scholarly journals Spectroscopic studies on lipoprotein structure modification under oxidative stress

2011 ◽  
Vol 26 (3) ◽  
pp. 167-178 ◽  
Author(s):  
Andreia Tache ◽  
Simona-Carmen Litescu ◽  
Gabriel-Lucian Radu
Keyword(s):  
Free Radicals ◽  
Metal Ion ◽  
Structural Changes ◽  
Oxidation Process ◽  
Spectroscopic Studies ◽  
Oxidative Modification ◽  
Hydroxyl Groups ◽  
Oxidative Damages ◽  
Endogenous Antioxidant

Matrix assisted laser desorption–ionization time of flight (MALDI-ToF) and infrared techniques were used to study oxidative modification of low density lipoproteins (LDL), considered to have the key role in biological process that initiates and accelerates the development of cardiovascular disease. The early identification of lipoperoxidation products creates the opportunity of the efficient prevention of eventual oxidative damages. MALDI analysis of LDL subjected toin vitrooxidation process initiated by 2,2-azobis(2-amidinopropane) dihydrochloride revealed that some fragments of lipoprotein changed the molecular weight by 16 and 32 Da due to the oxygen or hydroxyl groups attachment, and peroxide or hydroperoxide formation, while Fourier Transformed Infrared studies proved that lipoprotein changes its protein secondary conformation from predominantlyα-helix in predominantlyβ-turn. The increase in free radicals concentration correlated to structural changes, and the presence of transitional metal ion, copper (II), in the oxidation process lead to an enhancing of the damaging effects of free radicals on lipoprotein substrate. It was shown that the toxic effects of oxidants are delayed by the presence of glutathione (10 mM), an endogenous antioxidant.

Oxidative Modification of Fibrinogen Affects Its Binding Activity to Glycoprotein (GP) IIb/IIIa

2009 ◽  
Vol 16 (1) ◽  
pp. 51-59 ◽  
Author(s):  
Sermin Tetik ◽  
Kurtulus Kaya ◽  
M. Demir ◽  
Emel Eksioglu-Demiralp ◽  
Turay Yardimci
Keyword(s):  
Metal Ion ◽  
Degradation Products ◽  
Binding Capacity ◽  
Protein Structures ◽  
Human Platelets ◽  
Binding Activity ◽  
Oxidative Modification ◽  
Oxidized Fibrinogen ◽  
Protein Functions

Aim: Proteins are sensitive biomarkers of human diease condition associated with oxidative stress. Alteration of protein structures by oxidants may result in partial or complete loss of protein functions. We have investigated the effect of structural modifications induced by metal ion catalyzed oxidation of fibrinogen on its binding capacity to glycoprotein IIb/IIIa (GpIIb/IIIa) and human platelets. Methods: We identified and quantified of binding capacity of native and oxidized fibrinogen to its receptor in vitro by flow cytometer. Dityrosine formation on oxidized fibrinogen were detected spectrophotometrically. Elevated degradation products of fibrinogen after oxidation were revealed in the HPLC analysis. The native and oxidized fibrinogen were analyzed on mass spectrum upon digestion with tyripsin. Results: Oxidatively modified fibrinogen showed less binding activity than native fibrinogen to GpIIb/IIIa coated micro beads and human platelets whereas slightly higher binding capaticity to ADP induced stimulated platelets. Formation of dityrosines in the amino acid side chains of fibrinogen were observed upon oxidation. Decreased binding capacity of oxidized fibrinogen correlated with intensities of dityrosine formation. Oxidized fibrinogen had more ion-mass intensities at higher than native fibrinogen. Clinical implications: Important point is decreased of binding capacity of the oxidized fibrinogen to own receptor. The decreased rate of binding, leading to effect in the diseases of clot formation may acount for the association between oxidation of fibrinogen and the incidence of effect in human diseases.

scholarly journals Synthesis, Characterization and DNA-Binding Affinity of a New Zinc(II) Bis(5-methoxy-indol-3-yl)propane-1,3-dione Complex

2021 ◽  
Vol 14 (8) ◽  
pp. 760
Author(s):  
Luca Scapinello ◽  
Guglielmo Vesco ◽  
Luca Nardo ◽  
Angelo Maspero ◽  
Federico Vavassori ◽  
...  
Keyword(s):  
Metal Ion ◽  
Structural Changes ◽  
Fluorescence Emission ◽  
Spectroscopic Techniques ◽  
Time Resolved ◽  
Fluorescence Studies ◽  
High Affinity ◽  
Drug Substances ◽  
Calf Thymus

The novel zinc(II) µ-oxo-bridged-dimeric complex [Zn2(µ-O)2(BMIP)2] (BMIP = 1,3-bis(5-methoxy-1-methyl-1H-indol-3-yl)propane-1,3-dione), 1, was synthetized and fully characterized. The spectral data indicate a zincoxane molecular structure, with the BMIP ligand coordinating in its neutral form via its oxygen atoms. Structural changes in 1 in dimethylsulfoxide (DMSO) were evidenced by means of spectroscopic techniques including infrared absorption and nuclear magnetic resonance, showing DMSO entrance in the coordination sphere of the metal ion. The resulting complex [Zn2(µ-O)2(BMIP)2(DMSO)], 2, readily reacts in the presence of N-methyl-imidazole (NMI), a liquid-phase nucleoside mimic, to form [Zn2(µ-O)2(BMIP)2(NMI)], 3, through DMSO displacement. The three complexes show high thermal stability, demonstrating that 1 has high affinity for hard nucleophiles. Finally, with the aim of probing the suitability of this system as model scaffold for new potential anticancer metallodrugs, the interactions of 1 with calf thymus DNA were investigated in vitro in pseudo-physiological environment through UV-Vis absorption and fluorescence emission spectroscopy, as well as time-resolved fluorescence studies. The latter analyses revealed that [Zn2(µ-O)2(BMIP)2(DMSO)] binds to DNA with high affinity upon DMSO displacement, opening new perspectives for the development of optimized drug substances.

Structural Changes in CuII Complexes of Potential Octadentate Ligands by Coordination with Carboxylate/Carboxylic Acid: DFT, TD-DFT, and Experimental Studies

2010 ◽  
Vol 63 (6) ◽  
pp. 965 ◽  
Author(s):  
Enrique Montiel ◽  
Julian Cruz ◽  
Narayanan Jayanthi ◽  
Sylvain Bernés ◽  
Thangarasu Pandiyan
Keyword(s):  
Carboxylic Acid ◽  
Metal Ion ◽  
Density Functional ◽  
Structural Changes ◽  
Experimental Studies ◽  
Spectroscopic Studies ◽  
Td Dft ◽  
Axial Bond ◽  
Geometrical Change ◽  
Molecular Orbital Analysis

The structural and spectroscopic studies of N,N,N′,N′,N′-pentakis-(benzimidazol-2-yl-methyl)diethylenetriamine (L1) and N,N,N′,N′-tetrakis-(benzimidazol-2-yl-methyl)-N′-(carboxylmethyl)diethylenetriamine (L2H) and [CuL1]2+, [CuL2H]2+, and [CuL2]+ were carried out by density functional theory (DFT) and time-dependant (TD)-DFT techniques. The results show that a geometrical change occurs when carboxylate/carboxylic acid coordinates with the metal ion. For example, the ligand L2H forms an octahedral geometry with CuII and in the structure, four nitrogens (N3, N13, N44, N47) are equatorially coordinated with the metal ion, and atoms O50 (–COOH) and N41, which are weakly bonded at the axial positions, are in competition in the formation of an axial bond with CuII; however, for the ligand L2, only a square pyramidal (SP) geometry results with CuII because of the formation of a strong axial bond by O50 (–COO–) with CuII, which dictates non-bonding at its trans position. Molecular orbital analysis proves that both HOMO and HOMO – 1 are localized over the carboxylate ion that favours a strong axial bond with the metal ion; thus, the SP geometry results in the X-ray structure of [CuL2]ClO4. Furthermore, for the complexes, since the electronic spectroscopic bands were unseparated in the spectra, the TD-DFT was used to identify the bands.

scholarly journals Recent Developments in Effective Antioxidants: The Structure and Antioxidant Properties

Materials ◽  
2021 ◽  
Vol 14 (8) ◽  
pp. 1984
Author(s):  
Monika Parcheta ◽  
Renata Świsłocka ◽  
Sylwia Orzechowska ◽  
Monika Akimowicz ◽  
Renata Choińska ◽  
...  
Keyword(s):  
Free Radicals ◽  
Antioxidant Properties ◽  
Hydroxyl Group ◽  
Electronic Charge ◽  
Experimental Literature ◽  
Hydroxyl Groups ◽  
Food Ingredients ◽  
Group Position ◽  
Oxidative Damages ◽  
Recent Developments

Since the last few years, the growing interest in the use of natural and synthetic antioxidants as functional food ingredients and dietary supplements, is observed. The imbalance between the number of antioxidants and free radicals is the cause of oxidative damages of proteins, lipids, and DNA. The aim of the study was the review of recent developments in antioxidants. One of the crucial issues in food technology, medicine, and biotechnology is the excess free radicals reduction to obtain healthy food. The major problem is receiving more effective antioxidants. The study aimed to analyze the properties of efficient antioxidants and a better understanding of the molecular mechanism of antioxidant processes. Our researches and sparing literature data prove that the ligand antioxidant properties complexed by selected metals may significantly affect the free radical neutralization. According to our preliminary observation, this efficiency is improved mainly by the metals of high ion potential, e.g., Fe(III), Cr(III), Ln(III), Y(III). The complexes of delocalized electronic charge are better antioxidants. Experimental literature results of antioxidant assays, such as diphenylpicrylhydrazyl (DPPH) and ferric reducing activity power assay (FRAP), were compared to thermodynamic parameters obtained with computational methods. The mechanisms of free radicals creation were described based on the experimental literature data. Changes in HOMO energy distribution in phenolic acids with an increasing number of hydroxyl groups were observed. The antioxidant properties of flavonoids are strongly dependent on the hydroxyl group position and the catechol moiety. The number of methoxy groups in the phenolic acid molecules influences antioxidant activity. The use of synchrotron techniques in the antioxidants electronic structure analysis was proposed.

6-Gingerol prevents free transition metal Ion [Fe (Ii)] Induced free radicals mediated alterations by In vitro and Ndv growth in chicken eggs by In ovo

2018 ◽  
Vol 14 (55) ◽  
pp. 167
Author(s):  
GanjikuntaVenkata Subbaiah ◽  
KesireddySathyavelu Reddy ◽  
Yagani JayavardhanaRao ◽  
Bhasha Shanmugam ◽  
Sahukari Ravi ◽  
...  
Keyword(s):  
Free Radicals ◽  
Transition Metal ◽  
Metal Ion ◽  
In Ovo ◽  
Transition Metal Ion ◽  
Free Transition ◽  
Chicken Eggs

scholarly journals Biomimetic resorcinarene-based copper(II) complex

2014 ◽  
Vol 70 (a1) ◽  
pp. C1374-C1374
Author(s):  
Aleksandar Višnjevac ◽  
Jérôme Gout ◽  
Olivia Bistri-Aslanoff ◽  
Olivia Reinaud
Keyword(s):  
Active Site ◽  
Metal Ion ◽  
Spectroscopic Studies ◽  
Hydroxyl Groups ◽  
Residual Water ◽  
Amino Acid Residues ◽  
Tight Control ◽  
Guest Molecules ◽  
Group A ◽  
Solvent Molecules

"The synthesis, structural characterization, as well as the chemical activity studies of a Cu(II) ""bowl complex", based on the resorcin[4]arene scaffold with three imidazole-containing coordinating arms grafted at the large rim, is presented. This complex is a biomimetic model of a metalloenzyme active site where a cofacial triade of amino-acid residues holds the metal ion in the active site [1]. The trisimidazole ligand reacts with a stoichiometric amount of copper(II) perchlorate to produce a Cu(II) diperchloratocomplex 1. Spectroscopic studies revealed a 5-coordinate SBP environment for the Cu(II) center provided by three imidazole arms, and two extra donors, one embedded in the resorcinarene cavity, the other exposed to the solvent, in exo position. These two labile sites are occupied by either coordinating solvent molecules or residual water, and are readily displaced by carboxylate donors, the position of which (endo or exo) is under tight control of the bowl-cavity. The reaction of 1 with CH3COONa led to a formation of the Cu(II) acetatocomplex 2. Molecular structure of 2 features a rigidified resorcinarene bowl, which was constructed by the addition of the four methylene bridges between the eight hydroxyl groups of the octol precursor [2]. The isolated resorcinarene basket reveals an approximate, non-crystallographic, 4mm point symmetry, and can easily host small guest molecules. Three methylimidazole-containing coordination arms at the large rim coordinate the Cu (II) ion. Its coordination sphere is completed by two O atoms from the intra-cavity bound acetate. The electron donors form a distorted square pyramide, where one of the nitrogens is at the appical position. The endo-coordination of the acetate is supported by an extensive network of intramolecular C-H···O and C-H···π interactions. Complex 2 crystallizes in P21/c space group; a=32.3310 (4)Å, b=11.5490 (1)Å, c=21.6020 (2)Å, beta=102.281(3)0."

Synthesis, Characterization and Biological Studies of Some Transition Metal Complexes with Pyrazine Schiff Base Hydra zone Ligand

2020 ◽  
Vol 15 (2) ◽  
pp. 61-72
Keyword(s):  
Metal Complexes ◽  
Metal Ion ◽  
Metal Salt ◽  
Free Ligand ◽  
Spectroscopic Studies ◽  
Fungal Species ◽  
Molar Conductance ◽  
Central Metal ◽  
Biological Studies

New pyrazine carbohydra zone ligand N'-(1-(5-chloro-2-hydroxyphenyl) ethylidene) pyrazine-2-carbohydrazide (H2L), prepared by the condensation of equimolar amounts of pyrazine-2-carbohydrazide with 2-hydroxy-5-chloroacetophenone in methanol, reacts with suitable metal salt precursors to give complexes of two general formulae: [M(HL)(Cl)(H2O)2] {M = Mn(II), Co(II), Ni(II) and Cu(II)} and [M(L)(H2O)] {M = Zn(II) and Cd(II)}. Structure of ligand was confirmed by elemental analysis, IR, 1H and 13C NMR and mass spectroscopy, while synthesized complexes were additionally characterized by magnetic susceptibility measurements, molar conductivity measurements, XRD, ESR (for Cu(II)), SEM and thermogravimetric analysis. Spectroscopic studies confirmed a tridentate ONO donor behavior of the ligand towards the central metal ion. The molar conductance (12–17 W–1 cm2 mol–1) measurements in DMSO indicated non-electrolytic nature. Thermal behavior of the complexes suggests their extended stability and the thermal decomposition generally proceeds via partial loss of the organic moiety and ends with the formation of respective metal oxide as a final product. Various kinetic and thermodynamic parameters were evaluated using the Coats-Redfern method. The solid-state electrical conductivity of the complexes measured in the temperature range 303-463 K suggested their semiconducting behavior. The ligand and its metal complexes were screened in vitro for their antibacterial activity against the Gram-positive bacteria S. aureus and B. subtilis, the Gram-negative bacteria E. coli and S. typhi and the fungi C. albicans and A. niger. The obtained results indicated improved activity of the complexes compared to the free ligand against all studied bacterial and fungal species.

scholarly journals The First Metal Complexes of 4,6-diamino-1-hydro-5-hydroxy-pyrimidine-2-thione: Preparation, Physical and Spectroscopic Studies, and Preliminary Antimicrobial Properties

2008 ◽  
Vol 2008 ◽  
pp. 1-8 ◽  
Author(s):  
Sahar I. Mostafa ◽  
Constantina Papatriantafyllopoulou ◽  
Spyros P. Perlepes ◽  
Nick Hadjiliadis
Keyword(s):  
Metal Ion ◽  
Room Temperature ◽  
Free Ligand ◽  
Antimicrobial Properties ◽  
Spectroscopic Studies ◽  
Ligand Field ◽  
Square Planar ◽  
Elemental Analyses ◽  
Bidentate Chelate

The new complexes[M2O5L2(H2O)2]⋅H2O (M=Mo,1;M=W,2),[RuL2(H2O)2]⋅H2O (3),[ML3]⋅xH2O (M=Rh,x=2,4;M=Ir,x=1,5),[RhL2(PPh3)2](ClO4)⋅2H2O (6),[PdL2]⋅2H2O (7),[PdL(phen)]Cl⋅H2O (8),[Re⁡OL2(PPh3)]Cl (9)and[UO2L2] (10)are reported, where LH is 4,6-diamino-1-hydro-5-hydroxy-pyrimidine-2-thione. The complexes were characterized by elemental analyses, physical techniques (molar conductivity, room-temperature magnetic susceptibility), and spectroscopic (IR, Raman, UV/VIS/ligand field, NMR, mass) methods. The ligandL−is in its thione form and behaves as a bidentate chelate with the deprotonated (hydroxyl) oxygen and the nitrogen of one amino group as donor atoms. Oxobridged dinuclear(1, 2)and various mononuclear(3–10)structures are assigned for the complexes in the solid state. The metal ion coordination geometries are octahedral(1–6, 9, 10)or square planar(7, 8). The free ligand LH and complexes1,4,7, and8were assayed in vitro for antimicrobial activity against two bacterial and two fungal cultures.

The Role of Polyphenols in the Modulation of Plasma Non-Enzymatic Antioxidant Capacity (NEAC)

2012 ◽  
Vol 82 (3) ◽  
pp. 228-232 ◽  
Author(s):  
Mauro Serafini ◽  
Giuseppa Morabito
Keyword(s):  
Antioxidant Capacity ◽  
Dietary Intervention ◽  
Ex Vivo ◽  
The Body ◽  
Dietary Polyphenols ◽  
Enzymatic Antioxidant ◽  
Endogenous Antioxidant

Dietary polyphenols have been shown to scavenge free radicals, modulating cellular redox transcription factors in different in vitro and ex vivo models. Dietary intervention studies have shown that consumption of plant foods modulates plasma Non-Enzymatic Antioxidant Capacity (NEAC), a biomarker of the endogenous antioxidant network, in human subjects. However, the identification of the molecules responsible for this effect are yet to be obtained and evidences of an antioxidant in vivo action of polyphenols are conflicting. There is a clear discrepancy between polyphenols (PP) concentration in body fluids and the extent of increase of plasma NEAC. The low degree of absorption and the extensive metabolism of PP within the body have raised questions about their contribution to the endogenous antioxidant network. This work will discuss the role of polyphenols from galenic preparation, food extracts, and selected dietary sources as modulators of plasma NEAC in humans.

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