Author: Ramogida, C F ; Temerbulatova, N T ; Kurakina, E S ; McNeil, B L ; Hoehr, C ; Filosofov, D V ; Radchenko, V ; Magomedbekov, E P ; Khushvaktov, J ; Mirzayev, N A

INTRODUCTIONRadiolanthanides ¹³²La and ¹³⁵La form a promising chemically matched theranostic pair. With a half-life of 18.95 h, ¹³⁵La acts as the therapeutic isotope as it releases approximately 11 Auger electrons per decay, making it compatible with targeted Auger electron therapy (TAET), whereas ¹³²La with half-life of 4.58 h undergoes positron emission making it compatible with imaging via positron emission tomography (PET).METHODS^132/135La were produced via irradiation of natural barium targets (99.9 %) with 12.8 MeV protons. A two-step separation scheme using extraction chromatographic resin TK200 (50-100 μm) and cation exchange resin Dowex 50Wx4 (200-400 mesh) was designed. Inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify non-radioactive impurities in each fraction of the separation method. The distribution coefficients of La³⁺ in HNO₃ on the TK200 resin and on both Dowex 50Wx8 (200-400 mesh) and Dowex 50Wx4 resins in ammonium α-hydroxyisobutyrate (pH 4.8) were determined, respectively.RESULTSThis novel separation scheme allowed for reliable separation of [^132/135La]La³⁺ from the Ba²⁺ target material, resulting in a high radiochemical yield of 98.3 ± 2.1 % (n = 3) with the final elute being directly compatible with subsequent radiolabeling due to the use of ammonium α-hydroxyisobutyrate to eliminate steps in the radiopharmaceutical synthetic process.

13 Mar 2025·The Journal of Physical Chemistry A

DFT-Assisted Microkinetic Study of Transfer Hydrogenation over Homogeneous and Immobilized Cp*Ir Complexes

Article

Author: Podobedova, Anna ; Koltsova, Eleonora ; Blacker, A. John ; Goltz, Gert ; Mitrichev, Ivan ; Chapman, Michael ; Borissova, Antonia ; Kawakami, Yuji ; Vasilev, Mikhail

DFT calculations were done to investigate the kinetic mechanism of benzaldehyde transfer hydrogenation using [Cp*IrCl₂]₂ complexes in isopropyl alcohol in the presence of potassium tert-butoxide. Predicted energy barriers provide evidence that the inner-sphere (IS) mechanism (effective barrier 53.0 kJ/mol) is favored over the outer-sphere (OS) and Meerwein-Pondorf-Verley (MPV) mechanisms. Reaction kinetics was studied using both homogeneous and immobilized Cp*Ir complexes as catalysts. A mathematical model was developed to simulate the transfer hydrogenation of benzaldehyde on these catalysts, accounting for possible mass transfer limitations for the immobilized catalyst. A microkinetic model was constructed using both our density functional theory calculations and fitting of the kinetic parameters of catalyst activation and deactivation reactions. The simulation results predict that only about a quarter of Ir immobilized complexes are involved in the reaction, and this is the main reason for the observed higher activity of the homogeneous catalyst. The activity of the immobilized catalyst was found to be related to the hydride species concentration, which is a function of the base concentration. The results suggest that the amount of base has a drastic effect on the immobilized catalyst activity.

01 Mar 2025·Advanced Agrochem

Development of novel pyridine-based agrochemicals: A review

Author: Martsynkevich, Andrey M. ; Zakharychev, Vladimir V.

Pyridine-based agrochem. products have become the most com. successful in the 21st century.About half of the agrochems. with pyridine scaffold were released, registered or invented only in the current millennium.Some of them have a unique structure and previously unknown modes of action.The literature provides examples of the use of the pyridine ring in pesticides for reducing the dosage of the active ingredient, hence to take care of the environment due to their increased efficacy, overcoming the pest resistance, and also makes it possible to create patentable structures by dodging the parent patent, which sometimes leads to a change in the spectrum of activity of the compoundsThe newest 13 substances registered by the ISO from Jan. 2021 to June 2024, and not reviewed previously are considered.

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