One-pot bio-based myrtenol amination was studied in the presence of alumina supported Au, Au–Pd and Pd nanoparticles subjected to the thermal treatment under oxidizing or reducing atmosphere. ...Myrtenol amination with aniline was carried out under nitrogen atmosphere (9 bar) at 453 K using toluene as a solvent. The effect of the active metal along with the influence of redox pre-treatment on the catalytic behavior in the hydrogen borrowing reaction was explored. The catalyst characterization was done by transmission electron microscopy, X-ray photoelectron spectroscopy, inductively coupled plasma optical emission spectroscopy, nitrogen adsorption. The active metal and the catalysts redox pretreatment affected more noticeably selectivity to the reaction products rather than myrtenol conversion. Monometallic Au/Al
2
O
3
catalyst promoted predominantly formation of the target secondary amine and the corresponding imine without a significant impact of the side reaction of C=C bond hydrogenation in myrtenol, whereas monometallic Pd catalyst activated C=C bond resulting in its hydrogenation. At the same time in the presence of Au–Pd simultaneous hydrogenation of both C=C and C=N bond occurred. Au–Pd catalysts activated in oxygen and hydrogen showed different catalytic activity determined by the composition of surface active sites. Monometallic gold catalyst was more effective in the hydrogen transfer in the case of substrates with competitive unsaturated functional groups.
Graphic Abstract
Platinum nanoparticles supported on MgO, Al
2
O
3
, ZrO
2
, TiO
2
were utilized for monoterpenoid oximes hydrogenation. Monocyclic menthone and carvone oximes synthesized from bio-derived ...monoterpenoids with a different structure were used to explore the effect of substrate structure on the reaction regularities. The oximes hydrogenation was carried out under hydrogen atmosphere at 100 °C using methanol as a solvent. Platinum catalysts were prepared by the impregnation methods. The catalysts were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray fluorescence spectroscopy, nitrogen physisorption. Hydrogenation of carvone oxime containing a conjugated oxime group and several reducible functional groups resulted in both hydrogenation and deoximation giving 5-isopropyl-2-methylcyclohexanamine and carvomenthone over Pt/Al
2
O
3
and Pt/ZrO
2
catalysts. Menthone oxime hydrogenation over Pt/Al
2
O
3
catalysts with an average particle size of 0.8 nm provided the desired menthylamine formation with the selectivity of 90% at complete oxime conversion. Platinum catalysts based on MgO, ZrO
2
and TiO
2
enhanced menthone oxime deoximation to menthone.
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•Support and solvent nature affect both activity and selectivity to menthylamine.•Au NPs (2 nm) on alumina afford a higher yield of menthylamine.•Stereoselectivity to the amine is ...independent on temperature and hydrogen pressure.•First-order with respect to menthone oxime concentration.•The reaction rate is independent on hydrogen pressure.
In the current work gold nanoparticles supported on oxides (MgO, Al2O3, ZrO2, TiO2) were used for menthylamine synthesis via menthone oxime hydrogenation. An increase of the gold nanoparticles size and application of metal oxides with a strong basic character such as magnesia favored deoximation to menthone. Au/Al2O3 catalyst with the gold nanoparticles size of 2.0 nm afforded high catalytic activity and selectivity to menthylamine. The reaction kinetics including stereoselectivity to the reaction products and recyclability of the catalyst was studied using Au/Al2O3 in the temperature range 90−110 °C under hydrogen pressure of 5.5–7.5 bar. The catalytic behavior was influenced by the solvent nature, with higher selectivity to desired amine achieved using methanol. The reaction rate was pressure independent, while has first order with respect to menthone oxime concentration. Stereoselectivity to menthylamines and menthones was independent on the reaction temperature and the hydrogen pressure.
The genus
Taxus
(yew) is a source of a number of high-value medicinal substances, particularly, paclitaxel (taxol)—a complex diterpenoid compound with a powerful antitumor action (trade name of ...Taxol®). Paclitaxel is one of the most efficient drugs in chemotherapy owing to its specific ability to suppress proliferation of tumor cells via stabilization of their microtubules. The world-wide demand for taxol is 800–1000 kg a year and these figures annually rise by 20%. The growing need for paclitaxel and its derivatives and the shortage of plant resources necessary for their production made compounds of the taxane group one of the most important objects for development of biotechnological methods of their production. Out of all the possible ways of taxol production (isolation from wild or plantation trees, total chemical synthesis or semisynthesis, use of yew cell cultures, techniques of metabolic engineering, and use of yew endophytic fungi), the most promising is industrial cultivation of
Taxus
spp. cell cultures. This review examines the papers dealing with investigation of secondary metabolism in dedifferentiated cells in vitro of various yew species and feasibility of industrial use of cell cultures for production of taxoids. We revealed a number of specificity of
Taxus
spp. cell cultures: (1) from a cytophysiological aspect—difficult initiation of cell cultures, their low growth characteristics, specific media and culturing conditions; (2) from a phytochemical aspect—distinction from intact plants in qualitative composition and content of secondary metabolites accounted for by specificity of cell culture as a biological system; predominant formation of С14-hydroxylated rather than of С13-hydroxylated taxoids; an opportunity for elevation of the content of taxoids—including commercially valuable ones (paclitaxel and baccatin III) with the aid of different tools (elicitation, stress exposures, two-phase cultivation and some others); (3) from a biotechnological aspect—possibility of industrial cultivation of yew cell cultures; existence of several successful industries (Germany and the Republic of Korea).
•One-pot myrtenol amination over Au catalysts.•Different metal oxides as supports.•Products: biologically valuable compounds.•Correlation between support nature and catalytic performance.•The highest ...activity and selectivity in one-pot myrtenol amination with aniline over Au/ZrO2.
The one-pot amination of natural terpene alcohol (myrtenol, with a primary hydroxyl group) was studied over gold catalysts supported on different metal oxides such as ZrO2, MgO, Al2O3, CeO2, La2O3 using the equimolar amounts of substrates under nitrogen pressure. The synthesized catalysts were characterized by TEM, N2 adsorption techniques and XPS. The correlation between acid–base properties of support and catalytic performance was established. A nearly complete myrtenol conversion as well as the highest selectivity to secondary amine of about 52% were reached after 16h over Au/ZrO2 with both acidic and basic surface sites.
In 2018–2022 under the conditions of the southwest of Sverdlovsk oblast, an assessment of adaptability has been carried out, as well as the selection of promising samples of oats for the creation of ...productive varieties. The study has been conducted on 50 collection samples; the Sprint 2 variety bred by the Ural Federal Agrarian Research Center has been used as a standard. The following methods have been used to determine the parameters of environmental adaptability: regression coefficient and stability parameter (according to S.A. Eberhart and W.A. Russell), stress resistance and genetic flexibility (according to A.A. Goncharenko), adaptability (according to L.A. Zhivotkov and V.A. Dragavtsev), and ecological plasticity (according to A.A. Gryaznov). Under favorable growing conditions of 2018 and 2019 (
I
j
= 117.5 and 84.3, respectively) the average yields of samples were 669.4 and 636.4 g/m
2
. High grain yield was observed in samples of domestic selection 15335 SIG (600.2 g/m
2
) and 15338 Creole (601.4 g/m
2
), which was 122.6–123.8 g more than in the standard. The selected varieties with increased stress resistance ((
Y
min
–
Y
max
) = –300 to –314) are 14 800 Belle (United States), 15181 Stayer (Russia), and 15352 Haga (Norway); with compensatory ability ((
Y
min
+
Y
max
)/2 = 507–526), 14792 Bajka (Poland), 15281 120 h 2106 (Russia), and 15335 SIG (Russia); with high rates of adaptability (
AС
= 106.6–111.1%) and ecological plasticity (
EPI
= 1.07–1.11), 14792 Bajka (Poland), 15352 Haga (Norway), 15338 Creole (Russia), and 15335 SIG (Russia); stable in terms of relative stability of the trait (
= 0.0452–0.0624), 15181 Stayer, 14597 Sprint 2 (Russia), and 14800 Belle (United States); sensitive to growing conditions (
b
i
= 1.14–1.40), 15122 Fax (Belarus), 15374 Galaxy (Germany), 15376 KWS Contender (Germany), 15292 Farys (Poland), and 15315 Acton (Russia); adaptive samples with the lowest sum of ranks, 15345 Baiche (Kazakhstan), 15338 Creole (Russia), 15122 Fax (Belarus), and 15376 KWS Contender (Germany).
Taxane diterpenoids (taxoids) are found only in representatives of the Taxaceae family (different yew species); however, the unique structure and therapeutic properties of taxoids, which are in ...demand in medicine, have made these compounds one of the most studied secondary metabolites of higher plants. In this work, for the first time, a detailed study is performed into the structural diversity of polyesters of 14-hydroxylated taxoids in
Taxus canadensis
a yew species, for intact plants of which nonpolar 14-hydroxylated taxoids have not been previously described. At the first stage of the work, it was shown using chromato-mass spectrometry that polyesters of 14-hydroxylated taxoids (yunnanxan, taxuyunnanin C, sinenxan B, sinenxan C) are the dominant diterpenoid secondary metabolites in
T. canadensis
callus cell culture. Based on these results, as well as the similarity of the metabolism of cultivated in vitro plant cells and root cells in planta, it was suggested that polyesters of 14-hydroxylated taxoids will preferentially accumulate in the roots in intact
T. canadensis
plants. The validity of this hypothesis was confirmed using liquid chromatography-mass spectrometry and nuclear magnetic resonance spectroscopy (NMR). According to chromato-mass-spectrometric screening in
T. canadensis
needles, polyesters of 14-hydroxylated taxoids are actually found only in trace amounts, while they are one of the major (quantitatively) diterpenoids in the roots. One of the main 14-hydroxylated taxoids of
T. canadensis
roots, yunnanxan, was isolated preparatively and uniquely identified using NMR spectroscopy and high-resolution mass spectrometry. This work is the first report on the presence of polyesters of 14-hydroxylated taxoids in intact Canadian yew plants.
The aim of this work was to optimize the prognosis of early recurrences of uterine cancer by searching for informative laboratory biomarkers. The study included 343 patients with I-IV stages FIGO ...endometrial adenocarcinoma the ages of 53 and 76 years. In patients before surgery, as well as 3 and 6 months after the end of primary treatment, the concentration of oncological markers CA-125, HE4, DJ-1, DKK-1 was determined in blood serum by ELISA and electrochemiluminescence immunoassay. We analyzed the predictive informativeness of monitoring markers to assess the risk of early recurrences of cancer within two years after surgery. In patients with uterine cancer with the stage of the disease and the degree of tumor differentiation in the blood serum, the concentration of DJ-1 is changed. With myometrial invasion of more than 50%, increased serum levels of three markers - CA-125, HE4, and DJ-1. Depending on the risk of disease recurrence, the assessment of which was determined by intraoperative and histological characteristics, a difference was revealed in the content of HE4 and DJ-1 markers in the blood. It was found that the risk of early recurrence of uterine cancer increased (p<0,05) when the concentration of CA-125 exceeded the level of 29,3 U/ml, HE4 was above 79,3 pmol/l, DJ-1 was above 90,0 ng/ml and DKK-1 above 47,3 pg/ml 6 months after the end of primary treatment. The highest predictive information value was found for monitoring DJ-1 and HE4 in blood serum, which indicates that they are promising for use in continuous monitoring of the course of cancer.
The review presents an analysis of studies on the role of the intestinal microbiota and microbiome in lipid metabolism and the development of dyslipidemia, atherosclerosis and cardiovascular ...diseases. The role of the intestine as a metabolic organ with a multifactorial strain evolution, involved in lipid metabolism, cholesterol homeostasis and enterohepatic circulation is shown. The influence of microbial imbalance on the development of dyslipidemia and atherosclerosis is considered. Special attention is paid to preventive therapy with hypolipidemic probiotics. It is shown that the use of probiotics with hypolipidemic properties and consisting of a mixture of such strains asLactobacillus plantarumCECT7527, CET7528 and CECT7529, mixtures ofLactobacillus acidophilusLa-5,Bifidobacterium lactisBB-12,Bifidobacterium animalis lactisBB-12 contribute to reducing the level of LDL-C, CCS, TG, are safe and well tolerated, can be used as an adjuvant non-drug therapy in combination with hypolipidemic drugs for dyslipidemia, multifocal atherosclerosis.
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