Sodium Derivatives Research Articles

The Use of Thioxopyrimidine Derivatives as New Regulators of Growth and Photosynthesis of Barley

New synthetic compounds - thioxopyrimidine derivatives as regulators of vegetative growth and photosynthesis of spring barley (Hordeum vulgare L.) variety Acordine were studied. The growth-regulatory effect of new synthetic compounds, thioxopyrimidine derivatives, used in a concentration of 10-6M, was compared with the growth-regulatory effect of a plant hormone auxin IAA (1H-indol-3-yl)acetic acid) or synthetic plant growth regulators, derivatives of sodium and potassium salts of 6-methyl-2-mercapto-4-hydroxypyrimidine (Methyur, Kamethur), N-oxide-2,6-dimethylpyridine (Ivin), used in a similar concentration of 10-6M. The conducted study showed the similarity of the growth-regulatory effects of synthetic compounds, thioxopyrimidine derivatives, the plant hormone auxin IAA, and synthetic plant growth regulators Methyur, Kamethur, and Ivin. Morphometric parameters (average length of shoots (mm), average length of roots (mm), and average biomass of 10 plants (g)) and biochemical parameters (content of photosynthetic pigments chlorophylls a, b, a+b and carotenoids (µg/ml)) of barley plants treated with the plant hormone auxin IAA or synthetic plant growth regulators Methyur, Kamethur, Ivin or thioxopyrimidine derivatives were increased after 4 weeks compared to control plants. The dependence of the growth-regulatory effect of synthetic compounds, thioxopyrimidine derivatives on their chemical structure was analyzed. The use of the synthetic plant growth regulators, derivatives of sodium salt of 6-methyl-2-mercapto-4-hydroxypyrimidine (Methyur), potassium salt of 6-methyl-2-mercapto-4-hydroxypyrimidine (Kamethur), N-oxide-2,6-dimethylpyridine (Ivin) and selected most active synthetic compounds, thioxopyrimidine derivatives for regulating the growth and photosynthesis of spring barley (Hordeum vulgare L.) variety Acordine is proposed.

The use of thioxopyrimidine derivatives for the regulation of vegetative growth of wheat

The work is devoted to the screening of new effective wheat plant growth regulators based on synthetic compounds, thioxopyrimidine derivatives. The wheat (Triticum aestivum L.) variety Oksamit Mironivskyi was used as the object of the study. Morphometric parameters (average length of shoots and roots (mm), and average biomass of 10 plants (g)) of 4-week-old wheat plants were measured. Treatment of wheat plants with thioxopyrimidine derivatives at a concentration of 10-6 M contributed to the growth and development of shoots and roots compared to control wheat plants treated with distilled water. The regulatory effect of thioxopyrimidine derivatives on the vegetative growth of wheat plants was similar to the regulatory effect of auxin IAA (1H-indol-3-yl)acetic acid) or synthetic compounds, derivatives of sodium and potassium salts of 6-methyl-2-mercapto-4-hydroxypyrimidine (Methyur, Kamethur) and N-oxide-2,6-dimethylpyridine (Ivin) used in the same concentration of 10-6 M. The correlation between the growth regulatory effect and the chemical structure of synthetic compounds, thioxopyrimidine derivatives was established. The selected most active synthetic compounds, thioxopyrimidine derivatives, are proposed to be used to improve the vegetative growth of wheat (T. aestivum L.) variety Oksamit Mironivskyi.

Design, Molecular Docking, Synthesis, and Antimicrobial Evaluation of new Dipeptide derivatives of Ceftizoxime sodium

Newer cephalosporins that can be orally administered with significant oral bioavailability and resist β-lactamases are continuously and significantly requested. A method of using a potent third-generation cephalosporin, ceftizoxime, was suggested to synthesize new dipeptide derivatives. These derivatives were successfully synthesized by linking a dipeptide moiety, which includes L-Tryptophan-L-valine, L-Tryptophan-L-alanine, L-Tryptophan-L-histidine, and L-Tryptophan-L-phenylalanine as dipeptides to the aminothiazole moiety of ceftizoxime by an amide bond. Their chemical structures were confirmed by spectral analysis, including 1H-NMR,13CNMR, and FT-IR spectroscopy. Molecular docking for these new derivatives was performed on penicillin-binding proteins (PBPs) type 2a (3ZG0) of Methicillin-resistant Staphylococcus aureus, type 2X (5OJ0) of Streptococcus pneumonia and type 1b (5HLA) of E. coli, and has recorded higher affinity binding represented as PLP fitness on target enzymes. The binding scores were significant and may indicate better antimicrobial activities when compared with ceftizoxime. This improvement in affinity binding can be explained by the presence of indole and/or imidazole moieties in those derivatives. The indole and imidazole moieties are actual pharmacophores with various biological activities and may contribute to affinity binding, and the derivatives are considered molecular hybrids. Furthermore, a preliminary evaluation of the antibacterial activity of the synthesized derivatives was performed against two significant bacterial species (MRSA and E. coli), which showed better activity in compression to ceftizoxime. Moreover, the derivatives were tested on the protein oligopeptide (POT) family system and have recorded very interesting results for possible oral absorption when compared with Ceftizoxime, Val-acyclovir, and Val-Val-Acyclovir, as reference drugs. The Swiss ADME server was also used to analyze the pharmacokinetic characteristics and identify those likely to be absorbed orally.

АЦИЛИРОВАНИЕ N-ФОСФОРИЛИРОВАННЫХ ЦИАНОАЦЕТИМИДАТОВ

A method has been developed for the preparation of organophosphorus derivatives of imidic acids, based on the acylation of N-phosphorylated mono-carbon active methylene group. The interaction of sodium derivatives of monoimidates with acid chlorides leads to the formation of the corresponding monoacylated derivatives, for which inhibition of acetyl esterase, esterase hydrolase, cutinase and other enzymes is highly predicted.

Syntheses, Structures, and Corrosion Inhibition of Various Alkali Metal Carboxylate Complexes.

Complexes of the alkali metals Li-Cs with 3-thiophenecarboxylate (3tpc), 2-methyl-3-furoate (2m3fur), 3-furoate (3fur), 4-hydroxycinnamate (4hocin), and 4-hydroxybenzoate (4hob) ions were prepared via neutralisation reactions, and the structures of [Li2(3tpc)2]n (1Li); [K2(3tpc)2]n (1K); [Rb(3tpc)(H2O)]n (1Rb); [Cs{H(3tpc)2}]n (1Cs); [Li2(2m3fur)2(H2O)3] (2Li); [K2(2m3fur)2(H2O)]n (2K); [Li(3fur)]n(3Li); [K(4hocin](H2O)3]n (4K); [Rb{H(4hocin)2}]n.nH2O (4Rb); [Cs(4hocin)(H2O)]n (4Cs); [Li(4hob)]n (5Li); [K(4hob)(H2O)3]n (5K); [Rb(4hob)(H2O)]n (5Rb); and [Cs(4hob)(H2O)]n (5Cs) were determined via X-ray crystallography. Bulk products were also characterised via XPD, IR, and TGA measurements. No sodium derivatives could be obtained as crystallographically suitable single crystals. All were obtained as coordination polymers with a wide variety of carboxylate-binding modes, except for dinuclear 2Li. Under conditions that normally gave coordinated carboxylate ions, the ligation of hydrogen dicarboxylate ions was observed in 1Cs and 4Rb, with short H-bonds and short O…O distances associated with the acidic hydrogen. The alkali-metal carboxylates showed corrosion inhibitor properties inferior to those of the corresponding rare-earth carboxylates.

Crystal structure and ion-exchange property of a lepidocrocite-like sodium titanate

ABSTRACT A lepidocrocite-like potassium titanate, (Kx(LixTi1-x)O2; Lss) with a layered structure can provide a reactive interlayer space for soft-chemical reaction such as ion-exchange or intercalation and the hydrated sodium derivative (Lss-Na) was obtained by an ion-exchange reaction. The crystal structures of the hydrated and dehydrated Lss-Na were refined by using synchrotron powder X-ray diffraction data. Two steps of dehydrated processes for the Lss-Na were observed by in-situ synchrotron powder X-ray diffraction. The ion-exchange property for Lss-Na was superior to those for Lss and Lss-H and was corelated with the effective basal space which was expanded by formation of two layers of water molecules.

Influence of alkali metal cations on the formation of the heterobimetallic actinide tert-butoxides [AnM3(OtBu)7] and [AnM2(OtBu)6] (AnIV = Th, U; MI = Li, Na, K, Rb, Cs).

Heterobimetallic tert-butoxides of alkali metal cations with tetravalent actinide centers exhibit two distinctive structural motifs, [AnM2(OtBu)6] and [AnM3(OtBu)7] (AnIV = Th, U and MI = Li, Na, K, Rb, Cs), evidently governed by the size of the alkali metal ions. Both [AnM3(OtBu)7] AnM3 (AnIV = U, MI = Li; AnIV = Th, MI = Li, Na) and [AnM2(OtBu)6] AnM2 (AnIV = U, MI = Na-Cs; AnIV = Th, MI = K-Cs) compounds are obtained in nearly quantitative yields by reacting actinide and alkali metal silyl amides with an excess of tert-butyl alcohol. The AnM3 complexes form a cubane-type coordination motif, whereas the AnM2 complexes display a geometry resembling two face-shared bipyramids. The sodium derivatives of thorium and uranium (ThNa3 and UNa2) allow the determination of the structural transition threshold as a function of the ratio of the ionic radii ri(AnIV)/ri(MI). The AnM3 complexes are formed for ratios above 0.92 and the AnM2 type is formed for ratios below 0.87. All compounds are unambiguously characterized in both solution and solid states by NMR and IR spectroscopic studies and single crystal X-ray diffraction analyses, respectively.

Investigating Derivatives of Tanshinone IIA Sulfonate Sodium and Chloroxine for Their Inhibition Activities against the SARS-CoV-2 Papain-like Protease.

SARS-CoV-2 has caused a global pandemic of COVID-19, posing a huge threat to public health. The SARS-CoV-2 papain-like cysteine protease (PLpro) plays a significant role in virus replication and host immune regulation, which is a promising antiviral drug target. Several potential inhibitors have been identified in vitro. However, the detailed mechanism of action and structure-activity relationship require further studies. Here, we investigated the structure-activity relationships of the series of derivatives of tanshinone IIA sulfonate sodium (TSS) and chloroxine based on biochemical analysis and molecular dynamics simulation. We found that compound 7, a derivative of chloroxine, can disrupt PLpro-ISG15 interaction and exhibits an antiviral effect for SARS-CoV-2 variants (wild type, delta, and omicron) at the low micromolar level. These studies confirmed that inhibiting PLpro-ISG15 interaction and, thus, restoring the host's innate immunity are effective methods for fighting against viral infection.

Inhibition of Alkali Metal Reduction of 1‐Adamantanol by London Dispersion Effects

AbstractA series of alkali metal 1‐adamantoxide (OAd1) complexes of formula [M(OAd1)(HOAd1)2], where M=Li, Na or K, were synthesised by reduction of 1‐adamantanol with excess of the alkali metal. The syntheses indicated that only one out of every three HOAd1 molecules was reduced. An X‐ray diffraction study of the sodium derivative shows that the complex features two unreduced HOAd1 donors as well as the reduced alkoxide (OAd1), with the Ad1 fragments clustered together on the same side of the NaO3 plane, contrary to steric considerations. This is the first example of an alkali metal reduction of an alcohol that is inhibited from completion due to the formation of the [M(OAd1)(HOAd1)2] complexes, stabilized by London dispersion effects. NMR spectroscopic studies revealed similar structures for the lithium and potassium derivatives. Computational analyses indicate that decisive London dispersion effects in the molecular structure are a consequence of the many C−H⋅⋅⋅H−C interactions between the OAd1 groups.

Inhibition of Alkali Metal Reduction of 1‐Adamantanol by London Dispersion Effects

AbstractA series of alkali metal 1‐adamantoxide (OAd1) complexes of formula [M(OAd1)(HOAd1)2], where M=Li, Na or K, were synthesised by reduction of 1‐adamantanol with excess of the alkali metal. The syntheses indicated that only one out of every three HOAd1 molecules was reduced. An X‐ray diffraction study of the sodium derivative shows that the complex features two unreduced HOAd1 donors as well as the reduced alkoxide (OAd1), with the Ad1 fragments clustered together on the same side of the NaO3 plane, contrary to steric considerations. This is the first example of an alkali metal reduction of an alcohol that is inhibited from completion due to the formation of the [M(OAd1)(HOAd1)2] complexes, stabilized by London dispersion effects. NMR spectroscopic studies revealed similar structures for the lithium and potassium derivatives. Computational analyses indicate that decisive London dispersion effects in the molecular structure are a consequence of the many C−H⋅⋅⋅H−C interactions between the OAd1 groups.

Theoretical and structural studies of a stable dinuclear sodium complex of dicoumarol - 3,3′-(pyridin-3-ylmethanediyl)bis(4‑hydroxy-2H-chromen-2-one)

The synthesis of a dicoumarol derivative (C24H15NO6) is reported via fusing 4-hydroxycoumarin with 3-pyridinecarboxaldehyde. The sodium derivative [Na2(C24H14NO6)2(MeOH)2(H2O)2] was synthesized by treating sodium methoxide with the dicoumarol ligand (C24H15NO6). The resulting dinuclear sodium complex was structurally characterized using various spectroscopic and analytical techniques including 1H, 13C{1H}-NMR, high resolution ESI-MS(+), infrared spectroscopy, elemental and single crystal diffraction analyses. The molecular structure of [Na2(C24H14NO6)2(MeOH)2(H2O)2] exhibits coordination of methanol, water and dicoumarol. B3LYP calculations were carried out to optimize the theoretical structural parameters and theoretical 1H and 13C NMR spectra for comparison with the respective experimental data which are well correlated.

Alkali-Metal-Mediated Synergistic Effects in Polar Main Group Organometallic Chemistry.

The development of synthetic chemistry since the early 1900s owes much to the service of organolithium reagents. Brilliant bases (e.g., deprotonating C-H bonds), nucleophiles (e.g., adding to unsaturated molecules), and transfer agents (e.g., delivering ligands to other metals), these versatile virtuosi and to a lesser extent the organic derivatives of the other common alkali metals sodium and potassium have proved indispensable in both academia and technology. Today these monometallic compounds are still utilized widely in synthetic campaigns, but in recent years they have been joined by an assortment of bimetallic formulations that also contain an alkali metal but in company with another metal. These bimetallic formulations often exhibit unique chemistry that can be interpreted in terms of synergistic effects, for which the alkali metal is essential, though it is often the second metal that performs the synthetic transformation. Here, this "alkali-metal-mediated" chemistry is surveyed focusing mainly on bimetallic formulations containing two alkali metals or an alkali metal paired with magnesium, calcium, zinc, aluminum, or gallium. In this International Year of the Periodic Table (IYPT), we ponder whether a Pairiodic Table of Element Pairs will emerge in the future.

Tuning the Geometric and Electronic Structure of Synthetic High-Valent Heme Iron(IV)-Oxo Models in the Presence of a Lewis Acid and Various Axial Ligands.

High-valent ferryl species (e.g., (Por)FeIV═O, Cmpd-II) are observed or proposed key oxidizing intermediates in the catalytic cycles of heme-containing enzymes (P-450s, peroxidases, catalases, and cytochrome c oxidase) involved in biological respiration and oxidative metabolism. Herein, various axially ligated iron(IV)-oxo complexes were prepared to examine the influence of the identity of the base. These were generated by addition of various axial ligands (1,5-dicyclohexylimidazole (DCHIm), a tethered-imidazole system, and sodium derivatives of 3,5-dimethoxyphenolate and imidazolate). Characterization was carried out via UV-vis, electron paramagnetic resonance (EPR), 57Fe Mössbauer, Fe X-ray absorption (XAS), and 54/57Fe resonance Raman (rR) spectroscopies to confirm their formation and compare the axial ligand perturbation on the electronic and geometric structures of these heme iron(IV)-oxo species. Mössbauer studies confirmed that the axially ligated derivatives were iron(IV) and six-coordinate complexes. XAS and 54/57Fe rR data correlated with slight elongation of the iron-oxo bond with increasing donation from the axial ligands. The first reported synthetic H-bonded iron(IV)-oxo heme systems were made in the presence of the protic Lewis acid, 2,6-lutidinium triflate (LutH+), with (or without) DCHIm. Mössbauer, rR, and XAS spectroscopic data indicated the formation of molecular Lewis acid ferryl adducts (rather than full protonation). The reduction potentials of these novel Lewis acid adducts were bracketed through addition of outer-sphere reductants. The oxidizing capabilities of the ferryl species with or without Lewis acid vary drastically; addition of LutH+ to F8Cmpd-II (F8 = tetrakis(2,6-difluorophenyl)porphyrinate) increased its reduction potential by more than 890 mV, experimentally confirming that H-bonding interactions can increase the reactivity of ferryl species.

Structural Diversity of Lithium, Sodium, and Potassium Complexes of N‐Mesityl‐P,P‐diphenylphosphoryl Amide

Metalation of N‐mesityl‐P,P‐diphenylphosphinic amide Ph2P(=O)–N(H)Mes (1) with n‐butyllithium, sodium amide and potassium hydride yields the corresponding alkali metal N‐mesityl‐P,P‐diphenylphosphoryl amides of lithium (2), sodium (3), and potassium (4). The lithium complex 2 forms a dimer with an eight‐membered (Li–O–P–N)2 ring. The sodium derivative 3 crystallizes as a dinuclear centrosymmetric complex with a central Na2O2 ring. The potassium congener 4 precipitates as a tetranuclear compound with an inner K4O4 heterocubane cage. In these complexes the phosphoryl amido ligands act as bidentate Lewis bases and form strained four‐membered M–O–P–N rings. Due to this fact, the endocyclic M–O bonds of the M2O2 rings vary within a large range.

Preparation of Manganese Lignosulfonate and Its Application as the Precursor of Nanostructured MnOx for Oxidative Electrocatalysis

The synthesis of manganese lignosulfonates by a two-step method has been reported. It was based on the conversion of technical sodium derivative of lignosulfonate to its hydrogen form i.e., lignosulfonic acid and its further reaction with manganese hydroxide. The obtained product was electroactive, and could be applied as the precursor of electroactive manganese oxide. The product showed a reversible redox activity in the potential range of 0 to 1 V vs. an Ag/AgCl reference electrode. The electroactivity of the obtained product can be tentatively assigned to the redox activity of both the electrodeposited MnOx and the presence of lignosulfonate-derived quinones since the energy dispersive spectroscopy (EDS) confirmed the presence of organic matter in the deposit. It also showed substantial electrocatalytic activity towards the anodic oxidation of hydrogen peroxide. This suggests that manganese lignosulfonates could be a valuable compound for the electrochemical preparation of electroactive layers that are suitable in the development of electrochemical sensors.

N-substituted dibutoxyphosphorylacetimidates in phosphorylation reactions

Reaction of N-substituted dibutoxyphosphorylacetimidates with sodium followed by phosphorylation of sodium derivatives with dialkyl chlorophosphates and phenyl dichlorophosphate proceeds selectively under mild conditions to form products of phosphorylation of the methylene group. The synthesized compounds possess potential antisecretory, immunosuppressive, hypolipidemic, and other types of biological activity.

Alkali and Alkaline Earth Metal Complexes Ligated by an Ethynyl Substituted Cyclopentadienyl Ligand

Sodium, potassium, and calcium compounds of trimethyl((2,3,4,5-tetramethylcyclopentadien-1-yl)ethynyl)silane (CpMe4(C≡CSiMe3)) were synthesized and characterized by X-ray diffraction and standard analytical methods. The sodium derivative was obtained by deprotonation of CpMe4(C≡CSiMe3)H with Na{N(SiMe3)2} to give a monomeric complex [NaCpMe4(C≡CSiMe3)(THF)3]. In a similar reaction, starting from K{N(SiMe3)2} the corresponding potassium compound [KCpMe4(C≡CSiMe3)(THF)2]n, which forms a polymeric super sandwich structure in the solid state, was obtained. Subsequently, salt metathesis reactions were conducted in order to investigate the versatility of the CpMe4(C≡CSiMe3)− ligand in alkaline earth chemistry. The reaction of [KCpMe4(C≡CSiMe3)(THF)2]n with CaI2 afforded the dimeric complex [CaCpMe4(C≡CSiMe3)I(THF)2]2, in which both CpMe4(C≡CSiMe3)Ca units are bridged by iodide in a μ2 fashion. In-depth NMR investigation indicates that [CaCpMe4(C≡CSiMe3)I(THF)2]2 is in a Schlenk equilibrium with [{CpMe4(C≡CSiMe3)}2Ca(THF)x] and CaI2(THF)2, as is already known for [CaCp*I(THF)2].

Insights into the multistep transformation of titanate nanotubes into nanowires and nanoribbons

Abstract Different types of titanate one-dimensional nanostructured materials were synthesized and characterized using scanning and transmission electron microscopy, X-ray diffraction and Raman spectroscopy. The results presented in this work unquestionably showed dependence of morphology and structure of the titanate nanopowders on parameters of hydrothermal synthesis. It was found that nanotubes, nanowires and nanoribbons are three unavoidable kinetic products of hydrothermal reaction. Moreover, increasing temperature of reaction or hydrothermal treatment duration results in acceleration of nanotube-nanowire-nanoribbon transformation. However, the sequence of titanate morphology transformation is invariable. The detailed studies further revealed that the crystal structure of hydrothermally prepared nanotubes and nanowires are indistinguishable but the determination of the exact structure is practically impossible. Because of higher crystallinity, the structure of nanoribbons can be established. It was shown that it corresponds to the monoclinic layered trititanic acid H2Ti3O7 and is isostructural with sodium derivatives Na2_xHxTi3O7.nH20 (with x near 2).

Development of 1-Amino-4-(phenylamino)anthraquinone-2-sulfonate Sodium Derivatives as a New Class of Inhibitors of RANKL-Induced Osteoclastogenesis.

A series of 1-amino-4-(phenylamino)anthraquinone-2-sulfonate sodium derivatives was synthesized and evaluated for osteoclast inhibition using a TRAP-staining assay. Among them, two compounds, LCCY-13 and LCCY-15, dose-dependently suppressed receptor activator of nuclear factor-κB ligand (RANKL)-induced osteoclast formation. Moreover, the cytotoxicity assay on RAW264.7 cells suggested that the inhibition of osteoclastic bone resorption by these compounds was not a result of their cytotoxicity. Further, the inhibitory activities of compounds LCCY-13 and LCCY-15 were further confirmed by including specific inhibition of NFATc1 expression levels in nuclei using an immunofluorescent analysis. In addition, LCCY-13 and LCCY-15 also significantly attenuated the bone resorption activity of osteoclasts according to a pit formation assay. Thus, a new class of 1-amino-4-(phenylamino)anthraquinone-2-sulfonate sodium compounds might be considered as an essential lead structure for the further development of anti-resorptive agents.

Synthesis and Crystal Structures of Lithium, Sodium, and ­Potassium Derivatives of 2‐(Methylthio)aniline and 2‐(Phenylthio)aniline

Abstract2‐(Methylthio)aniline (H2L1) and 2‐(phenylthio)aniline (H2L2) were treated with n‐butyllithium to yield the corresponding anilides [LiHL1] and [LiHL2]. Recrystallization from diethyl ether and THF afforded the solvates [LiHL1(Et2O)] and [LiHL2(THF)2]. The X‐ray crystal structure determination revealed dimeric molecules which exhibit a centrosymmetric Li2N2 ring. In the case of [LiHL1(Et2O)] the SMe group is involved in Li coordination and in the case of [LiHL2(THF)2] the SPh group is part of an intramolecular N–H···S hydrogen bridge. The sodium anilides [NaHL1(DME)] and [NaHL2(DME)] were obtained from the reaction of H2L1 and H2L2 with sodium amide in DME as solvent. Like in the case of the lithium amides the sodium derivatives [NaHL1(DME)] and [NaHL2(DME)] display centrosymmetric Na2N2 cores. The coordination sphere of the sodium atoms is completed by DME molecules, which act as chelating ligands. In the case of [NaHL1(DME)] the DME molecules enable additionally a linkage of the dimeric subunits to give a chain structure. The potassium derivatives [KNHL1] and [KNHL2(DME)] were obtained from H2L1 and H2L2 and potassium hydride in DME as solvent. [KNHL1] displays a distinct structure based on [(KNHL1)2] dimers, which are linked by additional [KNHL1] units to give a 3D coordination polymer with {4.8.16(3)} topology. [KNHL2(DME)] forms dimers linked by bridging DME molecules to give a chain‐like coordination polymer.