Hydrazide Complex Research Articles

Synthesis, characterization, lipoxygenase, and tyrosinase inhibitory activities of non- cytotoxic titanium(III) and (IV) hydrazide complexes

ABSTRACT. Ti(III) and (IV) hydrazide complexes were synthesized, characterized, and screened for their tyrosinase and lipoxygenase inhibitory and cytotoxic activities. The geometry of Ti(III) hydrazide complexes is tentatively assigned as octahedral. Magnetic moments were found around 1.7 B.M. and electronic spectral transition in the range of 495-518 nm. Evaluation of Ti(IV) and Ti(III) hydrazide complexes for tyrosinase and lipoxygenase inhibitory activities revealed varying inhibition potential. Hydrazide ligands were inactive against tyrosinase, while significant activity was observed against lipoxygenase (LOX). Good to moderate inhibition activity was observed by Ti(IV) and Ti(III) hydrazide complexes against both enzymes. At the same time, promising results were obtained for Ti(IV) hydrazide complexes against tyrosinase enzymes suggesting their broad application as tyrosinase inhibitors. Complex 4d possess negative inhibition, thus behaving as a tyrosinase activator. The docking results showed a good correlation between complex experimental activities and binding energies. Cytotoxic investigation revealed the non-toxicity of complexes against normal cells.
 
 KEY WORDS: Titanium(III) and titanium(IV) hydrazide complex, Tyrosinase, Lipoxygenase, Inhibition, Molecular docking, Cytotoxicity
 
 Bull. Chem. Soc. Ethiop. 2023, 37(2), 315-333. 
 DOI: https://dx.doi.org/10.4314/bcse.v37i2.6

An "Off-On" Rhodamine 6G Hydrazide-Based Output Platform for Fluorescence and Visual Dual-Mode Detection of Lead(II).

In this study, the rhodamine 6G hydrazide (R6GH) complex was synthesized to develop an "off-on" output platform for fluorescence and visual dual-mode analysis of lead(II) (Pb2+). The prepared R6GH complex using the heat to reflux reaction of rhodamine 6G (R6G) and hydrazine hydrate was characterized through FT-IR, MS, 1H NMR, and 13C NMR and demonstrated to have good fluorescence stability and reversibility. The microenvironment for Pb2+ detection has been optimized in detail. Under the optimal conditions, the "off-on" R6GH-based fluorescence output platform showed a good response to Pb2+ in the concentration range of 0.05-6.0 μM (R2 = 0.9851) with a limit of detection (LOD) of 0.02 μM. Furthermore, at three spiked Pb2+ levels in the selected agricultural (tap water, soil) and food (fish, shrimp) samples, the developed R6GH-based fluorescence assays obtained a significant recovery range of 84.0-102.0% (RSD < 5.0%, n = 3), which had a good correlation with the results from ICP-MS (R2 = 0.9915). The developed R6GH immobilized paper-based array sensor can reach the lower LOD (2.5 μM) for Pb2+ through the naked eye. By combining with LAB analysis, a good linear response was obtained in the Pb2+ concentration range of 1.0-50.0 μM. These results indicated that the developed R6GH probe had great application potential in accurate detection of fluorescence and rapid visual and semiquantitative screening for Pb2+.

Structural basis of substrate recognition by the substrate binding protein (SBP) of a hydrazide transporter, obtained from Microbacterium hydrocarbonoxydans

Microbacterium hydrocarbonoxydans was isolated, using hydrazide compounds as its sole carbon source. The key enzyme that metabolizes these compounds was identified as hydrazidase, and the operon containing the gene coding for the enzyme, was revealed by genome sequencing. The operon also contained genes coding for an ATP-binding cassette transporter (ABC transporter), which was expected to transport the hydrazide compounds. Substrate binding protein (SBP), a component subunit of the transporter, plays an important role in recognizing the correct substrates for transport. Therefore, to elucidate the mechanism of recognition of the unnatural hydrazide compounds, we determined the crystal structures of the SBP, obtained from M. hydrocarbonoxydans (Mh-SBP), complexed with and without the hydrazide compound, at 2.2 Å and 1.75 Å resolutions, respectively. The overall structures of Mh-SBP were similar to those of the SBP in oligopeptide transporters such as OppA. On comparison, the liganded and unliganded structures of Mh-SBP showed an open – close conformation change. Interestingly, the binding mode of the compound to Mh-SBP was almost identical to that of the compound to hydrazidase, suggesting that the ABC transporter served transporting these compounds. Furthermore, based on the hydrazide complex structure, paraben, the other putative substrate of the protein, was successfully used with Mh-SBP to obtain the paraben complex structure.

Synthesis and spectroscopic characterization of diorganotin(iv) complexes of N′-(4-hydroxypent-3-en-2-ylidene)isonicotinohydrazide: chemotherapeutic potential validation by in vitro interaction studies with DNA/HSA, DFT, molecular docking and cytotoxic activity

A diorganotin(iv) hydrazide complex as a potential cancer chemotherapeutic agent targeting DNA using the carrier protein HSA.

Fast synthesis of high-quality reduced graphene oxide at room temperature under light exposure.

An approach of presenting new reducing reagents, sodium-benzophenone (Na-B) or Na-B in the presence of the hydrazine (Na-B-H) system under light exposure could produce rGOs with/without N-doping at room temperature in both the solution phase and on a solid substrate. Benzophenone activated those solutions acting as a photosensitizer under light. It was assumed that the newly generated radical anions with electrons from Na-B under light can reduce GO to rGO sheets (rGONa-B1). In addition, the Na-B-H system can allow a higher degree of reduction with the doping of nitrogen atoms by the introduction of hydrazine to produce radical anions and electrons with a sodium hydrazide complex, which helps decrease the sheet resistance of the as-made rGONa-B-H2. The excellent properties (very low oxygen content (C/O ∼16.2), and low sheet resistance (∼130 Ω square(-1))) of the rGOs were confirmed by XPS, XRD, IR, Raman spectroscopy, TGA, wettability, and sheet resistance measurements. High-quality rGO films on flexible substrates could be prepared by directly immersing the GO films in these solutions for several minutes.

Yttrium Hydride Complex Bearing CpPN/Amidinate Heteroleptic Ligands: Synthesis, Structure, and Reactivity

The reaction of the yttrium dialkyls (C5H4- PPh2=N (C6H3Pr2)-Pr-i)Y(CH2SiMe3)(2)(thf) (1) with an excess of N,N'-diisopropylcarbodiimide gave the yttrium monoalkyl complex (C5H4-PPh2=N-(C6H3Pr2)-Pr-i)Y(CH2SiMe3)[(PrN)-Pr-i= C(CH2SiMe3)-(NPr)-Pr-i] (2). 2 subsequently reacted with 1 equiv of PhSiH3 to generate the CpPN/amidinate heteroleptic yttrium hydride [(C5H4-PPh2=N (C6H3Pr2)-Pr-i)Y(CH2SiMe3)(2)-(NPr)-Pr-i](mu-H)}(2) (3). Hydride 3 showed good reactivity toward various substrates containing unsaturated C C, C-N, and N-N bonds, such as azobenzene, p-tolyacetylene, 1,4-bis(trimethylsily1)-1,3-butanediyne, N,N'-diisopropylcarbodiimide, and 4-dimethylaminopyridine, affording the yttrium hydrazide complex 4 with a rare eta(2)-Cp bonding mode, yttrium terminal alkynyl complex 5, yttrium eta(3)-propargyl complex 6, yttrium amidinate complex 7, and yttrium 2-hydro-4-dimethylaminopyridyl product 8, respectively.

Single and double substrate insertion into the TiNαbonds of terminal titanium hydrazides

Nitriles, CO(2) and isocyanates undergo net single or double insertion reactions into the Ti=N(alpha) multiple bonds of terminal titanium hydrazides. These are the first such examples of this type of reactivity for any transition metal hydrazide complex.

Copper patterned polystyrene panels by reducing of surface bound Cu (II)-sulfonyl hydrazide complex

A modified electroless metal deposition method has been developed for copper plating of polystyrene (PS) surfaces. The modified procedure avoids the plasma conditioning and surface activation steps in the classical electroless metal plating process. First step of the present procedure is chlorosulfonation of PS surface by soaking into chlorosulfonic acid, yielding chlorosulfonated surface with density of 0.046–0.110 mmolcm − 2 depending on contact time (10–60 min). In the second step chlorosulfone groups on the surface are converted to sulfonyl hydrazides almost quantitatively by reaction with hydrazine solution (80%). Green Cu (II)-sulfonylhydrazide complex is formed at the surface, in the third step, by interaction with ammoniacle Cu (II) solution at room temperature. The copper in the complex is reduced rapidly in the fourth step, by immersing the specimen into 5% of hydrazine solution. The elemental copper deposited onto the surface serves activating sites to accumulate more (5–7 mg per cm 2) elemental copper from electroless copper solutions in the final step. The present method avoids the surface activation with palladium and allows preparing copper patterns with reasonably high pull-off strengths (3.77 Nmm − 2 ) on PS panels. In the study the copper deposition has been investigated using standard analytical procedures, X-ray photoelectron spectrometry (XPS) and Scanning Electron Microscopy.

Planar Dimeric Six-Membered Spirane Aluminum Hydrazide: Synthesis and X-ray Crystal Structure of [LAlN(Me)NH]2 (L = HC{(2,6-i-Pr2C6H3N)(CMe)}2)

The reaction between stoichiometric amounts of β-diketiminato-stabilized aluminum dihydride and methylhydrazine affords reddish brown crystals of a planar dimeric spirane aluminum hydrazide complex, [LAlN(Me)NH]2 (2).

Low-temperature deposition of titanium nitride films from dialkylhydrazine-based precursors

The deposition of titanium nitride films from single-source precursors bearing alkylhydrazine-derived ligands is reported. The complex [Ti 2Cl 4(NN(CH 3) 2) 2(NH 2N(CH 3) 2) 2] sublimes at 140–150°C (0.1 mmHg) and affords titanium nitride films in a chemical vapor deposition reactor at substrate temperatures of ⩾400°C. By contrast, structurally related single-source precursors containing alkylamine- or ammonia-derived ligands deposit titanium (IV) nitride chloride films at 400°C in the same reactor, and only afford titanium nitride films at ⩾475°C. The hydrazide(1−) complex [TiCl 2(N(CH 3)N(CH 3) 2) 2] sublimes at 130°C (0.1 mmHg) and affords titanium nitride films at 600°C. At substrate temperatures of ⩽550°C, poorly adherent blue-colored coatings were obtained. The atmospheric pressure chemical vapor deposition reaction of titanium tetrachloride and 1,1-dimethylhydrazine affords titanium nitride films at >500°C, but gives titanium (IV) nitride chloride films at ⩽500°C. Characterization of the films obtained from the depositions is described. The results demonstrate that ligands derived from 1,1-dialkylhydrazines can be powerful reducing sources for high valent early transition metals, depending on the ligand coordination mode, and can lead to a significant reduction in deposition temperatures compared to traditional nitrogen sources in cases where a high valent metal source compound must be reduced to a lower oxidation state.

Imido Complexes of Titanium Bearing η2-Pyrazolato Ancillary Ligand Sets

Treatment of dichlorobis(3,5-di-tert-butylpyrazolato)titanium(IV) with Grignard (CH3MgCl, C6H5CH2MgCl) or organolithium (LiCH2Si(CH3)3) reagents (2 equiv) afforded the dialkyl derivatives dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) (93%), dibenzylbis(3,5-di-tert-butylpyrazolato)titanium(IV) (43%), and bis(methyltrimethylsilyl)bis(3,5-di-tert-butyl-pyrazolato)titanium(IV) (49%). Analogous methylation of chlorotris(3,5-di-tert-butylpyrazolato)titanium(IV) with CH3MgCl afforded methyltris(3,5-di-tert-butylpyrazolato)titanium(IV) (52%). Attempted alkylation of trichloro(3,5-di-tert-butylpyrazolato)titanium(IV) with CH3MgCl (3 equiv) afforded dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) (35%), along with extensive decomposition. This experiment indicates that trimethyl(3,5-di-tert-butylpyrazolato)titanium(IV) is unstable at ambient temperature. The reactivity of dichlorobis(3,5-di-tert-butylpyrazolato)titanium(IV) and dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) toward primary amines was studied. Treatment of dichlorobis(3,5-di-tert-butylpyrazolato)titanium(IV) with excess tert-butylamine afforded tert-butylimido(chloro)(3,5-di-tert-butylpyrazolato)titanium(IV) dimer (10%), chlorotris(3,5-di-tert-butylpyrazolato)titanium(IV) (56%), and tert-butylammonium chloride (85%). Analogous treatment of dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) with tert-butylamine gave the monomeric imido complex tert-butylimidobis(3,5-di-tert-butylpyrazolato)(tert-butylamine)titanium(IV) (33%). Addition of pyridine to the reaction between dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) and tert-butylamine or isopropylamine afforded the pyridine adducts tert-butylimidobis(3,5-di-tert-butylpyrazolato)(pyridine)titanium(IV) (80%) and isopropylimidobis(3,5-di-tert-butylpyrazolato)(tert-butylamine)titanium(IV) (46%), respectively. Treatment of dimethylbis(3,5-di-tert-butylpyrazolato)titanium(IV) with 1-amino-4-methylpiperazine led to the hydrazide(1−) complex 1-amido-4-methylpiperazine(methyl)bis(3,5-di-tert-butylpyrazolato)titanium(IV) (64%), which contains both a titanium−methyl bond and a primary hydrazide(1−) ligand. It is proposed that the thermal stability of this compound arises from bidentate coordination of the hydrazide(1−) ligand, which places the reactive nitrogen−hydrogen bond distal to the titanium−methyl bond. The reactivity of tert-butylimidobis(3,5-di-tert-butylpyrazolato)(tert-butylamine)titanium(IV) toward acetylenes, nitriles, and ketones is discussed. The X-ray crystal structures of bis(methyltrimethylsilyl)bis(3,5-di-tert-butyl-pyrazolato)titanium(IV), tert-butylimido(chloro)(3,5-di-tert-butylpyrazolato)titanium(IV) dimer, and isopropylimidobis(3,5-di-tert-butylpyrazolato)(tert-butylamine)titanium(IV) were determined.

Vanadium phenoxide complexes with oxide, nitride or hydrazide co-ligands: preparation and crystal structures of [V(OC 6H 3Pr i2-2,6) 3NLi(C 4H 8O) 3], [{VO 2(OC 6H 3Pr i2-2,6) 2} 2{μ-Li(C 4H 8O) 2} 2] and [V(NNMe 2)(OC 6H 3Pr i2-2,6) 3

Treatment of [V(OC 6H 3Pr i 2-2,6) 2(μ-OC 6H 3Pr i 2-2,6) 2Li(C 4H 8O)] ( 1) with SiMe 3N 3 in hexane gives two products. The first, [V(OC 6H 3Pr i 2-2,6) 3NLi(C 4H 8O) 3] ( 2), contains the V–N–Li linkage and has essentially tetrahedral vanadium ( d(V–N) 1.565(5), d(Li–N) 2.061(13), d(V–OC 6H 3Pr i 2-2,6) (average) 1.828(4) Å; angle (Li–N–V) 164.0(5)°). The second product, [{VO 2(OC 6H 3Pr i 2-2,6) 2} 2{μ-Li(C 4H 8O) 2} 2] ( 3), which is formed by adventitious entry of water into the reaction solution, contains an eight-membered ring structure formed by two Li(thf) 2 groups bridging two tetrahedral VO 2(OC 6H 3Pr i 2-2,6) 2 units ( d(V–O) (range) 1.557(10)–1.669(9), d(V–OC 6H 3Pr i 2-2,6) (average) 1.803(12), d(Li–O) (vanadium) (average) 1.91(7) Å). The hydrazide complex [V(NNMe 2)(OC 6H 3Pr i 2-2,6) 3] ( 4) has been synthesised by treatment of the dianion [{VCl 3} 2{μ-NNMe 2) 3] 2− with Li[OC 6H 3Pr i 2-2,6]. Compound 4 has distorted tetrahedral geometry at vanadium, ( d(V–N) 1.653(3), d(V–OC 6H 3Pr i 2-2,6) (average) 1.793(3) d(N–N) 1.311(4) Å, and angle (V–N–N) 175.8(3)°). Compound 4 reacts with N(CH 2CH 2SH) 3 to give [V(NNMe 2){N(CH 2CH 2S) 3}]. Spectroscopic and other physical data for these complexes are presented and discussed.

Protonation reactions of dinitrogen complexes of molybdenum and tungsten with PMe3 as Co-ligand. X-Ray structure of the hydrazidium complex [WCl(NNH3)(PMe3)4] Cl2

The reactions of cis-[M(N2)2(PMe3)4] or [M(N2)(PMe3)5](M = Mo or W) with HX (X = Cl or l) give the hydrazido (2–) complexes [MX(NNH2)(PMe3)4]X as intermediate products. For M = Mo, the final product is ammonia, but for M = W, X = Cl, the final product is the hydrazidium complex [WCl(NNH3)(PMe3)4]Cl2(A). These reactions have been monitored by 31P and 15N n.m.r. spectroscopy, and complex (A) has been structurally characterised by X-ray diffraction. It exists in the solid state as centrosymmetric dimer units consisting of two cations linked through Cl anions by strong hydrogen bonds. The W–N–N group is almost linear with W–N 1.785(15) and N–N 1.40(2)A. Compound (A) can also be prepared from [WCl(NNH2)(PMe3)4]Cl and HCl, but it is converted by Na[BPh4] in methanol into the hydrazide complex [WCl(NNH2)(PMe3)4][BPh4].

Effect of cupric-isonicotinic acid hydrazide complex on avian myeloblastosis virus reverse transcriptase and its associated enzyme activities

Cupric complex of isonicotinic acid hydrazide inhibits DNA synthesis by avian myloblastosis virus reverse transcriptase. This inhibition occurs in the presence of either ribonucleotide or deoxyribonucleotide templates. The inhibition of reverse transcriptase by cupric-INH complex is considerably reduced when stored or proteolytically cleaved enzyme was used in the reaction. The complex also inhibits the reverse transciptase-associated RNase H activity. The cupric-isonicotinic acid hydrazide complex cleaves pBR 322 from I DNA into smaller molecules in the presence or absence of reverse transcriptase-associated endonuclease. However, in the presence of the enzyme the DNA is cleaved to a greater extent.

Effect of cupric-isonicotinic acid hydrazide complex on normal and avian myeloblastosis virus-infected cells cultivatedin vitro

The cupric complex of isonicotinic acid hydrazide was found to be nontoxic to normal yolk sac macrophages upto a concentration of 100 ΜM. At this concentration the complex did not significantly inhibit DNA, RNA or protein synthesis in these cells. The complex inhibited the avian myeloblastosis virus multiplication in these cells when added 0–4 h post-infection as demonstrated by the inhibition of both focus formation and expression of viral specific antigens. This inhibition was not observed when the complex was added 8 and 16 h after avian myeloblastosis virus infection. The studies carried out on avian myeloblastosis virus-transformed myeloblasts indicated that the complex had no effect on the colony (focus) formation. The results suggest that the complex inhibits the virus multiplication by interfering in an early event of viral growth cycle, possibly the process of reverse transcription

Cuprous complexes formed with isonicotinic hydrazide.

Chelate formation by Cu(II) and isonicotinic acid hydrazide has been postulated as an important step in the antitubercular activity of isonicotinic hydrazide (Isoniazid). Reevaluation of the copper-isonicotinic hydrazide system gives evidence for the formation of a Cu(I) species rather than a Cu(II) species. The reduction of Cu(II) to Cu(I) and the subsequent formation of an isonicotinic hydrazide complex with the latter ion, therefore, may be the critical reaction responsible for the efficacy of isonicotinic hydrazide against Mycobacterium tuberculosis.