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Fluorescent sensors for the detection of hydrazine in environmental and biological systems: Recent advances and future prospects

Being a widely used raw material in the manufacture of synthetic catalysts, agricultural chemicals and pharmaceutical products, hydrazine (N2H4) caused irreversible pollution to air, water and soil in our environment owing to its high toxic impact and massive use. In addition, during the metabolism process of certain drugs, such as isoniazid (INH), hydrazine can also be released, causing serious harm to human body. It has been proved by previous researches that hydrazine could cause several adverse effects, including the inhibition of molecular metabolism, mitochondrial oxidation and DNA damage. Thus, methods which could sensitively and selectively detect hydrazine in vivo and in vitro are in urgent need. Fluorescent sensors, a powerful tool for efficiently evaluating the hydrazine levels in environmental and living systems with minimal perturbation, were widely studied over the past few years. Since the number of the fluorescent sensors for hydrazine detection has grown rapidly, this review attempted to present a well-organized overview of existing design strategies for developing fluorescent sensors for hydrazine, including both reaction-based sensors and material-based sensors from 2011 to the present. The molecular structures, sensing mechanisms and applications of these sensors were emphatically classified and discussed. Moreover, the following prospects and challenges of this field were also provided.

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Phthalazine – Wikipedia,
Phthalazine | C8H6N510 – PubChem

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Synthesis of 3,4-benzo-7-hydroxy-2,9-diazabicyclo[3.3.1]non-7-enes by cyclization of 1,3-bis(silyl enol ethers) with quinazolines

A variety of functionalized 3,4-benzo-7-hydroxy-2,9-diazabicyclo[3.3.1]non- 7-enes were prepared by one-pot cyclizations of 1,3-bis(silyl enol ethers) with quinazolines. The mechanism of the cyclization was studied by B3LYP/6-31G(d) density functional theory computations. The products could be functionalized by Suzuki cross-coupling reactions. The reaction of 1,3-bis(silyl enol ethers) with phthalazine afforded open-chain rather than cyclization products. The Royal Society of Chemistry.

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Phthalazine – Wikipedia,
Phthalazine | C8H6N222 – PubChem

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Olefin poly/oligomerizations by metal precatalysts bearing non?heterocyclic N?donor ligands

The use of transition metal complexes of non?heterocyclic N?donor ligands as olefin oligo/polymerization precatalysts is reviewed. These metal complexes with definite steric and electronic variations offer high catalytic activity resulting in the desired microstructure of the polymer products currently attracting significant attention by the catalysis community. This review primarily discusses the fundamental principles in the design of mononuclear, homodinuclear, heterodinuclear, homomultinuclear and heteromultinuclear transition metal complexes having non?heterocyclic N?donor ligands and their reactivity towards olefins in oligo/polymerization reactions. Numerous non?heterocyclic N?donor ligands of the donor types N2, NO, NP, NC, N2P, N2O, N2C, N2S, N3, NCP, NCp, NOCp, N3Cp, N2O2for mononuclear, N4, N2O2, N4O4, N3C, NCp2, N2Cp2, N2Indene2and N2S2Indene (Cp: cyclopentadiene) for bimetallic and N8, N8O4, N8O8and N12O4for multinuclear complex formations have been efficiently employed, and the resulting complexes display promising reactivity patterns with a variety of olefins. The majority of these catalytic systems are tethered with appropriate alkyl/aryl/alkyl?aryl substituents to afford the required steric hindrance to the metal center(s), and with functional groups for electronic variations. Such systems produce a linear polymer product in most of the cases, any deviation from this behavior resulting in the formation of oligomers. The major focus of this review is on reports published over the last 25 years in the research and development of non?heterocyclic, N?donor coordinated transition metal complexes with a variety of spacers. This review article is organized into main sections on the basis of the nuclearity of the transition metal complex; each subsection deals with complexes starting from late transition metals on the basis of ligand type.

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Phthalazine – Wikipedia,
Phthalazine | C8H6N86 – PubChem

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One-step exchange-labelling of pyridines and other N-heteroaromatics using deuterium gas: catalysis by heterogeneous rhodium and ruthenium catalysts

A wide range of pyridines and other nitrogen heteroaromatics can be labelled with deuterium at room temperature and pressure by isotopic exchange with deuterium gas in THF in the presence of rhodium black, ruthenium black or 5% rhodium on alumina. The labelling is rapid, isotope efficient and applicable to both electron-rich and electron-poor substrates. In a few cases, a degree of reduction accompanies the exchange.

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Phthalazine – Wikipedia,
Phthalazine | C8H6N30 – PubChem

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Structural basis for the role of mammalian aldehyde oxidases in the metabolism of drugs and xenobiotics

Aldehyde oxidases (AOXs) are molybdo-flavoenzymes characterized by broad substrate specificity, oxidizing aromatic/aliphatic aldehydes into the corresponding carboxylic acids and hydroxylating various heteroaromatic rings. Mammals are characterized by a complement of species-specific AOX isoenzymes, that varies from one in humans (AOX1) to four in rodents (AOX1, AOX2, AOX3 and AOX4). The physiological function of mammalian AOX isoenzymes is unknown, although human AOX1 is an emerging enzyme in phase-I drug metabolism. Indeed, the number of therapeutic molecules under development which act as AOX substrates is increasing. The recent crystallization and structure determination of human AOX1 as well as mouse AOX3 has brought new insights into the mechanisms underlying substrate/inhibitor binding as well as the catalytic activity of this class of enzymes.

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Phthalazine – Wikipedia,
Phthalazine | C8H6N369 – PubChem

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Luminescent hydrido-carbonyl clusters of rhenium containing bridging 1,2-diazine ligands

The reaction of the electronically unsaturated (56 valence electrons, ve) tetrahedral cluster [Re4(mu3-H)4(CO) 12] (1) with pyridazine (pydz) gives as the main initial product the tetranuclear cluster [Re4(mu-H)4(mu-pydz)(pydz) 2(CO)12] (2a), with 64 ve and four hydrogen-bridged metal-metal interactions, with a spiked-triangle geometry. One of the three pydz ligands bridges, in a cis configuration, the cluster edge opposite to the vertex bearing the spike, as indicated by the X-ray single-crystal analysis. This species slowly decomposes, affording the dinuclear unsaturated (32 ve) complex [Re2(mu-H)2(mu-pydz)(CO)6] (3a) and two isomers of the tetranuclear cluster [Re4(mu-H) 4(mu-pydz)2-(CO)12] (64 ve), sharing an unusual square cluster geometry and differing in the trans (major, 85%, 4a) or cis (4a?) configuration of the bridging pydz ligands. The structures of 3a and 4a have been ascertained by X-ray analysis, while the characterization of 4a? was hampered by its instability (slowly transforming into 3a in THF solution). Both the dimer and the square cluster 4a are also formed directly (and quickly) from 1, being present in solution since the beginning of the reaction. Cluster 4a is the main final reaction product. The reaction with phthalazine follows a similar course, with some differences in the relative amount of the final products 3b and 4b. Most of the novel complexes are able to emit light in solution at room temperature, and photophysical measurements were performed in CH2Cl2 solution on the main stable reaction products (i.e., the dinuclear species 3a and 3b and the trans square clusters 4a and 4b). The emission was in the range of 580-645 nm, from MLCT excited states, with lifetimes on the order of a hundred nanoseconds (50-473 ns). The quantum yields were 1 order of magnitude higher for the squares (1.7 and 1.3% for 4a and 4b, respectively, in CH2Cl2) than for the dinuclear complexes (?0.1%). In the case of 4a, a blue shift and an increase of the emission intensity were observed upon decreasing the solvent polarity.

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Phthalazine – Wikipedia,
Phthalazine | C8H6N331 – PubChem

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The one-pot synthesis of homoleptic phenylphthalazine iridium(III) complexes and their application in high efficiency OLEDs

A series of homoleptic cyclometalated iridium (III) complexes bearing a 1-phenylphthalazine framework have been synthesized with a facile one-pot method and characterized by X-ray single crystal diffraction. All complexes exhibited orange or red emission peaks at 583?623 nm with short lifetimes of 1.3?2.6 mus and high photoluminescence quantum yields of 41%?82%. These complexes exhibit good thermal stability with high Td of 275?394 C. The electronic states and orbital distributions of these iridium (III) complexes were studied by density functional theory. These complexes were used as emissive materials in Organic light-emitting diodes (OLEDs). The device based on 2 gave a peak current efficiency and external quantum efficiency (EQE) of 35.1 cd A?1 and 21.2%, respectively. The color coordinates of device based on 3 fully meet that of standard red of the National Television Standards Committee (NTSC). These results suggest that homoleptic phenylphthalazine iridium (III) complexes have potential application as efficient emitters in OLEDs.

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Phthalazine – Wikipedia,
Phthalazine | C8H6N193 – PubChem

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UHPLC-fluorescence method for the determination of trace levels of hydrazine in allopurinol and its formulations: Validation using total-error concept

The present approach poses an interesting way to quantify residues of the genotoxic impurity hydrazine in allopurinol and its pharmaceutical formulations using ultra high performance liquid chromatography coupled to fluorescence detection. Hydrazine was pre-column derivatized through a unique chemistry with o-phthalaldehyde under acidic conditions. Using highly acidic mobile phase the derivative exhibits a strong fluorescence intensity. Derivatization and chromatographic parameters were thoroughly investigated. The validation of the developed method has been carried out in the range of 10 to 200% of the target concentration limit of the analyte using the accuracy profiles as a graphical decision-making tool. The beta-expectation tolerance intervals did not exceed the acceptance criteria of ¡À20% which means that 95% of future results will be included in the defined bias limits. The variation of the relative bias ranged between ?6.0 and 0.5% and the RSD values for repeatability and intermediate precision were lower than 6.9% in all cases. The limit of detection (LOD) and the lower limit of quantification (LLOQ) were satisfactory and found to be 0.3 ng mL?1 (corresponding to 0.03 mug g?1 in solid sample). Experimental designs were constructed to study the robustness of the instrumental method and the derivatization procedure. The developed method has been successfully applied for the analysis of hydrazine in allopurinol API batches and tablets indicating that this methodology could be adopted from QC laboratories.

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Phthalazine – Wikipedia,
Phthalazine | C8H6N112 – PubChem

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Synthesis, structure, and in vitro anticancer activity of new polycyclic 1,2-diazines

The synthesis, structure, and in vitro anticancer activity of a new class of anticancer derivatives with dihydrobenzo[5,6]isoindolo[1,2-A]phthalazine and dihydrobenzo[f]pyridazino[6,1-A]isoindole skeletons are presented. The preparation is straight and efficient, involving two steps only: a N-Alkylation of the pyridazine or phthalazine heterocycle, followed by a [3 + 2] dipolar cycloaddition of 1,2-diazinium ylides to the corresponding dipolarophiles. The synthesis was performed under microwave and ultrasound (US) irradiation as well as under conventional thermal heating. The most effective conditions in term of yields and time were found to be US irradiation. The penta- and tetra-cyclic 1,2-diazines were evaluated for their in vitro anticancer activity. The pentacyclic 1,2-diazine derivatives exhibit a significant anticancer activity against Non-Small Cell Lung Cancer NCI-H460, Leukemia MOLT-4, Leukemia CCRF-CEM, and Breast Cancer MCF7. A feasible explanation for anticancer efficiency of the pentacyclic 1,2-diazines have been furnished, being correlated with the mechanisms of action. Graphical Abstract: The synthesis (conventional thermal heating, microwave and ultrasound irradiation), structure, and in vitro anticancer activity of a new class of anticancer molecules with polycyclic 1,2-diazines skeleton is presented.[Figure not available: see fulltext.]

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Phthalazine – Wikipedia,
Phthalazine | C8H6N278 – PubChem

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Hydrogen-bonded structures of the isomeric compounds of phthalazine with 3-chloro-2-nitro-benzoic acid, 4-chloro-2-nitro-benzoic acid and 4-chloro-3-nitro-benzoic acid

The structures of three isomeric compounds, C7H 4ClNO4¡¤C8H6N2, of phthalazine with chloro-and nitro-substituted benzoic acid, namely, 3-chloro-2-nitro-benzoic acid-phthalazine (1/1), (I), 4-chloro-2-nitro-benzoic acid-phthalazine (1/1), (II), and 4-chloro-3-nitro-benzoic acid-phthalazine (1/1), (III), have been determined at 190 K. In the asymmetric unit of each compound, there are two crystallographically independent chloro-nitro-benzoic acid-phthalazine units, in each of which the two components are held together by a short hydrogen bond between an N atom of the base and a carboxyl O atom. In one hydrogen-bonded unit of (I) and in two units of (II), a weak C-H…O inter-action is also observed between the two components. The N…O distances are 2.5715 (15) and 2.5397 (17) A for (I), 2.5655 (13) and 2.6081 (13) A for (II), and 2.613 (2) and 2.589 (2) A for (III). In both hydrogen-bonded units of (I) and (II), the H atoms are each disordered over two positions with (N site):(O site) occupancies of 0.35 (3):0.65 (3) and 0.31 (3):0.69 (3) for (I), and 0.32 (3):0.68 (3) and 0.30 (3):0.70 (3) for (II). The H atoms in the hydrogen-bonded units of (III) are located at the O-atom sites.

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Phthalazine – Wikipedia,
Phthalazine | C8H6N170 – PubChem