouse gas emissions: a bibliometric approach.

The Web of Science Core Collection platform was used to withdraw the papers included in this study. The studied period comprised from inception till 2018. Trends in research, journals of publication, subject areas of research, keywords most frequently used, countries of publication, international collaboration, and trends of funding research were also analyzed. A total of 3902 articles were published, most of them (52.5%) during the five-year period 2014-2018. The area with the highest number of papers was environmental sciences (41%), followed by energy fuels (16.6%) and engineering environmental (15.7%). "Nitrous oxide emissions" was the most frequent word, followed by "Carbon dioxide emissions" and "Methane emissions". Other words that stood out were "Life cycle assessment", "Climate change" and "Environmental impacts". The United States was the country with the highest productivity (27.9%), followed by China (12.8%) and the United Kingdom (9.6%). There was a concentration of research in recent years, as more than 80% of the papers were published in the last 10 years. The journals that published the largest number of publications were devoted mainly to environmental studies (sciences and engineering), sustainable and green science and technology, energy and fuels, economics, and agriculture. Half of the works were published in Europe and the other half between North America and Asia. Two thirds of the works (67%) were financed compared to a third that were not financed. The percentage of funded works has been increasing over the last decade, which is seen as an indication of the importance of GHGE.

Worldwide Scientific Research on Nanotechnology: A Bibliometric Analysis of Tendencies, Funding, and Challenges.

The main objective of this investigation was to analyze the scientific production in global research on nanotechnology, integrating scientific production, funding of studies, collaborations between countries, and the most cited publications. The source for obtaining the research papers for our analysis was the Science Citation Index Expanded from the Web of Science. A total of 3546 documents were extracted during the period of 1997-2018. Food science & technology, chemistry (applied and analytical), spectroscopy, and agriculture appeared as the main areas where the articles were published. Most prolific and cited journals were Analytical Methods, Journal of Agricultural and Food Chemistry, and Food Chemistry. The co-word analysis showed the relationships between "nanoparticles", which is the central word, and "silver nanoparticles", "delivery systems", and "zinc-nanoparticles". The most productive countries were China (1089 papers), the United States (523), Iran (427), and India (359). The main cited topics deal with the biomedical applications of nanoparticles, its synthesis from plants, and its applications in food science. The results highlight an important collaboration between institutions and countries. The availability of funding for research in nanotechnology was remarkable compared to other fields. The multidisciplinarity of the nanotechnology field is one of the main features as well as one of the central findings.

Tendencies and Challenges in Worldwide Scientific Research on Probiotics.

The central goal of this study was to analyze scientific trends in the research on probiotics, including the number of papers, funding, country collaborations, and most cited publications. The study makes use of bibliometric and social network analysis of papers included in the Science Citation Index Expanded from the Web of Science database. A total of 7221 papers were retrieved, from which 64% were funded papers. Papers were published in journals covering several areas, such as Food Science & Technology, Microbiology, Biotechnology and Applied Microbiology, Nutrition & Dietetics and Agriculture, and Dairy & Animal Science. Coword analysis shows the relationships between microorganisms, diseases, physiological phenomena, and other key words related to food, population, or type of study. The USA appeared as the world leader in the number of articles produced (n = 919), followed by China (n = 689), India (n = 633), and Brazil (n = 506). The most cited papers related to the consensus on the scope and appropriate use of the term probiotic, its effects on the prevention and treatment of some intestinal diseases, its effects on the suppression of immune disorders, the role of probiotics and prebiotics in obesity, the assessment of psychotropic-like properties, and the application for type 2 diabetes.

Viability of IR spectroscopy for the accurate measurement of yeast assimilable nitrogen content of grape juice.

Up to date, there have been only a few reports on the measurement of YAN and/or its components using IR spectroscopy, suffering from various limitations (number of samples, validation strategies, etc.). In this work, three IR spectral instruments measuring in different modes and ranges of the IR spectrum (FT-IR, FT-NIR, and ATR-MIR), were compared and evaluated for their accuracy to measure both total YAN as well as the components, FAN and ammonia separately, using over 900 grape juice samples from 28 cultivars over three seasons. The global and vintage-based models were evaluated using R2CAL/VAL, RMSEC/P, and RPDCAL/VAL. Randomization tests were used for pair-wise comparison of models. FT-IR and FT-NIR instruments gave the best results, while ATR-MIR can be used for screening purposes. Considering the accuracy, robustness, high throughput, and cost-effective nature, the models produced by both FT-IR and FT-NIR spectroscopy can provide winemakers with the opportunity to make timelier and more informed nutrient supplementation decisions, facilitating the achievement of their desired wine style and quality.

Towards on-line monitoring of phenolic content in red wine grapes: A feasibility study.

Spectroscopy techniques to efficiently measure phenolic composition in grape berries may be a suitable analytical practice, provided that robust calibrations are established. A contactless FT-NIR instrument was used for on-line spectral data collection from grapes transported on a conveyor belt system. Spectral data was also collected on static samples using the same NIR instrument. Spectral measurements of crushed berries captured from the conveyor belt system and the use of the homogenate extraction protocol as reference method provided the most accurate prediction models. Values obtained for errors in prediction (RMSEP%) and RPD were 12% and 2.37, 12.3% and 3.37, 7.8% and 3.2, 16.7% and 2.84 for tannins (mg/g) and anthocyanins (mg/g) on a fresh weight basis, total phenols and colour density (AU), respectively. The results observed in this study show the ability of NIR spectroscopy to monitor the phenolic composition of grape berries transported on a conveyor belt system online.

Basic In-Mouth Attribute Evaluation: A Comparison of Two Panels.

Astringency is often difficult to evaluate accurately in wine because of its complexity. This accuracy can improve through training sessions, but it can be time-consuming and expensive. A way to reduce these costs can be the use of wine experts, who are known to be reliable evaluators. Therefore, the aim of this work was to compare the sensory results and the panel performance obtained using trained panelists versus wine experts (winemakers). Judges evaluated twelve red wines for in-mouth basic perception (sweet, sour, bitter, astringent, and burning sensation) following the same tasting protocol and with the samples being presented in two different tasting modalities. Panels' performance and relationship between the chemical composition and the sensory perception were investigated. Both panels showed similar consistency and repeatability, and they were able to accurately measure the astringency of the wines. However, the significant correlations between sensory scores and chemical composition varied with the panel and the tasting modality. From our results, we could see that winemakers tended to discriminate better between the samples when the differences were very small.

Chemometric compositional analysis of phenolic compounds in fermenting samples and wines using different infrared spectroscopy techniques.

The wine industry requires reliable methods for the quantification of phenolic compounds during the winemaking process. Infrared spectroscopy appears as a suitable technique for process control and monitoring. The ability of Fourier transform near infrared (FT-NIR), attenuated total reflectance mid infrared (ATR-MIR) and Fourier transform infrared (FT-IR) spectroscopies to predict compositional phenolic levels during red wine fermentation and aging was investigated. Prediction models containing a large number of samples collected over two vintages from several industrial fermenting tanks as well as wine samples covering a varying number of vintages were validated. FT-NIR appeared as the most accurate technique to predict the phenolic content. Although slightly less accurate models were observed, ATR-MIR and FT-IR can also be used for the prediction of the majority of phenolic measurements. Additionally, the slope and intercept test indicated a systematic error for the three spectroscopies which seems to be slightly more pronounced for HPLC generated phenolics data than for the spectrophotometric parameters. However, the results also showed that the predictions made with the three instruments are statistically comparable. The robustness of the prediction models was also investigated and discussed.

Spectrophotometric Analysis of Phenolic Compounds in Grapes and Wines.

Phenolic compounds are of crucial importance for red wine color and mouthfeel attributes. A large number of enzymatic and chemical reactions involving phenolic compounds take place during winemaking and aging. Despite the large number of published analytical methods for phenolic analyses, the values obtained may vary considerably. In addition, the existing scientific knowledge needs to be updated, but also critically evaluated and simplified for newcomers and wine industry partners. The most used and widely cited spectrophotometric methods for grape and wine phenolic analysis were identified through a bibliometric search using the Science Citation Index-Expanded (SCIE) database accessed through the Web of Science (WOS) platform from Thompson Reuters. The selection of spectrophotometry was based on its ease of use as a routine analytical technique. On the basis of the number of citations, as well as the advantages and disadvantages reported, the modified Somers assay appears as a multistep, simple, and robust procedure that provides a good estimation of the state of the anthocyanins equilibria. Precipitation methods for total tannin levels have also been identified as preferred protocols for these types of compounds. Good reported correlations between methods (methylcellulose precipitable vs bovine serum albumin) and between these and perceived red wine astringency, in combination with the adaptation to high-throughput format, make them suitable for routine analysis. The bovine serum albumin tannin assay also allows for the estimation of the anthocyanins content with the measurement of small and large polymeric pigments. Finally, the measurement of wine color using the CIELab space approach is also suggested as the protocol of choice as it provides good insight into the wine's color properties.

Robust Ultraviolet-Visible (UV-Vis) Partial Least-Squares (PLS) Models for Tannin Quantification in Red Wine.

The validation of ultraviolet-visible (UV-vis) spectroscopy combined with partial least-squares (PLS) regression to quantify red wine tannins is reported. The methylcellulose precipitable (MCP) tannin assay and the bovine serum albumin (BSA) tannin assay were used as reference methods. To take the high variability of wine tannins into account when the calibration models were built, a diverse data set was collected from samples of South African red wines that consisted of 18 different cultivars, from regions spanning the wine grape-growing areas of South Africa with their various sites, climates, and soils, ranging in vintage from 2000 to 2012. A total of 240 wine samples were analyzed, and these were divided into a calibration set (n = 120) and a validation set (n = 120) to evaluate the predictive ability of the models. To test the robustness of the PLS calibration models, the predictive ability of the classifying variables cultivar, vintage year, and experimental versus commercial wines was also tested. In general, the statistics obtained when BSA was used as a reference method were slightly better than those obtained with MCP. Despite this, the MCP tannin assay should also be considered as a valid reference method for developing PLS calibrations. The best calibration statistics for the prediction of new samples were coefficient of correlation (R2val) = 0.89, root mean standard error of prediction (RMSEP) = 0.16, and residual predictive deviation (RPD) = 3.49 for MCP and R2val = 0.93, RMSEP = 0.08, and RPD = 4.07 for BSA, when only the UV region (260-310 nm) was selected, which also led to a faster analysis time. In addition, a difference in the results obtained when the predictive ability of the classifying variables vintage, cultivar, or commercial versus experimental wines was studied suggests that tannin composition is highly affected by many factors. This study also discusses the correlations in tannin values between the methylcellulose and protein precipitation methods.

Impact of caffeic acid addition on phenolic composition of tempranillo wines from different winemaking techniques.

The effect of prefermentative and postfermentative caffeic acid (CFA) addition, prefermentative cold maceration, and a simulation of the micro-oxygenation technique through acetaldehyde addition on the phenolic and color composition of Tempranillo wines was investigated. Cold soaking and dry ice addition were performed as prefermentative techniques. Wines were analyzed after the end of the malolactic fermentation and after 6 and 12 months' storage. The results showed an important effect in wines to which CFA had been added, suggesting intramolecular copigmentation reactions through direct interaction between anthocyanins and free phenolic acids, thereby increasing the acylated anthocyanin fraction with an increase in color stability. The higher concentration of total phenols and lower hue values in CFA-added wines also contributed to the stability of these compounds during storage. Prefermentative cold maceration was shown to be influenced by the vintage. Phenolic acids, the acylated anthocyanin fraction, and total phenolics showed higher values in CFA-added and acetaldehyde-added wines. No differences were found in color density between the control wines and both the prefermentative and postfermentative CFA-added wines. However, a higher anthocyanin polymeric fraction and higher acylated anthocyanins, phenolic acids, and total phenols were observed in the CFA-added wines. The implications of this for the color stability of Tempranillo are also discussed.