Structural Insight into Binary Protein Metal–Organic Frameworks with Ferritin Nanocages as Linkers and Nickel Clusters as Nodes

Metal–organic frameworks (MOFs) hold great promise for numerous applications. However, proteins, carriers of biological functions in living systems, have not yet been fully explored as building blocks for the construction of MOFs. This work presents a strategy for the fabrication of binary MOFs. Considering octahedral ferritin symmetry, four His₂ (His–His) motifs were first incorporated into the exterior surface of a ferritin nanocage near each C₄ channel, yielding protein linkers with multiple metal-binding sites (bisH-SF). Secondly, by adding nickel ions to bisH-SF solutions triggers the self-assembly of ferritin nanocages into a porous 3D crystalline MOF with designed protein lattice, where two adjacent ferritin molecules along the C₄ symmetry axes are bridged by four dinuclear or tetranuclear nickel clusters depending on Ni²⁺ concentration. This work provides a simple approach for precise control over a binary protein–metal crystalline framework, and the resulting MOFs exhibited inherent ferroxidase activity and peroxidase-like catalytic activity.     

A Non‐Invasive NMR Method Based on Histidine Imidazoles to Analyze the pH‐Modulation of Protein–Nucleic Acid Interfaces

A useful ²J(N?H) coupling‐based NMR spectroscopic approach is proposed to unveil, at the molecular level, the contribution of the imidazole groups of histidines from RNA/DNA‐binding proteins on the modulation of binding to nucleic acids by pH. Such protonation/deprotonation events have been monitored on the single His96 located at the second RNA/DNA recognition motif (RRM2) of T‐cell intracellular antigen‐1 (TIA‐1) protein. The pK_a values of the His96 ionizable groups were substantially higher in the complexes with short U‐rich RNA and T‐rich DNA oligonucleotides than those of the isolated TIA‐1 RRM2. Herein, the methodology applied to determine changes in pK_a of histidine side chains upon DNA/RNA binding, gives valuable information to understand the pH effect on multidomain DNA/RNA‐binding proteins that shuttle among different cellular compartments.     

A Convenient Synthesis of New Macrocyclic Thioether-Esters and Ether-Esters: Extraction Properties of These Esters for Alkali,Alkaline Earth,and Transition Metal Cations

Macrocyclic thioether-esters and ether-esters have been prepared by treating 2,2′-dithiobenzoic acid dichloride and 1,2-benzendicarboxylic acid dichloride with appropriate glycols or dithiol. The complexing ability of these thioether-esters and ether-esters toward Li⁺, Na⁺, K⁺, Mg ^{2 +} , Ca ^{2 +} , Sr ²⁺ , Ba ^{2 +} , Co ^{2 +} , and Ni ^{2 +} has been measured by the solvent extraction method. The extraction data indicate that compound 2 exhibits stronger selectivity toward Li⁺, 3 toward Ba ^{2 +} , 4 toward K⁺, 5 toward Mg ^{2 +} , 6 toward Ba ^{2 +} and Sr ^{2 +} , and 7 toward Co ^{2 +} and Ni ^{2 +} when compared with other cations.     

Insight into the Complexation Mode of Bis(nitrilotriacetic acid) (NTA) Ligands with Ni2+ Involved in the Labeling of Histidine‐Tagged Proteins

According to literature reports and our own findings, the binding of new Ni²⁺‐preloaded bis(nitrilotriacetic acid) (NTA) ligands with polyhistidine‐tagged proteins has been found to be accompanied by a one‐ to two‐order‐of‐magnitude increase in affinity, compared to the binding of a single Ni²⁺‐preloaded NTA moiety. In spite of the introduction of a second NTA chelating group, a cooperative effect that is less than the theoretical maximum has been observed. Herein, we present a rational explanation for the observed stability of the ternary complex involving the postulated bis‐NTA–(Ni²⁺)₂ species and multivalent polyhistidine tags. We have found that prior to the formation of the ternary complex, the Ni²⁺‐preloading step of bis‐NTA ligands does not form the expected bis‐NTA–(Ni²⁺)₂ exclusively. Instead of the major formation of bis‐NTA–(Ni²⁺)₂ species, it appears that cyclic discrete 1:1 and 2:2 entities are predominantly formed. It is proposed that these species interact upon ring‐opening with multivalent histidine tags. The occurrence of this phenomena accounts for the overall one‐ to two‐order‐of‐magnitude increase in affinity of ternary complexes involving bis‐NTA ligands.     

Substrate-induced adjustment of “slipped” π–π stacking: en route to obtain 1D sandwich chain and higher order self-assembly supramolecular structures in solid state

‘Slipped’ π?π stacking between flexible macrocycle 1⁴⁺ (cyclo[2](2,6-di(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylene benzene)) and neutral small molecules induce one-dimensional (1D) ‘sandwich’ chain self-assembly. Unlike most of the reported π?π stacking system, the 1D “sandwich” chain expands with the direction parallel to stacking π surfaces on 1⁴⁺ and that on molecule 2, 3, 4 or 5 (2 = p-xylene, 3 = benzene-1,4-diamine, 4 = 4,4′-bipyridine, 5 = [1,1′-biphenyl]-4,4′-diol). Moreover, the π?π stacking modes of 1D self-assembly are seriously small molecule adduct dependent. Combined with the other weak interactions (e.g. intermolecular hydrogen bonding), the new substrate design and control strategy can expand the 1D ‘sandwich’ chain (e.g. [1⁴⁺·4]_n) into higher order structure (e.g. two-dimensional (2D) network [1⁴⁺·4·6]_n, 6 = hydroquinone) even in large scale (~280 mg). This 2D network structure, which keeps stable under 423 K, shows highly selective gas absorption of CO₂ over N₂.     

Dimorphic Modification of the Trinuclear Nickel(II) Complex [Ni3(NCS)6(pdz)6]: Synthesis,Crystal Structure,Thermal, Magnetic and Spectroscopic Properties

Reaction of nickel(II) thiocyanate and pyridazine (pdz) as organic spacer ligand leads to the formation of the ligand‐rich 1:2 (1:2 = metal to ligand ratio) trinuclear nickel(II) complex of composition [Ni₃(NCS)₆(pdz)₆]. Depending on the reaction solvent, different polymorphic modifications are obtained: Reaction in acetonitrile leads to the formation of the new modification 1I and reaction in ethanol leads to the formation of modification 1II reported recently. In their crystal structures discrete [Ni₃(NCS)₆(pdz)₆] units are found, in which each of the Ni²⁺ cations exhibits a NiN₆ distorted octahedral arrangement. The central Ni²⁺ cation is coordinated by four bridging pdz ligands and two thiocyanato anions in trans positions. Both thiocyanato anions exhibit the end‐on bridging mode. The peripheral Ni²⁺ cations are bridged by one thiocyanato anion and by two pdz ligands with the central Ni²⁺ cation. Further they are coordinated by two terminal N‐bonded thiocyanato anions and one terminal N‐bonded pdz ligand. The structure of 1I was determined by X‐ray single crystal structure investigation and emphasized by infrared spectroscopy. Magnetic measurements revealed a quasi Curie behavior with net ferromagnetic interactions for 1I and net antiferromagnetic interactions for 1II . Solvent‐mediated conversion experiments clearly show that modification 1I represents the thermodynamic most stable form at room temperature and that modification 1II is metastable. On thermal decomposition, both modification transform quantitatively in a new ligand‐deficient intermediate. Elemental analysis revealed a 3:4 compound of composition [Ni₃(NCS)₆(pdz)₄]. A structure model supported by IR spectroscopic investigations was assumed, in which three coordination modes of the thiocyanato anion exist, resulting in a 2D polymeric network.     

Syntheses,crystal structures,and DNA-binding of some nickel(II) complexes of 1,3-bis(2-pyridylmethylthio)propane and pseudohalides

A series of neutral octahedral nickel(II) complexes of 1,3-bis(2-pyridylmethylthio)propane (L) and pseudohalide (X), formulated as [Ni^II(L)X₂] (where X?=?azide (1), cyanate (2), and isothiocyanate (3)), was synthesized. The complexes were characterized by physico-chemical and spectroscopic methods, and 1 and 3 also by single-crystal X-ray diffraction analyses. The structural study shows nickel in a distorted octahedral geometry comprised of the tetradentate NSSN ligand with trans pyridines and monocoordinated pseudohalides in cis positions. In dimethylformamide solution, the complexes had quasi-reversible Ni^II/Ni^III redox couples in cyclic voltammograms with E _1/2 values of +0.732, +0.747, and +0.815?V for 1, 2, and 3, respectively. To examine the biological activities of these complexes, interaction of 3 with calf thymus DNA was studied spectroscopically, showing groove-binding interaction.     

2,7-萘二磺酸阴离子导向五元瓜环基超分子自组装体的制备及其荧光检测性能

通过引入2,7-萘二磺酸(2,7-NDA^2-)阴离子作为结构导向剂,与五元瓜环(Q[5])和过渡金属离子(Co²⁺、Ni²⁺、Zn²⁺、Cd²⁺)在水热条件下制备了4种新颖的Q[5]基超分子自组装体(Q[5]-SA),即{[M (H₂O)₄(Q[5])]·(NDA)}·xH₂O (M=Co (1)、Ni (2)、Zn (3))和{[Cd₂Cl₂(H₂O)₄(Q[5])]·(NDA)}·13H₂O (4)。单晶X射线衍射测试结果表明,自组装体1~3同构,其中Q[5]仅一端的部分端口羰基氧原子与金属离子配位形成简单配合物;而4中Q[5]的2个端口均与金属离子Cd²⁺配位形成了一维配位链。在自组装体1~4中,配体2,7-H₂NDA均全脱质子,形成2,7-NDA^2-阴离子平衡体系电荷,但均未能与金属离子配位,而在2,7-NDA^2-阴离子与Q[5]外壁之间的瓜环外壁作用下进一步形成三维超分子结构。此外,还研究了自组装体1和4的荧光传感性能,结果表明它们都能够作为抗生素诺氟沙星(NFX)的比率型荧光探针。     

Preparation of thermosensitive,calix[4]arene incorporated P(NIPAM‐co‐HBCalix) hydrogel as a reusable adsorbent of nickel(II) ions

A calix‐conjugated thermo‐responsive hydrogel containing 15% tetra(5‐hexenyloxy)‐p‐tert‐butylcalix[4]arene (HBCalix), P(NIPAM‐co‐HBCalix), was used to remove nickel(II) ions from water. Both thermo‐sensitive properties and the Ni²⁺‐adsorption capabilities of the prepared P(NIPAM‐co‐HBCalix) hydrogels are investigated. Introduction of the monomer HBCalix considerably enhanced the adsorption of Ni²⁺ onto the hydrogel by chelation between hexenyloxy groups and metal ion. When HBCalix units capture Ni²⁺ and forms HBCalix/Ni²⁺ host–guest complexes, the lower critical solution temperature of the hydrogel shifts to a higher temperature due to both the repulsion between charged HBCali/Ni²⁺ groups and the osmotic pressure within the hydrogel. Adsorption studies were carried out by varying contact time, counter ion and initial concentration of Ni²⁺. The evaluation of adsorption properties showed that the hydrogel exhibited better correlation with Langmuir isotherm model. P(NIPAM‐co‐HBCalix) could be used repeatedly with little loss in adsorption capacity by simply changing the environmental temperature. This kind of ion‐recognition hydrogel is promising as a novel adsorption material for adsorption and separation of Ni²⁺ ions. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2401–2408     

Spektralphotometrische Ermittlung der Koordinationsverhältnisse in Kristallgittern, 2. Mitt.: Die Dimorphie von Zn7Sb2O12

Zusammenfassung Im System ZnO–Sb₂O₅ existieren zwei Spinellphasen (I) und (III) gleicher Zusammensetzung Zn₇Sb₂O₁₂. Außerdem konnte noch eine weitere Modifikation (II) mit einer niedrigsymmetrischen Struktur aufgefunden werden.In (II) und (III) wurden Cu²⁺, Ni²⁺ und Co²⁺ als farbgebende Kationen eingebaut. Die spektralphotometrische Untersuchung ergab, daß Zn²⁺ in (II) sowohl oktaedrisch als auch tetraedrisch koordiniert ist. Im Spinell (III) wird Cu²⁺ sowohl in Tetraeder-und Oktaederlücken, Ni²⁺ nur in Oktaeder- und Co²⁺ vorwiegend in Oktaederlücken eingebaut.In the system ZnO–Sb₂O₅ exist two phases (I) and (III) with the spinel structure and the same composition Zn₇Sb₂O₁₂. Besides these another modification (II) with a structure of lower symmetry could be found.The colouring cations Cu²⁺, Ni²⁺, Co²⁺ have been incorporated in (II) and (III). The spectrophotometrical investigation shows that Zn²⁺ occupies in (II) octahedral and tetrahedral sites. In the spinel (III) Cu²⁺ is incorporated tetrahedrally and octahedrally, Ni²⁺ only octahedrally and Co²⁺ predominantly octahedrally.Mit 4 Abbildungen1. Mitt.:H. Kasper, Z. anorg. allgem. Chem. (im Druck).     

Synthesis of silica nanospheres with Ni2+-iminodiacetic acid for protein separation

Silica (SiO₂) nanospheres (NSs) with immobilized metal ligands have been prepared for the affinity separation of proteins. First, SiO₂ NSs were prepared by controlled hydrolysis of tetraethoxysilane in a basic aqueous-ethanol solution. Then through reaction of iminodiacetic acid (IDA) with 3-glycidoxypropyltrimethoxysilane and immobilization of them onto the surfaces of above SiO₂ NSs, novel affinity adsorbents with IDA chelating groups were obtained. After chelating Ni²⁺ ions, the SiO₂–IDA–Ni²⁺ NSs were applied to separate his-tagged proteins directly from the mixture of lysed cells. The SiO₂–IDA–Ni²⁺ NSs present negligible nonspecific protein adsorption and high protein binding ability (28.3 mg/g).     

Selective extraction of toxic heavy metals and biological activity studies using pyrimidylthioamide functionalised calix[4]arene

The current study comprises synthesis of pyrimidylthioamide derivatized calix[4]arene (5), and its comparative liquid–liquid extraction properties with the compound 4 towards the selected transition metal ions (Cu²⁺, Co²⁺, Ni²⁺, Pb²⁺, Hg²⁺ and Cd²⁺) were investigated. Experimental results revealed that the compound 5 shows better efficiency and affinity for Pb²⁺ and Hg²⁺ ions as compared to compound 4. The antibacterial and antifungal effects of compound 5 were also investigated on various bacteria and fungi. It has been observed that compound 5 has some effects against Salmonella typhimurium NRRLB 4420, Bacillus cereus ATCC 11778, Staphylococcus aureus NRRL B767 and Bacillus subtilis NRS 744.     

Experimental evidences for some unusual divalent cation complexes of valinomycin

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M ²⁺ (aq) + 1 · Sr²⁺ (nb) ⇄ 1 · M ²⁺ (nb) + Sr²⁺ (aq) taking place in the two-phase water-nitrobenzene system (M ²⁺ = Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, UO₂ ²⁺, Fe²⁺, Co²⁺, and Ni²⁺; 1 = valinomycin; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Moreover, the stability constants of the 1 · M ²⁺ complexes in water saturated nitrobenzene were calculated; they were found to increase in the order Fe²⁺ < Cd²⁺, Co²⁺ < Ni²⁺ < UO₂ ²⁺, Zn²⁺ < Cu²⁺ < Pb²⁺.     

Kinetic and Thermodynamic Control in Self-Assembly: Sequential Formation of Linear and Circular Helicates

NMR and MS analysis as a function of time has shown that the self-assembly of a linear ligand with Fe²⁺ or Ni²⁺, metal ions of octahedral coordination geometry, generates first a triple helicate and thereafter the circular helicate 1 as kinetic and thermodynamic products, respectively. The results provide insight into features of the energy hypersurface on which this self-assembly operates and point to the general role of kinetic and thermodynamic control in such processes.     

Experimental evidences for some unusual divalent cation complexes of valinomycin

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M ²⁺ (aq) + 1 · Sr²⁺ (nb) ⇄ 1 · M ²⁺ (nb) + Sr²⁺ (aq) taking place in the two-phase water-nitrobenzene system (M ²⁺ = Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, UO₂ ²⁺, Fe²⁺, Co²⁺, and Ni²⁺; 1 = valinomycin; aq = aqueous phase, nb = nitrobenzene phase) were evaluated. Moreover, the stability constants of the 1 · M ²⁺ complexes in water saturated nitrobenzene were calculated; they were found to increase in the order Fe²⁺ < Cd²⁺, Co²⁺ < Ni²⁺ < UO₂ ²⁺, Zn²⁺ < Cu²⁺ < Pb²⁺. Correspondence: Emanuel Makrlík, Faculty of Applied Sciences, University of West Bohemia, Pilsen, Czech Republic.     

Post-synthetic modification of divalent nickel acetate cubanes with carboxylates

Starting from nickel(II) cubane [Ni^II₄(HL)₄(OAc)₄] (2a), five different tetranuclear cubic complexes [Ni^II₄(HL)₄(O₂CR)₄] (3) were generated simply by applying a post-synthetic cubane modification strategy via a complete acetate-to-carboxylate co-ligand exchange. This was achieved by stirring the parent complex 2a with a large excess of the corresponding sodium carboxylate salt 4 for three days in THF. Single-crystal X-ray structure analyses of Ni^II cubanes 3a·2 Et₂O and 3b·0.5 CH₂Cl₂·0.5 Et₂O reveal unequivocally that both are isostructural in terms of the [Ni₄(μ₃-O₄]⁴⁺ core and crystallize in the triclinic space group P-1 with two molecules in the unit cell. In the solid state, the cubic centers of 3a,b differ only slightly in bond lengths and angles mainly due to the different substituents in the carboxylate co-ligand and packing in the unit cell. The orientation of 3a,b and the formation of supramolecular aggregates in the crystal packing were controlled by π–π interactions as well as intra- and intermolecular O–H?O hydrogen bonds. Variable-temperature magnetic susceptibility measurements reveal that 3a–c show a ferrimagnetic coupling scheme that leads to a diamagnetic ground state for all investigated complexes.     

Cobalt(III)‐Mediated Permanent and Stable Immobilization of Histidine‐Tagged Proteins on NTA‐Functionalized Surfaces

We present the cobalt(III)‐mediated interaction between polyhistidine (His)‐tagged proteins and nitrilotriacetic acid (NTA)‐modified surfaces as a general approach for a permanent, oriented, and specific protein immobilization. In this approach, we first form the well‐established Co²⁺‐mediated interaction between NTA and His‐tagged proteins and subsequently oxidize the Co²⁺ center in the complex to Co³⁺. Unlike conventionally used Ni²⁺‐ or Co²⁺‐mediated immobilization, the resulting Co³⁺‐mediated immobilization is resistant toward strong ligands, such as imidazole and ethylenediaminetetraacetic acid (EDTA), and washing off over time because of the high thermodynamic and kinetic stability of the Co³⁺ complex. This immobilization method is compatible with a wide variety of surface coatings, including silane self‐assembled monolayers (SAMs) on glass, thiol SAMs on gold surfaces, and supported lipid bilayers. Furthermore, once the cobalt center has been oxidized, it becomes inert toward reducing agents, specific and unspecific interactions, so that it can be used to orthogonally functionalize surfaces with multiple proteins. Overall, the large number of available His‐tagged proteins and materials with NTA groups make the Co³⁺‐mediated interaction an attractive and widely applicable platform for protein immobilization.     

Synthesis and structure of a nickel coordination polymer with channels hosting polyanion chains

A porous coordination polymer, {[Ni(Dpdo)₄(H₂O)₂][H(H₂O)_6.5](PMo₁₂O₄₀)} _n (I), where Dpdo is 4,4′-ipyridine-N,N′-hoxide, templated by polyanion chains has been synthesized through the self-assembly of Ni²⁺ ions and Dpdo ligands in acetonitrile-water solutions and characterized by elemental analysis, IR spectra, and single-crystal X-ray diffraction. The structure of compound I constructed from the polyanion [PMo₁₂O₄₀]³⁻ and the coordinated cation [Ni(Dpdo)₄(H₂O)₂]²⁺ exhibits a 3D non-interwoven frameworks with large channels occupied by the poly-Keggin anion chains as guests.     

过渡金属与新型硝基酚臂式氮杂18-冠-6配位性能的研究

合成并表征了1,10-二氧-4,7,13,16-四氮杂18-冠-6 (1)母体及其四取代硝基酚臂式衍生物 (2)。在H₂O-DMSO(V/V=1/4)混合溶剂中用UV-Vis光谱法对冠醚2与H⁺、Mn²⁺、Co²⁺、Ni²⁺、Cu²⁺、Zn²⁺、Cd²⁺和Hg^{2+相似文献}