Metal Ion Coordination Research Articles

Self-Assembled Metal-Coordination Nanohelices as Efficient and Robust Chiral Supramolecular Catalysts for Enantioselective Reactions.

The development of chiral nanostructures-based supramolecular catalysts with satisfied enantioselectivity remains a significantly more challenging task. Herein, the synthesis and self-assembly of various amino acid amphiphiles as chiral supramolecular catalysts after metal ion coordination is reported and systematically investigate their enantioselectivity in asymmetric Diels-Alder reactions. In particular, the self-assembly of l/d-phenylglycine-based amphiphiles (l/d-PhgC16) and Cu(II) into chiral supramolecular catalysts in the methanol/water solution mixture is described, which features the interesting M/P nanohelices (diameter ≈8nm) and mostly well-aligned M/P nanoribbons (NRs). The M/P supramolecular catalysts show both high but inverse enantioselectivity (>90% ee) in Diels-Alder reactions, while their monomeric counterparts display nearly racemic products. Analysis of the catalytic results suggests the outstanding enantioselectivities are closely related to the specific stereochemical microenvironment provided by the arrangement of the amphiphiles in the supramolecular assembly. Based on the experimental evidence of chirality transfer from supramolecular nanohelices to coordinated Cu(II) and substrate aza-chalcone and the molecular dynamics simulations, the enantioselective catalytic mechanisms are proposed. Moreover, the relationships between molecular structures of amino acid amphiphiles (the hydrophilic head group and hydrophobic alkyl chain length) in supramolecular catalysts and enantioselectivity in Diels-Alder reactions are elaborated.

Synthesis of Dielectric Al-Doped HfO2 Thin Film by Polymer-Assisted Deposition

As transistors scale down, demands for high-k dielectric materials increase. Among various dielectric materials, HfO2 have drawn attention because of its large band gap, high dielectric constant, and excellent physical/chemical stability. Although several solution-based synthesis have been developed, their dielectric properties are inferior to those obtained by conventional vacuum processes (e.g., atomic layer deposition, sputtering). This study demonstrates a solution-based polymer-assisted deposition (PAD) of high-k Al-doped HfO2 thin films exhibiting excellent dielectric properties comparable to the conventional deposition methods. The PAD process enables the control of film thickness (≥3 nm) and the homogenous Al doping in the entire thin film. The key to the success is HCl-mediated coordination of metal ions and polymer. Systematic analysis on the structure and chemical composition of the dielectric layer is carried out. It is found that the phase transition from monoclinic phase to a mixture of tetragonal and amorphous phases results in excellent dielectric properties. The 7.8 nm thick thin film doped with 4.1 at% of Al exhibits a high dielectric constant of 30.2 with a high areal capacitance (674 nF cm−2 at 1.0 kHz), a low leakage current (3.3 × 10−9 A cm−2 at 2.0 MV cm−1), and a high breakdown voltage (7.7 V).

Engineering Synthetic Electron Transfer Chains from Metallopeptide Membranes.

The energetic and geometric features enabling redox chemistry across the copper cupredoxin fold contain key components of electron transfer chains (ETC), which have been extended here by templating the cross-β bilayer assembly of a synthetic nonapeptide, HHQALVFFA-NH2 (K16A), with copper ions. Similar to ETC cupredoxin plastocyanin, these assemblies contain copper sites with blue-shifted (λmax 573 nm) electronic transitions and strongly oxidizing reduction potentials. Electron spin echo envelope modulation and X-ray absorption spectroscopies define square planar Cu(II) sites containing a single His ligand. Restrained molecular dynamics of the cross-β peptide bilayer architecture support metal ion coordination stabilizing the leaflet interface and indicate that the relatively high reduction potential is not simply the result of distorted coordination geometry (entasis). Cyclic voltammetry (CV) supports a charge-hopping mechanism across multiple copper centers placed 10-12 Å apart within the assembled peptide leaflet interface. This metal-templated scaffold accordingly captures the electron shuttle and cupredoxin functionality in a peptide membrane-localized electron transport chain.

Acenaphthenediimine complex-bridged porphyrin porous organic polymer with enriched active sites as a robust water splitting electrocatalyst

To realize efficient water splitting, a highly promising hydrogen evolution reaction (HER) electrocatalyst is needed for the generation of hydrogen. Herein, we demonstrate a novel acenaphthenediimine complex-bridged porphyrin porous organic polymer (NiTAPP-NiACQ) with enriched active metal sites and hierarchical pores. The as-prepared NiTAPP-NiACQ exhibits good long-term durability and remarkable HER performance in 1.0 M KOH with a low overpotential of 117 mV at 10 mA cm−2, which is comparable to many previously reported electrocatalytic HER systems. Furthermore, a simple water-alkali electrolyzer using NiTAPP-NiACQ as the cathode requires a small cell voltage of 1.59 V to deliver a current density of 10 mA cm−2 at room temperature, along with outstanding durability. NiTAPP-NiACQ features not only a metal ion as the catalytic active center in the porphyrin core but also metal ion coordination on the anthraquinone component to promote HER performance, enabling multiple metal ions as the electrocatalytic active sites for the HER reaction. The excellent HER activity of NiTAPP-NiACQ is ascribed to a combination of mechanisms. These findings highlight the viability of porphyrin-derived porous organic polymers in energy conversion processes.

Ferrocene-Based Electrochemical Sensors for Cations

This study investigates novel ferrocene-based electrochemical sensors for metal cation detection via the design, synthesis and characterisation of ferrocene derivatives. Specifically, this research determines the redox potentials of ferrocene versus decamethylferrocene to provide insight into the redox potential variations. The investigation also examines how electrochemical oxidation of the ferrocene moiety can modulate host affinity for transition metal cations via effects such as electrostatic interactions and changes to coordination chemistry. Metal ion coordination to receptors containing functional groups like imine and quinoline is explored to elucidate selectivity mechanisms. These findings advance the fundamental understanding of ferrocene electrochemistry and host–guest interactions, supporting the development of improved cation sensors with optimised recognition properties, sensitivity and selectivity. Overall, this work lays the necessary groundwork for applications in analytical chemistry and sensor technologies via customised ferrocene-derived materials.

Effect of the nature of the chelated metal on the photodynamic activity of metalloporphyrins

Coordination of metal ions by the tetrapyrrolic macrocyclic ring of porphyrin-based photosensitizers (PSs) affects their photophysical properties and consequently, their photodynamic activity. Diamagnetic metals increase the singlet oxygen quantum yield while paramagnetic metals have the opposite effect. Since singlet oxygen is considered the main cell-damaging species in photodynamic therapy (PDT), the nature of the chelated cation would directly affect PDT efficacy. This expectation, however, is not always supported by experimental results and numerous exceptions have been reported. Understanding the effect of the chelated metal is hindered because different chelators were used. The aim of this work was to investigate the effect of the nature of chelated cation on the photophysical and photodynamic properties of metalloporphyrins, using the same tetrapyrrole core as a chelator of Ag(II), Cu(II), Fe(III), In(III), Mn(III), or Zn(II). Results demonstrated that with the exception of Ag(II), all paramagnetic metalloporphyrins were inefficient as generators of singlet oxygen and did not act as PSs. In contrast, the coordination of diamagnetic ions produced highly efficient PSs. The unexpected photodynamic activity of the Ag(II)-containing porphyrin was attributed to reduction of the chelated Ag(II) to Ag(I) or to demetallation of the complex, caused by cellular reductants and/or by exposure to light. Our results indicate that in biological systems, where PSs localize to various organelles and are subjected to the action of enzymes, reactive metabolites, and reducing or oxidizing agents, their physicochemical and photosensitizing properties change. Consequently, the photophysical properties alone cannot predict the anticancer efficacy of a PS.

Design and Modulation of Selectivity toward Vanadium(V) and Uranium(VI) Ions: Coordination Properties and Affinity of Hydroxylamino-Triazine Siderophores.

Based on the strong binding and high selectivity properties of 2,6-bis[hydroxy(methyl)amino]-4-morpholino-1,3,5-triazine (H2bihyat) for [UVIO2]2+, novel binucleating ligands (BLs) N,N',N″,N‴-((1,4-phenylenebis(oxy))bis(1,3,5-triazine-6,2,4-triyl))tetrakis(N-methylhydroxylamine) (H4qtn), N1,N4-bis(4,6-bis(hydroxy(methyl)amino)-1,3,5-triazin-2-yl)benzene-1,4-diamine (H4pdl), and N1,N2-bis(4,6-bis(hydroxy(methyl)amino)-1,3,5-triazin-2-yl)ethane-1,2-diamine (H4enl) were synthesized. Binuclear complexes formed by coordination of hard metal ions with H4qtn are thermodynamically more stable than their mononuclear analogues with H2bihyat due to the increase in entropy accompanying the formation of more chelate rings. Reaction of either H4qtn or H4pdl or H4enl with [UVIO2]2+ and [VVO2]+ resulted in the isolation of the binuclear complexes [(UVIO2)2(μ-qtn)(H2O)4] (1), [(VVO2)2(μ-qtn)][PPh4]2[PPh4] (2), [(UVIO2)2(μ-pdl)(H2O)2(MeOH)2] (3), [(VVO2)2(μ-pdl)][PPh4]2 (4), [(UVIO2)2(μ-enl)(H2O)4] (5), and [(VVO2)2(μ-enl)][PPh4]2 (6). The binuclear complexes 1-6 were characterized by single-crystal X-ray diffraction analysis in solid state and by NMR and ESI-MS in solution. The comparison of the coordination ability of the BLs with either pyridine-2,6-dicarboxylic acid (H2dipic) or H2bihyat or CO32- toward [UVIO2]2+ and [VVO2]+ was investigated by NMR and UV-vis spectroscopies and DFT theoretical calculations, revealing a superior performance of BLs. The selectivity of the BLs for [UVIO2]2+ over [VVO2]+ is decreased compared to that of H2bihyat but increases considerably at pH > 9 values. Formation of the mixed-metal binuclear species [UVIO2(μ-O)VVO2] influences the selectivity and dynamics of the reaction of H4qtn for [UVIO2]2+ and [VVO2]+ in aqueous solution. The results of this study provide crucial information for the ligand design and the development of stronger and more selective systems.

Facile and green fabrication of algal protein/M(n+) hydrogel through coordination with cations for sustained release of vitamin B6

This study presents a facile method to prepare functional hydrogels based on spirulina algae protein/M(n+) and compares its properties with the conventional heat-induced method. Hence, algae protein isolate was extracted at the isoelectric point (pH 3.1) and hydrogels were synthesized through coordination with various cationic metals (Ca2+, Mg2+, Fe3+, Zn2+, and Cu2+) as a cross-linker. Morphological experiments (SEM) showed that the prepared hydrogels had a porous to dense and integrated structure depending on the type and concentration of metal cations. Fourier transform infrared (FTIR) spectra revealed the interaction of protein functional groups with coordinating metal ions. X-ray diffraction (XRD) patterns showed amorphous structures in algal protein/M(n+) hydrogels. The capacity of water absorption was strongly affected by pH and the type of metal cations and was much higher at pH 7.4 (490–801 %) than at acidic pH (pH 2.1, 212–419 %). The maximum release rate of vitamin B6 (83%) was obtained in Ca2+-hydrogels at pH 7.4 after 8 h. The Peppas-Sahlin model showed the best fit with the release profile of vitamin B6 (0.96–0.99), and it was also determined that the release process was based on Fickian diffusion (n ≤ 0.45) or anomalous transport (0.45 < n < 0.89). In conclusion, the study provided a new perspective on the fabrication of algal protein-based hydrogels, suggesting this matrix could be a novel delivery system for the controlled release of drugs/nutrients.

Equipping 1,4,7-Triazacyclononane with Substituents via Solid-Phase Synthesis.

Metal ion complexes frequently show substituted 1,4,7-triazacyclononane (tacn) as the ligand. Besides providing donor atoms for complex formation, tacn serves as a scaffold for equipping the complex with further functional units that are needed for the complementation and electronic tuning of the metal ion coordination sphere and/or add other features, e.g., light-absorbing antennas and groups for bioconjugation. To exploit the full potential of substituted tacn, strategies for directed syntheses of NO(R1,R1,R2) and NO(R1,R2,R3), i.e., tacn with two and even three different substituents R, are needed. Herein, we report a strategy that takes advantage of solid-phase synthesis in the assembly of the precursors NO(R1,R1,H) and NO(R1,R2,H). The assembly of NO(R1,R2,H) is based on a highly selective formation of NO(Cbz,tfAc,H), with Cbz being the link between tacn and solid phase. For this, tacn was loaded onto (4-nitrophenyl carbonate)-resin, thereby forming resin-bound (rb)-tacn, which corresponds to NO(Cbz,H,H) bound to the solid phase. Treatment of rb-tacn with ethyl trifluoroacetate gave rb-NO(tfAc,H), which corresponds to NO(Cbz,tfAc,H). With rb-tacn and rb-NO(tfAc,H) in hand, a variety of NO(R1,R1,H) and NO(R1,R2,H) were prepared, showing the broad applicability of the strategy with respect to the type of substituents and of reactions (nucleophilic substitution, reductive amination, aza-Michael addition, addition to epoxides, acylation). The study also identified limitations and points for improvement.

Sulfur-nitrogen synergistic active sites enable continuous and fast removal of organic pollutants in practical water matrix

The rational design of active sites in nanocarbons are the long-term pursuit for their practical applications. However, N, as the most potential active site, still encounters the problems of low atom utilization efficiency and stability in practical environmental remediation. Herein, we successfully constructed synergistic active sites consisting of graphitic N, pyridinic N, and thiophene S in heavy S, N co-doped hollow graphene spheres (HSNGS). The HSNGS exhibited exceptional efficiency in degrading tetracycline in real water, with a turnover frequency of 6.24 min−1, which is among the highest reported. Moreover, tetracycline dissolved in practical water could be continuously and rapidly eliminated by passing through a column filled with HSNGS, maintaining its high performance even after 40 consecutive cycles. In the synergistic active sites, graphitic N and pyridinic N species accepted electrons from peroxymonosulfate, generating singlet oxygen for tetracycline degradation. Simultaneously, thiophene S coordinated with metal ions present in the practical water, synergistically enhancing the degradation of tetracycline. Additionally, the coordinated metal ions provided protection for the synergistic active sites during peroxymonosulfate activation, preventing their oxidation and enabling the continuous and rapid degradation of tetracycline. This work opens up possibilities for the industrial application of nanocarbon materials in environmental remediation.

Mechanical Enhancement of the Gelatin/Poly(zinc acrylate) Hydrogel Stent in Bile.

Hydrogels with the features of softness, biocompatibility, and modifiability have emerged as excellent materials in the biomedical field. However, the poor mechanical properties of the hydrogels limit their further practical applications. Double-network and metal ion coordination, such as Cu2+ and Zn2+, have achieved a significant reinforcement of the mechanical strength of the hydrogels. Herein, we report a Zn2+-enhanced polyelectrolyte double-network hydrogel stent with a mechanical enhancement phenomenon in bile. The gelatin/poly(zinc acrylate) (PZA) stent was constructed by dip-coating and UV irradiation. Although the mechanical strength of the as-prepared stent was quite weak, it was discovered to be mechanically enhanced by the natural bile. After exploring the effect of different components on the stents according to the components of bile, we found that Ca2+ in bile made a contribution to the mechanical enhancement of the stent. It is envisioned that this bile-enhanced gelatin/PZA stent provides a train of thought for the potential application of hydrogels in the biliary environment.

Concomitant role of metal clusters and ligands in the synthesis and control of porosity in Metal-Organic Frameworks: A literature review

A clossal increase in the number of research articles on metal–organic frameworks (MOFs) have recently been anticipated as next-generation functional materials. The characteristic coordination behavior between metal ion and organic linker in MOFs provide them hydrid functional features of both the moieties. For the substantial improved performance of MOFs and to achieve widespread applications of MOFs in diverse fields, it is essential to develop effective synthetic strategies and understand the role of metal ion cluster or coordination sphere or secondary building units (SBU’s) and organic linker in detail. The augmentation in porosity and large surface area with multitude in diverse topologies provide a boost for the application of these materials in diverse allied fields. This review article provides a detailed introduction of the porous MOF materials; encompassing the role of secondary building units or metal cluster and organic linkers in defining the porosity of MOF materials. Detailed investigations about the role of metal ion clusters and expanded organic linkers that lead to MOFs with ultrahigh porosity have been done and portrayed carefully. The structural aspects of zirconium, zinc and copper cluster based porous MOFs and organic linkers (porphyrin and pyrene based) have been thoroughly portrayed owing to their various application in various fields. This review article will provide better understanding about the various factors involved in synthesis and controll of the porosity toward desired applications.

Bio‐inspired metal ion coordination cross‐linking synergistic strategy to enhance the interfacial properties of carbon fiber composites

AbstractThe application of carbon fiber (CF) in carbon fiber composites has faced limitations due to its surface chemical inertness. To overcome this challenge, this study draws inspiration from metal ion‐enhancing exquisite hierarchical and multiphase structures observed in biological materials. The research proposes a novel approach to enhance the interfacial bonding of CF/Epoxy (E‐51) composites by utilizing tannic acid (TA), carboxylated cellulose nanocrystals (CNCs), Fe3+ ions, and polyvinyl alcohol (PVA). This approach aims to create hydrogen bonding and metal synergistic networks on the surface of CFs through metal ion (Mn+) coordination cross‐linking synergistic (MCCS) interactions. Implementing MCCS strategy resulted in significant improvements in the mechanical properties of the hybrid reinforcements compared to untreated CF composites. The flexural strength, flexural modulus, interlaminar shear strength, and interfacial shear strength experienced respective increase of 50.9%, 72.8% 59.4%, and 61.9%. Moreover, the damping properties of the composites exhibited significant improvements. These positive outcomes can be attributed to the formation of chelation and dense hydrogen bonding networks between TA, Fe3+, CNC, and PVA. Furthermore, CNC and PVA formed cross‐linked nanolayers that effectively deflected cracks and facilitated high energy consumption at the interface. This proposed approach provides a sustainable, environmentally friendly, and efficient method for surface modification in the preparation of high‐performance fiber composites.Highlights Metal ion (Mn+) coordination cross‐linking synergistic strategy is proposed. Tannins/Fe3+/CNCs/PVA form multiphase nanolayers. Metal ion coordination cross‐linking enhances delicate multiphase structures. The prepared carbon fiber composites exhibit excellent properties. The as‐prepared carbon fiber composite has promising applications.

Coordination of Primer Initiation Within the Catalytic Domain of Human PrimPol

To facilitate the eukaryotic repriming pathway of DNA damage tolerance, PrimPol synthesises de novo oligonucleotide primers downstream of polymerase-stalling obstacles. These primers enable replicative polymerases to resume synthesis and ensure the timely completion of DNA replication. Initiating synthesis de novo requires the coordination of single-stranded DNA, initiating nucleotides, and metal ions within PrimPol’s active site to catalyze the formation of the first phosphodiester bond. Here we examine the interactions between human PrimPol’s catalytic domain, nucleotides, and DNA template during each of the various catalytic steps to determine the ‘choreography’ of primer synthesis, where substrates bind in an ordered manner. Our findings show that the ability of PrimPol to conduct de novo primer synthesis is underpinned by a network of stabilising interactions between the enzyme, template, and nucleotides, as we previously observed for related primase CRISPR-Associated Prim-Pol (CAPP). Together, these findings establish a detailed model for the initiation of DNA synthesis by human PrimPol, which appears highly conserved.

Enhanced Mechanical Strength of Metal Ion-Doped MXene-Based Double-Network Hydrogels for Highly Sensitive and Durable Flexible Sensors.

Development of conductive hydrogels with high sensitivity and excellent mechanical properties remains a challenge for constructing flexible sensor devices. Herein, a universal strategy is presented for enhancing the mechanical strength of Mxene-based double-network hydrogels through metal ion coordination effects. Polyacrylamide (PAM)/sodium alginate (SA)/Mxene double-network (PSM-DN) hydrogels were prepared by metal ion impregnation of PAM/SA/Mxene (PSM) hydrogels. High electrical conductivity is achieved due to MXene nanosheets, while the strong coordination bond between metal ions and SA constructs a second network that increases the mechanical strength of the hydrogel by an order of magnitude. Mechanical tests demonstrated that the elastic modulus of hydrogels matches that of human tissues. Hence, they can be used as a highly sensitive electronic skin sensor to recognize the movement of different joints in humans and also as a pressure sensing interface to recognize characters for anticounterfeiting and information transfer. This work can promote the practical application of conductive hydrogels in high-tech fields, such as flexible electronic skin and interface interaction.

Structural and functional insights into the enzymatic plasticity of the SARS-CoV-2 NiRAN domain

The enzymatic activity of the SARS-CoV-2 nidovirus RdRp-associated nucleotidyltransferase (NiRAN) domain is essential for viral propagation, with three distinct activities associated with modification of the nsp9N terminus, NMPylation, RNAylation, and deRNAylation/capping via a GDP-polyribonucleotidyltransferase reaction. The latter two activities comprise an unconventional mechanism for initiating viral RNA 5' cap formation, while the role of NMPylation is unclear. The structural mechanisms for these diverse enzymatic activities have not been properly delineated. Here, we determine high-resolution cryoelectron microscopy (cryo-EM) structures of catalytic intermediates for the NMPylation and deRNAylation/capping reactions, revealing diverse nucleotide binding poses and divalent metal ion coordination sites to promote its repertoire of activities. The deRNAylation/capping structure explains why GDP is a preferred substrate for the capping reaction over GTP. Altogether, these findings enhance our understanding of the promiscuous coronaviral NiRAN domain, a therapeutic target, and provide an accurate structural platform for drug development.

Designed Metal-Containing Peptoid Membranes as Enzyme Mimetics for Catalytic Organophosphate Degradation.

The detoxification of lethal organophosphate (OP) residues in the environment is crucial to prevent human exposure and protect modern society. Despite serving as excellent catalysts for OP degradation, natural enzymes require costly preparation and readily deactivate upon exposure to environmental conditions. Herein, we designed and prepared a series of phosphotriesterase mimics based on stable, self-assembled peptoid membranes to overcome these limitations of the enzymes and effectively catalyze the hydrolysis of dimethyl p-nitrophenyl phosphate (DMNP)─a nerve agent simulant. By covalently attaching metal-binding ligands to peptoid N-termini, we attained enzyme mimetics in the form of surface-functionalized crystalline nanomembranes. These nanomembranes display a precisely controlled arrangement of coordinated metal ions, which resemble the active sites found in phosphotriesterases to promote DMNP hydrolysis. Moreover, using these highly programmable peptoid nanomembranes allows for tuning the local chemical environment of the coordinated metal ion to achieve enhanced hydrolysis activity. Among the crystalline membranes that are active for DMNP degradation, those assembled from peptoids containing bis-quinoline ligands with an adjacent phenyl side chain showed the highest hydrolytic activity with a 219-fold rate acceleration over the background, demonstrating the important role of the hydrophobic environment in proximity to the active sites. Furthermore, these membranes exhibited remarkable stability and were able to retain their catalytic activity after heating to 60 °C and after multiple uses. This work provides insights into the principal features to construct a new class of biomimetic materials with high catalytic efficiency, cost-effectiveness, and reusability applied in nerve agent detoxification.

Strong and Tough Antifreezing Hydrogel Sensor via the Synergy of Coordination and Hydrogen Bonds.

Hydrogel sensors are fascinating as flexible sensors and electronic skin due to their excellent biocompatibility and structure controllability. However, developing conductive hydrogels possessing both excellent mechanical and antifreezing properties for environmental-adaptive sensors remains a challenge. Herein, a strategy of combining betaine and metal ions to construct poly(acrylic acid) (PAA)-based high-conductive hydrogels has been reported. PAA-Al3+/betaine hydrogels with high toughness and antifreezing property were prepared by a one-step UV curing method. Their high toughness is attributed to the coordination of metal ions with the carboxylic groups in PAA, the interaction of betaine with PAA, and the formation of hydrogen bonds between them and water molecules. Moreover, the significant antifreezing property is due to the reduction of free water in the hydrogel. This, in turn, is attributed to the hydration of metal ions and the synergistic hydrogen bonding between betaine and water. The experiments demonstrate that the hydrogel has excellent mechanical property, high conductivity, superior transparency, antiswelling property, antipuncture as well as shape memory properties, and especially, low cytotoxicity. It can be used as a sensor for motion detection and information recognition. This work provides new insights into the application of flexible sensors and human-machine interfaces in multienvironmental conditions.

Structural snapshots of Mycobacterium tuberculosis enolase reveal dual mode of 2PG binding and its implication in enzyme catalysis.

Enolase, a ubiquitous enzyme, catalyzes the reversible conversion of 2-phosphoglycerate (2PG) to phosphoenolpyruvate (PEP) in the glycolytic pathway of organisms of all three domains of life. The underlying mechanism of the 2PG to PEP conversion has been studied in great detail in previous work, however that of the reverse reaction remains to be explored. Here we present structural snapshots of Mycobacterium tuberculosis (Mtb) enolase in apo, PEP-bound and two 2PG-bound forms as it catalyzes the conversion of PEP to 2PG. The two 2PG-bound complex structures differed in the conformation of the bound product (2PG) viz the widely reported canonical conformation and a novel binding pose, which we refer to here as the alternate conformation. Notably, we observed two major differences compared with the forward reaction: the presence of MgB is non-obligatory for the reaction and 2PG assumes an alternate conformation that is likely to facilitate its dissociation from the active site. Molecular dynamics studies and binding free energy calculations further substantiate that the alternate conformation of 2PG causes distortions in both metal ion coordination and hydrogen-bonding interactions, resulting in an increased flexibility of the active-site loops and aiding product release. Taken together, this study presents a probable mechanism involved in PEP to 2PG catalysis that is likely to be mediated by the conformational change of 2PG at the active site.

Palladium Complexes of N-Methylcorroles.

Alkylation of one of the inner-core nitrogen atoms is one possible approach to obtain dianionic corrole ligands, suitable for the coordination of divalent metal ions, such as PdII . Inner-core N-methylation can be obtained by treating the corrole with CH3 I, but the reaction conditions should be optimized to limit the formation of the dimethylated derivative. Two regioisomers, the N-21 and the N-22 methyl derivatives are obtained from the reaction, with the first product achieved in a higher amount. Structural characterization of the reaction products evidenced the distortion induced by the introduction of the methyl groups; the N-methylcorroles are chiral compounds, and the enantiomers were separated by chromatography, with their absolute configuration assigned by ECD computation. Palladium insertion was achieved in the case of monosubstituted corroles, but not with the dimethylated macrocycle; X-ray characterization of the complexes showed the distortion of the macrocycles. The Pd complexes do not show luminescence emission, but are able to produce singlet oxygen upon irradiation. The PdII complexes were also inserted in human serum albumin (HSA) and dispersed in water; in this case, the protein protects the corroles from photobleaching, and a switch from the type II to the type I mechanism in reactive oxygen species (ROS) production is observed.