Molecular Markers Help with Breeding for Agronomic Traits of Spring Wheat in Kazakhstan and Siberia.

The Kazakhstan-Siberia Network for Spring Wheat Improvement (KASIB) was established in 2000, forming a collaboration between breeding and research programs through biannual yield trials. A core set of 142 genotypes from 15 breeding programs was selected, genotyped for 81 DNA functional markers and phenotyped for 10 agronomic traits at three sites in Kazakhstan (Karabalyk, Shortandy and Shagalaly) and one site in Russia (Omsk) in 2020-2022. The study aim was to identify markers demonstrating significant effects on agronomic traits. The average grain yield of individual trials varied from 118 to 569 g/m2. Grain yield was positively associated with the number of days to heading, plant height, number of grains per spike and 1000-kernel weight. Eight DNA markers demonstrated significant effects. The spring-type allele of the Vrn-A1 gene accelerated heading by two days (5.6%) and was present in 80% of the germplasm. The winter allele of the Vrn-A1 gene significantly increased grain yield by 2.7%. The late allele of the earliness marker per se, TaMOT1-D1, delayed development by 1.9% and increased yield by 4.5%. Translocation of 1B.1R was present in 21.8% of the material, which resulted in a 6.2% yield advantage compared to 1B.1B germplasm and a reduction in stem rust severity from 27.6 to 6.6%. The favorable allele of TaGS-D1 increased both kernel weight and yield by 2-3%. Four markers identified in ICARDA germplasm, ISBW2-GY (Kukri_c3243_1065, 3B), ISBW3-BM (TA004946-0577, 1B), ISBW10-SM2 (BS00076246_51, 5A), ISBW11-GY (wsnp_Ex_c12812_20324622, 4A), showed an improved yield in this study of 3-4%. The study recommends simultaneous validation and use of selected markers in KASIB's network.

Exciplex luminescence of difluoroboron meta- and para-Nitrodibenzoylmethanates in solutions and polymer matrix.

Molecular systems with intense exciplex luminescence are promising for the creation of OLEDs and light-transforming materials. The luminescent properties of difluoroboron meta- and para-nitrodibenzoylmethanates (1 and 2) were studied by the steady-state and time-resolved luminescence spectroscopy methods and quantum chemistry simulation. The influence of the position of the nitro group on the spectral properties of the complexes was revealed. The nitro group withdraws the electron density upon photoexcitation in the para-isomer in contrast to the meta-isomer. The bond order of the CC bond between the phenyl and chelate rings decreases in the excited relaxed state of 2, which leads to rotation of the substituent and a low quantum yield. Formation of exciplexes of 1 and 2 in benzene, toluene and polystyrene was found. The formation of the ground and excited-state electron donor-acceptor complexes based on difluoroboron nitrodibenzoylmethanates and benzene was revealed. The TDDFT method showed that the complexes are characterized by the presence of short contacts between the fluorine atom of the dye molecule and the hydrogen atoms of the aromatic hydrocarbon molecule. These contacts shorten during the transition from the ground state to the excited state. Polymeric compositions based on polystyrene (PS) and poly(methyl methacrylate) (PMMA) doped with 1 and 2 were obtained. The luminescence intensity of dyes 1 and 2 increases during the transition from PMMA to PS. A significant bathochromic shift of the luminescence maximum of 1 is observed, which is associated with the formation of exciplexes and triplexes. The obtained polymeric materials are promising for the development of optical smart materials.

Fluorescent boron difluoride curcuminoides as perspective materials for bio-visualization.

Curcuminoids of boron difluoride, 1-aryl(hetaryl)-5-phenylpenta-2,4-dien-1-onates of boron difluoride, have been synthesized. A comparative study of the electronic structure, luminescent properties and their potential for applications in bio-imaging has been carried out. The influence of the electronic structure of α-substituents on the luminescence of compounds was studied by the methods of stationary and time-resolved luminescence spectroscopy and DFT modeling. The introduction of π-donor substituents leads to a noticeable bathochromic shift and an increase in the Stokes shift in the luminescence spectra. On going from σ-donor substituents in the phenyl ring to π-donor substituents, the luminescence quantum yield increases from 0.03 to 0.22. The maximum Stokes shift and high quantum yield of luminescence is exhibited by the complex with a stilbene substituent, which has the longest π-system and the maximum efficiency of charge transfer. Dyes are able to penetrate into the cells of the model cell line and accumulate, moreover, accumulation occurs mainly in the cytoplasm of cells. The compounds penetrate into the cells by 12 h of incubation without damaging it's structure and without causing rapid cell death. The submicromolar range of non-toxic concentrations during long-term incubation for a model cell line was determined, which is a characteristic of fluorescent imaging. Due to uniform distribution in the cytoplasm of cells dye with naphtyl substituent is promising for visualization of the cell cytoplasm. This leader compound has the lowest cytotoxicity for cells from the synthesized series of dyes, which makes it promising for further studies as a fluorescent imaging agent. The leader compound has the lowest cytotoxicity for cells from the synthesized series of dyes, which makes it promising for further studies as a fluorescent imaging agent.

Identification of quantitative trait loci of agronomic traits in bread wheat using a Pamyati Azieva × Paragon mapping population harvested in three regions of Kazakhstan.

Background: Although genome-wide association studies (GWAS) are an increasingly informative tool in the mining of new quantitative trait loci (QTLs), a classical biparental mapping approach is still a powerful, widely used method to search the unique genetic factors associated with important agronomic traits in bread wheat. Methods: In this study, a newly constructed mapping population of Pamyati Azieva (Russian Federation) × Paragon (UK), consisting of 94 recombinant inbred lines (RILs), was tested in three different regions of Kazakhstan with the purpose of QTL identification for key agronomic traits. The RILs were tested in 11 environments of two northern breeding stations (Petropavlovsk, North Kazakhstan region, and Shortandy, Aqmola region) and one southeastern station (Almalybak, Almaty region). The following eight agronomic traits were studied: heading days, seed maturation days, plant height, spike length, number of productive spikes, number of kernels per spike, thousand kernel weight, and yield per square meter. The 94 RILs of the PAxP cross were genotyped using Illumina's iSelect 20K single nucleotide polymorphism (SNP) array and resulted in the identification of 4595 polymorphic SNP markers. Results: The application of the QTL Cartographer statistical package allowed the identification of 53 stable QTLs for the studied traits. A survey of published studies related to common wheat QTL identification suggested that 28 of those 53 QTLs were presumably novel genetic factors. The SNP markers for the identified QTLs of the analyzed agronomic traits of common wheat can be efficiently applied in ongoing breeding activities in the wheat breeding community using a marker-assisted selection approach.

Polymer films doped with boron difluoride ortho-hydroxydibenzoylmethanates: Solvatochromism and solvent-induced exciplex formation.

The spectral properties and solvatochromic behavior of boron difluoride ortho-hydroxydibenzoylmethanates in polymer matrices with different polarity (polystyrene, polyvinyl chloride, polycarbonate, poly(methyl methacrylate)) were investigated. The specific interaction of polystyrene, polycarbonate and poly(methyl methacrylate) with the investigated fluorophores was revealed. It was shown that the dyes are capable to form exciplexes with phenyl rings of polystyrene. The spectral properties of polystyrene films doped with boron difluoride ortho-hydroxydibenzoylmethanates, which were obtained by the pouring method, significantly depend on the solvent from which they were formed. This makes it possible to control the luminescence color of the films at the manufacturing stage.

Synthesis of Poly(methacrylic acid)-block-Polystyrene Diblock Copolymers at High Solid Contents via RAFT Emulsion Polymerization.

The combination of polymerization-induced self-assembly (PISA) and reversible-addition fragmentation chain transfer (RAFT) emulsion polymerization offers a powerful technique to synthesize diblock copolymers and polymeric nanoparticles in a controlled manner. The RAFT emulsion diblock copolymerization of styrene and methacrylic acid (MAA) by using a trithiocarbonate as surfactant and RAFT agent was investigated. The Z-group of the RAFT agent was modified with a propyl-, butyl- and dodecyl- sidechain, increasing the hydrophobicity of the RAFT agent to offer well-controlled polymerization of poly(methacrylic acid)-block-polystyrene (PMAA-b-PS) diblock copolymers at high solid contents between 30-50 wt% in water. The kinetic data of the PMAA homopolymerization with the three different RAFT agents for various solvents was investigated as well as the RAFT emulsion polymerization of the diblock copolymers in pure water. While the polymerization of PMAA-b-PS with a propyl terminus as a Z-group suffered from slow polymerization rates at solid contents above 30 wt%, the polymerization with a dodecyl sidechain as a Z-group led to full conversion within 2 h, narrow molar mass distributions and all that at a remarkable solid content of up to 50 wt%.

Anthracene-containing complexes of boron difluoride. Dual luminescence, formation of excimers, and mechanochromism.

A comparative study of the luminescence properties and crystal structure of boron difluoride 1-(anthracen-9-yl)butane-1,3-dionate (1) and their nitrogen-containing analogs with hydrogen and methyl substituents (2 and 3) has been performed. For boron difluoride beta-diketonate (1) and beta-ketoiminate with a hydrogen substituent (2), which does not create significant steric difficulties, the luminescence of crystals is determined by that of excimers and aggregates based on them. For the compounds 1-3, mechanofluorochromism has been observed, the spectral manifestation of which is different: at grinding the crystals of 1 and 2, a hypsochromic shift of the excitation and luminescence bands occurs, whereas in the case of crystals of 3, a bathochromic shift takes place. Dual luminescence has been detected for the solutions of 1. During the relaxation in the excited state of a molecule of 1 (S1 â†’ S'1), TICT is formed. It was possible to register the short-wavelength luminescence from the LE state in the dilute solutions of 1. TICT or LE luminescence can be excited, in the case of 1, by varying the wavelength of the exciting light.

Hydrogenative Depolymerization of End-of-Life Polycarbonates by an Iron Pincer Complex.

Chemical recycling processes can contribute to a resource-efficient plastic economy. Herein, a procedure for the iron-catalyzed hydrogenation of the carbonate function of end-of-life polycarbonates under simultaneous depolymerization is presented. The use of a straightforward iron pincer complex leads to high rate of depolymerization of poly(bisphenol A carbonate) and poly(propylene carbonate) yielding the monomers bisphenol A and 1,2-propanediol, respectively, as products under mild reaction conditions. Furthermore, the iron complex was able to depolymerize polycarbonates containing goods and mixture of plastics containing polycarbonates.

Ruthenium-Catalyzed Hydrogenative Degradation of End-of-Life Poly(lactide) to Produce 1,2-Propanediol as Platform Chemical.

The chemical recycling of end-of-life polymers can add some value to a future circular economy. In this regard, the hydrogenative degradation of end-of-life PLA was investigated to produce 1,2-propanediol as product, which is a useful building block in polymer chemistry. In more detail, the commercially available Ru-MACHO-BH complex was applied as catalyst to degrade end-of-life PLA efficiently to 1,2-propanediol under mild conditions. After investigations of the reaction conditions a set of end-of-life PLA goods were subjected to degradation.

o-Hydroxydibenzoylmethanate of boron difluoride: A complex with multi-stimuli-responsive emission effects.

The structural, luminescence and chemosensor properties of boron difluoride o-hydroxydibenzoylmethanate (1) have been investigated. In the concentrated solution, PE (polyethylene) matrix, and crystals of 1, one observes the formation of J-aggregates. The crystal structure of 1 is in compliance with that of J-aggregates of the "brickwork type" consisting of dimers that comprise excimer traps. In time-resolved luminescence spectra of 1 in PE films and crystals, one observes luminescence bands corresponding to the luminescence of excimer J-aggregates. At application of external stimuli on the crystals of 1 (heating, grinding), one observes changes in the luminescence spectrum caused by redistribution of intensities of excimer and J-aggregate bands. 1 could act as an optic chemosensor for probing amines vapors with different response rates and different sensitivities controlled by their morphologies.

Spectroscopic and quantum chemical study of difluoroboron ß-diketonate luminophores: Isomeric acetylnaphtholate chelates.

The electronic structure and optical properties of the isomeric difluoroboron ß-diketonates, 2,2-difluoro-4-methylnaphtho-[2,1-e]-1,3,2-dioxaborin (I) and 2,2-difluoro-4-methylnaphtho-[1,2-e]-1,3,2-dioxaborin (II), were studied by means of X-ray photoelectron, absorption and luminescence spectroscopies. The experimental results were interpreted using high-level ab initio quantum chemical computations, including the algebraic-diagrammatic construction method for the polarization propagator of the second and third orders (ADC(2) and ADC(3)), the outer-valence Green's function (OVGF) method, and the time-dependent density functional (TDDFT) approach. The X-ray photoelectron measurements were assigned in the entire energy range using the results of the Kohn-Sham orbital calculations which employed the B3LYP functional. Pronounced hypsochromic shift of crystal-state fluorescence was observed in I upon the lowering of temperature, which can be explained by the deterioration of the conditions for excimers formation. According to our results, remarkable feature of II, absent in I, is its phosphorescence at room temperature. Basing on our calculations, a decay mechanism for the S1 state was proposed, explaining the observed differences in the phosphorescence of I and II.

Boron difluoride dibenzoylmethane derivatives: Electronic structure and luminescence.

Electronic structure and optical properties of boron difluoride dibenzoylmethanate and four of its derivatives have been studied by X-ray photoelectron spectroscopy, absorption and luminescence spectroscopy and quantum chemistry (DFT, TDDFT). The relative quantum luminescence yields have been revealed to correlate with charge transfers of HOMO-LUMO transitions, energy barriers of aromatic substituents rotation and the lifetime of excited states in the investigated complexes. The bathochromic shift of intensive bands in the optical spectra has been observed to occur when the functional groups are introduced into p-positions of phenyl cycles due to destabilizing HOMO levels. Calculated energy intervals between electronic levels correlate well with XPS spectra structure of valence and core electrons.

Design, Synthesis, and Crystallization-Induced Emission of Boron Difluorides ß-Ketoiminates.

A series of new nitrogen-containing analogues of boron difluoride benzoylacetonates with hydrogen and methyl substituents at the nitrogen atom have been synthesized. A comparative study of boron difluoride ß-ketoiminates and their oxygen-containing analogues by means of luminescence and IR spectroscopic methods as well as quantum chemistry simulations was also performed.

Electronic Structure and Optical Properties of Boron Difluoride Dibenzoylmethane Derivatives.

Electronic structure and optical properties of boron difluoride dibenzoylmethanate BF2Dbm and its four derivatives were studied using X-ray photoelectron spectroscopy, absorption and luminescence spectroscopy, and quantum chemistry (DFT and TDDFT). In a series of the studied compounds, the relationship of molecular design and optical properties has been revealed. At the transition from BF2Dbm to BF2Dbm(OCH3)2, the HOMO-LUMO energy gap decreases, resulting in a bathochromic shift of the optical spectra. Substitution of one methoxy group by the nitro group in BF2Dbm(OCH3)2 causes a decrease in the contribution of the chelate ring π-orbital in the LUMO, resulting in a lower value of charge transfer from the substituents to the chelate ring in the case of the first excited state, which determines the characteristics of the main absorption bands. The nitro group transition from the m- to p-position of the benzene ring causes a change in the nature of the main bands of the optical spectra due to the increase of the splitting value of the LUMO and LUMO+1 levels. The main band in the optical spectra of the complex containing the C10H7 group is associated with the charge transfer transitions.

Nitrogen-Containing Analog of Dibenzoylmethanate of Boron Difluoride: Luminescence, Structure, Quantum Chemical Modeling, and Delay Fluorescence.

Boron difluoride of 3-amino-1,3-diphenyl-2-propene-1-onate (1) has been synthesized and its crystal structure has been determined. The comparative studies of 1 and its oxygen analog 1,3-diphenyl-1,3-dionate (dibenzoylmethanate) of boron difluoride (2) have been performed using the methods of stationary and time-resolved spectroscopy and quantum chemical modeling. It was established that at the transition from solutions to crystals, a bathochromic shift of the spectra and a significant increase of luminescence intensity of 1 take place. The luminescent properties of solutions of 1 and 2 are similar. The peculiarities of crystal packings of 1 and 2 are responsible for differences in crystals luminescent properties. For crystals of 2, one observes the luminescence of J-aggregates and excimers, while for 1, in which a dimer is an elementary structural fragment, only the excimer luminescence is registered. A delayed excimer fluorescence of the P-type was observed for crystals of 1 and 2 at room temperature. The intensity of the delayed fluorescence of 1 is 300-fold higher than that of 2. Graphical Abstract Luminescence of J-aggregates and the formation of excimers in crystals of 1 and 2.

The conformational analysis of push-pull enaminoketones using Fourier transform IR and NMR spectroscopy, and quantum chemical calculations: II. Beta-dimethylaminoacrolein.

IR Fourier and (1)H NMR spectra of beta-dimethylaminoacrolein (DMAA) were investigated in various pure solvents. Quantum chemical calculations by the method AM1 also was carried out to evaluate relative energy and dipole moment of each conformer. On the basis of NMR and IR-spectra we showed that the (DMAA) presented in solutions as equilibrium of two conformers, (E-s-Z) <==> (E-s-E). Constant of this equilibrium, K(eq) = C(E-s-E)/C(E-s-Z), depended strongly on the total (DMAA) concentration: ln K(eq) = ln K(eq0) + a(1 - e(-bC) total). Besides, (E-s-Z) conformer of the (DMAA) was more polar and more stable than the (E-s-E) conformer. Correlation of the out-of-phase nu(C=O) and in-phase nu(C=C) vibrations with solvatochromic parameters of Kamlet, Abbot, and Taft (KAT) revealed that the main contribution to the shift of the out-of-phase nu(C=O) vibrations of the both conformers made solvent's hydrogen bond acceptor (HBA) (beta) term, whereas hydrogen bond donor (HBD) acidity (alpha) term influenced predominantly on the shift of the in-phase nu(C=C) vibrations of the conformers. Moreover, influence of these dominated terms was more pronounced for the (E-s-Z) conformer in comparison with the (E-s-E) conformer, hence the first conformer was more polarized than the last. Investigations of the enthalpies of the (E-s-Z) <==> (E-s-E) equilibrium in carbon tetrachloride, 1,4-dioxane and their mixtures showed that these enthalpies depended predominantly on the solvent's atomic and electronic polarization and dispersive interactions.