Methyl Amino Research Articles

“Synergistic Innovation: Crafting Indazole Derivatives for Advanced Anticancer, Antioxidant, and Antimicrobial Efficacy through Integrative Design and Holistic Evaluation”

AbstractThis study presents the synthesis and characterization of a newer series of N‐(1‐(2‐(phenylamino) pyrimidin‐4‐yl)‐1H‐indazol‐5‐yl)benzenesulfonamide (6 a–6 n) and N‐(6‐ethoxy‐1‐(2‐(phenylamino) pyrimidin‐4‐yl)‐1H‐indazol‐5‐yl)benzenesulfonamide (7 a–7 c) derivatives through the reaction of N‐(1‐(2‐chloropyrimidin‐4‐yl)‐1H‐indazol‐5‐yl) benzenesulfonamide (4 a–i) and N‐(1‐(2‐chloropyrimidin‐4‐yl)‐6‐ethoxy‐1H‐indazol‐5‐yl) benzenesulfonamide (5 a–i) with various aniline derivatives in isopropanol. The compounds were thoroughly evaluated for their biological activities, encompassing antifungal, antibacterial, and anticancer assays, as well as antioxidant potential in DPPH and ABTS assays. Compound 7 b (IC50: 0.0125 MIC), 6 e (IC50: 0.0128 MIC), and 6 i (IC50: 0.0128 MIC) demonstrated exceptional antibacterial efficacy, while 6 d (IC50: 0.0124 MIC), 6 f (IC50: 0.0125 MIC) and 7 c (IC50: 0.0118 MIC), exhibited notable antifungal activity. Compounds 6 c (IC50: 13.31±0.32 μM, A459) & (IC50: 22.36±1.76 μM, MCF7) displayed significant anticancer activity comparable to established drugs. Moreover, 6 b (IC50: 11.22±0.16 μM, A459) & (IC50: 18.21±1.32 μM, MCF7) and 6 d (IC50: 11.23±0.17 μM, A459) & (IC50: 18.31±1.41 μM, MCF7) showed remarkable anticancer potency. Notably, compound N‐(1‐(2‐(methyl(phenyl)amino)pyrimidin‐4‐yl)‐1H‐indazol‐5‐yl)‐4‐nitrobenzenesulfonamide (IC50:0.1090 μmol/mL for DPPH and IC50: 0.1286 μmol/mL for ABTS) exhibited the most significant antioxidant activity. Computational docking studies revealed robust binding interactions with target enzymes (PDB ID: 4JT3 for anticancer, PDB ID: 1EA1 for antifungal, PDB ID: 1KZN for antibacterial, PDB ID: 3SRG for antioxidant), supported by molecular dynamics simulations indicating consistent stability of the most potent compound within the binding sites of the target proteins. These findings underscore the therapeutic potential of these derivatives, warranting further investigation for potential clinical applications.

Dual molecule targeting HDAC6 leads to intratumoral CD4+ cytotoxic lymphocytes recruitment through MHC-II upregulation on lung cancer cells

BackgroundDespite the current therapeutic treatments including surgery, chemotherapy, radiotherapy and more recently immunotherapy, the mortality rate of lung cancer stays high. Regarding lung cancer, epigenetic modifications altering cell cycle, angiogenesis...

Abstract 1862: ZW191 - a FRα-targeting antibody drug conjugate with strong preclinical activity across multiple FRα-expressing indications

Abstract Background: Folate Receptor alpha (FRα) is a validated cancer target that is prevalently expressed in multiple cancers with high unmet need, including ovarian cancer and other gynecological cancers, NSCLC, endometrial cancer and TNBC. Due to FRα’s favorable expression profile, multiple antibody-drug conjugates (ADCs) are being explored in this setting. Here we present the preclinical characterization of a new anti-FRα ADC, ZW191. ZW191 is a bystander active antibody drug conjugate (ADC) comprised of a humanized IgG1 antibody conjugated to a novel camptothecin-based topoisomerase 1 inhibitor (TOPO1i) payload, ZD06519, via a maleimidocaproyl (MC) anchor and a glycyl glycyl phenylalanyl glycyl (GGFG)-aminomethyl (AM) cleavable linker at a drug-to-antibody ratio (DAR) of 8. ZW191 is projected to undergo IND submission in 2024. Materials and Methods: The novel antibody and drug-linker components of ZW191 were generated, characterized, and optimally integrated. The apparent binding affinity and cellular internalization of the ZW191 antibody were determined in FRα-expressing cells. Tumor spheroid cancer cell cultures were utilized to determine ZW191’s degree of tissue penetration and its cytotoxicity. The bystander activity of ZW191 was assessed using antigen positive and negative co-culture experiments. The anti-tumor activity of ZW191 was evaluated in a panel of ovarian cancer, NSCLC, endometrial cancer and TNBC patient-derived xenografts (PDX) spanning a range of FRα expression. ZW191 was evaluated in toxicology and pharmacokinetic (PK) studies performed in non-human primates (NHP). Results: The antibody component of ZW191 features a favorable binding profile with strong binding to FRα, and drives superior tumor spheroid penetration, cellular internalization, and payload delivery compared to FRα targeted antibodies used in multiple other ADCs. ZW191 demonstrates potent activity in FRα expressing cell cultures and effective bystander activity. In a panel of PDX models representing a range of FRα expression, ZW191 demonstrates compelling anti-tumor activity across ovarian and endometrial cancers, NSCLC and TNBC. ZW191 demonstrates an encouraging tolerability profile in NHP, with favorable PK. The promising efficacy, tolerability, and PK support the potential of ZW191 as a novel therapeutic agent that may help address unmet need in patients with high and low FRα expressing cancers. Citation Format: Sam Lawn, Andrea Hernandez Rojas, Raffaele Colombo, Jodi Wong, Kaylee Wu, Vincent Fung, Manuel Lasalle, Mark E. Petersen, Lemlem Degefie, Araba Sagoe-Wagner, Dunja Urosev, Luying Yang, Ambroise Wu, Catrina Kim, Amos Chua, Kurt Stahl, Geoffrey C. Winters, John C. Fann, Jamie Rich, Stuart Barnscher. ZW191 - a FRα-targeting antibody drug conjugate with strong preclinical activity across multiple FRα-expressing indications [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2024; Part 1 (Regular Abstracts); 2024 Apr 5-10; San Diego, CA. Philadelphia (PA): AACR; Cancer Res 2024;84(6_Suppl):Abstract nr 1862.

Unraveling sources of cyanate in the marine environment: insights from cyanate distributions and production during the photochemical degradation of dissolved organic matter

Cyanate is a nitrogen and energy source for diverse marine microorganisms, playing important roles in the nitrogen cycle. Despite the extensive research on cyanate utilization, the sources of this nitrogen compound remain largely enigmatic. To unravel the sources of cyanate, distributions and production of cyanate during photochemical degradation of natural dissolved organic matter (DOM) were investigated across various environments, including freshwater, estuarine, coastal areas in Florida, and the continental and slope regions of the North American mid-Atlantic Ocean (NATL). Cyanate production was also examined during the photochemical degradation of exudates from a typical strain of Synechococcus, an important phytoplankton component. To deepen our understanding of the sources and production mechanisms of cyanate, its production was assessed during the photochemical degradation of a natural seawater DOM supplemented with five nitrogen–containing compounds with distinguishing structures and functional groups. Generally, cyanate exhibited higher concentrations in the Florida coastal, estuarine, and freshwater environments than the NATL. However, cyanate distribution did not consistently align with its production rates. Despite significantly low concentrations in the NATL, DOM from this region exhibited cyanate production rates comparable to estuarine and Florida coastal environments. Although relatively high cyanate concentrations were observed in the freshwaters, DOM in this environment exhibited very low cyanate production rates. A highly significant correlation was observed between cyanate and chlorophyll a (Chl a) concentrations in these areas. Moreover, in most estuarine and NATL stations, cyanate concentration and production rate in the Chl a maximum layer were significantly higher than in other layers. Cyanate was produced during the photochemical degradation of the Synechococcus exudates. The cyanate production was significantly enhanced when the natural seawater DOM was supplemented with GlycylGlycine, 4-(methylamino) benzoic acid, 4-[ethyl(methyl)amino] benzaldehyde or methyl 2-aminobenzoate. Our study implies that photochemical degradation of marine DOM, especially phytoplankton-derived DOM, is a substantial source of cyanate in the ocean. Additionally, cyanate may form during the degradation of peptides and small aromatic compounds in DOM, providing novel insights into the nitrogen cycle.

R-phycoerythrin alginate/shellac beads by external gelation: Process optimization and the effects of gastrointestinal digestion for nutraceutical applications

This study aimed to evaluate an alginate/shellac mixture as wall material to develop an aqueous phycoerythrin (R-PE) encapsulation system by external gelation and to determine the effect of encapsulation on the biological properties of R-PE released during simulated gastrointestinal digestion. The Taguchi method was implemented to formulate beads with a high R-PE encapsulation efficiency (EE). The effect of the variables: feeding flow (90 and 20 mL h−1), distance (5 and 10 cms), and CaCl2 (5 and 15 g L−1) were optimized, and the bead size, sphericity factor (SF), and total R-PE content were characterized. Finally, the optimal alginate/shellac beads were subjected to in vitro dynamic gastrointestinal digestion. The results show that the beads formed under optimal conditions reached an EE value of 97.5 %. The CaCl2 concentration and feeding flow most affected the R-PE EE. The release of R-PE from alginate/shellac was affected at acid pH 1; however, the concentration was under 10 % of the total R-PE content showing promising targeting properties in terms of time and pH. The R-PE extracts and capsules were partially degraded in gastric and intestinal conditions; the mouth did not detect signals from the protein profile. The encapsulation of alginate/shellac led to higher R-PE contents at the end of digestion than non-encapsulated R-PE, suggesting a protective role. Significantly, from permeate streams, equivalent to the absorption of encapsulated R-PE, the bioavailability was 2.5 times higher than non-encapsulated R-PE. NMR results indicate the presence of R-PE and its methyl amino acids and oligosaccharides between 0.5 and 2.5 and 3.8–6.8 ppm, respectively. Cytotoxicity activity was observed for the R-PE extract on the HCT-116 human colon cancer cell line. The alginate/shellac as a wall material and ionic gelation technology used may determine the release of the R-PE pigment at an intestinal site and its antiproliferative effect on health.

Research Progress on Benzimidazole Fungicides: A Review.

Benzimidazole fungicides are a class of highly effective, low-toxicity, systemic broad-spectrum fungicides developed in the 1960s and 1970s, based on the fungicidal activity of the benzimidazole ring structure. They exhibit biological activities including anticancer, antibacterial, and antiparasitic effects. Due to their particularly outstanding antibacterial properties, they are widely used in agriculture to prevent and control various plant diseases caused by fungi. The main products of benzimidazole fungicides include benomyl, carbendazim, thiabendazole, albendazole, thiophanate, thiophanate-methyl, fuberidazole, methyl (1-{[(5-cyanopentyl)amino]carbonyl}-1H-benzimidazol-2-yl) carbamate, and carbendazim salicylate. This article mainly reviews the physicochemical properties, toxicological properties, disease control efficacy, and pesticide residue and detection technologies of the aforementioned nine benzimidazole fungicides and their main metabolite (2-aminobenzimidazole). On this basis, a brief outlook on the future research directions of benzimidazole fungicides is presented.

Structure-based drug design and characterization of novel pyrazine hydrazinylidene derivatives with a benzenesulfonate scaffold as noncovalent inhibitors of DprE1 tor tuberculosis treatment.

In this study, we present a novel series of (E)-4-((2-(pyrazine-2-carbonyl) hydrazineylidene)methyl)phenyl benzenesulfonate (T1-T8) and 4-((E)-(((Z)-amino(pyrazin-2-yl)methylene)hydrazineylidene)methyl)phenyl benzenesulfonate (T9-T16) derivatives which exert their inhibitory effects on decaprenylphosphoryl-β-D-ribose 2'-epimerase (DprE1) through the formation of hydrogen bonds with the pivotal active site Cys387 residue. Their effectiveness against the M. tuberculosis H37Rv strain was examined and notably, three compounds (namely T4, T7, and T12) exhibited promising antitubercular activity, with a minimum inhibitory concentration (MIC) of 1.56µg/mL. The target compounds were screened for their antibacterial activity against a range of bacterial strains, encompassing S. aureus, B. subtilis, S. mutans, E. coli, S. typhi, and K. pneumoniae. Additionally, their antifungal efficacy against A. fumigatus and A. niger also was scrutinized. Compounds T6 and T12 demonstrated significant antibacterial activity, while compound T6 exhibited substantial antifungal activity. Importantly, all of these active compounds demonstrated exceedingly low toxicity without any adverse effects on normal cells. To deepen our understanding of these compounds, we have undertaken an in silico analysis encompassing Absorption, Distribution, Metabolism, and Excretion (ADME) considerations. Furthermore, molecular docking analyses against the DprE1 enzyme was conducted and Density-Functional Theory (DFT) studies were employed to elucidate the electronic properties of the compounds, thereby enhancing our understanding of their pharmacological potential.

Sustainable golden nanoflowers grafted food-waste derived biotemplate for the direct SERS-detection of carcinogenic herbicides from agro-farms

Surface Enhanced Raman Scattering (SERS) is emerging as a potent analytical tool for the detection of various pollutants in complex environments due to its distinctive vibrational fingerprint ability and pronounced detection sensitivity. Precautious of adverse blue-green economies and ecological impacts, sustainable generation of SERS active substrates and analyte casting matrices are getting prioritized. Herein, gold nanoflowers (AuNFs) of ∼75 ± 15 nm were initially biofabricated using an expended cell culture medium as a one-step synthesis cum stabilization strategy. Then the heavy architecture of multi-faceted AuNFs with deep pits and edges, that acted as hotspots for enhancing the localized electromagnetic fields, was utilized for the direct SERS detection of commonly used carcinogenic herbicides collected from agro-farms at nanomolar regimes with 0.44 ppm and 0.27 ppm for Glyphosate and amino methyl phosphonic acid, respectively. Such a low level detection is superior by 8.33% when compared to the reported values. Computational finite-difference time-domain (FDTD) simulations affirmed the enhanced SERS effect from the multi-faceted nanostructure of AuNFs with structural heterogeneities that provide numerous hotspots to amplify the localized electromagnetic field. More eminently, fish scale derived biotemplate through AuNF-analyte drop casting contributed to the exceptional intensities, attributed to the naturally grooved hierarchically porous hydrophilic lamellar structures contact angle of 73°. Overall, the adapted bioengineering of SERS substrate is safe, robust, affordable and reproducible, fostered by bioderived durable biomatrix offering potent sustainable SERS detection of various biomedically and environmentally relevant molecules.

Synthesis, Spectroscopic Evaluations and UV-Vis Titration Studies of New Symmetrical Amide Compounds Derived from N-6-[(4-pyridylmethylamino)carbonyl]-pyridine-2-carboxylic Acid Methyl Ester

In this study, 2 flexible and pre-organized tetraamide compounds derived from N-6-[(4-pyridylmethylamino)carbonyl]-pyridine-2-carboxylic acid methyl ester namely 1,2-bis[N,N’-6-(4-pyridylmethylamido)pyridyl-2-carboxyamido]pentane (L1) and 1,2-bis[N,N’-6-(4-pyridylmethylamido)pyridyl-2-carboxyamido]hexane (L2) have been successfully synthesized when reacted with diamines in 1:2 ratio. These new compounds were built from combination of 3 main components, as a trend requires for anion receptor which are (i) 2,6-pyridine dicarboxamide moieties as targeted anion binding host, (ii) amino methyl pyridine pendants arms as the flexible moieties and (iii) pentyl (-C5H10-) and hexyl (-C6H12-) unit as the spacer. Compounds L1-L2 were fully characterized by using elemental analyzer, Fourier transform infrared (FTIR) spectroscopy, gas chromatography-mass spectroscopy (GC-MS), 1H, 2D NOESY and 13C Nuclear Magnetic Resonance (NMR) spectroscopies, and Ultraviolet-visible (UV-Vis) spectroscopies. In this study, anion titration methods were used to identify the affinity towards selected anions. The results showed that L1 (having a pentyl spacer) had the highest affinity towards phosphate anions as compared to L2, where the red shift changes were observed in the UV-vis spectrum at the amide region. HIGHLIGHTS Two novel amide compounds with flexible and pre-organized structure are designed for use as potential anion receptors The flexible moieties at the amide and the linker allow hydrogen bonding interaction of the molecules with variety anions with different geometries Anion titration studies revealed good affinities towards phosphate anions as suggested in Hofmeister trend GRAPHICAL ABSTRACT

A novel corrosion inhibitor based on a Schiff base for mild steel in 1M HCl: synthesis and anticorrosion study

PurposeThe aim of this study was to investigate the activity of 4-((4-((2-hydroxyethyl)(methyl)amino)benzylidene) amino)-1,5-dimethyl-2-phenyl-1,2-dihydro-3H-pyrazol-3-one (HEMAP), a Schiff base synthesized and characterized for the first time, to the authors’ knowledge, as a novel inhibitor against corrosion of mild steel (MS) in hydrochloric acid solution.Design/methodology/approachHEMAP was characterized by some spectroscopic methods including High-Resolution Mass Spectrometry (HRMS), Proton Nuclear Magnetic Resonance (1H NMR), Carbon-13 (C13) nuclear magnetic resonance (13C NMR) and Fourier Transform Infrared Spectroscopy (FT-IR). Then, the inhibition efficiency of HEMAP on MS in a hydrochloric acid solution was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). To explain the inhibition mechanism, the surface charge, adsorption isotherms and thermodynamic parameters of MS in the inhibitor solution were studied.FindingsEIS tests displayed that the highest inhibition efficiency was calculated approximately as 99.5% for 5 × 10−2 M HEMAP in 1 M HCl solution. The adsorption of HEMAP on the MS surface was found to be compatible with the Langmuir model isotherm. The thermodynamic parameter results showed that the standard free energy of adsorption of HEMAP on the MS surface was found to be more chemical than physical.Originality/valueThis study is important in terms of demonstrating the performance of the first synthesized HEMAP molecule as an inhibitor against the corrosion of MS in acidic media. EIS tests displayed that the highest inhibition efficiency was calculated approximately as 99.5% for 5 × 10−2 M HEMAP in 1 M HCl solution.

Tobacco-Specific Nitrosamines in Current Commercial Large Cigars, Cigarillos, and Little Cigars.

We measured levels of nitrosonornicotine (NNN) and 4-[methyl(nitroso)amino]-1-(3-pyridinyl)-1-butanone (NNK), the two most carcinogenic tobacco-specific nitrosamines, in the filler, binder, and wrapper of 50 cigars: 19 large cigars, 23 cigarillos, and 8 little cigars. The average NNN and NNK levels were 10.6 and 3.70 μg/g, respectively. These levels are 5- and 7-fold higher, respectively, than those of commercial cigarettes. The differences in NNN and NNK levels between cigars and cigarettes reflect differences in tobacco blends and tobacco treatments, such as fermentation. The average tobacco NNN and NNK levels of large cigars were 3- and 5-fold higher than those of cigarillos and little cigars, respectively. Large cigars also exhibited a significantly broader range of NNN and NNK than cigarillos and little cigars. The NNN and NNK levels in cigarillos are comparable to those of little cigars. These results are consistent with earlier studies finding that cigarillos and little cigars have similar tobacco blends with lower NNN and NNK content than large cigar tobacco blends.

Design, Synthesis, Pharmacology, and In Silico Studies of (1S,2S,3S)-2-((S)-Amino(carboxy)methyl)-3-(carboxymethyl)cyclopropane-1-carboxylic Acid (LBG30300): A Picomolar Potency Subtype-Selective mGlu2 Receptor Agonist.

Metabotropic glutamate (Glu) receptors (mGlu receptors) play a key role in modulating excitatory neurotransmission in the central nervous system (CNS). In this study, we report the structure-based design and pharmacological evaluation of densely functionalized, conformationally restricted glutamate analogue (1S,2S,3S)-2-((S)-amino(carboxy)methyl)-3-(carboxymethyl)cyclopropane-1-carboxylic acid (LBG30300). LBG30300 was synthesized in a stereocontrolled fashion in nine steps from a commercially available optically active epoxide. Functional characterization of all eight mGlu receptor subtypes showed that LBG30300 is a picomolar agonist at mGlu2 with excellent selectivity over mGlu3 and the other six mGlu receptor subtypes. Bioavailability studies on mice (IV administration) confirm CNS exposure, and an in silico study predicts a binding mode of LBG30300 which induces a flipping of Tyr144 to allow for a salt bridge interaction of the acetate group with Arg271. The Tyr144 residue now prevents Arg271 from interacting with Asp146, which is a residue of differentiation between mGlu2 and mGlu3 and thus could explain the observed subtype selectivity.

A NEW SERIES OF 1,3,4-THIADIAZOLE SUBSTITUTED AZETIDINONE AND THIAZOLIDINONE DERIVATIVES AND THEIR ANTIMICROBIAL ACTIVITY

The new series of 2-({[5-(3-chloro-2-oxo-4-substituted-phenylazetidin-1-yl)-1,3,4-thiadiazol-2- yl]methyl}amino)benzoic acid (13-20) and 2-({[5-(4-oxo-2- substituted-phenyl-1,3-thiazolidin-3-yl)- 1,3,4- thiadiazol-2-yl]methyl}amino)benzoic acid (21-28) have been synthesized from 2-[({5-[(benzylideneamino]- 1,3,4- thiadiazol-2-yl }methyl)amino]-benzoic acid (5-12). All these synthesized compounds were tested for their antimicrobial activity and established by spectroscopic data, and elemental analyses.

Transesterification or polymerization? Reaction mechanism and kinetics of 2-(diethylamino)ethyl methacrylate with methanol and the competitive effect on free-radical polymerization

Transesterification of 2-(diethylamino)ethyl methacrylate (DEAEMA) with methanol leads to the formation of methyl methacrylate (MMA) and amino alcohol. This reaction significantly affects DEAEMA polymerization giving rise to poly(DEAEMA-co-MMA).

Macromolecular hydrogels for the colorimetric detection and efficient separation of cobalt (II) in complex aqueous media

Azobenzene quinolinol–based hydrogels were developed for the highly selective detection and separation of Co(II) ions in complex aqueous media. (E)-2-((4-(Diazenyl(8-hydroxyquinolin-5-yl))phenyl)(methyl)amino)ethyl acrylate (DHPMAA) and N,N-dimethylacrylamide (DMA) were copolymerized to yield p(DMA-co-DHPMAA). The polymeric probe exhibited high selectivity and sensitivity toward Co(II) ions in aqueous solutions. Hydrogels based on p(DMA-co-DHPMAA) were synthesized via photopolymerization and were demonstrated to effectively separate Co(II) ions from various other metal ions. The selectivity was further demonstrated under challenging conditions in which the concentration of Fe(II) ions substantially exceeded that of Co(II) ions, simulating radioactive waste in cooling channels of nuclear power plants. The synthesized hydrogels were able to selectively separate Co(II) ions from a complex mixture containing excess Fe(II) ions at a concentration five times that of the Co(II) ions, demonstrating the application potential of the hydrogels for Co(II) ions removal.

Molecular Revealing the High‐stable Polycyclic Azine Derivatives for Long‐Lifetime Aqueous Organic Flow Batteries

AbstractSoluble organic molecules with diverse and highly tunable structures are receiving more and more attention as redox‐active materials for aqueous organic flow batteries (AOFBs). However, the undesirable parasitic reactions of redox‐active molecules restrict their practical application. Herein, a general molecular stabilization strategy is proposed by introducing amino groups on 3,7‐positions of polycyclic azine derivatives (phenothiazine and phenoxazine compounds) to effectively enhance the redox activity and electrochemical stability of molecules. The theoretical calculation and a series of electrochemical analyses revealed that the 3,7‐substituted amino groups serving as the redox active sites can stabilize the intermediate radicals by delocalizing the electron density in the acidic solution, preventing nucleophilic/electrophilic attack. As a result, the designed 3,7‐bis‐((2‐hydroxyethyl)(methyl)amino)phenothiazin‐5‐ium bromide not only achieved the remarkable electrochemical cycling performance in the flow cell with an ultra‐low‐capacity fade rate of 0.00029% per cycle for 18000 cycles (62 days) and but also delivered a stable high capacity of 47 Ah L−1 (with capacity fade 0.0056% per cycle, 0.077% per day) under ambient condition. Such finding undoubtedly provides a guidance to design stable redox‐active molecules for AOFBs.

A chiral pool-derived calcium catalyst for intramolecular hydroamination with enhanced enantioselectivity

The synthesis of (2S,3S)-3-methyl-2-(methyl(pyridin-2-yl-methyl)amino)-1,1-diphenylpentan-1-ol 5 and its use together with [Ca(N(SiMe3)2)2(thf)2] 6 as in situ generated catalytic system in the enantioselective intramolecular hydroamination of 2,2-diphenylpent-4-en-1-amine 7 as benchmark substrate is discussed. Enantiomeric excesses of up to 77 %, the highest yet reported for calcium-based systems, as well as significantly shortened reaction times while only requiring 5 mol-% of catalyst, were achieved.

Design and Modulation of Selectivity toward Vanadium(V) and Uranium(VI) Ions: Coordination Properties and Affinity of Hydroxylamino-Triazine Siderophores.

Based on the strong binding and high selectivity properties of 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H2bihyat) for [UVIO2]2+, novel binucleating ligands (BLs) N,N',N″,N‴-((1,4-phenylenebis(oxy))bis(1,3,5-triazine-6,2,4-triyl))tetrakis(N-methylhydroxylamine) (H4qtn), N1,N4-bis(4,6-bis(hydroxy(methyl)amino)-1,3,5-triazin-2-yl)benzene-1,4-diamine (H4pdl), and N1,N2-bis(4,6-bis(hydroxy(methyl)amino)-1,3,5-triazin-2-yl)ethane-1,2-diamine (H4enl) were synthesized. Binuclear complexes formed by coordination of hard metal ions with H4qtn are thermodynamically more stable than their mononuclear analogues with H2bihyat due to the increase in entropy accompanying the formation of more chelate rings. Reaction of either H4qtn or H4pdl or H4enl with [UVIO2]2+ and [VVO2]+ resulted in the isolation of the binuclear complexes [(UVIO2)2(μ-qtn)(H2O)4] (1), [(VVO2)2(μ-qtn)][PPh4]2[PPh4] (2), [(UVIO2)2(μ-pdl)(H2O)2(MeOH)2] (3), [(VVO2)2(μ-pdl)][PPh4]2 (4), [(UVIO2)2(μ-enl)(H2O)4] (5), and [(VVO2)2(μ-enl)][PPh4]2 (6). The binuclear complexes 1-6 were characterized by single-crystal X-ray diffraction analysis in solid state and by NMR and ESI-MS in solution. The comparison of the coordination ability of the BLs with either pyridine-2,6-dicarboxylic acid (H2dipic) or H2bihyat or CO32- toward [UVIO2]2+ and [VVO2]+ was investigated by NMR and UV-vis spectroscopies and DFT theoretical calculations, revealing a superior performance of BLs. The selectivity of the BLs for [UVIO2]2+ over [VVO2]+ is decreased compared to that of H2bihyat but increases considerably at pH > 9 values. Formation of the mixed-metal binuclear species [UVIO2(μ-O)VVO2] influences the selectivity and dynamics of the reaction of H4qtn for [UVIO2]2+ and [VVO2]+ in aqueous solution. The results of this study provide crucial information for the ligand design and the development of stronger and more selective systems.

Recyclization of 5-Amino- oxazoles as a Route to new Functionalized Heterocycles (Developments of V.P. Kukhar Institute of Bioorganic Chemistry and Petrochemistry of the NAS of Ukraine).

The recyclizations of 5-amino- and 5-hydrazine-1,3-oxazoles mainly with electron-withdrawing group in 4th position are considered. The chemical behavior of these heterocycles is due to the presence of two hidden amide fragments; therefore, the recyclization processes include a stage of nucleophile attack on 2nd or 5th position of the oxazole cycle. When the nitrile group is present in 4th position, it is often involved in the recyclization forming α-aminoazoles. 5-Amino/hydrazine-1,3-oxazoles undergo recyclization both in nucleophilic (amines, hydrazine, thionating agents) and electrophilic medium ((trifluoro)acetic acid, other acylating agents). The numerous types of functionalized heterocycles can be easily obtained with the usage of these recyclizations, such as the derivatives of 3-amino-6,7-dihydro-5H-pyrrolo[1,2-a]imidazole, imidazolidine-2,4-dione, 1H-pyrazole-3,4,5-triamine, 5,6-diamino-2,3-diphenylpyrimidin-4(3H)-one, 2-(2-R-7-oxo-5-(trifluoromethyl)oxazolo[5,4-d]pyrimidin-6(7H)-yl)acetic acid, 2-R-4-(5-R'-1,3,4-oxadiazol-2-yl)oxazol-5-amine, (amino(5-amino-1,3,4-thiadiazol-2-yl)methyl)phosphonate.

Capability of phytoremediation of glyphosate in environment by Vulpia myuros

Glyphosate is an herbicide extensively used worldwide that can remain in the soil. Phytoremediation to decontaminate polluted water or soil requires a plant that can accumulate the target compound. Vulpia myuros is an annual fescue that can be used as a heavy mental phytoremediation strategy. Recently, it has been used to intercrop with tea plant to prohibit the germination and growth of other weeds in tea garden. In order to know whether it can be used an decontaminating glyphosate’ plant in water or soil, in this study, glyphosate degradation behavior was investigated in Vulpia myuros cultivated in a hydroponic system. The results showed that the concentration of glyphosate in the nutrient solution decreased from 43.09 μg mL−1 to 0.45 μg mL−1 in 30 days and that 99% of the glyphosate molecules were absorbed by V. myuros. The contents of glyphosate in the roots reached the maximum (224.33 mg kg−1) on day 1 and then decreased. After 3 days, the content of glyphosate in the leaves reached the highest value (215.64 mg kg−1), while it decreased to 156.26 mg kg−1 in the roots. The dissipation dynamics of glyphosate in the whole hydroponic system fits the first-order kinetic model C = 455.76e−0.21 t, with a half-life of 5.08 days. Over 30 days, 80% of the glyphosate was degraded. The contents of the glyphosate metabolite amino methyl phosphoric acid (AMPA), ranged from 0.103 mg kg−1 on day 1–0.098 mg kg−1 on day 30, not changing significantly over time. The Croot/solution, Cleaf/solution and Cleaf/root were used to express the absorption, transfer, and distribution of glyphosate in V. myuros. These results indicated that glyphosate entered into the root system through free diffusion, which was influenced by both the log Kow and the concentration of glyphosate in the nutrient solution, and that glyphosate was either easily transferred to the leaves through the transpiration stream, accumulated, or degraded. The degradation of glyphosate in V. myuros indicated that it has potential as a remediating plant for environmental restoration.