- A Simple Synthesis of Alliin and allo-Alliin: X-ray Diffraction Analysis and Determination of Their Absolute Configurations
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A simple method for the isolation of the bioactive compound alliin from garlic, as well as a method for the synthesis of diastereomerically pure alliin and allo-alliin on a preparative laboratory scale, was developed. The absolute configuration of the sulfur atom in alliin and allo-alliin was assigned on the basis of enzyme reactivity, optical rotatory dispersion, and circular dichroism analyses. A comparison of the results from these analyses, in combination with an X-ray diffraction study on a protected allo-alliin derivative, revealed S and R configurations of the sulfur atoms in alliin and allo-alliin, respectively. In addition, the same 1H NMR spectrum was observed for synthetic and natural alliin. The absolute configuration of natural alliin was assigned for the first time on the basis of the NMR spectrum and X-ray coordinates.
- Hakamata, Wataru,Koyama, Ryosuke,Tanida, Mizuki,Haga, Tomomi,Hirano, Takako,Akao, Makoto,Kumagai, Hitomi,Nishio, Toshiyuki
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- Effect of physicochemical parameters on the stability and activity of garlic alliinase and its use for in-situ allicin synthesis
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Garlic is a well-known example of natural self-defence system consisting of an inactive substrate (alliin) and enzyme (alliinase) which, when combined, produce highly antimicrobial allicin. Increase of alliinase stability and its activity are of paramount importance in various applications relying on its use for in-situ synthesis of allicin or its analogues, e.g., pulmonary drug delivery, treatment of superficial injuries, or urease inhibitors in fertilizers. Here, we discuss the effect of temperature, pH, buffers, salts, and additives, i.e. antioxidants, chelating agents, reducing agents and cosolvents, on the stability and the activity of alliinase extracted from garlic. The effects of the storage temperature and relative humidity on the stability of lyophilized alliinase was demonstrated. A combination of the short half-life, high reactivity and non-specificity to particular proteins are reasons most bacteria cannot deal with allicin's mode of action and develop effective defence mechanism, which could be the key to sustainable drug design addressing serious problems with escalating emergence of multidrug-resistant (MDR) bacterial strains.
- Janska, Petra,Knejzlík, Zdenek,Perumal, Ayyappasamy Sudalaiyadum,Jurok, Radek,Tokarova, Viola,Nicolau, Dan V.,Tepanek, FrantisekS,Kaspar, Ondrej
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- Type of complex-BSA binding forces affected by different coordination modes of alliin in novel water-soluble ruthenium complexes
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Three novel water-soluble ruthenium complexes having differently bound alliin ligands were prepared by solution synthesis and characterized by chemical analysis, and infrared, mass, nuclear magnetic resonance and electron paramagnetic resonance spectrosco
- Zahirovi?, Adnan,?ili?, Dijana,Paveli?, Sandra Kraljevi?,Huki?, Mirsada,Muratovi?, Senada,Harej, Anja,Kahrovi?, Emira
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p. 5791 - 5804
(2019/04/17)
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- S-allyl-L-cysteine sulfoxide, a garlic odor precursor, suppresses elevation in blood ethanol concentration by accelerating ethanol metabolism and preventing ethanol absorption from gut
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Alcoholic beverages are enjoyed together with meals worldwide, but their excessive intake is associated with an increased risk of various diseases. We investigated whether S-allyl-L-cysteine sulfoxide (ACSO), a sulfuric odor precursor of garlic, suppresses elevation in plasma ethanol concentration by accelerating ethanol metabolism and preventing ethanol absorption from the gut in rats. ACSO and garlic extract with a high ACSO content (Garlic-H) suppressed elevation in concentrations of ethanol and acetaldehyde in plasma and promoted the activities of alcohol dehydrogenase and aldehyde dehydrogenase. However, ACSO and Garlic-H did not affect plasma acetate so much. Furthermore, we examined the change in plasma ethanol concentration by injecting ACSO or Garlic-H into the ligated stomach or jejunum together with ethanol solution. ACSO and Garlic-H suppressed the absorption of ethanol from the stomach and jejunum, but suppression in the jejunum was less than in the stomach. In conclusion, ACSO inhibits ethanol absorption and accelerates ethanol metabolism.
- Uto-Kondo, Harumi,Hase, Ayumu,Yamaguchi, Yusuke,Sakurai, Ayaka,Akao, Makoto,Saito, Takeshi,Kumagai, Hitomi
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p. 724 - 731
(2018/04/12)
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- Changes of S-Allylmercaptocysteine and γ-Glutamyl- S-allylmercaptocysteine Contents and Their Putative Production Mechanisms in Garlic Extract during the Aging Process
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γ-Glutamyl-S-allylmercaptocysteine (GSAMC), a putative precursor compound of S-allylmercaptocysteine (SAMC), was isolated and identified from aged garlic extract (AGE). We analyzed the change of their contents in AGE during the aging process, chronologica
- Fujii, Takuto,Matsutomo, Toshiaki,Kodera, Yukihiro
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p. 10506 - 10512
(2018/10/15)
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- A step-by-step crystallization for preparing thio alkyl/alkenyl cysteine sulfoxide method
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The invention discloses a method for preparing thioalkyl/alkenyl cysteine sulfoxide by fractional crystallization, belonging to the technical field of compound preparation. The method comprises the following steps: adding cysteine or cysteine salts, a sodium hydroxide solution and an R group (alkyl or alkenyl)-derived material into absolute ethanol in sequence for reaction to synthesize coarse ACSs, re-crystallizing ACSs, purifying, oxidizing to form ACSOs, and fractionally crystallizing to obtain natural dextrorotatory ACSOs, wherein the R group-derived material is replaced to synthesize different types of ACSOs in allium; enantiomers in racemes are separated by adopting the fractional crystallization method to obtain natural dextrorotatory ACSOs with optical activity. Compared with a conventional extraction method, the method has the characteristics that the yield and the purity are high, a conventional complicated extraction process is avoided, the product has the optical activity, and the physical property is close to that of natural extract; the product is used in the fields of health products, pharmaceuticals and the like, the effects of resisting bacteria and cancers, reducing blood fat and the like of ACSOs are brought into play, or the product serves as an intermediate such as an active ingredient-diallyl thiosulfinate for synthesizing allium.
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Paragraph 0055; 0056
(2017/05/26)
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- IMPROVEMENTS IN OR RELATING TO ALLIUM EXTRACTS
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The present invention relates to improvements in or relating to Allium extracts. In particular, it relates to improvements in or relating to extending the therapeutic half- life or duration of Allium extracts. The invention also relates to the synthesis of certain thiosulfinate compounds, especially to the synthesis of methyl allyl thiosulfinate and allyl methyl thiosulfinate, in particular from either methiin or alliin alone or a mixture of both. The invention further relates to the synthesis of methyl allyl thiosulfinate, allyl methyl thiosulfinate, allicin, and methyl methyl thiosulfinate in a mixture with varying molar or mass ratios depending on the reaction conditions, in particular from either methiin or alliin alone or a mixture of both. A high yielding, optimized synthesis of allicin starts from alliin, whereas methyl methyl thiosulfinate is advantageously obtained from methiin. Also provided is a kit comprising methiin in a first container and/or alliin in a second container and an allinase source, in particular garlic powder in a third container. Finally, the invention provides a method of preparing a mixture of methyl allyl thiosulfinate, allyl methyl thiosulfinate, allyl allyl thiosulfinate (allicin) and methyl methyl thiosulfinate from methiin and pieces of an Allium species.
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Page/Page column 83
(2015/02/02)
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- Enzymatic synthesis of chiral amino acid sulfoxides by Fe(II)/α- ketoglutarate-dependent dioxygenase
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Asymmetric sulfoxidation of sulfur-containing l-amino acids was successfully achieved through bioconversion using IDO, which is an Fe(II)/α-ketoglutarate-dependent dioxygenase previously found in Bacillus thuringiensis strain 2e2. The IDO catalyzed sulfoxidation of l-methionine, l-ethionine, S-methyl-l-cysteine, S-ethyl-l-cysteine, and S-allyl-l-cysteine into the corresponding (S)-configured sulfoxides such as (+)-methiin and (+)-alliin, which are responsible for valuable physiological activities in mammals, and have high stereoselectivity. Herein we have established an effective preparative laboratory scale production method to obtain enantiomerically pure chiral sulfoxides using an IDO biocatalyst.
- Hibi, Makoto,Kawashima, Takashi,Yajima, Hiroko,Smirnov, Sergey V.,Kodera, Tomohiro,Sugiyama, Masakazu,Shimizu, Sakayu,Yokozeki, Kenzo,Ogawa, Jun
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p. 990 - 994
(2013/09/23)
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- Synthesis, spectroscopic characterization, DFT studies, and antibacterial and antitumor activities of a novel water soluble Pd(II) complex with l-alliin
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A new water soluble Pd(II) complex with l-alliin (S-allyl-l-cysteine sulfoxide) was obtained and characterized by a set of chemical and spectroscopic measurements. Elemental and mass spectrometric data are consistent with the formula [Pd(C6Hsu
- Abbehausen, Camilla,Sucena, Suelen F.,Lancellotti, Marcelo,Heinrich, Tassiele A.,Abr?o, Emiliana P.,Costa-Neto, Claudio M.,Formiga, André L.B.,Corbi, Pedro P.
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p. 421 - 426
(2013/03/29)
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- Antiviral composition derived from allium CEPA and therapeutic use thereof
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Novel medicinal extracts derived from Allium species, preferablyAllium cepaare provided. These extracts have broad medicinal properties, especially for treatment of AIDS and other viral infections.
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- Differential inhibition of human platelet aggregation by selected Allium thiosulfinates
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Thiosulfinates (TSs) have been implicated as a principle source of the antiplatelet property of raw onion and garlic juice. The in vitro responses of human platelets to dosages of four TSs were measured using whole blood aggregometry and compared by regression analysis. Of the compounds evaluated, methyl methane-TS (MMTS), propyl propane-TS (PPTS), and 2-propenyl 2-propene-TS (allicin) are present in freshly cut Allium vegetables, whereas ethyl ethane-TS (EETS) has not been detected. All TSs were synthesized using a model reaction system. PPTS and allicin had the strongest antiplatelet activity at 0.4 mM, inhibiting aggregation by 90 and 89%, respectively. At the same concentration, EETS and MMTS were significantly weaker, inhibiting 74 and 26%, respectively. Combinations of TSs were not additive in their inhibition of aggregation, indicating that the antiplatelet potential of Allium extracts cannot be easily predicted by quantifying organosulfur components. EETS, PPTS, and allicin were significantly more potent platelet inhibitors than aspirin at nearly equivalent concentrations.
- Briggs, William H.,Xiao, Hang,Parkin, Kirk L.,Shen, Cunxi,Goldman, Irwin L.
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p. 5731 - 5735
(2007/10/03)
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- In vitro biogeneration of pure thiosulfinates and propanethial-S-oxide
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A model reaction system was developed for generating, pure thiosulfinates and propanethial-S-oxide (PTSO) using an isolated alliinase (EC 4.4.1.4) and isolated or synthetic alk(en)yl-L-cysteine sulfoxides (ACSO). Reaction yields ranged from 30 to 60% after 3 h at 21-23°C, and organosulfur reaction products were extracted into CHCl3 to yield product preparations of controlled composition. A pure thiosulfinate or PTSO was derived from a single ACSO, and a preparation containing a mixture of four thiosulfinate species was derived from reaction mixtures employing binary ACSO substrate systems. Identities of homologous thiosulfinates and PTSO were confirmed by 1H NMR. This approach has the potential to be used as a preparative tool for yielding pure thiosulfinates and PTSO to facilitate the study of chemical and biological properties of this group of compounds or as a means to study the dynamics of organosulfur chemistry in preparations from Allium spp.
- Shen, Cunxi,Parkin, Kirk L.
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p. 6254 - 6260
(2007/10/03)
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- Diastereoselective synthesis of alliin by an asymmetric sulfur oxidation
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L-(+)-Alliin (7) has been synthesized from S-allyl-L-cysteine (3) by an asymmetric sulfur oxidation using tetraisopropyl-ortho-titanate [Ti(O-iPr)4] in equimolar amounts. Chirality of the resulting sulfoxide was guided by either (+)- or (-)diethyl tartrate as chiral auxiliary which led to the (-)- or (+)- isomer of L-alliin (7, 8), respectively. To allow this type of oxidation, the amino acid functions of 3 were protected by a tert.-butoxycarbonyl- and a 9- fluorenylmethyl group. Alternatively, an enzyme catalysed asymmetric sulfur oxidation by cyclohexanone oxygenase was carded out. The products were investigated by 1R, MS and NMR spectroscopy. The ratio between the diastereomers 7 and 8 was determined by HPLC. Also IR spectroscopy allowed an estimation of the approximate ratio 7/8.
- Koch,Keusgen, Michael
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p. 668 - 671
(2007/10/03)
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- Oxidation of cysteine S-conjugates by rabbit liver microsomes and cDNA- expressed flavin-containing mono-oxygenases: Studies with S-(1,2- dichlorovinyl)-L-cysteine, S(1,2,2-trichlorovinyl)-L-cysteine, S-allyl-L- cysteine, and S-benzyl-L-cysteine
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Rabbit liver microsomes catalyzed the highly stereoselective, NADPH- and time-dependent S-oxidation of S-benzyl-L-cysteine (SBC), S-allyl-L-cysteine (SAC), S-(1,2-dichlorovinyl)-L-cysteine (DCVC), and S-(1,2,2-trichlorovinyl)- L-cysteine (TCVC) to their r
- Ripp, Sharon L.,Overby, Lila H.,Philpot, Richard M.,Elfarra, Adnan A.
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p. 507 - 515
(2007/10/03)
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- RELATION BETWEEN THE STRUCTURE OF ALLIIN ANALOGUES AND THEIR INHIBITORY EFFECT ON PLATELET AGGREGATION
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Key Word Index - Alliin; S-allyl-L-cysteine sulphoxide; allicin; dihydroalliin; platelet aggregation inhibitors. - Alliin analogues have been synthesized and tested for their inhibitory activity on platelet aggregation.It is found that only allicin, the S-oxodiallyl disulphide, has a strong inhibitory effect, comparable to that of alliin, while all the other tested compounds do not show any inhibitory effect even at concentrations of 10-3 M.
- Liakopoulou-Kyriakides, M.
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p. 1593 - 1594
(2007/10/02)
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