Analogs of carbohydrate-metabolish coenzymes. Communication 4. Synthesis of 6-azauridine diphosphate glucose

Summary The synthesis is described of a new UDPG analog, 6-azauridine diphosphate glucose.The authors are deeply grateful to the group of workers at the Institute of Organic Chemistry and Biochemistry of the Czechoslovakian Academy of Sciences, headed by Dr. Smrt, for placing a preparation of 6-azauridine at our disposal.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1236–1241, July, 1964     

Determination of S-Adenosylmethionine and S-Adenosylhomocysteine from Human Blood Samples by HPLC-FL

Abstract

S-adenosylmethionine plays an important role in many biochemical reactions, including human health maintenance and disease prevention. This paper proposes a simplified, rapid, and easy high performance liquid chromatography (HPLC) with fluorimetric detection method of S-adenosylmethionine and its product, S-adenosylhomocysteine. Determination of S-adenosylmethionine and S-adenosylhomocysteine was by HPLC with fluorimetric detection by the formation of the fluorescent 1,N ⁶-ethanoderivatives of these compounds, which showed a linear concentration range of 310^?6–310^?8 molL^?1 for S-adenosylmethionine and 510^?7–510^?9for S-adenosylhomocysteine; the detection limits of the method ranged in the nanomolar domain. The method applied to real plasma samples lead to values of 60.1±19.6 for S-adenosylmethionine and 24±14.1 nmolL^?1 for S-adenosylhomocysteine.     

Synthesis of Pseudobaptigenin Analogs

Homologs of the natural isoflavonoid pseudobaptigenin containing benzodioxane and benzodioxepane fragments were synthesized. Methanesulfonyl, carbamoyl, aminomethyl, and coumarin-containing isoflavone derivatives were prepared.     

Plant-Based Seafood Analogs

There is a growing global need to shift from animal- towards plant-based diets. The main motivations are environmental/sustainability-, human health- and animal welfare concerns. The aim is to replace traditional animal-based food with various alternatives, predominantly plant-based analogs. The elevated consumption of fish and seafood, leads to negative impacts on the ecosystem, due to dwindling biodiversity, environmental damage and fish diseases related to large-scale marine farming, and increased intake of toxic substances, particularly heavy metals, which accumulate in fish due to water pollution. While these facts lead to increased awareness and rising dietary shifts towards vegetarian and vegan lifestyles, still the majority of seafood consumers seek traditional products. This encourages the development of plant-based analogs for fish and seafood, mimicking the texture and sensorial properties of fish-meat, seafood, or processed fish products. Mimicking the internal structure and texture of fish or seafood requires simulating their nanometric fibrous-gel structure. Common techniques of structuring plant-based proteins into such textures include hydrospinning, electrospinning, extrusion, and 3D printing. The conditions required in each technique, the physicochemical and functional properties of the proteins, along with the use of other non-protein functional ingredients are reviewed. Trends and possible future developments are discussed.     

Analogs of pyrimidine nucleosides

The UV absorption spectra of 5-substituted N¹-(tetrahydrofuran-2-yl)- and N¹-(2oxotetrahydrofuran-3-yl)uracils have been studied and their protolysis constants have been determined by the spectrophotometric method. A comparison is given with the spectra and pKa values of the corresponding N¹-methyl derivatives and ribosides and deoxyribosides.For part IV see [11].The work was carried out with analytical samples of compounds obtained by us previously [9–12].     

Analogs of pyrimidine nucleosides

N₁-(-Tetrahydrofuranyl)- and N₁-(-tetrahydropyranyl)uracils and the corresponding 6-azauracils have been obtained by the condensation of bistrimethylsilyl derivatives of uracils and 6-azauracils with-chlorotetrahydrofuran and-chlorotetrahydropyran. The superiority of the silyl method over the mercury method used previously has been demonstrated.For part III, see [9].     

Thiazole Analogs of Isoflavolignans

Modified analogs of isoflavolignans are prepared by annelation of dioxole, dioxane, and dioxepan fragments to 3-thiazolyl-7,8-dihydroxychromones     

Analogs of carbohydrate-metabolism coenzymes

Summary A new analog of uridine pyrophosphate glucosyl ester, namely 4-thiouridine pyrophosphate -D-glucopyranosyl ester, was synthesized.For preliminary communication see Biochim. Biophys. Acta59, 747 (1962).The authors, thank N. D. Gabriélyan and R. S. Kudryavtseva for carrying out the analyses.     

Synthesis of Phenylalanine Analogs

A straightforward synthesis of phenylalanine analogs is described. Cerium ammonium nitrate (CAN) mediated addition of azide to cinnamic ester, followed by reaction with sodium acetate afforded the α‐azidocinnamate in moderate yield. Hydrogenation of α‐azidocinnamate, followed by BOC, CBZ or Fmoc protection gave phenylalanine analogs. A new approach for synthesizing racemic p‐boronophenylalanine analog was also explored.     

Analogs of carbohydrate-metabolism coenzymes

Conclusions We synthesized two analogs of the natural coenzyme adenosine diphosphate glucose: N₆-methyl-ADPG and N₆, N₆-dimethyl-ADPG.For communication 11, see [1].The following abbreviations are used in this article: ADPG) adenosine-5'-diphosphate-a-D-glucopyranose; N₆-methyl-ADPG) N₆-methylamino-9--D-ribofuranosylpurine-5-diphosphate--D-glucopyranose; N₆, N₆-dimethyl-ADPG) N₆, Ng-dimethylamino-9--D-ribofuranosylpurine-5-diphosphate--D-glucopyranose.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2514–2521, November, 1969.     

Analogs of pyrimidine nucleosides

α-(1-Cytosinyl)-γ-butyrolactone was obtained by condensation of bis(trimethylsilyl)cytosine with α-bromobutyrolactone. The reduction of α-(1-cytosinyl)-γ-butyrolactone with sodium borohydride gave N₁-(1,4-dihydroxy-2-butyl)cytosine, the acylation of which with benzoyl chloride and subsequent partial hydrolysis gave N₁-(1,4-dihydroxy-2-butyl)-N₄-benzoylcytosine.     

Analogs of pyrimidine nucleosides

The reaction of alkoxy bromides with N₁-(-tetrahydrofuryl) derivatives of pyrimidine bases has given a series of 6-alkoxy-5-bromo-1-(-tetrahydrofuryl)-5, 6-dihydrouracils. The hydrogenation of the 1-(-tetrahydrofuryl) derivatives of uracil and of 5-fluorouracil has been studied. It has been shown that in both cases 1-(-tetrahydrofuryl)-5, 6-dihydrouracil is formed.     

Analogs of pyrimidine nucleosides

A number of N₁-(-butyrolactono) derivatives of 5-substituted uracils have been synthesized by condensing the sodium derivatives of the corresponding bases with -bromobutyrolactone or by the halogenation of N₁-(-butyrolactono)uracil.For part I, see [1].     

Synthesis of Formononetin Analogs

Derivatives of the natural isoflavone formononetin were synthesized. Acylation and alkylation of the phenolic hydroxyls and the chromone ring were investigated.     

Analogs of pyrimidine nucleosides

A new method for the synthesis ofN₁-(dihydroxyalkyl)uracils by reduction of substituted α- (1-uracilyl)- and γ-[(1-uracilyl)methyl]-γ-butyrolactones with sodium borohydride was found.