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BACKGROUND: This research explores the efficacy of mutagenesis, specifically using sodium azide (SA) and hydrazine hydrate (HZ) treatments, to introduce genetic diversity and enhance traits in three wheat (Triticum aestivum L.) genotypes. The experiment entails subjecting the seeds to different doses of SA and HZ and cultivating them in the field for two consecutive generations: M1 (first generation) and M2 (second generation). We then employed selective breeding techniques with Start Codon Targeted (SCoT) markers to select traits within the wheat gene pool. Also, the correlation between SCoT markers and specific agronomic traits provides insights into the genetic mechanisms underlying mutagenesis-induced changes in wheat. RESULTS: In the study, eleven genotypes were derived from parent varieties Sids1, Sids12, and Giza 168, and eight mutant genotypes were selected from the M1 generation and further cultivated to establish the M2 generation. The results revealed that various morphological and agronomical characteristics, such as plant height, spikes per plant, spike length, spikelet per spike, grains per spikelet, and 100-grain weight, showed increases in different genotypes from M1 to M2. SCoT markers were employed to assess genetic diversity among the eleven genotypes. The bioinformatics analysis identified a correlation between SCoT markers and the transcription factors ABSCISIC ACID INSENSITIVE3 (ABI3) and VIVIPAROUS1 (VP1), crucial for plant development, growth, and stress adaptation. A comprehensive examination of genetic distance and the function identification of gene-associated SCoT markers may provide valuable insights into the mechanisms by which SA and HZ act as mutagens, enhancing wheat agronomic qualities. CONCLUSIONS: This study demonstrates the effective use of SA and HZ treatments to induce gene diversity through mutagenesis in the wheat gene pool, resulting in the enhancement of agronomic traits, as revealed by SCoT markers. The significant improvements in morphological and agronomical characteristics highlight the potential of mutagenesis techniques for crop improvement. These findings offer valuable information for breeders to develop effective breeding programs to enhance wheat quality and resilience through increased genetic diversity.
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Variación Genética , Mutagénesis , Triticum , Triticum/genética , Triticum/crecimiento & desarrollo , Marcadores Genéticos , Pool de Genes , Genotipo , Fitomejoramiento/métodos , Codón Iniciador/genética , Fenotipo , Genes de PlantasRESUMEN
Herein, the construction of a heterostructured 1D/3D CoN-Co2 N@NF (nickel foam) electrode used for thermodynamically favorable hydrazine oxidation reaction (HzOR), as an alternative to sluggish anodic oxygen evolution reaction (OER) in water splitting for hydrogen production, is reported. The electrode exhibits remarkable catalytic activities, with an onset potential of -0.11 V in HzOR and -71 mV for a current density of 10 mA cm-2 in hydrogen evolution reaction (HER). Consequently, an extraordinary low cell voltage of 53 mV is required to achieve 10 mA cm-2 for overall hydrazine splitting in a two-electrode system, demonstrating significant energy-saving advantages over conventional water splitting. The HzOR proceeds through the 4e- reaction pathway to release N2 while the 1e- pathway to emit NH3 is uncompetitive, as evidenced by differential electrochemical mass spectrometric measurements. The X-ray absorption spectroscopy, in situ Raman spectroscopy, and theoretical calculations identify cobalt nitrides rather than corresponding oxides/(oxy)hydroxides as catalytic species for HzOR and illustrate advantages of heterostructured CoN-Co2 N in optimizing adsorption energies of intermediates/reagents and promoting catalytic activities toward both HzOR and HER. The CoN-Co2 N@NF is also an excellent supercapacitive material, exhibiting an increased specific capacity (938 F g-1 at 1 A g-1 ) with excellent cycling stability (95.8%, 5000 cycles).
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The convergence of water electrolysis and alkaline fuel cells offers captivating solutions for sustainably harvesting energy. The research explores both hydrazine-assisted seawater electrolysis (hydrazine oxidation reaction (HzOR) and hydrogen production reaction (HER)), as well as alkaline hydrazine fuel cell reactions (HzOR and Oxygen reduction reaction (ORR)) by using a bifunctional cobalt polyaniline derived (Co PANI/C) catalyst. The catalyst shows excellent performance for hydrazine-assisted seawater electrolysis in harsh seawater environments to produce H2 as fuel with nearly 85% Faradaic efficiency and during alkaline HzOR, the bifunctional catalyst generates H2 with 95% Faradaic efficiency by acting as both anode and cathode side catalyst. Also, the same catalyst requires only a potential of 0.34 V versus RHE and 0.906 V versus RHE for HzOR and ORR, respectively, in 1 m KOH, which makes this overall process useful for a Hz/O2 fuel cell.
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Hydrogen (H2) has emerged as a highly promising energy carrier owing to its remarkable energy density and carbon emission-free properties. However, the widespread application of H2 fuel has been limited by the difficulty of storage. In this work, spontaneous electrochemical hydrogen production is demonstrated using hydrazine (N2H4) as a liquid hydrogen storage medium and enabled by a highly active Co catalyst for hydrazine electrooxidation reaction (HzOR). The HzOR electrocatalyst is developed by a self-limited growth of Co nanoparticles from a Co-based zeolitic imidazolate framework (ZIF), exhibiting abundant defective surface atoms as active sites for HzOR. Notably, these self-limited Co nanoparticles exhibit remarkable HzOR activity with a negative working potential of -0.1 V (at 10 mA cm-2) in 0.1 m N2H4/1 m KOH electrolyte. Density functional theory (DFT) calculations are employed to validate the superior performance of low-coordinated Co active sites in facilitating HzOR. By taking advantage of the potential difference between HzOR and the hydrogen evolution reaction (HER), a novel HzOR||HER electrochemical system is developed to spontaneously produce H2 without external energy input. Overall, the work offers valuable guidance for developing active HzOR catalyst. The novel HzOR||HER electrochemical system represents a promising and innovative solution for energy-efficient hydrogen production.
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Acid-treated multi-walled carbon nanotube (MWCNT) covalently functionalized with cobalt triphenothiazine porphyrin (CoTriPTZ-OH) A3B type porphyrin, containing three phenothiazine moieties (represented as MWCNT-CoTriPTZ) is synthesized and characterized by various spectroscopic and microscopic techniques. The nanoconjugate, MWCNT-CoTriPTZ, exhibits a pair of distinct redox peaks due to the Co2+/Co3+ redox process in 0.1 M pH 7.0 phosphate buffer. Further, it electrocatalytically oxidizes hydrazine at a low overpotential with a high current. This property is advantageously utilized for the sensitive determination of hydrazine. The developed electrochemical sensor exhibits high sensitivity (0.99 µAµM-1cm-2), a low limit of detection (4.5 ppb), and a broad linear calibration range (0.1 µM to 3.0 mM) for the determination of hydrazine. Further, MWCNT-CoTriPTZ is exploited for hydrazine-assisted green hydrogen synthesis. The high efficiency of hydrazine oxidation is confirmed by the low onset potential (0.45 V (vs RHE)) and 0.60 V (vs RHE) at the current density of 10 mA.cm-2. MWCNT-CoTriPTZ displays a high current density (77.29 mA.cm-2) at 1.45 V (vs RHE).
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The urgent need for the development of micro-thin shields against electromagnetic interference (EMI) has sparked interest in MXene materials owing to their metallic electrical conductivity and ease of film processing. Meanwhile, postprocessing treatments can potentially exert profound impacts on their shielding effectiveness (SE). This work comprehensively compares two reduction methods, hydrazine versus thermal, to fabricate foamed titanium carbonitride (Ti3CNTx) MXene films for efficient EMI shielding. Upon treatment of ≈ 100 µm-thick MXene films, gaseous transformations of oxygen-containing surface groups induce highly porous structures (up to ≈ 74.0% porosity). The controlled application of hydrazine and heat allows precise regulation of the reduction processes, enabling tailored control over the morphology, thickness, chemistry, and electrical properties of the MXene films. Accordingly, the EMI SE values are theoretically and experimentally determined. The treated MXene films exhibit significantly enhanced SE values compared to the pristine MXene film (≈ 52.2 dB), with ≈ 38% and ≈ 83% maximum improvements for the hydrazine and heat-treated samples, respectively. Particularly, heat treatment is more effective in terms of this enhancement such that an SE of 118.4 dB is achieved at 14.3 GHz, unprecedented for synthetic materials. Overall, the findings of this work hold significant practical implications for advancing high-performance, non-metallic EMI shielding materials.
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Nitrogen-Nitrogen (N-N) bond-containing functional groups in natural products and synthetic drugs play significant roles in exerting biological activities. The mechanisms of N-N bond formation in natural organic molecules have garnered increasing attention over the decades. Recent advances have illuminated various enzymatic and nonenzymatic strategies, and our understanding of natural N-N bond construction is rapidly expanding. A group of didomain proteins with zinc-binding cupin/methionyl-tRNA synthetase (MetRS)-like domains, also known as hydrazine synthetases, generates amino acid-based hydrazines, which serve as key biosynthetic precursors of diverse N-N bond-containing functionalities such as hydrazone, diazo, triazene, pyrazole, and pyridazinone groups. In this review, we summarize the current knowledge on hydrazine synthetase mechanisms and the various pathways employing this unique bond-forming machinery.
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Hidrazinas , Hidrazinas/química , Hidrazinas/metabolismo , Metionina-ARNt Ligasa/metabolismo , Bacterias/enzimología , Bacterias/metabolismo , Vías BiosintéticasRESUMEN
Cupin/methionyl-tRNA synthetase (MetRS)-like didomain enzymes catalyze nitrogen-nitrogen (N-N) bond formation between Nω-hydroxylamines and amino acids to generate hydrazines, key biosynthetic intermediates of various natural products containing N-N bonds. While the combination of these two building blocks leads to the creation of diverse hydrazine products, the full extent of their structural diversity remains largely unknown. To explore this, we herein conducted phylogeny-guided genome-mining of related hydrazine biosynthetic pathways consisting of two enzymes: flavin-dependent Nω-hydroxylating monooxygenases (NMOs) that produce Nω-hydroxylamine precursors and cupin/MetRS-like enzymes that couple the Nω-hydroxylamines with amino acids via N-N bonds. A phylogenetic analysis identified the largely unexplored sequence spaces of these enzyme families. The biochemical characterization of NMOs demonstrated their capabilities to produce various Nω-hydroxylamines, including those previously not known as precursors of N-N bonds. Furthermore, the characterization of cupin/MetRS-like enzymes identified five new hydrazine products with novel combinations of building blocks, including one containing non-amino acid building blocks: 1,3-diaminopropane and putrescine. This study substantially expanded the variety of N-N bond forming pathways mediated by cupin/MetRS-like enzymes.
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Metionina-ARNt Ligasa , Metionina-ARNt Ligasa/química , Metionina-ARNt Ligasa/genética , Metionina-ARNt Ligasa/metabolismo , Filogenia , Hidrazinas , Bacterias/metabolismo , Aminoácidos/genética , Hidroxilaminas , NitrógenoRESUMEN
The reaction of hydrazine hydrate, N2 H4 â H2 O, and SO3 leads to hydrazine sulfonic acid (Pca21 , a=849.59(4)â pm, b=482.18(2)â pm, c=832.17(4)â pm). Structure elucidation reveals the zwitter-anionic nature of the compound according to NH3 NH(SO3 ). With the barium salt Ba[NH2 NH(SO3 )]2 (H2 O), a first salt of hydrazine sulfonic acid has been prepared (P 1 â¾ $\bar 1$ , a=489.75(5)â pm, b=737.52(7)â pm, c=1317.4(1)â pm, α=88.238(4)°, ß=84.761(4)°, γ=79.701(4)°). The compounds were characterized by vibrational spectroscopy, DFT calculations and thermal analyses.
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The reaction of hydrazinium sulfate and chlorosulfonic acid in pyridine leads to the pyridinium salt of the hydrazine disulfonate anion, [(SO3)HNNH(SO3)]2-. The salt is the starting material for the preparation of further hydrazine disulfonates, for example of alkaline metals and barium. In all compounds, the [(SO3)HNNH(SO3)]2- anion adopts the gauche conformation. The conformer is chiral but all of the investigated compounds crystallize as racemates. The disulfonate anion can occur in another constitution with the two sulfonate groups attached to only one nitrogen atom. This so-called hydrazine iso-disulfonate, [H2NN(SO3)2]2-, has been prepared through a substitution reaction between potassium imidodisulfonate, K[HN(SO3)2], and hydroxylamine-O-sulfonic acid, H2NOSO3H. The hydrazine iso-disulfonate anion has been crystallized as potassium and barium compound, respectively. The compounds were characterized by XRD, vibrational spectroscopy, DFT calculations and thermal analyses.
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Nucleophilic moieties in polysaccharides (PS) with distinct higher reactivity compared with the hydroxy group are interesting for sustainable applications in chemistry, medicine, and pharmacy. An efficient heterogeneous method for the formation of such nucleophilic PS is described. Employing alcohols as slurry medium, protonated carboxymethyl (CM) PS and hydrazine hydrate are allowed to react at elevated temperatures. The CM derivatives of starch and pullulan can be transformed almost quantitatively to the corresponding hydrazides. The reaction is less efficient for CM dextrans and CM xylans. As slurry media, 2-propanol and ethanol were probed, and the results are compared with a homogeneous procedure performed in water. Overall, the heterogeneous procedure is superior compared with the homogeneous route. 2-Propanol is the best slurry medium investigated yielding PS hydrazides with the highest nitrogen content.
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Hidrazinas , Polisacáridos , Hidrazinas/química , Polisacáridos/química , Polisacáridos/síntesis química , Glucanos/química , Glucanos/síntesis química , Almidón/química , Almidón/análogos & derivados , Almidón/síntesis química , 2-Propanol/química , Dextranos/química , Dextranos/síntesis química , Etanol/química , Xilanos/químicaRESUMEN
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.
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Anammox bacteria performed the reaction of NH4+ and NO with hydrazine synthase to produce N2H4, followed by the decomposition of N2H4 with hydrazine dehydrogenase to generate N2. Ferroheme/ferriheme, which serves as the active center of both hydrazine synthase and hydrazine dehydrogenase, is thought to play a crucial role in the synthesis and decomposition of N2H4 during Anammox due to its high redox activity. However, this has yet to be proven and the exact mechanisms by which ferroheme/ferriheme is involved in the Anammox process remain unclear. In this study, abiotic and biological assays confirmed that ferroheme participated in NH4+ and NO reactions to generate N2H4 and ferriheme, and the produced N2H4 reacted with ferriheme to generate N2 and ferroheme. In other words, the ferroheme/ferriheme cycle drove the continuous reaction between NH4+ and NO. Raman, ultraviolet-visible spectroscopy, and X-ray absorption fine structure spectroscopy confirmed that ferroheme/ferriheme is involved in the synthesis and decomposition of N2H4 via the core FeII/FeIII cycle. The mechanism of ferroheme/ferriheme participation in the synthesis and decomposition of N2H4 was proposed by density functional theory calculations. These findings revealed for the first time the heme electron transfer mechanisms, which are of great significance for deepening the understanding of Anammox.
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Hidrazinas , Oxidación-Reducción , Hidrazinas/químicaRESUMEN
Hydrazine (N2H4) has toxic effects on the environment. Although a variety of reactive probes have been used to identify hydrazine, practical applications required continuous development of hydrazine fluorescent probes with improved performance. Here, we applied the neighboring group participation (NGP) to the design of a fluorescent probe for hydrazine. The probe exhibited a rapid response to N2H4 and strong anti-interference ability, with detection limited to 0.031 µmol/L. Theoretical calculation showed that the energy barrier could be reduced by NGP. The cyclic intermediate formed by the indole ring and the α-ester carbonyl group significantly reduced the activation energy of the reaction. Practically, the probe could detect hydrazine in actual water samples.
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This work established a newly designed and synthesized carbazole N-phenyl π-conjugated vinyl malononitrile (CPM) fluorescent sensor, which showed typical and remarkable redshift emission properties with different polarity index solvents. Investigative probe CPM is colorimetric and fluorimetric ultrafast and ultrasensitive detection of hazardous hydrazine in an aqueous medium. Furthermore, CPM showed colorimetric and fluorometric responses to interference tests with other amines and high selectivity for detecting hydrazine without interference with other amines in colorimetric and fluorimetric methods. This probe CPM for hydrazine was as low as the lower detection limit value of 2.21 × 10- 8 M. The probe CPM expects significant attention due to its simplicity and cost-effectiveness in detecting hazardous hydrazine. UV-vis, PL, NMR, and MS spectra confirmed the mechanism of probe CPM detection of hazardous hydrazine. However, making a piece test kit attractive for practical hydrazine vapor leak-detection applications is easy. This study can be applied to many pipeline gas transmission industries and transportation facility sectors.
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Designed and synthesized linear pyrazine-based D-π-A-π-A probe is investigated to study the colorimetric and emission properties with different polarity index solvents. Their molar extinction coefficients were estimated for each solvent. This TLP probe was investigated in THF/water binary solution aggregates, and a redshifted AIE was observed reaching a water fraction of 70%. Also, this TLP probe was applied to the multifunctional, rapid, sensitive and selective detection of acid-base (TFA/TEA) and hydrazine (N2H4) in colorimetric and fluorimetric sensors. The pyrazine unit probe demonstrated an acidochromic effect and explored the acid-sensing behavior. The TLP probe containing malononitrile functional groups has extensively detected hazardous hydrazine species due to nucleophilic attack of hydrazine at the α-position of dicyano. This TLP probe allowed the quick and fast-sensitive detection of hydrazine hydride with a low detection limit of 1.08 nM. According to the results, the mechanism was confirmed by UV-Vis, PL, NMR and MS spectra for the detection of hydrazine, and further evidence of the protonation-deprotonation process in added TFA/TEA was made by titration studies by 1H NMR. Therefore, this work can be used for test strip kits for multifunction applications.
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The Schiff base fluorescent probe (Dz-Jul), containing julolidine aldehyde and dansyl hydrazine, was derived using a simple condensation. This chemosensor showed high selectivity towards Zn2+ and quick response (170 s) in DMSO/H2O solutions (8/2, v/v, pH 7.2 buffer). A fluorometric titration determined that Dz-Jul-Zn2+ has a binding ratio of 1:1, and the association constant (Ka) is 1.03 × 105 M-1. The Dz-Jul detection limit of Zn2+ ions was 15 nM, much lower than the WHO standard (76.0 nM). DFT, ESI mass, and FTIR spectral demonstrated a plausible complexation mode between Dz-Jul and Zn2+ ions. In actual water samples, Zn2+ has been detected with good detection performance using Dz-Jul. Additionally, Dz-Jul-coated test strips allowed for rapid and qualitative monitoring of Zn2+ ions in a visible manner.
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A novel colorimetric and fluorogenic probe L based on hydrazine carbothioamide and 1,8-naphthalimide moieties has been designed and synthesized for the hypersensitive detection of Hg2+ or Ag+ ions. The observed probe L showed colorimetric and fluorometric responses for these studies when Hg2+ or Ag+ was added to the DMSO - HEPES buffer solution (pH = 7). An interference test with other metal ions was determined, and the high selectivity of Hg2+ and Ag+ did not interfere with other metal ions in colorimetric and fluorogenic methods. The possible mechanism of binding of these metal ions and the probe L 1:1 complex was determined by H1 NMR. Additionally, the reversibility of the affinity of probe L with mercury (Hg2+) and silver (Ag+) ions was investigated by adding Na2EDTA. The naked eye detected the "Off-On" type fluorescence sensor in the presence of Hg2+ and EDTA. The tested test strip kits provided a strong probability of probe L with high response and rapid, sensitive detection with Hg2+ ion, which may be suitable for practical use.
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Devising of materials that afforded dual applicability in decontamination and pollutant detection were still a towering challenge owing to the increasing flux of discharge toxic contaminants over the years. Herein, the NiFe2O4 nanoparticles-loaded on cube-like SrTiO3 (NiFe2O4/SrTiO3) composite was fabricated by a two-step hydrothermal approach providing remarkable photocatalytic treatment and electrochemical sensing of noxious pollutants in wastewater. The material traits of the fabricated composite were scrutinized by myriad characterization approaches. The NiFe2O4/SrTiO3 hybrid material demonstrated high surface area of 19.81 m2/g, adequate band gap energy of 2.75 eV, and prominent photoluminescence characteristics. In the presence of visible light, the NiFe2O4/SrTiO3 exhibited profound photocatalysis capability to eliminate sewage effluent-bearing chlortetracycline hydrochloride (CTCH) with 88.6% COD removal in 120 min, outperforming other pure materials. Meanwhile, the toxicity examination of effluent, the possible degradation pathway of CTCH and the proposed photocatalysis mechanism were also divulged. More importantly, the glassy carbon electrode was modified with synergized NiFe2O4/SrTiO3 (NiFe2O4/SrTiO3-GCE) was adopted for the precise quantification of Hydrazine (Hz). The NiFe2O4/SrTiO3-GCE obeyed first-order response for the Hz detection within the range of 1-10 mM: cyclic voltametric: limit of detection (LOD) of 0.119 µM with sensitivity of 18.9 µA µM-1 cm-2, and linear sweep voltametric: LOD of 0.222 µM with a sensitivity of 12.05 µA µM-1 cm-2. The stability and interference of modified electrode were also inspected. This work furnished valuable insights to yield a composite with the prominent S-scheme heterojunction system for quenching of charge carrier recombination and consequently contributing to the future realization into the domains of environmental clean-up and toxic chemical detection.
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As a neurotoxin, it is necessary to establish a low cost, stable and sensitive method for the quantitative detection of hydrazine. Using Co-ZIF (zeolite imidazole framework) nanorods as precursor, CoS2 hollow nanotube array heterogeneous structure loaded with Cu nanoparticles were prepared on carbon cloth (CC) by etching, calcination and plasma magnetron sputtering (CoS2@Cu HNTA/CC). As a self-supporting electrode, its hollow heterogeneous structure provides a large area of electron transfer channel for the oxidation of the food pollutant hydrazine. In addition, bimetallic synergies and in situ N doping regulated the electronic structure of CoS2@Cu HNTA/CC, and thus significantly improved the electrical conductivity and catalytic activity. As an efficient hydrazine sensor with a wide linear range of 1 µM L-1-10 mM (1 µM-1 mM and 1 mM-10 mM), its sensitivity and the limit of detection are 7996 µA mM-1 cm-2, 3772 µA mM-1 cm-2 and 0.276 µM (S/N = 3), respectively. This study provides a new strategy for the construction of MOFs (Metal Organic Framework)-derived bimetallic composites and their application in electrochemical sensing.