Synthetic Vanillin Research Articles

Production of Vanillin from Pineapple Peels Using Alkaline Hydrolysis and Microbial Fermentation

Vanillin is one of the most commonly utilized aromatic flavoring chemicals in the food and cosmetics industries. It is derived from natural sources, making it more expensive than synthetic vanillin, and it constitutes less than one percent of the annual market demand. Pineapple peel stands out as a valuable source for extracting ferulic acid, which in turn is utilized in the synthesis of vanillin. As a result, researchers are exploring alternative methods for producing vanillin, such as biotechnological production from ferulic acid. In this study, the capability of pineapple peels as a substrate for the microbial fermentation of ferulic acid by Aspergillus niger to produce vanillin in a single step was investigated. The biotransformation of ferulic acid from pineapple peel by alkaline hydrolysis was optimized using different concentrations of NaOH. Further, the detection and quantification of vanillin and ferulic acid were carried out using High-Performance Liquid Chromatography and thiobarbituric acid (TBA) method. Through HPLC analysis, the amount of vanillin concentration produced from the supernatant culture was 1.47±0.24 µg/ml from 1.0 M NaOH concentration and 2.83±0.44 µg/ml from 2.0 M NaOH concentration. From this study, 57.09±1.84 µg/ml and 83.84±4.01 µg/ml of ferulic acid were produced from the 1.0 M NaOH and 2.0M NaOH, respectively. In addition, using the TBA technique, vanillin concentrations were calculated, resulting in 12.92 ± 0.54 µg/ml and 15.38 ± 0.77 µg/ml from 1.0 M and 2.0 M NaOH concentrations, respectively. Briefly, the pineapple peel has been discovered as a good source for vanillin production using Aspergillus niger in the fermentation method.

Sniffing Out the Sustainable Future: The Renewability Revolution in Fragrance Chemistry.

In this review, the impact of the transition from today's resource-wasting petrochemical economy towards a 100/100 renewable and biodegradable future is discussed with respect to the fragrance families: "citrus", "green", "fruity", "floral", "floriental", "oriental", "woody", "chypre" and "fougère". After benchmark data on ingredients usage, definitions on biodegradation and sustainability are given. Celebrating the 150th anniversary of synthetic vanillin, its historic synthesis from renewable starting materials serves as introduction. In the grand scheme of things, citrus scents upcycled from the beverages industry, are already an ideal case for 100/100 with new opportunities for artificial essential oils. In the fruity domain, transparent and lactonic ingredients are available in a sustainable manner. However, in the domain of green odorants, there is a lack of green chemistry for important key materials. In the floral family, renewability is more critical than biodegradability, but cost is an issue. Thanks to Ambrox and maltol, florientals and orientals will persist, while woody notes severely lack an Iso E Super replacer. In the chypre genre, patchouli became the new moss, but more musks are increasingly in demand. With their high percentage of linalool and dihydromyrcenol, the construction of fougères could well become a precedent for other families, despite challenges in vetiver and salicylates. Still, the challenges exemplified here create immense opportunities for new perfumery materials.

The agroforests of the east coast of Madagascar

This article explores the significance, challenges, and future prospects of Madagascar’s cash crops: vanilla, cloves, lychees, black pepper and cinnamon. Cultivated by small-scale farmers in biodiverse agroforestry plots, these cash crops have historical importance in Madagascar's export-oriented economy that has seen Madagascar become the world's leading producer of vanilla, the second largest exporter of cloves and essential clove oil, and the leading exporter of lychees to the European market. Despite contributing substantially to the country's exports, farmers remain vulnerable, as the markets for these products are controlled by global food industry giants and are subject to significant price fluctuations. Other factors that contribute towards farmer’s vulnerability include climate change, local security conditions, competition from other producing countries and the introduction of synthetic vanillin. Despite the volatilities, farmers’ income and food security remain tied to these cash crops. Diversification is recommended to ensure better resilience against volatile conditions, including diversification of crops, land management practices, and product uses. By adapting agroforests to integrate a variety of cash crops and food crops, farmers’ income and food security will be protected long-term. Further research on agro-biodiversity management is now needed to continue to mitigate market dynamics and environmental challenges.

From Waste to Value: Recent Insights into Producing Vanillin from Lignin.

Vanillin, one of the most widely used and appreciated flavoring agents worldwide, is the main constituent of vanilla bean extract, obtained from the seed pods of various members belonging to the Orchidaceae family. Due to the great demand in the food confectionery industry, as well as in the perfume industry, medicine, and more, the majority of vanillin used today is produced synthetically, and only less than one percent of the world's vanilla flavoring market comes directly from the traditional natural sources. The increasing global demand for vanillin requires alternative and overall sustainable new production methods, and the recovery from biobased polymers, like lignin, is an environmentally friendly alternative to chemical synthesis. The present review provides firstly an overview of the different types of vanillin, followed by a description of the main differences between natural and synthetic vanillin, their preparation, the market of interest, and the authentication issues and the related analytical techniques. Then, the review explores the real potentialities of lignin for vanillin production, presenting firstly the well-assessed classical methods and moving towards the most recent promising approaches through chemical, biotechnological and photocatalytic methodologies, together with the challenges and the principal issues associated with each technique.

Solvay plans synbio hub in the US

The big Belgian chemical maker Solvay has formed a partnership with the US synthetic biology firm Ginkgo Bioworks in a bid to develop more biobased products. As part of the agreement, Solvay will acquire a lab in Cambridge, Massachusetts, that Ginkgo got in 2022 as part of its $300 million purchase of Zymergen . The partnership’s initial focus will be on developing biopolymers and specialty chemicals for markets including home and personal care, agriculture, and food. Solvay is seeking to develop biomaterials for both existing and new markets, CEO Ilham Kadri says in a press release . “Biotech is the future and this step is an important milestone for our growth platform,” she says. Biobased products that Solvay already produces include a natural alternative to synthetic vanillin, a polymer sourced from guar seeds, and rice-husk-derived silica for tires . Ginkgo’s core capability is the programming of cells to make food,

Characterization of vanillin carbon isotope delta reference materials

Stable carbon isotope ratio measurements are used to investigate the provenance of vanillin. In this study, a variety of commercial vanillin samples and vanilla products were analyzed to provide a frame of reference for the variability of carbon isotope delta values in various vanillin samples, with the results ranging from −20.6 to −36.7‰ relative to the Vienna Peedee Belemnite (VPDB). We present information on the development of two synthetic vanillin reference materials, VANA-1 and VANB-1, prepared in 0.75 g units in glass vials, to be used for the calibration of carbon isotope delta measurements of vanillin and other easily combustible organic materials. Characterization of 40 vials each of VANA-1 and VANB-1 was performed by three laboratories over several measurement sequences. The certified carbon isotope delta values are −31.30 ± 0.06‰ (VANA-1) and −25.85 ± 0.05‰ (VANB-1). These uncertainties, for the 95% confidence level, include considerations for measurement uncertainty, coherence of the reference materials used for calibration, batch homogeneity, and stability during storage and transportation. The results are traceable to the VPDB through a set of nine reference materials (IAEA-CH-6, USGS65, IAEA-600, NBS22, USGS61, IAEA-603, IAEA-610, IAEA-611, and IAEA-612). For up to date certified values, users should refer to doi.org/10.4224/crm.2022.vana-1 and doi.org/10.4224/crm.2022.vanb-1.

Olfactory impact of guaiacol, ortho-vanillin, 5-methyl, and 5-formyl-vanillin as byproducts in synthetic vanillin.

To better control the quality of synthetic vanillin obtained by using the guaiacol synthesis method, the olfactory impacts of byproducts on the aroma of the synthetic vanillin samples were evaluated and their optimum concentration ranges were determined. Four byproducts (guaiacol, ortho-vanillin, 5-methyl-vanillin, and 5-formyl-vanillin) were identified by gas chromatography-mass spectrometry (GC-MS) and quantified by gas chromatography-flame ionization detection (GC-FID) in the synthetic vanillin samples with different degrees of purity. The aroma intensities (AIs) of the four byproducts obtained by gas chromatography-olfactometry (GC-O) were: guaiacol (AI: 3.5-4.0, smoke), ortho-vanillin (AI: 1.6-2.5, almond), 5-methyl-vanillin (AI: 2.5-3.3, aldehyde), and 5-formyl-vanillin (AI: 3.2-3.8, green). The aroma perceptual interactions of the four byproducts and the vanillin in the synthetic vanillin samples were determined by S-curve analysis. Guaiacol and 5-methyl-vanillin showed synergistic effects by Feller's additive model. Combined with the results of an addition experiment, when the contents of guaiacol, ortho-vanillin, 5-methyl-vanillin, and 5-formyl-vanillin were within 50, 10, 400, and 1,000mg/kg respectively, the byproducts had no effects on the aroma quality of the synthetic vanillin samples. PRACTICAL APPLICATION: Synthetic vanillin is one of the most commonly used food additives. Currently, the purity of synthetic vanillin can reach 99.9%, but trace byproducts are still present. Continuing to improve the purity of synthetic vanillin will significantly increase its production costs. Therefore, it is necessary to determine whether the presence of these byproducts affects the aroma quality of the synthetic vanillin samples or not. If they have a negative effect on its aroma, it will be important to reduce their content. If they have no influence or positive role, there is no need to control the content of these byproducts to very low levels. This study determined the content of the byproducts produced during the synthesis of vanillin by guaiacol glyoxylic acid method, judged the perceptual interaction between the byproducts and the vanillin in the synthetic vanillin samples, and determined the optimum range within which the byproducts had no effects on the aroma quality. This study provides a theoretical basis for improving the aroma quality of synthetic vanillin while controlling the production costs.

Effect-directed profiling of 32 vanilla products, characterization of multi-potent compounds and quantification of vanillin and ethylvanillin

Food testing is of great importance to the food industry and organizations to verify the authenticity claims, to prove the quality of raw materials and products, and to ensure food safety. The market prices of vanilla differed by a factor of about 20 in the last three decades. Therefore the risk of adulteration and counterfeiting of vanilla products is high. Instead of commonly used target analyses and sum parameter assays, a complementary non-target multi-imaging effect-directed screening was developed, which provided a new perspective on the wide range of vanilla product qualities on the market. Planar chromatography was combined with effect-directed assays, and the obtained biological and biochemical profiles of 32 vanilla products from nine different categories revealed a variety of active ingredients. Depending on the region, typical vanilla product profiles and activity patterns were obtained for pods, tinctures, paste (inner part), oleoresin and powders. However, some vanilla products showed additional active compounds and a different intensity pattern. The vanilla product profiles substantially differed from those of vanilla aroma or products containing synthetic vanillin or vanilla-flavored food products. Bioactive compounds of interest were online eluted and further characterized via HPTLC−HRMS, which allowed their tentative assignment. After purchase of the standards, these were successfully confirmed by co-chromatography. Quantification of vanillin across nine different product categories revealed levels ranging from 1 µg/g to 36 mg/g with a mean repeatability of 1.9%. The synthetic ethylvanillin was not detected in the investigated samples in significant concentrations. The assessment of differences in the activity patterns pointed to highly active compounds, which were not detected at UV/Vis/FLD but first via the biological and enzymatic assays. This effect-directed profiling bridges the gap from analytical food chemistry to food toxicology, and thus, makes an important contribution to consumer safety. In the same way, it would accelerate investigations for Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH) according to Regulation (EC) No. 1907/2006.

184 Evaluation of Aviplus on Growth Performance of Nursery and Growing-finishing Pigs

Abstract A total of 1,215 pigs (L337×1050, PIC, Hendersonville, TN) were used in a 156-d wean-to-finish experiment. Pigs were weaned at 21 d of age and placed in pens based on initial body weight (BW) with 27 pigs/pen. There were three dietary treatments including a: 1) control; 2) pigs fed diets containing AviPlus (micro-encapsulated sorbic and citric acids and synthetic thymol and vanillin botanicals; Vetagro Inc., Chicago, IL) during the nursery and finisher phases; or 3) pigs fed AviPlus during the nursery but not the finishing phase. AviPlus was included at 2.72 kg/ton from d 0 to 21, 0.90 kg/ton from d 21 to 42, and 0.45 kg/ton from d 42 to 156. Thus, there were 15 control pens and 30 Aviplus pens in the nursery and 15 pens for the 3 treatments in the finisher phase. On d 42, pigs were transported as intact pens to the finishing facility. Data were analyzed as a RCBD with pen as experimental unit. For the overall nursery period (d 0 to 42), pigs fed AviPlus had improved (P < 0.05) G:F, with no evidence of difference (P > 0.05) for d 42 BW, ADG, or ADFI. For the overall finishing period (d 42 to 156) and overall experimental period (d 0 to 156), there was no evidence of difference (P > 0.05) for BW, ADG, ADFI, or G:F. There was no evidence of difference (P > 0.05) observed for mortality and removals during the nursery, finisher, or overall. In summary, providing AviPlus during the nursery improved nursery G:F, but there was no effect on overall wean-to-finish performance.

Identifying environmental hotspots and improvement strategies of vanillin production with life cycle assessment

Vanillin, an important aroma chemical, can be synthesized through industrial oxidation processes and biotechnological processes. Studying the environmental impacts of synthetic vanillin production processes is fundamental to making these processes feasible and sustainable; however, few studies have focused on such analyses. This study involved performing a life cycle assessment (LCA) to evaluate multiple industrial synthesis and biosynthesis processes for producing synthetic vanillin. The results indicated that human toxicity potential (HTP) appeared to be the most affected indicator among all the impact categories considered. The dominant drivers of the HTP of the vanillin synthesis process were electricity consumption and ultrapure water consumption. Improvement strategies were then proposed to investigate the possibility of reducing the environmental burdens created by vanillin synthesis. Natural gas power generation was determined to be the best choice for replacing traditional coal-fired power generation, thus reducing the negative impacts of these processes on the environment. The best ways to reduce chemical consumption were to recover organic solvents and to replace ultrapure water with industrial or distilled water. All these improvement strategies were demonstrated to be able to effectively reduce the HTP. In addition, suggestions for evaluating scaled-up vanillin production, increasing the LCA coverage to include technological advancements in biosynthesis techniques, and introducing cost-benefit analysis into the LCA were discussed.

ЗМІНА ЧИСЕЛЬНОСТІ У DROSOPHILA MELANOGASTER НА ФОНІ ВИКОРИСТАННЯ КОНДИТЕРСЬКОГО АРОМАТИЗАТОРА «ВАНІЛІН»

Nowadays it is difficult to imagine the food industry without the use of various food additives, such as flavors, flavor enhancers, emulsifiers, dyes and other food mixtures, which make food both tasty looking and delicious.
 Vanilla is found in many essential oils, particularly in the pods of Vanilla planifolia and Vanilla pompona. Natural extract of the most popular fragrance in the world is very expensive and is not available in stores. Therefore, in order to meet the needs of the food industry, the artificial Vanillin flavor is made.
 The negative effect of synthetic vanillin is quite obvious, because it contains chemical compounds harmful to health. The most dangerous component of this fragrance is coumarine. Since this mixture is a carcinogen, it can ruin the liver. In addition, imitation of natural vanillin does not contain the salubrious components present in the authentic product.
 Taking into consideration the fact that the use of synthetic “Vanillin” flavor is widely used by the food industry and the harmful effects on the body have not been properly studied, there is a need to study the effect of “Vanillin” flavor on the physiological and reproductive functions of organisms.
 As the object of study, Drosophila melanogaster of lines Normal, vestigial, and white have been used, their descendants have been counted. Aiming to study the genotoxic effects of the liquid synthetic “Vanillin” flavor, it was added to a standard nutrient medium (50 ml) at the recommended dose (0.25 mg), a dose of 10-fold (2.5 mg) and a dose of 20-fold (5 mg) The medium was dispensed into test tubes, each of them containing 14 Drosophila melanogaster flies (6 females and 8 males). The quantity of each line has been calculated on the 8th, 12th and 16th days.
 It was experimentally determined that the use of the recommended dose of flavoring as well as the doses increased by 10 and 20 times, contributed to the increase in the number of Normal line compared to the control group by 10.98%, 9.89% and 5.92% respectively. An increase in number was also observed in the vestigial line. The white line showed a decrease in offspring by 21.3% and 11.1%, respectively, after the addition of the recommended dose and the dose increased by 10 times. However, the addition of 10-fold increased dose resulted in an increase by 137%.

Medicinal and Pharmaceutical Properties of Vanilla planifolia

Introduction: Spices are an ingredient that today is considered indispensable in the kitchen not only for the important role of flavoring and coloring food, but also for the antibacterial, antioxidant, eupeptic, antidiabetic and anticancer properties, which have been highlighted through chemical and pharmacological analysis. Methods: In order to use spices in the food sector, it is necessary to have a product with characteristics of authenticity and genuineness such as to protect the consumers from possible health risks. The aim of the present study was to find the best extractive conditions for vanilla capsules with the use of different solvents such as ethyl ether, methyl alcohol and dichloromethane and subjecting the extracts obtained to qualitative and quantitative analysis. Results: From the analysis carried out it was possible to highlight that the main component of the vanilla pod is vanillin from which the particular aroma derives. Other important compounds are: vanillic acid, p-hydroxybenzoic acid, p-hydroxybenzaldehyde, anisic alcohol; and vanillin degradation products which are also available in small concentrations. In addition, the following flavonoids have been identified: rutin, morine, quercetin, myricetin, kaempferol, apigenin, whci are considered to be responsible for pharmacological activities. Conclusions: Knowledge of chemical composition of a spice is necessary to guarantee its authenticity. In the case of vanilla, possible sophistications can be highlighted considering the relationship between vanillin and the other main components which in the natural extract is well defined and, in addition to being an index of good quality, allows to identify the origin of the plant and to discover any adulterations,as by adding synthetic vanillin or other spices.

Isotopic characterization of vanillin ex glucose by GC-IRMS - New challenge for natural vanilla flavour authentication?

Vanilla flavour is highly vulnerable to economically motivated adulteration as the main component vanillin can be derived by much cheaper production methods than by the extraction from vanilla pods. The δ13C ranges for synthetic vanillin from petroleum and C3 plants are depleted in comparison to the reported δ13C range for vanillin from vanilla orchids. However, with the invention of new biosynthetic pathways, vanillin overlapping with the characteristic δ13C range reported for vanillin from vanilla pods can be produced. Here, we present bulk and site-specific analysis by GC-IRMS of stable carbon and hydrogen isotope ratios of vanillin derived from glucose. This is the first time a δ13C value for biovanillin that is higher compared to vanillin from vanilla pods is reported. The possibility to simulate the δ13C range of vanillin from vanilla pods by combining vanillin derived from inexpensive sources constitutes an increased risk for fraud being perpetrated while remaining unnoticed.

C and H stable isotope ratio analysis using solid-phase microextraction and gas chromatography-isotope ratio mass spectrometry for vanillin authentication

It is possible to distinguish precious vanillin from Vanilla species (planifolia or tahitensis) from much less expensive synthetic and nature-identical vanillin on the basis of the stable isotope ratios of H and C (2H/1H, 13C/12C). Analysis is usually performed using GC-IRMS (Gas Chromatography - Isotope Ratio Mass Spectrometry) after solvent extraction of vanillin from the sample. Recently, head-space solid-phase microextraction (HS-SPME) has been proposed as an alternative for determining 13C/12C.The aim of this study was to develop a method to analyse 2H/1H in vanillin using SPME-GC-IRMS for the first time, by testing different operating conditions and comparing the results with those obtained after solvent extraction. The ultimate scope was to develop a quick, robust and effective method to measure 2H/1H and 13C/12C in vanillin to assess the authenticity of labelling.Almost 50 authentic samples from vanilla pods, nature-identical (ex) and synthetic vanillin and 4 commercial food products were taken into account. All the samples were subjected to HS-SPME-GC-IRMS analysis and most of them to GC-IRMS analysis after solvent extraction of vanillin.The SPME method developed for 2H/1H analysis guarantees the absence of isotopic fractionation, repeatability and reproducibility standard deviation of below 7‰ and savings in terms of time (from 30 to 5 min) and solvent.HS-SPME GC-IRMS analysis of δ2H and δ13C can be proposed as a rapid and robust method to discriminate different types of vanillin and assess the authenticity of natural vanillin, also contained in food matrices.

Societal and Ethical Issues in Industrial Biotechnology.

In this chapter we aim to give an overview of the main societal and ethical issues that are currently voiced around industrial biotechnology. We will illustrate this with some recent cases, such as the development of synthetic artemisinin, synthetic vanillin and vegetable oil produced by engineered algae. We show that current societal and ethical issues in industrial biotechnology centre on the following five themes: sustainability, naturalness, innovation trajectories, risk management and economic justice. In each of these themes, clashing public opinions fuel the public debate on the acceptability of new industrial biotechnology. In some cases this has led to the failure of otherwise promising innovations. In the last part, we provide suggestions on how to deal with these ethical and societal aspects based on the approach of Responsible Research and Innovation (RRI).

Differentiation of wood-derived vanillin from synthetic vanillin in distillates using gas chromatography/combustion/isotope ratio mass spectrometry for δ13 C analysis.

Typical storage in oak barrels releases in distillates different degradation products such as vanillin, which play an important role in flavour and aroma. The addition of vanillin, as well as other aroma compounds, of different origin is prohibited by European laws. As vanillin samples from different sources have different δ13 C values, the δ13 C value could be used to determine whether the vanillin is authentic (lignin-derived), or if it has been added from another source (e.g. synthetic). The δ13 C values for vanillin derived from different sources, including natural, synthetic and tannins, were measured by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS), after diethyl ether addition and/or ethanol dilution. A method for analysing vanillin in distillates after dichloromethane extraction was developed. Tests were undertaken to prove the reliability, reproducibility and accuracy of the method with standards and samples. Distillate samples were run to measure the δ13 C values of vanillin and to compare them with values for other sources of vanillin. δ13 C values were determined for: natural vanillin extracts (-21.0 to -19.3‰, 16 samples); vanillin ex-lignin (-28.2‰, 1 sample); and synthetic vanillin (-32.6 to -29.3‰, 7 samples). Seventeen tannin samples were found to have δ13 C values of -29.5 to -26.7‰, which were significantly different (p < 0.05) from those of the natural and synthetic vanillins. The vanillin δ13 C values measured in distillates (-28.9 to -25.7‰) were mainly in the tannin range, although one spirit (-32.5‰) was found to contain synthetic vanillin. The results show that synthetic vanillin added to a distillate could be differentiated from vanillin derived from oak barrels by their respective δ13 C values. The GC/C/IRMS method could be a useful tool in the determination of adulteration of distillates.

Making a global sensation: Vanilla flavor, synthetic chemistry, and the meanings of purity.

How did vanilla, once a rare luxury, become a global sensation? Rather than taking the vanilla flavor of vanilla beans as a pre-existing natural fact, this essay argues that the sensory experience that came to be recognized as vanilla was a hybrid artifact produced by an expanding global trade in a diverse set of pleasurable substances, including cured beans from artificially pollinated vanilla orchids, synthetic vanillin, sugar, and a far-flung miscellany of other botanical and chemical materials. Global trade and large-scale production resulted not in the production of a homogenous, stable commodity, but in a range of local vanillas, heterogeneous mixtures with a range of qualities and virtues. As local commercial and regulatory interests competed to define the origins, and thus the market value, of authentic vanilla flavor, scientific experts were called upon to adjudicate these rival claims. In the United States, these debates played out in the context of the 1906 Pure Food and Drug Act, where efforts to define and chemically enforce a 'standard' vanilla extract, in contradistinction from adulterated, 'imitation' extracts, clashed with the interests of makers and users of both synthetic and 'genuine' vanilla flavorings. As regulatory chemists grappled with the growing variety of vanillas, they were required to determine the appropriate chemical components of genuine vanilla, and consequently to delimit the subjective sensory effects proper to the flavor. Nonetheless, the materials, experiences, and meanings popularly associated with vanilla flavor continued to exceed the limits prescribed by officials.

Artificial Ingredients In The Crosshairs

This holiday season will be a little less colorful, at least in the grocery store. Earlier this year, General Mills and Kellogg’s—both makers of rainbow-hued cereals aimed at kids—vowed to remove artificial colors and flavors from many of their products. Naturally colored versions of General Mills’ Trix cereal, among others, will hit shelves later this winter. In a similar move, food giant Kraft said it will remove synthetic colors from its iconic macaroni and cheese dinners starting in January. Chocolate lovers may notice that holiday versions of Hershey’s Kisses will not contain ingredients such as synthetic vanillin. Even fast-food chains Taco Bell and Pizza Hut promised to nix additives. Food makers stress that they are reformulating recipes in response to growing consumer preferences, not because the artificial ingredients pose a risk to health. General Mills said its own research shows “49% of households are making an effort to avoid artificial ...

Vanillins relax isolated porcine coronary arterial smooth muscle by inhibiting L‐type Ca2+ channels (LB574)

Vanillin (VA) and vanillyl alcohol (VAA) are major components of natural vanilla, while ethyl vanillin (EtVA) is a synthetic vanillin analog with antioxidant and anti‐inflammatory properties. This study compared the relaxing effect of vanillins (VA, VAA, EtVA) and poly(vanillin) oxalate (PVO) nanoparticles (Ø 260nm) containing VA in porcine coronary artery rings by measuring isometric tension. Vanillins but not PVO caused concentration‐dependent, endothelium‐independent and complete relaxations during contractions to U46619, KCl or endothelin‐1 with an order of potency of VAA&lt;VA&lt;EtVA. The relaxations of U46619 contracted preparations were unaffected by inhibitors of NOS (L‐NAME), cyclooxygenases (indomethacin), soluble guanylyl cyclase (ODQ), KCa (TRAM‐34, UCL‐1684, iberiotoxin), KATP (glibenclamide), Kir (BaCl2), and TRPV3 channels (camphor) or by antioxidants (catalase, apocynin, tempol, N‐acetylcysteine, tiron). Vanillins inhibited contractions induced by both Ca2+ reintroduction in 40mM KCl solution and BayK8644. Both VA and PVOs caused partial relaxation of XO/XOD contracted rings. In conclusion, relaxation to vanillin(s) is solely due to the inhibition of L‐type Ca2+ channels in porcine coronary arteries. Both VA and PVO can prevent contractions induced by superoxide anions, and thus could be used to relieve coronary vasospasm associated with elevated oxidative stress.Grant Funding Source: Supported by Brain Korea 21 PLUS Project, NRF and NRF‐2012M3A9C6050204

APLIKASI REAKSI KATALISIS HETEROGEN UNTUK PEMBUATAN VANILI SINTETIK (3-HIDROKSI-2-METOKSIBENZALDEHIDA) DARI EUGENOL (4-ALLIL-2-METOKSIFENOL) MINYAK CENGKEH

An Application of heterogenous catalysis reaction for synthesis of synthetic vanillin (3-hydroxy-2- methoxybenzaldehyde) from eugenol (4-allyl-2-methoxyphenol) of clove oil. It has been already known, that heterogeneous catalysts have more advantages compared to homogeneous catalysts. This research tried to utilize heterogeneous catalysts for an alternative reaction on synthesis of vanillin from eugenol of clove stem oil. This synthesis needs two steps reactions, isomerization reaction of eugenol to produce isoeugenol and oxidation reaction of isoeugenol to produce vanillin. Two types catalysts were used: (1) solid superbase, which was used on eugenol isomerization, and (2) phase transfer catalyst [18]-crown ether-6, which was used on oxidation of isoeugenol. Solid superbase catalyst was prepared using γ- and η-alumina, treated with sodium hydroxide and sodium metal. Alumina was extracted from kaolin from Belitung island by acid process, and the yield of aluminas were 9.0% γ-Al2O3 and 10.28% η-Al2O3. Heterogeneous catalysis study on eugenol isomerization showed that the reaction could proceed at low temperature. The eugenol isomerization reaction conditions were : temperature 10oC, reaction time 9 hours, clove stem oil 25 mmol, and solid catalyst superbase γ-Al2O3/NaOH/Na 2 g. The result of products conversion were 64.42% transisoeugenol and 6.11% cis-isoeugenol. This study included the comparison activities study of three solid superbase catalysts : γ-Al2O3/NaOH/Na, η-Al2O3/NaOH/Na, and γ-Al2O3 (E.Merck)/NaOH/Na, which showed that γ-Al2O3/NaOH/Na had better activity than those two latter solid superbase catalysts. Study on isoeugenol oxidation reaction using KMnO4 as an oxidazing agent and phase transfer catalyst [18]-crown ether-6, gave the indication that vanillin was produced mixed with other compounds. The yield of vanillin in acid medium (pH 2) was 0.021%, in neutral medium (pH 7) was 0.028% and in basic medium (pH 9) was 0.015%. Keywords: vanillin, heterogeneous catalysis, superbase catalyst; phase transfer catalyst