Geographically indicated amasya apple cider vinegar, enriched with ultrasonically processed horsetail herb

Abstract

This invention relates to a novel vinegar type, specifically an apple cider vinegar produced through a method distinct from standard vinegar production techniques in the food industry, involving the unprecedented addition of horsetail herb and the application of ultrasonic technology to fortify total phenolic content and antioxidant activity, resulting in a vinegar enriched in total phenolics, total flavonoids, phenolic compounds, antioxidant activity, and mineral content, while also exhibiting favourable sensory properties.

Description

[0001]DESCRIPTION GEOGRAPHICALLY INDICATED AMASYA APPLE CIDER VINEGAR, ENRICHED WITH ULTRASONICALLY PROCESSED HORSETAIL HERB TECHNICAL FIELD This invention relates to a novel vinegar variety, distinct from standard vinegar production methods in the food industry, involving the preparation of apple cider vinegar enriched with horsetail and treated with ultrasonic technology to achieve a product rich in total phenolics, total flavonoids, phenolic compounds, antioxidant activity, and mineral content, while also exhibiting favourable sensory properties. STATE OF THE ART According to TS 1880 Vinegar Standard, ‘vinegar is defined as a unique product produced biologically by two separate fermentations (alcoholic and acetic acid fermentation) from liquids or other substances of agricultural origin’. In the same standard, vinegar types according to the raw materials used in vinegar production are as follows: wine vinegar, fruit vinegar, fruit wine vinegar, cider vinegar, alcohol vinegar, spicy vinegar (flavoured vinegar), cereal vinegar, malt vinegar, honey vinegar, whey vinegar and beer vinegar. Vinegar is a fermentation product obtained from different raw materials by different methods. Vinegar is defined as the product of a biochemical phenomenon in which ethyl alcohol is converted into acetic acid by acetic acid bacteria in acetic acid fermentation. In the vinegar types for which patent applications were previously made, it was determined that vinegar types produced from various plants and fruits and production methods were discussed (Patent numbers; 2021 / 010763, 2021 / 004175, 2020 / 19026, 2019 / 22934, 2019 / 07305, 2019 / 05253, 2019 / 03043, 2018 / 14093, 2018 / 03037, 2017 / 19753, 2017 / 17971, 2017 / 15122, 2017 / 14904, 2016 / 07467, 2009 / 03835, 2007 / 04554, GE-534255, G-36092, G-129554, CN202310624096A, CN201710119882A, RO135510A2, RO135309A2. The innovations and differences in our invention from the state of the art (prior art) can be summarised as follows; -It differs from international patents GE-534255, G-36092 and G-129554 as raw material. In the patent GE-534255, the process and the product obtained is completely different from the organic throat lozenge with sage, honey and apple cider vinegar. In the G-36092 patent; 25- 35% dried, shredded medicinal plants (St. John's wort, horse chestnut, mistletoe, nettle, moxibustion, moxibustion, sheep's eye -May chamomile- and horsetail) were mixed with 65- 70% apple cider vinegar for five to ten minutes every two days for at least three weeks. The product obtained is completely different from our invention. In the patent G-129554, 25-35% dried and shredded medicinal plants (St. John's wort, horse chestnut, mistletoe, nettle, moxibustion, moxibustion, sheep's eye -May chamomile- and horsetail) are mixed with 65-70% apple cider vinegar for five to ten minutes every two days for at least three weeks and apple cider vinegar tincture (solution, manufacturing method) is obtained and is completely different from our invention. CN202310624096A relates to a method for enhancing the flavour of vinegar and rapid ageing of vinegar by applying first ultrasound treatment and then freezing process under micro-aerobic environment, which is completely different from our invention. The patent CN201710119882A includes a pre-mixing stage, a mechanical mixing and ultrasound stage and a packaging stage applied to the vinegar; the aim is to ensure homogeneous mixing and the same appearance in all parts of the encapsulated vinegar, but it is completely different from our invention. RO135510A2 is intended to obtain porous structures based on calcium pyrophosphate using biocellulose membranes as template. It is to produce implants in mineral structure after filling the cellulosic structure with calcium phosphate by using apple cider vinegar and applying ultrasound for bone repair and regeneration. RO135309A2 comprises ultrasonic extraction or pressure leaching processes for the extraction of bioactive substances from medicinal and aromatic plants and is completely different from our work. The vinegar produced from geographical indicated Amasya apple fortified with ultrasound- treated horsetail herb has the following important features. - Pine honey preferred as a carbohydrate source was not used in other studies. - The mass ratios of raw materials and microorganism cultures used in production differ from other studies. -As in other studies, alcohol fermentation and acetic acid fermentation is a known technique in vinegar production. However, in this invention, a non-thermal technology, ultrasound, was applied in order to give new properties to vinegar and to be innovative. Response surface methodology (RSM) and adaptive network based fuzzy inference system model (ANFIS) were used to optimise the ultrasound conditions. Ultrasound with time and amplitude specific to our invention was applied to the apple cider vinegar produced by using the firstly obtained horsetail herb and pine honey, and vinegar produced from geographical indicated Amasya apples fortified with ultrasound-treated horsetail herb was obtained. - Ultrasound-treated Amasya apple cider vinegar with geographical indication is rich in total phenolic, total flavonoid, phenolic compound and mineral content and has good sensory properties compared to untreated, unenriched apple cider vinegar. Unlike other vinegar types, the quality values and superiorities of the vinegar produced from geographical indicated Amasya apple cider vinegar fortified with ultrasound-treated horsetail herb were determined with our laboratory study results (total phenolic, total flavonoid, phenolic component, mineral content, physical properties, sensory properties and changes of all components and properties during 24 months of storage). The differences from other vinegar types are clearly stated with the features we have mentioned above. The production of vinegar obtained from Amasya apple with geographical indication fortified with ultrasound-treated horsetail herb is schematised in Figure 1. DEFINITION OF THE INVENTION The vinegar subject to the application is a new type of vinegar fortified with geographical indicated Amasya apple and horsetail herb, processed using non-thermal ultrasound technology, rich in total phenolic, total flavonoid, phenolic component and mineral content and having superior sensory properties. The inventive product does not contain any additives and preservatives. It also contains no synthetic dyes or other colouring agents. At the same time, natural pine honey is used as carbohydrate source. It does not contain glucose and sweeteners. The present invention represents a type of vinegar which is rich in total phenolics, total flavonoids, phenolic compounds and mineral content and whose good sensory properties have been proven by optimisation (Response Surface Method and Adaptive network based fuzzy inference system) through laboratory studies. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1: Flowchart of the present invention DESCRIPTION OF THE INVENTION The invention is described with the lettering indicated in the flow diagram to facilitate understanding. The apples to be used in the production were collected (A). The apples were made ready for vinegar production by sorting and cleaning (B). Then, apple juice was obtained from the apples (C). Raw materials were mixed with pine honey as carbohydrate source to fortify the yeast and acetic acid bacteria substrate (Ç). For the first fermentation of the production process, Saccharomyces cerevisiae yeast was inoculated into the mixture at a rate of 0.4% by considering the environmental hygiene and microbiological rules and left for fermentation at 28 °C and terminated after 24 days (D-E). For the second fermentation, 5% acetic acid culture was inoculated and the second fermentation was carried out at 28 °C for 60 days (F-G). The second fermentation was analysed to contain about 4% acetic acid and the microorganism with cellulosic structure called mother of vinegar was removed from the vinegar and vinegar formation was terminated (Ğ-H). Various quantities of horsetail herb (Equisetum arvense) were added (1%, 3%, and 5%) (I). The filtered vinegars were treated with ultrasonicator at different amplitudes and durations [amplitude (40%, 60% and 80%), treatment time (4, 7 and 10 minutes)] (İ). The obtained data were modelled by Response Surface Method (RSM) and Adaptive Network Based Fuzzy Inference System (ANFIS) model and the best optimisation result was obtained as apple cider vinegar with the addition of horsetail herb, which is rich in total phenolic, total flavonoid, phenolic compound and mineral content and has good sensory properties (J). Optimisation process conditions (2.6% horsetail herb; 7.3 minutes and 57.4% amplitude ultrasound treatment) were determined for obtaining the best product (K). The rested, ultrasonically treated apple cider vinegar supplemented with the horsetail herb was bottled in sterile glass bottles of different volumes under aseptic conditions (L). The bottled ultrasonically treated apple cider vinegar supplemented with horsetail herb was finalised to be stored under normal room conditions (M). Table 1 shows the results of the analysis of the vinegar produced from geographical indicated Amasya apple, which is rich in total phenolic, total flavonoid, phenolic compound and mineral content and has good sensory properties. At the same time, appropriate equations 1 and 2 for RSM and ANFIS models are shown below. Total phenolic substance Table 1. Optimisation results of total phenolic substance and DPPH values of vinegar produced from geographically indicated Amasya apples fortified with ultrasound-treated horsetail herb Some quality values of the vinegar produced from geographical indicated Amasya apple cider vinegar fortified with ultrasound-treated horsetail herb were proved by analyses. The phenolic contents detected in the traditional apple cider vinegar fortified with ultrasound-treated horsetail herb are shown in Table 2. Among the phenolic contents evaluated during the study, kaempferol was found to have the highest concentration in the traditional apple cider vinegar fortified with ultrasound-treated horsetail herb. It was found that phenolic contents generally decreased with 24 months of storage, but the concentrations of some phenolic components increased with time. Table 2. Phenolic compounds of vinegar produced from geographical indicated Amasya apples fortified with ultrasound-treated horsetail herb during storage Storage Period (months) The mineral analysis results of the vinegar produced from geographical indicated Amasya apples fortified with ultrasound-treated horsetail herb are shown in Table 3. According to the analysis results, the highest mineral concentration was K (9 ppm). In this study, Na, Zn, Mg and Mn were measured at 0.56 ppm, 0.06 ppm, 0.02 ppm and 0.02 ppm, respectively. A significant amount of iron (0.18 ppm) was detected in vinegar samples produced from geographical indicated Amasya apple fortified with ultrasound-treated horsetail herb. At the end of 12 months, no significant change in sodium concentration was observed (p<0.05). Table 3. Mineral content of vinegar produced from geographical indicated Amasya apples fortified with ultrasound-treated horsetail herb during storage The results of total phenolic content (TPC), total flavonoid content (TFC), DPPH (1,1-diphenyl- 2-picrylhydrazyl) Radical Capture (%) and Copper Reducing Antioxidant Capacity (CUPRAC) values during storage of vinegar samples produced from geographical indicated Amasya apples fortified with ultrasound-treated horsetail herb are given in Table 4. In this study, TPC, TFC, DPPH and CUPRAC were found to be 96.91±0.75 mg GAE / L, 46.69±0.76 mg CE / L, 0.487±0.013 mg TEAC / mL and 59.94±1.81%, respectively at the beginning of storage and it was determined that a significant decrease occurred in TPC, TFC, DPPH and CUPRAC values according to the results at 24th month. Table 4. Total phenolic, total flavonoid, phenolic compound, antioxidant activity values of vinegar produced from geographical indicated Amasya apples fortified with ultrasound-treated horsetail herb during storage The colour, TA, pH and Brix results of the vinegar samples produced from geographical indicated Amasya apple fortified with ultrasound-treated horsetail herb are shown in Table 5. In the study, pH and TA were determined as 3,57±0,01 and 5,21±0,03 g / 100 ml. While a high level of acid was detected in the vinegar samples at the beginning, a significant decrease in acid levels was detected after 24 months of storage. There was no statistically significant difference between all samples in terms of Brix value during the storage period. In this study, L* value (lightness) increased and a* (green) value decreased during 24 months of storage. Table 5. Physicochemical properties of vinegar produced from geographical indicated Amasya apples fortified with ultrasound-treated horsetail herb during storage The sensory properties of vinegar samples produced from geographical indicated Amasya apples fortified with ultrasound-treated horsetail herb were evaluated at 0, 6, 12, 18 and 24 months by 34 trained panellists (Table 6). Sensory characteristics of the vinegar samples during storage (colour, pungency, aroma richness, overall impression, taste, aromatic intensity, ethyl acetate odour) were investigated. For all sensory characteristics, the first month scores were higher than the scores at the end of storage (24 months). As shown in Table 6, the sensation of pungency was not significantly affected during storage of apple cider vinegar. Table 6. Sensory properties of vinegar produced from geographical indicated Amasya apples fortified with ultrasound-treated horsetail herb during storage

Claims

CLAIMS 1. The invention is the production of geographical indicated Amasya apple cider vinegar fortified with ultrasound-treated horsetail herb, characterised in that it comprises the following process steps: - Sorting and cleaning the apples, adding carbohydrate source (10 % pine honey by weight) and water to obtain the first mixture, - adding 60% water by weight to the mixture and obtaining apple juice, - inoculation of Saccharomyces cerevisiae into the prepared mixture to induce ethyl alcohol fermentation, - Addition of Ellipsoideus yeast at 0.4%, - After the formation of ethyl alcohol, adding acetic acid bacteria (Acetobacter spp. and Gluconobacter spp. culture) at the rate of 5% for acetic acid fermentation to complete vinegarisation, - fermentation at 28 ◦C for 60 days, - removal of the mother vinegar after fermentation and filtration, - Addition of a determined amount of horsetail herb (preferably 2.6% horsetail; 7.3 minutes and 57.4% amplitude ultrasound treatment) to increase total phenolic matter and antioxidant activity after vinegar formation, optimised by response surface method and adaptive network based fuzzy inference system, - ultrasonic processing, preferably with amplitudes of 40%, 60% and 80% and preferably with processing times of 4, 7 and 10 minutes, - Resting process with Response Surface Method (RSM) and Adaptive Network Based Fuzzy Inference System (ANFIS) for optimisation of the conditions, - bottling under aseptic conditions.

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