Metal Coordination Sites Research Articles

Periplasmic HupE region-Ni2+ interactions: Thermodynamics, binding mode and competition with Cu2+ and Zn2+

Nickel ions are the key element of metabolism in numerous lower organisms. They are required for the activity of nine enzymes, e.g. [NiFe] hydrogenase, which catalyzes the reversible oxidation of molecular hydrogen for energy production. Nickel homeostasis and nickel transport into the cell are strictly controlled.HupE is a transmembrane nickel transporter in Rhizobium leguminosarum hydrogenase system which has a conserved, periplasmic, N-terminal domain responsible for nickel binding. This work focuses on the interactions of this region with native Ni2+ and two other metal ions (Cu2+ and Zn2+), which might interfere with nickel binding to the HupE fragment. Metal coordination sites are assigned and thermodynamic parameters are discussed in detail in order to evaluate the potential effectiveness of different soil concentrations of Cu2+ and Zn2+ to displace Ni2+ from its binding site.At physiological pH, the coordination sphere of all three metal complexes consists of the imidazole and amine nitrogens of His1 (a histamine-like binding) and of the imidazole of His5. Cu2+ is able to displace Ni2+ from its binding site, while Zn2+ cannot, neither at equimolar concentrations, nor at soil metal concentrations at which Rhizobium leguminosarum numbers are expected to decrease by several orders of magnitude.

A Typical Metal‐Ion‐Responsive Color‐Tunable Emitting Insulated π‐Conjugated Polymer Film

AbstractWe report the synthesis of an insulated π‐conjugated polymer containing 2,2′‐bipyridine moieties as metal coordination sites. Metal coordination to the polymer enabled easy and reversible tuning of the luminescent color without changes to the main chain skeleton. The permethylated α‐cyclodextrin (PM α‐CD)‐based insulation structure allowed the metalated polymers to demonstrate efficient emission even in the solid state, with identical spectral shapes to the dilute solutions. In addition, the coordination ability of the metal‐free polymer was maintained in the solid state, resulting in reversible changes in the luminescent color in response to the metal ions. The synthesized polymer is expected to be suitable for application in recyclable luminescent sensors to distinguish different metal ions.

A Typical Metal-Ion-Responsive Color-Tunable Emitting Insulated π-Conjugated Polymer Film.

We report the synthesis of an insulated π-conjugated polymer containing 2,2'-bipyridine moieties as metal coordination sites. Metal coordination to the polymer enabled easy and reversible tuning of the luminescent color without changes to the main chain skeleton. The permethylated α-cyclodextrin (PM α-CD)-based insulation structure allowed the metalated polymers to demonstrate efficient emission even in the solid state, with identical spectral shapes to the dilute solutions. In addition, the coordination ability of the metal-free polymer was maintained in the solid state, resulting in reversible changes in the luminescent color in response to the metal ions. The synthesized polymer is expected to be suitable for application in recyclable luminescent sensors to distinguish different metal ions.

Capturing Guest Dynamics in Metal-Organic Framework CPO-27-M (M = Mg, Zn) by (2)H Solid-State NMR Spectroscopy.

Metal-organic frameworks (MOFs) are promising porous materials for gas separation and storage as well as sensing. In particular, a series of isostructural MOFs with coordinately unsaturated metal centers, namely, CPO-27-M or M-MOF-74 (M = Mg, Zn, Mn, Fe, Ni, Co, Cu), have shown exceptional adsorption capacity and selectivity compared to those of classical MOFs that contain only fully coordinated metal sites. Although it is widely accepted that the interaction between guest molecules and exposed metal centers is responsible for good selectivity and large maximum uptake, the investigation of such guest-metal interaction is very challenging because adsorbed molecules are usually disordered in the pores and undergo rapid thermal motions. (2)H solid-state NMR (SSNMR) spectroscopy is one of the most extensively used techniques for capturing guest dynamics in porous materials. In this work, variable-temperature (2)H wide-line SSNMR experiments were performed on CPO-27-M (M = Mg, Zn) loaded with four prototypical guest molecules: D2O, CD3CN, acetone-d6, and C6D6. The results indicate that different guest molecules possess distinct dynamic behaviors inside the channel of CPO-27-M. For a given guest molecule, its dynamic behavior also depends on the nature of the metal centers. The binding strength of guest molecules is discussed on the basis of the (2)H SSNMR data.

Structural and Functional Investigation of the Ag(+)/Cu(+) Binding Domains of the Periplasmic Adaptor Protein SilB from Cupriavidus metallidurans CH34.

Silver ion resistance in bacteria mainly relies on efflux systems, and notably on tripartite efflux complexes involving a transporter from the resistance-nodulation-cell division (RND) superfamily, such as the SilCBA system from Cupriavidus metallidurans CH34. The periplasmic adaptor protein SilB hosts two specific metal coordination sites, located in the N-terminal and C-terminal domains, respectively, that are believed to play a different role in the efflux mechanism and the trafficking of metal ions from the periplasm to the RND transporter. On the basis of the known domain structure of periplasmic adaptor proteins, we designed different protein constructs derived from SilB domains with either one or two metal binding sites per protein chain. ITC data acquired on proteins with single metal sites suggest a slightly higher affinity of Ag(+) for the N-terminal metal site, compared to that for the C-terminal one. Remarkably, via the study of a protein construct featuring both metal sites, nuclear magnetic resonance (NMR) and fluorescence spectroscopies concordantly show that the C-terminal site is saturated prior to the N-terminal one. The C-terminal binding site is supposed to transfer the metal ions to the RND protein, while the transport driven by this latter is activated upon binding of the metal ion to the N-terminal site. Our results suggest that the filling of the C-terminal metal site is a key prerequisite for preventing futile activation of the transport system. Exhaustive NMR studies reveal for the first time the structure and dynamics of the functionally important N-terminal domain connected to the membrane proximal domain as well as of its Ag(+) binding site.

Framework Cationization by Preemptive Coordination of Open Metal Sites for Anion-Exchange Encapsulation of Nucleotides and Coenzymes.

Cationic frameworks can selectively trap anions through ion exchange, and have applications in ion chromatography and drug delivery. However, cationic frameworks are much rarer than anionic or neutral ones. Herein, we propose a concept, preemptive coordination (PC), for targeting positively charged metal-organic frameworks (P-MOFs). PC refers to proactive blocking of metal coordination sites to preclude their occupation by neutralizing ligands such as OH(-) . We use 20 MOFs to show that this PC concept is an effective approach for developing P-MOFs whose high stability, porosity, and anion-exchange capability allow immobilization of anionic nucleotides and coenzymes, in addition to charge- and size-selective capture or separation of organic dyes. The CO2 and C2 H2 uptake capacity of 117.9 cm(3) g(-1) and 148.5 cm(3) g(-1) , respectively, at 273 K and 1 atm, is exceptionally high among cationic framework materials.

Framework Cationization by Preemptive Coordination of Open Metal Sites for Anion‐Exchange Encapsulation of Nucleotides and Coenzymes

AbstractCationic frameworks can selectively trap anions through ion exchange, and have applications in ion chromatography and drug delivery. However, cationic frameworks are much rarer than anionic or neutral ones. Herein, we propose a concept, preemptive coordination (PC), for targeting positively charged metal–organic frameworks (P‐MOFs). PC refers to proactive blocking of metal coordination sites to preclude their occupation by neutralizing ligands such as OH−. We use 20 MOFs to show that this PC concept is an effective approach for developing P‐MOFs whose high stability, porosity, and anion‐exchange capability allow immobilization of anionic nucleotides and coenzymes, in addition to charge‐ and size‐selective capture or separation of organic dyes. The CO2 and C2H2 uptake capacity of 117.9 cm3 g−1 and 148.5 cm3 g−1, respectively, at 273 K and 1 atm, is exceptionally high among cationic framework materials.

Probing the roles of two tryptophans surrounding the unique zinc coordination site in lipase family I.5.

A unique zinc domain found in all of the identified members of the lipase family I.5 is surrounded by two conserved tryptophans (W61 and W212). In this study, we investigated the role of these hydrophobic residues in thermostability and thermoactivity of the lipase from Bacillus thermocatenulatus (BTL2) taken as the representative of the family. Circular dichroism spectroscopy revealed that the secondary structure of BTL2 is conserved by the tryptophan mutations (W61A, W212A, and W61A/W212A), and that W61 is located in a more rigid and less solvent exposed region than is W212. Thermal denaturation and optimal activity analyses pointed out that zinc induces thermostability and thermoactivity of BTL2, in which both tryptophans W61 and W212 play contributing roles. Molecular explanations describing the roles of these tryptophans were pursued by X-ray crystallography of the open form of the W61A mutant and molecular dynamics simulations which highlighted a critical function for W212 in zinc binding to the coordination site. This study reflects the potential use of hydrophobic amino acids in vicinity of metal coordination sites in lipase biocatalysts design.

Photochemistry of a Puckered Ferracyclobutadiene in Liquid Solution Studied by Time-Resolved Fourier-Transform Infrared Spectroscopy.

Flash photolysis combined with step-scan and rapid-scan Fourier-transform infrared spectroscopy was carried out to explore the photochemistry of a puckered, quasi-square pyramidal ferracyclobutadiene, [Fe{κ(2) -C3 (NEt2 )3 }(CO)3 ]BF4 ([1]BF4 ), that features three additional carbonyl ligands in the metal coordination sphere. In liquid solution at room temperature, an excitation with λ=355 nm light resulted in the loss of one CO ligand, which is cleaved from a basal metal-coordination site. Within the time resolution of the experiment, a solvent molecule promptly refills the resultant vacancy at the coordinatively unsaturated metal center. In the weakly interacting liquid, dichloromethane, the counterion of the complex is subsequently able to substitute the solvent in the coordination sphere of the iron center, thereby forming as a stable product a neutral dicarbonyl tetrafluoroborato iron(0) species containing a four-membered ferracycle.

Metal–organic frameworks for alcohol gas sensor

Metal–organic frameworks (MOFs) containing unsaturated coordination metal(II) sites (or open metal sites) have shown high selectivity for gas adsorption, separation and chemical sensor applications. The compound Zn3(btc)2·12H2O (Zn-btc), a coordination polymer with specific binding sites for guest molecules consist of Zn(II) ions and benzene tricarboxylic acid (btc) as anionic organic linkers, stabilized by numerous hydrogen bonds from crystal water molecules was synthesized. For the first time alcohol gas sensing interaction with Zn-btc framework was studied by using work function change methods. The as prepared Zn-btc thin layers show good response with reference to the alcohol concentration, chain length and a pronounced influence of humidity. The results are interpreted starting from the known crystal structure of Zn-btc. It is argued that the sensing mechanism is based on the exchange of Zn-coordinated water against alcohol molecules. The unfavourable loss of hydrogen bonds when replacing water against alcohol in the structure can be partially balanced by van der Waals interactions between alcohols alkyl chains and the aromatic rings of the btc linker molecules. These non-polar interactions should also be responsible for the work function change induced by alcohol adsorption in the framework.

DFT study on the tautomerism of organic linker 1H-imidazole-4,5-tetrazole (HIT)

In this study the tautomerism of 1H-imidazole-4,5-tetrazole (HIT) are investigated in liquid and gas phases using density functional theory. The intramolecular hydrogen bond proves to be the key factor for the stability and the chemical properties of the tautomers. Boltzmann population analysis shows that the probability for the existence of the most stable tautomers is prominent in both gas and liquid phases. The dipole moment of all the tautomers increases with increase in polarity of the medium considered. 15N NMR and 13C NMR chemical shift along with MESP predict that the nitrogen atoms in both tetrazole and imidazole rings are excellent metal coordination sites. The pKa value predicts that the tautomers to be acidic in nature. A linear relationship between the redox potential and the ionization potential shows that all the tautomers tend to lose electrons, hence can coordinate with metals strongly.

Models for the Metal Transfer Complex of the N-Terminal Region of CusB and CusF.

The tripartite CusCFBA pump in Escherichia coli is a very effective heavy metal extrusion system specific for Cu(I) and Ag(I). The N-terminal region of the membrane fusion protein CusB (CusB-NT) is highly disordered, and hence, experimentally characterizing its structure is challenging. In a previous study, this disorder was confirmed with molecular dynamics simulations, although some key structural elements were determined. It was experimentally shown that CusB-NT is fully functional in transferring the metal from the metallochaperone CusF. In this study, we docked these two entities together and formed two representative metal coordination modes, which consist of residues from both proteins. In this way, we created two potential CusB-NT/CusF complexes that share coordination of Cu(I) and thereby represent structural models for the metal transfer process. Each model complex was simulated for 4 μs. The previously observed structural disorder in CusB-NT disappeared upon complexation with CusF. The only differences between the two models occurred in the M21-M36 loop region of CusB-NT and the open flap of CusF: we observed the model with two CusB-NT methionine residues and a CusF methionine as the metal coordination site (termed "MMM") to be more stable than the model with a CusB-NT methionine, a CusF methionine, and a CusF histidine ligating the metal (termed "MMH"). The observed stability of the MMM model was probed for an additional 2 μs, yielding a total simulation time of 6 μs. We hypothesize that both MMM and MMH configurations might take part in the metal exchange process in which the MMH configuration would appear first and would be followed by the MMM configuration. Given the experimental finding of comparable binding affinities of CusB-NT and CusF, the increased stability of the MMM configuration might be a determinant for the transfer from CusF to CusB-NT. The metal would be transferred from the more CusF-dominated metal binding environment (MMH model) to a more CusB-dominated one (MMM model) in which the coordination environment is more stable. From the MMM model, the metal ion would ultimately be coordinated by the CusB methionines only, which would complete the Cu(I) transfer process.

Computation and Functional Studies Provide a Model for the Structure of the Zinc Transporter hZIP4

Members of the Zrt and Irt protein (ZIP) family are a central participant in transition metal homeostasis as they function to increase the cytosolic concentration of zinc and/or iron. However, the lack of a crystal structure hinders elucidation of the molecular mechanism of ZIP proteins. Here, we employed GREMLIN, a co-evolution-based contact prediction approach in conjunction with the Rosetta structure prediction program to construct a structural model of the human (h) ZIP4 transporter. The predicted contact data are best fit by modeling hZIP4 as a dimer. Mutagenesis of residues that comprise a central putative hZIP4 transmembrane transition metal coordination site in the structural model alter the kinetics and specificity of hZIP4. Comparison of the hZIP4 dimer model to all known membrane protein structures identifies the 12-transmembrane monomeric Piriformospora indica phosphate transporter (PiPT), a member of the major facilitator superfamily (MFS), as a likely structural homolog.

Cu(II)-Metal–Organic Framework with Open Coordination Metal Sites for Low Temperature Thermochemical Water Oxidation

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTCu(II)-Metal–Organic Framework with Open Coordination Metal Sites for Low Temperature Thermochemical Water OxidationJian-Ping Ma*, Shen-Qing Wang, Chao-Wei Zhao, Yang Yu, and Yu-Bin Dong*View Author Information College of Chemistry, Chemical Engineering and Materials Science, Collaborative Innovation Center of Functionalized Probes for Chemical Imaging in Universities of Shandong, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan 250014, P. R. China*(Y.-B.D.) E-mail: [email protected]*(J.P.M.) E-mail: [email protected]Cite this: Chem. Mater. 2015, 27, 11, 3805–3808Publication Date (Web):May 13, 2015Publication History Received27 February 2015Revised13 May 2015Published online18 May 2015Published inissue 9 June 2015https://doi.org/10.1021/acs.chemmater.5b00754Copyright © 2015 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views2533Altmetric-Citations26LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit Read OnlinePDF (3 MB) Get e-AlertsSupporting Info (3)»Supporting Information Supporting Information SUBJECTS:Hydrothermal reactions,Metal organic frameworks,Molecules,Solution chemistry,Water oxidation Get e-Alerts

Synthesis, structure, photo- and electroluminescent properties of zinc(II) complexes with aminomethylene derivatives of 1-phenyl-3-methyl-4-formylpyrazol-5-one and 3- and 6-aminoquinolines

Quinolyl-3-pyrazole (I) and quinolyl-6-pyrazole (II) azomethines have been used as precursors to novel zinc complexes (III, IV, correspondingly) that have been synthesized and thoroughly investigated by IR, UV–vis, NMR 1H spectroscopy. The atomic structure of the complexes was determined by quantum-chemical calculations (DFT-optimization of the molecules geometry). The results obtained were compared with quantitative characteristics of the local atomic environment of zinc ions derived from Zn K-edge EXAFS. Theoretical and experimental data on the bond lengths within the metal coordination sites are in a good agreement. Bands in experimental UV–vis spectra have been assigned based on computational results. Photo- and electroluminescent properties of zinc complexes have been investigated. The photoluminescence maximum occurs around λ=478nm for both compounds. Prototypes of electroluminescent devices utilizing the complexes as active media were designed and tested. The device with III as the electroluminescent layer shows a luminance of 800Cd/m2 at 10V with conversion efficiency of 0.5Lm/W, whereas the device with IV as the electroluminescent layer demonstrates somewhat lower characteristics, viz., 200Cd/m2 at 13V.

ChemInform Abstract: Pyridine Coordination Chemistry for Molecular Assemblies on Surfaces

AbstractReview: 50 refs.

Clean Hydrogen Release from Ammonia Borane in a Metal–Organic Framework with Unsaturated Coordinated Tm3+

A hybrid of ammonia borane (AB) and a metal–organic framework (MOF), which contains unsaturated coordinated Tm3+, Tm(BTC) (BTC = 1,3,5-benzenetricarboxylic), was synthesized through the solvent-based impregnation method (named as AB@Tm(BTC)–CH3OH). Also two other materials AB@Tm(BTC)-milled and AB@Tm2O3-milled were prepared by physical milling separately. TPD-MS results show that the H2-release peaks of the three materials shift to lower temperature, 77, 79, and 85 °C, respectively, compared with neat AB (114 and 150 °C). To avoid the undesirable volatile byproduct, only AB@Tm(BTC)–CH3OH shows superior performance without any byproduct, especially ammonia. The three samples exhibit enhanced dehydrogenation kinetics compared to neat AB, but AB@Tm2O3-milled presents much slower than the other two materials. The dehydrogenation activation energies of AB@Tm(BTC)–CH3OH, AB@Tm(BTC)-milled, and AB@Tm2O3-milled are 98.1, 103.1, and 116.4 kJ·mol–1, respectively. The mechanisms of the AB@MOF thermal dehydrogenation system especially for the prevention of ammonia have been discussed. The interaction between AB and the unsaturated coordinated metal sites in MOFs plays a key role for inhibiting ammonia during AB thermolysis.

Pyridine coordination chemistry for molecular assemblies on surfaces.

CONSPECTUS: Since the first description of coordination complexes, many types of metal-ligand interactions have creatively been used in the chemical sciences. The rich coordination chemistry of pyridine-type ligands has contributed significantly to the incorporation of diverse metal ions into functional materials. Here we discuss molecular assemblies (MAs) formed with a variety of pyridine-type compounds and a metal containing cross-linker (e.g., PdCl2(PhCN2)). These MAs are formed using Layer-by-Layer (LbL) deposition from solution that allows for precise fitting of the assembly properties through molecular programming. The position of each component can be controlled by altering the assembly sequence, while the degree of intermolecular interactions can be varied by the level of π-conjugation and the availability of metal coordination sites. By setting the structural parameters (e.g., bond angles, number of coordination sites, geometry) of the ligand, control over MA structure was achieved, resulting in surface-confined metal-organic networks and oligomers. Unlike MAs that are constructed with organic ligands, MAs with polypyridyl complexes of ruthenium, osmium, and cobalt are active participants in their own formation and amplify the growth of the incoming molecular layer. Such a self-propagating behavior for molecular systems is rare, and the mechanism of their formation will be discussed. These exponentially growing MAs are capable of storing metal salts that can be used during the buildup of additional molecular layers. Various parameters influencing the film growth mechanism will be presented, including (i) the number of binding sites and geometry of the organic ligands, (ii) the metal and the structure of the polypyridyl complexes, (iii) the influence of the metal cross-linker (e.g., second or third row transition metals), and (iv) the deposition conditions. By systematic variation of these parameters, switching between linear and exponential growth could be demonstrated for MAs containing structurally well-defined polypyridyl complexes. The porosity of the MAs has been estimated by using electrochemically active probes. Incorporating multiple polypyridyl complexes of osmium and ruthenium into a single assembly give rise to composite materials that exhibit interesting electrochemical and electrochromic properties. These functional composites are especially attractive as they exhibit properties that neither of each metal complex possesses individually. Some of our MAs have very high coloration efficiencies, redox stability, fast responsive times and operate at voltages < 1.5 V. Moreover, their electrochemical properties are dependent on the deposition sequence of the polypyridyl complexes, resulting in MAs that possesses distinctive electron transfer pathways. Finally, some of these MAs are described in terms of their practical applications in electrochromic materials, storage-release chemistry, solar cells, and electron transport properties.

Mid‐ and Far‐Infrared Marker Bands of the Metal Coordination Sites of the Histidine Side Chains in the Protein Cu,Zn‐Superoxide Dismutase

AbstractVibrational spectroscopy gives important information on the properties of ligand and metal–ligand bonds in metalloenzymes. Infrared spectroscopy is appealing for the study of metal active sites that are not amenable to Raman spectroscopy. We present a combined experimental and theoretical approach to analyze the mid‐ and far‐IR spectra of Cu,Zn‐superoxide dismutase (Cu,Zn‐SOD) as a probe of the histidine ligands. This metalloenzyme provides a unique model to identify specific IR signatures of metal–histidine coordination and to study their alterations as a function of the metal (copper/zinc), the copper valence state (+I/+II), the histidine coordination mode (Nτ and Nπ) and the histidine protonation state. DFT calculations combined with normal mode descriptions from potential energy distribution calculations were performed on two slightly different cluster models. Differences in the constraints at the side chain of one histidine Cu ligand sensibly modify the geometric parameters and vibrational properties. Electrochemically induced FTIR difference spectroscopy provided mid‐ and far‐IR fingerprint spectra of the Cu protein in aqueous media that are sensitive to the redox state of the Cu centre at the active site. Comparisons of the DFT predictions with the experimental IR modes of the histidine ligands at the Cu,Zn‐SOD active site showed that useful mid‐IR markers of histidine Nτ and Nπ coordination were predicted with good accuracy. The DFT analysis further demonstrated a link between the ν(C4–C5) mode frequency of His46 and the specific properties of the His46–Cu bond in Cu,Zn‐SOD. A combined theoretical and experimental approach on samples in H2O and 2H2O or 15N‐labelled samples identified the contributions from the histidine side chain modes in the 669–629 cm–1 region.

Metal-ion effects on the polarization of metal-bound water and infrared vibrational modes of the coordinated metal center of Mycobacterium tuberculosis pyrazinamidase via quantum mechanical calculations.

Mycobacterium tuberculosis pyrazinamidase (PZAse) is a key enzyme to activate the pro-drug pyrazinamide (PZA). PZAse is a metalloenzyme that coordinates in vitro different divalent metal cofactors in the metal coordination site (MCS). Several metals including Co2+, Mn2+, and Zn2+ are able to reactivate the metal-depleted PZAse in vitro. We use quantum mechanical calculations to investigate the Zn2+, Fe2+, and Mn2+ metal cofactor effects on the local MCS structure, metal–ligand or metal–residue binding energy, and charge distribution. Results suggest that the major metal-dependent changes occur in the metal–ligand binding energy and charge distribution. Zn2+ shows the highest binding energy to the ligands (residues). In addition, Zn2+ and Mn2+ within the PZAse MCS highly polarize the O–H bond of coordinated water molecules in comparison with Fe2+. This suggests that the coordination of Zn2+ or Mn2+ to the PZAse protein facilitates the deprotonation of coordinated water to generate a nucleophile for catalysis as in carboxypeptidase A. Because metal ion binding is relevant to enzymatic reaction, identification of the metal binding event is important. The infrared vibrational mode shift of the C=Nε (His) bond from the M. tuberculosis MCS is the best IR probe to metal complexation.