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Ruthenium(II) 1,4,7-trithiacyclononane complexes of curcumin and bisdemethoxycurcumin: Synthesis, characterization, and biological activity.

PMID: 33721720
ISSN 2412-0324 (English ed. Online) AGRICULTURAL BIOLOGY, 2022, V. 57, Iss. 6, pp. 1166-1177 [SEL’SKOKHOZYAISTVENNAYA BIOLOGIYA] ISSN 0131-6397 (Russian ed. Print) ISSN 2313-4836 (Russian ed. Online) UDC 636.085.19:573.6.086.83:577.21 doi: 10.15389/agrobiology.2022.6.1166eng doi: 10.15389/agrobiology.2022.6.1166rus A NEW PRODUCER OF A RECOMBINANT AFLATOXIN-DEGRADING ENZYME OBTAINED VIA HETEROLOGOUS EXPRESSION IN Pichia pastoris I.G. SINELNIKOV1, 2, I.N. ZOROV2, Yu.A. DENISENKO1, 2, O.D. MIKITYUK1, A.P. SINITSYN1, 2, L.A. SHCHERBAKOVA1  1All-Russian Research Institute of Phytopathology, 5, ul. Institute, Bolshie Vyazemy, Odintsovsky District, Moscow Province, 143050 Russia, e-mail mod-39@list.ru, larisavniif@yahoo.com ( corresponding author); 2Federal Research Center Fundamentals of Biotechnology RAS, 33/2, Leninskii prospect, Moscow, 119071 Russia, e-mailsinelnikov.i@list.ru, inzorov@mail.ru, denisenkoyura@mail.ru, apsinitsyn@gmail.com ORCID: Sinelnikov I.G. orcid.org/0000-0001-6359-1125 Mikityuk O.D. orcid.org/0000-0003-2022-7256 Zorov I.N. orcid.org/0000-0001-6888-172X Sinitsyn A.P. orcid.org/0000-0001-6429-8254 Denisenko Yu.A. orcid.org/0000-0003-2363-0374 Shcherbakova L.A. orcid.org/0000-0003-0254-379X The authors declare no conflict of interests Acknowledgements: Supported financially by the Russian Scientific Foundation (project No. 22-16-00153) Received September 20, 2022 Abstract Contamination of food and feed with mycotoxins causes significant economic losses in the food and feed industry and poses a serious threat to the human health and animal life because of mutagenic, carcinogenic and other disruptive properties of these secondary metabolites of fungi. Enzymatic degradation of mycotoxins represents an efficient and environmentally safe alternative to the chemical decontamination of agricultural and food products. In this study, a synthetic adtz gene encoding ADTZ, an aflatoxin-degrading oxidase from Armillaria tabescens, was integrated into the genome of a Pichia pastoris GS115 strain under the control of a glyceraldehyde-3-phosphate dehydrogenase promoter. To amplify the adtz gene, oligonucleotide sequences were constructed with specific restriction sites HindIII and NotI added to the 5' end. The adtz gene-containing pPIG-ADTZ plasmid obtained with the use of the pPIG-1 vector was linearized by digestion with restriction endonuclease ApaI, followed by transforming the cells of P. pastoris recipient strain GS115 by electroporation. The transformed yeast cell were selected on YPD medium with an antibiotic. PCR amplification, restriction analysis and Sanger sequencing confirmed insertion of the target gene. As a result, 54 transformed clones containing the target gene were obtained, and the most productive clone secreting the recombinant ADTZ-14 (2.1 mg/ml of the total extracellular protein) was selected. Recombinant ADTZ represented a monomeric protein (78±3 kDa) possessing a high affinity to aflatoxin B1 (AFB1). Saving the functional properties of the recombinant protein was shown using experiments on assessment of its ability to degrade AFB1 during short-time and prolonged incubation. The obtained protein was able to degrade AFB1 by 14 % after a 2-h incubation at 40 С; after 72 and 120 h of incubation at 30 С, the content of AFB1 in ADTZ-14 culture liquid (CL) reduced by 50 and 80 %, respectively, compared to content in CL of non-transformed control GS115. These data suggest a quite high biotechnological potential of a new recombinant ADTZ preparation in relation to the decontamination of agricultural products contaminated with AFB1. Thus, the earlier developed expression system intended to increase the copy number of heterologous genes in Pichia pastoris was first used to obtain a recombinant protein able to degrade AFB 1. Using this approach, we transformed yeast cells with the pPIG-ADTZ plasmid and obtained 154 recombinant clones of P. pastoris, 77 % of which contained the target sequence of the adtz gene. Productivity of the best transformant (clone ADTZ-14) was 2.1 mg of protein per 1 ml of culture liquid, and about half of the pool of the extracellular proteins fell to the share of recombinant ADTZ able to degrade 80 % of AFB 1 incubated in cell-free culture broth at 30 С and pH 7.0. Keywords: aflatoxin B1, mycotoxins, enzymatic degradation, ADTZ from Armillaria tabescens, synthetic adtz gene, recombinant proteins, heterologous expression, Pichia pastoris Aflatoxins, a group of structurally similar secondary metabolites of the 1166 fungal genus Aspergillius widely distributed in nature, are known as dangerous mycotoxins that contaminate feed and other agricultural products [1-4]. Currently, more than 20 aflatoxins (AF), their derivatives and closely related compounds have been identified [5]. Contamination of feeds for livestock and poultry with Band G-type AF raises the most serious concern [6, 7]. These mycotoxins are derivatives of difuranocoumarin which have a bifuran group linked to the coumarin core and a cyclopentane (in B-type AF) or lactone ring (in G-type AF) [8, 9]. Due to the toxicity, carcinogenicity and mutagenicity of these compounds, and their resistance to heat treatments [10, 11], feed and other crop products contaminated with AF above the concentrations allowed by hygienic regulations are not suitable for direct use or further processing into food products. Globally, contamination with these mycotoxins, especially AFB1 which surpasses all other AFs in hepatotoxicity and danger to warm-blooded animals [6, 7], causes serious economic damage to both agriculture and the food industry, and also create risks for human health [1, 3]. For decontamination, physical, chemical, and microbiological methods are used, which, however, have a number of well-known limitations [1, 12]. Therefore, there is a constant search for other effective, environmentally friendly means and methods of AF degradation and detoxification that do not affect the quality of agricultural products. From this point of view, an approach based on the ability of a number of fungi [13-15] and bacteria [16-19] to synthesize enzymes that transform AF to non-toxic or less toxic compounds seems to be very promising [20, 22]. The use of cell-free preparations containing such enzymes makes it possible to avoid problems that may arise when using the producers themselves (for example, deterioration of the organoleptic properties of processed products, a decrease in their nutritional value). In addition, enzyme preparations are technologically more convenient for feed processing [23] and, unlike those for the food industry, do not require expensive multi-stage purification of the target product. It is known that some xylotrophic basidiomycetes of the genera Pleurotus [24, 25], Phanerochaete, and Armillaria [26-28] can be sources of enzymes for AF degrading and detoxifying. An enzyme with oxidase activity [28] called by the authors aflatoxin-detoxifizyme (ADTZ) was isolated from the mycelium of Armillaria tabescens using hydrophobic and metal chelate chromatography. It turned out that ADTZ can catalyze the opening and subsequent hydrolysis of the difuran ring [29], a structure associated with B-type AF toxicity. Further studies have shown that ADTZ is a 76 kDa monomeric protein with high affinity for AFB1 [29]. Upon contact with ADTZ, the toxicity and mutagenicity of AFB1 were significantly reduced [28, 30]. These data indicate the prospects for the development of detoxifying drugs containing ADTZ. However, their creation is primarily hampered by the lack of available technology for obtaining intracellular ADTZ from A. tabescens mycelium and, in part, by the fact that deep cultures of A. tabescens requires liquid media of complex composition, including very specific and expensive components [31], or a multi-stage fermentation procedure [28]. These obstacles could be overcome by using a heterologous expression system and creating an accessible producer of the recombinant ADTZ protein. However, there is still no suitable system for obtaining extracellular heterologous ADTZ in an amount sufficient for its use in decontamination of crop products. Nevertheless, a number of modern works [32, 33] report on the successful use of Pichia pastoris yeast cells as recipients for heterologous expression. 1167 Previously, we adapted the expression system in P. pastoris by modifying the integration vector to increase the copy number of heterologous genes in the yeast chromosome (the integration vector and its preparation are patented) [34]. In the present study, this approach was used for the first time to create a new producer of the aflatoxin-degrading enzyme. Our goal was to optimize and use this system for the heterologous expression of ADTZ in Pichia pastoris GS115 and to evaluate the ability of a cell-free culture liquid (CL) preparation of the resulting P. pastoris ADTZ-14 strain containing the extracellular recombinant ADTZ enzyme to degrade AFB1. Materials and methods. For the expression of the adtz gene encoding aflatoxin-detoxifizim, the yeast strain Pichia pastoris GS115 (syn. Komagataella phaffii) (Thermo Fisher Scientific, USA) was used. Yeast cells were cultured for 3 days at 30 С in liquid YPD medium (glucose 20.0 g/l; yeast extract 10.0 g/l; meat peptone 20.0 g/l). For plasmid DNA, Escherichia coli XL1-Blue (Agilent, USA) was grown at 37 С in Luria-Bertrani medium (tryptone 10 g/l; yeast extract 5 g/l; NaCl 5 g/l; pH 7.2-7.5). The pPIG-1 plasmid was used to express ADTZ [34]. The adtz gene encoding the aflatoxin degradation enzyme in A. tabescens (GenBank AY941095.1) was synthesized at ZAO Evrogen (Russia) according to the codon compositions in P. pastoris. PCR mix for the adtz gene amplification (50 µl) contained 1½ buffer with 3 mM MgCl2 and 5 U Taq polymerase (NEB, UK), 0.2 μM ADTZ-fwd (5´-gaagcttctATGGCTACTACAACTG-3´) and ADTZ-rev (5´-cgcggccgcTTACAATCTTCTCTC-3´) oligonucleotides, and 0.1 ng DNA as a matrix. The reaction was carried out under the following conditions: 95 С for 15 s, 62 С for 15 s, and 72 С for 120 s (25 cycles) (a T-100 amplifier, Bio-RAD, USA). The PCR products were evaluated electrophoretically (a 1% agarose gel, a Sub-Cell GT Cell, Bio-RAD, USA). The amplification product, vector pPIG-1, was digested with HindIII and NotI restriction endonucleases according to the manufacturer’s recommendations (NEB, UK). The processed fragments were ligated with T4 DNA ligase (ZAO Evrogen, Russia), and Escherichia coli XL1-blue cells (Agilent, USA) were transformed with the 2 μl mixture by the heat shock method. Transformants were selected on Luria-Bertrani agar medium containing ampicillin (100 μg/ml). The pPIG-ADTZ plasmid was isolated from ampicillin-resistant transformants using the Plasmid Mini-prep kit (ZAO Evrogen, Russia). The presence of the target gene insert in the pPIG-ADTZ plasmid was confirmed by PCR amplification, restriction analysis as described above, and Sanger sequencing. Sequencing was performed in both directions from primers used for the gene amplification. Gene sequencing and synthesis of primers used for amplification were performed at OOO Sintol (Russia). The pPIG-ADTZ plasmid was linearized by digestion with restriction endonuclease ApaI (NEB, UK) according to the manufacturer's protocol and transferred into P. pastoris GS115 by electroporation [35]. Transformants were selected on a YPD agar medium supplemented with 200 μg/ml antibiotic zeocin (Thermo Fisher Scientific, USA). DNA was isolated from antibiotic-resistant colonies [36] and the ADTZ insert was checked by PCR. The recombinant ADTZ protein was produced by culturing the P. pastoris ADTZ-14 producer strain in 24-well plates (3 ml YNB liquid medium, 30 С, aeration 200 rpm, 3 days). Every 24 hours, 40% glucose solution in 20 mM 1168 potassium phosphate buffer (pH 6.0) was added to the wells to a final concentration of 2%. The recombinant ADTZ in cell-free CL was detected by polyacrylamide gel electrophoresis with sodium dodecyl sulfate (DNS-PAGE, Mini-PROTEAN® Tetra, Bio-RAD, USA). Total protein concentration was measured by the Lowry method [37]. The degradation kinetics of AFB1 and AFG1 was studied in experiments with short-term incubation of P. pastoris ADTZ-14 cell-free CL. Commercial preparations of AFB1 and AFG1 (VNIIVSGE, Russia) were dissolved in 20 mM Na-phosphate buffer (pH 6.7) to a final concentration of 2.5 μg/ml each. The concentration was controlled using the molar extinction coefficients  = 21800 and  = 17700 (at  = 362 nm) for AFB1 and AFG1, respectively. The CL of the P. pastoris ADTZ-14 transformant was incubated with toxins in the wells of a thermostated autosampler plate (30 or 40 С). A 5 µl aliquots were taken from the reaction mixture every 30 min for 2.5 h and the AF content was determined by reverse-phase chromatography on a thermostated (30 С) Kromasil Ethernity 5C18 column (4.6½250 mm) (Akzo Nobel, Sweden) equipped with an appropriate guard column. An Agilent 1200 chromatographic system (Agilent Technologies, USA) with diode array detection was used. Chromatographic separation was performed in a water/acetonitrile gradient (from 40% to 68% acetonitrile in 20 min, detection at 360, 235, and 225 nm, slit width 8 nm). The degree of AFB1 and AFG1 degradation was assessed by the change in the area of the corresponding chromatographic peak. The CL of the untransformed strain P. pastoris GS115 was a control. To assess the ability of the recombinant ADTZ enzyme to degrade AFB1 during prolonged incubation, 1 ml of P. pastoris ADTZ-14 CL samples (2.1 mg total protein/ml) after pre-sterilization by filtration (membranes with a pore size of 0.22 μm, Millipore, USA) were added with 1.0 μg of AFB1 (Sigma-Aldrich, USA) dissolved in a minimum volume of methanol. Samples (1 ml) of CL of nontransformed strain P. pastoris GS115 addedd with the same amount of AFB1 were used as a control. Samples were incubated for 3 and 5 days at pH 7.0 and 30 С. The post-incubztion AFB1 concentration was measured using high-performance liquid chromatography (HPLC) on a thermostated (27 С) Symmetry C18 column (5 µm, 150½4.6 mm) in isocratic elution mode (mobile phase methanol:water 60:40, 10 µl sample injected, λ = 362 nm) using a Waters 1525 Breeze system with a Waters UV 2487 detector (Waters Corp., USA) [12, 38]. Prior to HPLC analysis, CL samples were diluted 100-fold with the mobile phase. Toxin concentrations were measured in the linear detection range in the test and control samples, The concentrations were calculated from the calibration curve for the AFB1 standard (Sigma-Aldrich, USA). The percentage of degradation was determined relative to the amount of toxin detected in the corresponding control sample. Statistical processing of AFB1 quantification data was performed using the STATISTICA 6.1 program (StatSoft, Inc., USA). Significance of differences at p  0.05 was confirmed using Student’s t-test for independent variables. The table and figures indicate the mean values (M) of two measurements for each of the three biological repetitions with standard deviations (±SD). Results. The gene for the aflatoxin-degrading enzyme from A. tabescens was cloned by PCR using the developed oligonucleotides. The size of the amplification product corresponding to the synthesized adtz gene was 2088 bp. Sequencing of the obtained product confirmed its identity with the sequence of A. tabescens (GenBank AY941095.1) (Fig. 1). 1169 Fig. 1. Sequence alignment visualization of the codon-optimized adtz gene and the natural adtz gene 1170 of Armillaria tabescens (GenBank AY941095.1, https://www.ncbi.nlm.nih.gov/genbank/). Optimization of the codon composition was carried out by ZAO Evrogen (Russia) using the codon frequency table for Pichia pastoris (https://www.kazusa.or.jp). Fig. 2. A map of the pPIG-ADTZ plasmid obtained by cloning the sequence of the synthesized aflatoxindetoxphyzyme (ADTZ) adtz (synthetic_ADTZ) gene into the pPIG-1 vector. The resulting recombinant gene was integrated into the pPIG-1 vector by the restriction ligation method. Restriction analysis of the resulting new plasmid, after double digestion with HindIII and NotI, resulted in 5500 and 2100 bp products, confirming the correct integration of the target sequence into the pPIG1 vector. The resulting recombinant plasmid (Fig. 2) was called pPIG-ADTZ. Plasmid pPIG-ADTZ, linearized with restriction endonuclease ApaI, was electroporated into competent P. pastoris GS115 cells, and transformants were selected on YPD medium added with zeocin. Cloning resulted in 154 clonal colonies. Genomic DNA isolated from 70 randomly selected transformed clones was analyzed by PCR to identify the adtz gene insert. PCR analysis of the DNA of these transformants grown on the selective media showed that at least 54 clones contained the target adtz insert. Among them, the ADTZ-14 clone turned out to be the most productive and was used for further work. Already after 72 h of culture, expression of ADTZ in this clone led to the accumulation in the CL of the extracellular recombinant protein. The size of this protein according to the SDS-PAGE analysis was 78±3 kDa (Fig. 3), while in the CL of the nontransformed recipient P. pastoris GS115 we did not find proteins of a comparable size. In the CL of the transformed ADTZ-14 clone, the total protein concentration was 2.1 mg/ml. 1171 Fid. 3. Electrophoregram of the culture liquid proteins of the strain Pichia pastoris ADTZ-14 (1) transformed with the recombinant pPIG-ADTZ vector containing the synthesized aflatoxin-detoxifizyme (ADTZ) adtz gene, and the recipient P. pastoris GS115 (2). M — molecular weight marker PageRuler™ 26614 (Thermo Fisher Scientific, USA). Comparison of the degradation kinetics of AFB1 and AFG1 in CL of P. pastoris ADTZ-14 showed that the recombinant enzyme is capable of destroying both toxins; however, its efficiency against AFB1 turned out to be significantly higher than for AFG1. Thus, under the action of CL of the producer of recombinant extracellular ADTZ, already after 2 h of incubation, the concentration of AFB1 toxin decreased by approximately 14% compared to the initial level, while for AFG1 the decrease was only 4% (Fig. 4). Fig. 4. Degradation kinetics of aflatoxins G1 (1) and B1 (2) in the cell-free culture fluid of the Pichia pastoris ADTZ-14 strain transformed with the pPIG-ADTZ recombinant vector conyaining the synthesized aflatoxindetoxphyzyme (ADTZ) adtz gene at 40 С and pH 6.7 (n = 3, М±SD). The obtained results were consistent with the data of other authors who noted the high specificity of intracellular ADTZ from A. tabescens to AFV1 [29]. In this regard, we studied the degradation activity of recombinant ADTZ with respect to the indicated toxin during its longer incubation with cell-free CL of the P. pastoris ADTZ-14 strain. Fig. 5. Chromatograms of culture liquid (CL) samples of Pichia pastoris (incubation at 30 С and pH 7.0). A: CL of the non-transformed recipient strain GS115 (control). B: CL GS115 + aflatoxin B1 (APB1, 1 µg/ml) after incubation (control sample). The peak on the chromatogram corresponds to 10 ng of AFB1 in the injected sample. C and D: CL of the P. pastoris ADTZ-14 strain transformed with the pPIG-ADTZ recom- 1172 binant vector containing the synthesized aflatoxin-detoxiphyzyme (ADTZ) adtz gene, + AFV1 (1 μg/ml) after 3 and 5 days of incubation, respectively. In these experiments, it was found that after 3 days the concentration of the toxin added to the CL decreased by almost 2 times, and after 5 days the efficiency of its degradation reached 80% (Fig. 5, Table). Dynamics of enzymatic degradation of aflatoxin B1 (AFB1) in the cell-free culture liquid (CL) of the Pichia pastoris ADTZ-14 transformant straindecreting the recombinant aflatoxin-detoxphyzyme (ADTZ) (n = 6, M±SD) Strain 0h AFB1, g/ml Incubation time 72 h 120 h AFB1, g/ml degradation, % AFB1, g/ml degradation, % ADTZ-14 0.97±0.01 0.57±0.06 41.2а 0.19±0.04 80.4b GS115 (control) 0.98±0.01 1.01±0.01 0.0с 0.90±0.05 0.1с N o t е. The ADTZ-14 strain was obtained by transformation of the P. рastoris GS115 recipient with the pPIGADTZ recombinant vector with the synthesized aflatoxin-detoxphyzyme (ADTZ) adtz gene. Before incubation, AFB1 was added to the culture liquid (CL) to a concentration of 1 μg/ml; for 0 h, the concentrations detected in the CL samples before incubation are indicated (opening from 96 to 99%). abc Differences between percent degradation marked with different letters are statistically significant at p  0.05. The data we presented here indicate a rather high biotechnological potential of the new producer of recombinant ADTZ and expand the so far limited spectrum of recombinant enzymes of other xylothorophic fungi degrading AFB1 obtained using the system of heterologous expression in P. pastoris [39]. It should also be noted that the ADTZ-14 producer was characterized by a rather high level of expression of extracellular proteins for P. pastoris. Probably, the use of a synthetic gene with optimized codons contributed to an increase in the productivity of yeast cells. A similar approach has been successfully used previously for the expression of bacterial -amylase in P. pastoris [40]. However, according to recent data, the use of synthetic genes can lead to protein misfolding, degradation, and a decrease in its activity and stability. This may be the cause of partial degradation of secreted recombinant proteins [41], which, as noted above, we also observed in our experiments with electrophoretic analysis of the CL of the transformed clone ADTZ-14. Therefore, it is necessary to continue research on increasing the efficiency of AFB1 degradation by recombinant ADTZ, additional testing of the effect of this recombinant enzyme on other aflatoxins, as well as experiments on the treatment of crop products contaminated with AFB1 with the enzyme preparation. It is also possible that heterologous expression using other eukaryotes, e.g., filamentous fungi which are used for bioprocessing of feed to increase its nutritional value, will allow for obtaining new producers of highly active extracellular ADTZ. Such producers could be promising for the simultaneous decontamination of plant raw material contaminated with aflatoxin and increasing the availability of their nutritional components. Thus, this article is the first report on the production of a recombinant protein capable of cleaving AFB1 using an expression system developed by us earlier to increase the copy number of heterologous genes in Pichia pastoris. Yeast cells were transformed with the pPIG-ADTZ plasmid and 154 recombinant clones of P. pastoris were generated, 77% of which contained the target sequence of the ADTZ synthetic aflatoxin-detoxiphyzyme adtz gene. The protein yield of the most productive ADTZ-14 transformant was 2.1 mg/ml cell-free culture liquid, and in this case, about half of all extracellular protein pool was recombinant ADTZ. Incubation of AFB1 with this recombinant ADTZ led to 80% degradation of the added toxin. The transformant strain P. pastoris ADTZ-14, secreting functional ADTZ, can be a producer of an accessible and sufficiently active recombinant enzyme for AFB1 degradation. Based on P. pastoris ADTZ-14, preparations for the enzymatic degradation of AFB1 can be developed in the future. Confirmation 1173 of the decontamination potential of the recombinant enzyme will indicate the feasibility of optimizing biotechnology to increase the yield of the target product and develop its formulation. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. Dzhavakhiya V.G., Statsyuk N.V., Shcherbakova L.A., Popletaeva S.B. Aflatoksiny: ingibirovanie biosinteza, profilaktika zagryazneniya i dekontaminatsiya agroproduktsii [Aflatoxins: biosynthesis inhibition, conatamination prevention and decontamination of agricultural products]. Moscow, 2017 (in Russ.). Coppock R.W., Christian R.G., Jacobsen B.J. Aflatoxins. In: Veterinary toxicology. R.C. Gupta (ed.). Academic Press, 2018: 983-994 (doi: 10.1016/B978-0-12-811410-0.00069-6). Kononenko G.P., Zotova E.V., Burkin A.A. Advances in mycotoxicological research of forage grain crops. Sel'skokhozyaistvennaya biologiya [Agricultural Biology], 2021, 56(5): 958-967 (doi: 10.15389/agrobiology.2021.5.958eng). Kononenko G.P., Burkin A.A. Toxins of micromycetes in generative organs of plants of the family Fabacea. Sel'skokhozyaistvennaya biologiya [Agricultural Biology], 2021, 56(5): 968-978 (doi: 10.15389/agrobiology.2021.5.968eng). Kumar P., Mahato D.K., Kamle M., Mohanta T.K., Kang S.G. Aflatoxins: A global concern for food safety, human health and their management. Front. Microbiol., 2017, 7: 2170 (doi: 10.3389/fmicb.2016.02170). Romani L. Immunity to fungal infections. Nat. Rev. Immunol., 2004, 4(11): 1-23 (doi: 10.1038/nri1255). El-Sayed R.A., Jebur A.B., Kang W., El-Demerdash F.M. An overview on the major mycotoxins in food products: characteristics, toxicity, and analysis. Journal of Future Foods, 2022, 2(2): 91102 (doi: 10.1016/j.jfutfo.2022.03.002). Schuda P.F. Aflatoxin chemistry and syntheses. In: Syntheses of natural products. Topics in current chemistry, V. 91. Springer, Berlin, Heidelberg, 1980: 79-81 (doi: 10.1007/3-540-09827-5_3). Mahato D.K., Lee K.E., Kamle M., Devi S., Dewangan K.N., Kumar P., Kang S.G. Aflatoxins in food and feed: an overview on prevalence, detection and control strategies. Front. Microbiol., 2019, 10: 2266 (doi: 10.3389/fmicb.2019.02266). Probst C., Njapau H., Cotty P.J. Outbreak of an acute aflatoxicosis in Kenya in 2004: identification of the causal agent. Appl. Environ. Microbiol., 2007, 73(8): 2762-2764 (doi: 10.1128/aem.02370-06). Medina A., Gilbert M.K., Mack B.M., O’Brian G.R., Rodriguez A., Bhatnagar D., Payne G., MaganN. Interactions between water activity and temperature on the Aspergillus flavus transcriptome and aflatoxin B1 production. Int. J. Food Microbiol., 2017, 256: 36-44 (doi: 10.1016/j.ijfoodmicro.2017.05.020). Shcherbakova L.A., Statsyuk N.V., Mikityuk O.D., Nazarova N.A., Dzhavakhiya V.G. Aflatoxin B1 degradation by metabolites of Phoma glomerata PG41 isolated from natural substrate colonized by aflatoxigenic Aspergillus flavus. Jundishapur J. Microbiol., 2015, 8(1): e24324 (doi: 10.5812/jjm.24324). Ji C., Fan Y., Zhao L. Review on biological degradation of mycotoxins. Anim. Nutr., 2016, 2(3): 127-133 (doi: 10.1016/j.aninu.2016.07.003). Verheecke C., Liboz T., Mathieu F. Microbial degradation of aflatoxin B1: current status and future advances. Int. J. Food Microbiol., 2016, 237: 1-9 (doi: 10.1016/j.ijfoodmicro.2016.07.028). Alberts J.F, Gelderblom W.C.A., Botha A., van Zyl W.H. Degradation of aflatoxin B1 by fungal laccase enzymes. Int. J. Food Microbiol., 2009, 135: 47-52 (doi:10.1016/j.ijfoodmicro.2009.07.022). Taylor M.C., Jackson C.J., Tattersall D.B., French N., Peat T.S., Newman J., Briggs L.J., Lapalikar G.V., Campbell P.M., Scott C., Russell R.J., Oakeshott J.G. Identification and characterization of two families of F420H2-dependent reductases from Mycobacteria that catalyse aflatoxin degradation. Mol. Microbiol., 2010, 78(3): 561-575 (doi: 10.1111/j.1365-2958.2010.07356.x). Zhao L.H., Guan S., Gao X., Ma Q.G., Lei Y.P., Bai X.M., Ji C. Preparation, purification and characteristics of an aflatoxin degradation enzyme from Myxococcus fulvus ANSM068. J. Appl. Microbiol., 2011, 110(1): 147-155 (doi: 10.1111/j.1365-2672.2010.04867.x). Wang Y., Zhao C., Zhang D., Zhao M., Zheng D., Lyu Y., Cheng W., Guo P., Cui Z. Effective degradation of aflatoxin B1 using a novel thermophilic microbial consortium TADC7. Bioresource Technology, 2017, 224: 166-173 (doi: 10.1016/j.biortech.2016.11.033). Guo Y.P., Qin X.J., Tang Y., Ma Q.G., Zhang J.Y., Zhao L.H. CotA laccase, a novel aflatoxin oxidase from Bacillus licheniformis, transforms aflatoxin B-1 to aflatoxin Q(1) and epi-aflatoxin Q(1). Food Chem., 2020, 325: 126877 (doi: 10.1016/j.foodchem.2020.126877). Adebo O.A., Njobeh P.B., Gbashi S., Nwinyi O.C., Mavumengwana V. Review on microbial degradation of aflatoxins. Crit. Rev. Food Sci. Nutr., 2017, 57(15): 3208-3217 (doi: 10.1080/10408398.2015.1106440). Xu H.W., Wang L.Z., Sun J.D., Wang L.P., Guo H.Y., Ye Y.L., Sun X.L. Microbial detoxification of mycotoxins in food and feed.Crit. Rev. Food Sci. Nutr., 2022, 62(18): 4951-4969 (doi: 1174 10.1080/10408398.2021.1879730). 22. Li C.H., Li W.Y., Hsu I.N., Liao Y.Y., Yang C.Y., Taylor M.C., Liu Y.F., Huang W.H., Chang H.H., Huang H.L., Lo S.C., Lin T.Y., Sun W.C., Chuang Y.Y., Yang Y.C., Fu R.H., Tsai R.T. Recombinant aflatoxin-degrading F420H2-dependent reductase from Mycobacterium smegmatis protects mammalian cells from aflatoxin toxicity. Toxins, 2019, 11(5): 259 (doi: 10.3390/toxins11050259). 23. Kolosova A., Stroka J. Substances for reduction of the contamination of feed by mycotoxins: a review. World Mycotoxin Journal, 2011, 4(3): 225-256 (doi: 10.3920/WMJ2011.1288). 24. Loi M., Fanelli F., Zucca P., Liuzzi V.C., Quintieri L., Cimmarusti M.T., Monaci L., Haidukowski M., Logrieco A.F., Sanjust E., Mulè G. Aflatoxin B1 and M1 degradation by Lac2 from Pleurotus pulmonarius and redox mediators. Toxins, 2016, 8(9): 245 (doi: 10.3390/toxins8090245). 25. Brana M.T., Sergio L., Haidukowski M., Logrieco A.F., Altomare C. Degradation of aflatoxin B-1 by a sustainable enzymatic extract from spent mushroom substrate of Pleurotus eryngii. Toxins, 2020, 12(1): 49 (doi: 10.3390/toxins12010049). 26. Wang J., Ogata M., Hirai H., Kawagishi H. Detoxification of aflatoxin B1 by manganese peroxidase from the white-rot fungus Phanerochaete sordid YK-624. FEMS Microbiol. Lett., 2011, 314(2): 164-169 (doi: 10.1111/j.1574-6968.2010.02158.x). 27. Yao D.S., Liang R., Liu, D.L., Gu L.Q., Ma L., Chen W.Q. Screening of the fungus whose multienzyme system has catalytic detoxification activity towards aflatoxin B 1 (Part I). Ann. N.Y. Acad. Sci., 1998, 864: 579-585 (doi: 10.1111/j.1749-6632.1998.tb10385.x). 28. Liu D.-L., Yao D.-S., Liang Y.Q., Zhou T.-H., Song Y.-P., Zhao L., Ma L. Production, purification, and characterization of an intracellular aflatoxin-detoxifizyme from Armillariella tabescens (E-20). Food Chem. Toxicol., 2001, 39(5): 461-466 (doi: 10.1016/s0278-6915(00)00161-7). 29. Cao H., Liu D., Mo X., Xie C., Yao D. A fungal enzyme with the ability of aflatoxin B1 conversion: purification and ESI-MS/MS identification. Microbiol. Res., 2011, 166(6): 475-483 (doi: 10.1016/j.micres. 2010.09.002). 30. Wu Y.Z., Lu F.P., Jiang H.L., Tan C.P., Yao D.S., Xie C.F., Liu D.L. The furofuran-ring selectivity, hydrogen peroxide-production and low Km value are the three elements for highly effective detoxification of aflatoxin oxidase. Food Chem. Toxicol., 2015, 76: 125-131 (doi: 10.1016/j.fct.2014.12.004). 31. Xingming Y. Oral liquid medicine from ferments of Armilarilla tabescens. China PAT # CN1679642. Priority date 11. 05.2004. Publication date 01.08.2007. 32. Chahardooli M., Niazi A., Aram F., Sohrabi S.M. Expression of recombinant Arabian camel lactoferricin-related peptide in Pichia pastoris and its antimicrobial identification. J. Sci. Food Agric., 2016, 96(2): 569-575 (doi: 10.1002/jsfa.7125). 33. Wang Y., Wang Y., Jiang J., Zhao Y., Xing F., Zhou L. High expression of zearalenone degrading enzyme in Pichia pastoris. Chinese Journal of Biotechnology, 2020, 36(2): 372-380 (doi: 10.13345/j.cjb.190150). 34. Sinel’nikov I.G., Zorov I.N., Sinitsyna O.A., Sinitsyn A.P., Rozhkova A.M. Integratsionnyy vektor dlya mnogokopiynoy integratsii genov v 18Sr RNK drozhzhey Pichia pastoris. № RU 2752904C1, Mosk. FGU Issledovatel’skiy Tsentr «Osnovy Biotekhnologii» RAN (RF). Zayavl. 02.09.20. Opubl. 11.08.21. Byul. № 23 [A vector for multicopy gene integration into 18Sp RNA of the yeast Pichia pastoris. No. RU 2752904C1, Moscow. FGU Research Center «Fundamentals of Biotechnology» RAS (RF). Appl. 09.02.20. Publ. 08.11.21. Bull. № 23] (in Russ.). 35. Lin-Cereghino J., Wong W.W., Xiong S., Giang W., Luong L.T., Vu J., Johnson S.D., LinCereghino G.P. Condensed protocol for competent cell preparation and transformation of the methylotrophic yeast Pichia pastoris. Biotechniques, 2005, 38(1): 44-48 (doi: 10.2144/05381BM04). 36. Lõoke M., Kristjuhan K., Kristjuhan A. Extraction of genomic DNA from yeasts for PCR-based applications. Biotechniques, 2011, 50(5): 325-328 (doi: 10.2144/000113672). 37. Waterborg J.H., Matthews H.R. The Lowry method for protein quantitation. In: Proteins. Methods in molecular biology™, vol 1. J.M. Walker (ed.). Humana Press, 1984: 1-3 (doi: 10.1385/0-89603062-8:1). 38. Dzhavakhiya V.G., Voinova T.M., Popletaeva S.B., Statsyuk N.V., Limantseva L.A., Shcherbakova L.A. Effect of various compounds blocking the colony pigmentation on the aflatoxin B 1 production by Aspergillus flavus. Toxins, 2016, 8(11): 313 (doi: 10.3390/toxins8110313). 39. Yang P., Xiao W., Lu S., Jiang S., Zheng Z., Zhang D., Zhang M., Jiang S., Jiang S. Recombinant expression of Trametes versicolor aflatoxin B1-degrading enzyme (TV-AFB1D) in engineering Pichia pastoris GS115 and application in AFB1 degradation in AFB1-contaminated peanuts. Toxins, 2021, 13(5): 349 (doi: 10.3390/toxins13050349). 40. Wang J.R., Li Y.Y., Liu D.N., Liu J.S., Li P., Chen L.Z., Xu S.D. Codon optimization significantly improves the expression level of -amylase gene from Bacillus licheniformis in Pichia pastoris. BioMed Research International, 2015, 2015: 248680 (doi: 10.1155/2015/248680). 41. Liu K., Ouyang Y., Lin R., Ge C., Zhou M. Strong negative correlation between codon usage bias and protein structural disorder impedes protein expression after codon optimization. J. Biotechnol., 2022, 343: 15-24 (doi: org/10.1016/j.jbiotec.2021.11.001). 1175