scholarly journals Reaction with Proteins of a Five-Coordinate Platinum(II) Compound

2019 ◽  
Vol 20 (3) ◽  
pp. 520 ◽  
Author(s):  
Giarita Ferraro ◽  
Tiziano Marzo ◽  
Maria Cucciolito ◽  
Francesco Ruffo ◽  
Luigi Messori ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Platinum Complexes ◽  
Rnase A ◽  
Side Chain ◽  
Planar Geometry ◽  
Ionization Mass ◽  
X Ray ◽  
X Ray Crystallography ◽  
Egg White Lysozyme ◽  
Square Planar

Stable five-coordinate Pt(II) complexes have been highlighted as a promising and original platform for the development of new cytotoxic drugs. Their interaction with proteins has been scarcely studied. Here, the reactivity of the five-coordinate Pt(II) compound [Pt(I)(Me) (dmphen)(olefin)] (Me = methyl, dmphen = 2,9-dimethyl-1,10-phenanthroline, olefin = dimethylfumarate) with the model proteins hen egg white lysozyme (HEWL) and bovine pancreatic ribonuclease (RNase A) has been investigated by X-ray crystallography and electrospray ionization mass spectrometry. The X-ray structures of the adducts of RNase A and HEWL with [Pt(I)(Me)(dmphen)(olefin)] are not of very high quality, but overall data indicate that, upon reaction with RNase A, the compound coordinates the side chain of His105 upon releasing the iodide ligand, but retains the pentacoordination. On the contrary, upon reaction with HEWL, the trigonal bi-pyramidal Pt geometry is lost, the iodide and the olefin ligands are released, and the metal center coordinates the side chain of His15 probably adopting a nearly square-planar geometry. This work underlines the importance of the combined use of crystallographic and mass spectrometry techniques to characterize, in detail, the protein–metallodrug recognition process. Our findings also suggest that five-coordinate Pt(II) complexes can act either retaining their uncommon structure or functioning as prodrugs, i.e., releasing square-planar platinum complexes as bioactive species.

scholarly journals Weak protein–cationic co-ion interactions addressed by X-ray crystallography and mass spectrometry

2014 ◽  
Vol 70 (8) ◽  
pp. 2217-2231 ◽  
Author(s):  
Philippe Bénas ◽  
Nicolas Auzeil ◽  
Laurent Legrand ◽  
Franck Brachet ◽  
Anne Regazzetti ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Protein Solubility ◽  
Ionization Mass ◽  
X Ray ◽  
Esi Ms ◽  
X Ray Crystallography ◽  
Egg White Lysozyme ◽  
Ion Interactions ◽  
Carboxylic Groups ◽  
Hen Egg White

The adsorption of Rb+, Cs+, Mn2+, Co2+and Yb3+onto the positively charged hen egg-white lysozyme (HEWL) has been investigated by solving 13 X-ray structures of HEWL crystallized with their chlorides and by applying electrospray ionization mass spectrometry (ESI-MS) first to dissolved protein crystals and then to the protein in buffered salt solutions. The number of bound cations follows the order Cs+< Mn2+≃ Co2+< Yb3+at 293 K. HEWL binds less Rb+(qtot= 0.7) than Cs+(qtot= 3.9) at 100 K. Crystal flash-cooling drastically increases the binding of Cs+, but poorly affects that of Yb3+, suggesting different interactions. The addition of glycerol increases the number of bound Yb3+cations, but only slightly increases that of Rb+. HEWL titrations with the same chlorides, followed by ESI-MS analysis, show that only about 10% of HEWL binds Cs+and about 40% binds 1–2 Yb3+cations, while the highest binding reaches 60–70% for protein binding 1–3 Mn2+or Co2+cations. The binding sites identified by X-ray crystallography show that the monovalent Rb+and Cs+preferentially bind to carbonyl groups, whereas the multivalent Mn2+, Co2+and Yb3+interact with carboxylic groups. This work elucidates the basis of the effect of the Hofmeister cation series on protein solubility.

Mapping the protein-binding sites for iridium(iii)-based CO-releasing molecules

2016 ◽  
Vol 45 (30) ◽  
pp. 12206-12214 ◽  
Author(s):  
Marco Caterino ◽  
Ariel A. Petruk ◽  
Alessandro Vergara ◽  
Giarita Ferraro ◽  
Daniela Marasco ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Protein Binding ◽  
Binding Sites ◽  
Raman Microspectroscopy ◽  
Rnase A ◽  
Protein Binding Sites ◽  
X Ray ◽  
X Ray Crystallography ◽  
Model Protein ◽  
Circular Dichroïsm

Mass spectrometry, Raman microspectroscopy, circular dichroism and X-ray crystallography have been used to investigate the reaction of CO-releasing molecule Cs2IrCl5CO with the model protein RNase A.

Coordination chemistry of thioether–pyridazine macrocycles. III. Synthetic, structural, and spectroscopic studies of Cu(II), Cu(II)Cu(I), and Cu(I) complexes of a hexathiapyridazinophane macrocyclic ligand

1993 ◽  
Vol 71 (7) ◽  
pp. 1086-1093 ◽  
Author(s):  
Liqin Chen ◽  
Laurence K. Thompson ◽  
John N. Bridson
Keyword(s):  
Mass Spectrometry ◽  
Macrocyclic Ligand ◽  
Spectroscopic Studies ◽  
Orthorhombic System ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Triclinic System ◽  
Square Planar ◽  
Copper Centre

The preparation and properties of the thioether–pyridazine macrocycle (L4; C16H20S6N4) containing two pyridazine subunits, and its Cu(II), Cu(II)Cu(I), and Cu(I) complexes are described. The ligand is characterized by 1H nuclear magnetic resonance and mass spectrometry, and the complexes by infrared, eleetronic spectra, and magnetism, and in some cases by X-ray crystallography. The complex [Cu2(L4)Cl4]x, (1) crystallized in the triclinic system, space group [Formula: see text] with a = 8.6204(8) Å, b = 9.850(1) Å, c = 8.348(1) Å, α = 111.46(1)°, β = 102.50(1)°, γ = 71.818(9)°, V = 622.6(1) Å3, and Z = 1 (R = 0.043, Rw = 0.042 for 1312 reflections). Two monodentate pyridazine rings in the same ligand bind to one trans square-planar copper centre (CuN2Cl2) with two sulfurs from each ligand binding to another trans square-planar copper centre (CuS2Cl2) to form a polynuclear chain. The complex [Cu(L4)Cl2] (3) crystallized in the triclinic system, space group [Formula: see text] with a = 11.001(1) Å, b = 12.888(2) Å, c = 8.704(1) Å, α = 102.89(1)°, β = 103.36(1)°,γ = 75.84(1)°, V = 1145.8(3) Å3 and Z = 2 (R = 0.056, Rw = 0.044 for 2059 reflections). A trans square-planar structure (CuN2Cl2) exists for 3 with monodentate pyridazines. [Cu(L4)(NO3)2] (4) crystallized in the orthorhombic system, space group P212121, with a = 15.148(2) Å, b = 15.562(3) Å, c = 11.064(1) Å, V = 2608.2(7) Å3 and Z = 4 (R = 0.039, Rw = 0.034 for 1864 reflections). Two monodentate pyridazine rings and two bidentate nitrates bind to a pseudo-octahedral copper(II) centre.

Influence of metal ions on the formation of new metal complexes constructed from tetrachlorophthalic acid

2015 ◽  
Vol 70 (10) ◽  
pp. 711-718
Author(s):  
An-Qi Dai ◽  
Qi Yan ◽  
Jing Zhong ◽  
Sheng-Chun Chen ◽  
Ming-Yang He ◽  
...  
Keyword(s):  
Metal Ions ◽  
Significant Contribution ◽  
Transition Metal Ions ◽  
Planar Geometry ◽  
X Ray ◽  
X Ray Crystallography ◽  
Transitional Metal ◽  
Square Planar ◽  
Structural Differences ◽  
Metal Effect

AbstractReaction of 3,4,5,6-tetrachloro-1,2-benzenedicarboxylyic acid (1,2-H2BDC-Cl4) with transitional metal salts at room temperature in mixed DMF/H2O solvent affords three complexes formulated as [Cu(1,2-HBDC-Cl4)2(DMF)2] (1), {[Cd(1,2-HBDC-Cl4)2(H2O)4]·2DMF} (2), and {[Ni(1,2-BDC-Cl4)(H2O)5]·DMF·H2O} (3) (DMF = N,N-dimethylformamide). All these complexes have been characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray crystallography. In 1, the CuII ion is four-coordinated with a square-planar geometry formed by two 1,2-HBDC-Cl4 anions and two DMF ligands; in 2, the CdII ion takes an octahedral geometry coordinated by two 1,2-HBDC-Cl4 anions and four aqua ligands; while in 3, the NiII ion is octahedrally coordinated by one 1,2-BDC-Cl4 dianion and five aqua ligands. Intermolecular O–H···O hydrogen bonds and Cl···Cl (or C–H···Cl) interactions provide a significant contribution to stabilizing the three mononuclear structures in the solid state. The results suggest that structural differences among them are attributed to the influence of transition metal ions. The fluorescence of the complexes and of 1,2-H2BDC-Cl4 has been investigated. No significant metal effect has been observed.

scholarly journals Synthesis, Crystal Structure and Interaction with Bovine Serum Albumin (BSA) of Two α-Aminophosphonic Acids Derivatives

2019 ◽  
pp. 1-7
Author(s):  
Wei Huang ◽  
Wen-Ling Wang
Keyword(s):  
Crystal Structure ◽  
Mass Spectrometry ◽  
Binding Constants ◽  
Ionization Mass ◽  
Monoclinic System ◽  
X Ray ◽  
X Ray Crystallography ◽  
Aminophosphonic Acids ◽  
Amino Phosphonate ◽  
Ft Ir

Two α-amino-phosphonate derivatives (1 & 2) were synthesized and their compositions and structures were characterized by Elemental Analysis (EA), FT-IR Spectrascopy (FT-IR), Electrospray Ionization Mass Spectrometry (ESI-MS), Nuclear Magnetic Resonance (NMR, 1H, 13C and 31P) and X-ray crystallography. Compound 1 & 2 were crystallized in monoclinic system with the space group P2(1)/n and P2(1)/c, respectively. The interaction effects of two α-aminophosphonate derivatives (1 & 2) with BSA were investigated and the binding constants were 1.07 × 104 M-1, 1.68 × 104 M-1, respectively. Besides, the values of n were indicated that 1:1 complex was formed between BSA and 1&2.

Combined analysis of 1,3-benzodioxoles by crystalline sponge X-ray crystallography and laser desorption ionization mass spectrometry

The Analyst ◽  
2018 ◽  
Vol 143 (6) ◽  
pp. 1475-1481 ◽  
Author(s):  
Yukako Hayashi ◽  
Kazuaki Ohara ◽  
Rika Taki ◽  
Tomomi Saeki ◽  
Kentaro Yamaguchi
Keyword(s):  
Mass Spectrometry ◽  
Laser Desorption ◽  
Promising Method ◽  
Ionization Mass Spectrometry ◽  
Ionization Mass ◽  
Laser Desorption Ionization ◽  
Combined Analysis ◽  
X Ray ◽  
X Ray Crystallography ◽  
Desorption Ionization

The combination of X-ray analysis and laser desorption ionization by using crystalline sponge will be a promising method to determine guest structures.

Homonuclear PdII and PtII and heteronuclear PdII-AuI and PtII-AuI complexes of a tripod triphosphine ligand: synthesis, characterization and reactions with molecules of biological relevance

2000 ◽  
Vol 53 (8) ◽  
pp. 635 ◽  
Author(s):  
Paloma Sevillano ◽  
Abraha Habtemariam ◽  
M. Inés García Seijo ◽  
Alfonso Castiñeiras ◽  
Simon Parsons ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Mass Spectrometry ◽  
Partial Oxidation ◽  
Bond Cleavage ◽  
Planar Geometry ◽  
Conductivity Measurements ◽  
Initial Attack ◽  
X Ray ◽  
Square Planar ◽  
Linear Geometry

Complexes of the type Pd(tripod)X2 [tripod = MeC(CH2PPh2)3; X = Cl (1), Br (2), I (3)] and Pt(tripod)X2 [X = Cl (4), Br (5), I (6)] have been synthesized. In these complexes tripod acts as a bidentate chelating ligand. The uncoordinated phosphorus atom can bind to AuI to form the bimetallic complexes PdAu(tripod)X3 [X = Cl (7), Br (8), I (9)] and PtAu(tripod)X3 [X = Cl (10), Br (11), I (12)]. Complexes (1)–(12) have been characterized by microanalysis, f.a.b. mass spectrometry, i.r. spectroscopy, 31P and 195Pt n.m.r. spectroscopies, and conductivity measurements. The structures of complexes (1), (4) and (11), as well as that of the unusual complex Cl2Pt(tripod)AuBr0.5Cl0.5 (13), isolated from reaction of Pt(tripod)Br2 (5), and [Au(thiodiglycol)Cl], have been determined. All complexes show square-planar geometry for PdII or PtII and linear geometry for AuI. The X-ray crystal structure of (1) showed partial oxidation of the dangling phosphorus of the ligand in 50% of the molecule distributed randomly over the lattice. Reactions of complex (4), Pt(tripod)Cl2, with the tripeptide glutathione (GSH) showed the formation of [Pt2(tripod)2(GS-µ–S)2]2+ (15a). No reaction with N-acetyl-L-methionine (AcMet) or guanosine 5´-monophosphate (5´-GMP) was observed. Reactions of [Pt(tripod–O)(ONO2)2] (14) with GSH resulted in the formation of [Pt2(tripod–O)2(GS-µ-S)2]2+ (15b). Displacement of the S-containing molecules by 5´-GMP in the presence of AuI, via Pt–S bond cleavage, was observed for complex (15b). PtAu(tripod)Cl3 (10) reacted with GSH, with initial attack on the AuI centre.

Hemilabile imino-phosphine palladium(II) complexes: synthesis, molecular structure, and evaluation in Heck reactions

2014 ◽  
Vol 68 (7) ◽  
Author(s):  
William Motswainyana ◽  
Martin Onani ◽  
Roger Lalancette ◽  
Paul Tarus
Keyword(s):  
Molecular Structure ◽  
Planar Geometry ◽  
Coordination Geometry ◽  
Coupling Reactions ◽  
Heck Coupling ◽  
Heck Reactions ◽  
Reaction Conditions ◽  
X Ray ◽  
X Ray Crystallography ◽  
Square Planar

AbstractThe ligands 2-(diphenylphosphino)benzyl-(2-thiophene)methylimine (V) and 2-(diphenylphosphino) benzyl-(2-thiophene)ethylimine (VI) were prepared from 2-(diphenylphosphino)benzaldehyde and thiophene amines with very good yields. An equimolar reaction of V and VI with either PdCl2(cod) (cod = cyclooctadiene) or PdClMe(cod) afforded palladium(II) complexes I–IV. The molecular structure of II was confirmed by X-ray crystallography. The coordination geometry around the palladium atom exhibited distorted square planar geometry at the palladium centre. Complexes I, II, and IV were evaluated as catalysts for Heck coupling reactions of iodobenzene with methyl acrylate under mild reaction conditions; 0.1 mole % catalyst, Et3N base, MeCN reflux for 8 h, 80°C; isolated yield on a 10 mmol scale with catalyst I (64 %), II (68 %), and IV (58 %). They all exhibited significant activities.

Protein interactions of dirhodium tetraacetate: a structural study

2020 ◽  
Vol 49 (8) ◽  
pp. 2412-2416 ◽  
Author(s):  
Giarita Ferraro ◽  
Alessandro Pratesi ◽  
Luigi Messori ◽  
Antonello Merlino
Keyword(s):  
Mass Spectrometry ◽  
High Resolution ◽  
Protein Interactions ◽  
High Resolution Mass Spectrometry ◽  
Rnase A ◽  
Pancreatic Ribonuclease ◽  
X Ray ◽  
X Ray Crystallography ◽  
Model Protein ◽  
Resolution Mass

The interactions between the cytotoxic paddlewheel dirhodium complex [Rh2(μ-O2CCH3)4] and the model protein bovine pancreatic ribonuclease (RNase A) were investigated by high-resolution mass spectrometry and X-ray crystallography.

Syntheses and Structures of Silver(I) and Palladium(II) Complexes with Ferrocenyl-phosphonodithiolate Ligands

2010 ◽  
Vol 65 (1) ◽  
pp. 32-36 ◽  
Author(s):  
Xi-Ying Wang ◽  
Hua-Tian Shi ◽  
Qing Ma ◽  
Qian-Feng Zhang
Keyword(s):  
Mass Spectrometry ◽  
Ir Spectroscopy ◽  
Elemental Analysis ◽  
X Ray ◽  
X Ray Crystallography ◽  
Square Planar

Coordinative interaction of [Ag(PPh3)2NO3] or [Pd(MeCN)2Cl2] with in situ-prepared Na[FcP- (OR)S2] afforded 1 : 1 products [FcP(OR)S2Ag(PPh3)2] (R = Me 1, n-Pr 2) or the 1 : 2 product [{FcP(OMe)S2}2Pd] (3). Complexes 1 - 3 were characterized by elemental analysis, mass spectrometry, NMR (1H, 31P) and IR spectroscopy, as well as by X-ray crystallography. The distorted tetrahedral silver(I) coordination led to non-planar and distorted four-membered AgS2P rings in 1 and 2, whereas the square-planar palladium(II) coordination resulted in four-membered co-planar PdS2P rings in 3

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