Structural characteristics of some metallo-organic discogens

We have recently analysed the crystal and molecular structures of six metalloorganic discogens with substituted β-diketone ligands. The molecules consist of a rigid 11 atom core and a fringe made up of four phenyl rings substituted with alkyl/alkoxy chains. In complex (i), with four octyloxy chains, there are four oxygen atoms around the core. Complex (ii) is asymmetrically substituted with two heptyloxy and two heptyl chains and therefore has two oxygen atoms and complexes (iii) to (vi) have only alkyl chains and hence no oxygen atoms around the core. The metal atom used for coordination has been chosen as Cu/Pd/Ni. Determination of the crystal and molecular structures of these discogens has led to the identification of the following similarities: (1) All the six discogens crystallize in the triclinic space group P1. The recurrence of the space group may be correlated with the structural requirements for efficient packing of the molecules in the crystal lattice. (2) The coordination around the metal atom is square planar. (3) The 11 atom core is only nearly planar. (4) The phenyl rings and the chains are tilted with respect to the core. (5) The molecular conformation in the crystal confers a nearly rectangular shape to these discogens. (6) The chains are fully extended in an all trans conformation. (7) The molecular arrangement is tilted columnar except for the crystal structure of complex (ii).

In addition to the similarities, distinct differences in the crystal structural characteristics have also been observed. For example, when oxygen atoms are present in the fringe, the molecules have no crystallographic symmetry and they tend to pair. In the crystal structure of (i) where the repeat unit along the column is a molecular pair, the metal atoms are distributed in a zig-zag fashion. In the other crystals with columnar arrangement, the metal atoms are stacked one over another. Complex (ii) has a layer-like molecular arrangement in the crystalline phase.     

A self-assembled, metallo-organic supramolecular frequency doubler

The dimeric self-assembly program of a new, multidentate ligand with cuprous ions overcomes crystal packing forces, which leads to C(i) symmetry in the solid state, to form a no less than partially C(2)-symmetric structure in solution. The resulting tetranitro-substituted dicopper(i) metallocyclophane displays an exceptionally strong second harmonic frequency response (β = (3000 ± 600) × 10(-30) esu for a fundamental at 800 nm).     

From purely organic to metallo-organic chiral magnetic materials

There is presently a widespread search for materials which present magnetic ordering and appropriate chiroptical properties which would allow the observation of magneto-chiral effects. In this paper, we reflect on the possible uses of organic materials to probe this phenomenon, either as pure compounds or as their coordination compounds with metal ions.     

Electrostatically mediated specific adsorption of small molecules in metallo-organic frameworks

We investigate the interaction of ethylene and ethane with a Cu-tricarboxylate complex and show that at low loadings the lighter molecule has a higher binding energy as a result of an increased interaction with the framework Cu and stronger hydrogen bonding with the basic framework oxygens. This leads to selective adsorption of ethylene by a factor of about 2 at low pressure, which is overcome by the stronger van der Waals interaction of ethane at high loadings, explaining recent literature data. The results suggest the possibility of separation of light hydrocarbons at low pressures or in trace amounts.     

Meshed tert-butyl gears on a quasirigid backbone

MM3-based calculations showed that bicycles and polycycles with four- to six-membered rings-components of the bi- and polycyclic backbone are sufficiently rigid to keep a syn-periplanar orientation of vicinal tert-butyl substituents. As a result of the spatial proximity of these groups, their rotation occurs in a concerted manner as demonstrated by conformational schemes that are built using MM3-derived methodology. Only correlated disrotation in saturated systems with four- to five-membered rings-components and in the adamantane system leads to isochronism for Me groups of the tert-Bu substituents (i.e., to dynamic gearing in Mislow's terms). Moreover, correlated rotation of these substituents is coupled with a change of the backbone geometry (pseudorotation) except in the most rigid bicyclo[2.1.1]hexa-2-ene system. Thus, a new type of dynamic gearing, correlated rotation–rotation–pseudorotation, is predicted for quasirigid bi- and polycycles with syn-periplanar oriented tert-Bu substituents. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 1786–1794, 1998     

A study of solid-state thermal decomposition characteristics of some metallo-organic compounds

The solid-state dehydration of the hydrated Ca(II), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) salts of pyridine-2-carboxylic acid (picolinic acid) and subsequent decarboxylation of the corresponding anhydrous salts have been studied by simultaneous TG, DTA and DTG. The sequences of thermal stability of the hydrated and the anhydrous compounds have been established from analysis of the TG, DTA and DTG traces for dehydration of the hydrated salts and for decarboxylation of the anhydrous compounds. Thermal parameters such as activation energy, enthalpy change and order of reaction for the different stages of each process have been computed by standard methods. An attempt has been made to account for the observed trend in the thermal stability of the anhydrous salts towards decarboxylation. A mechanism of thermal decraboxylation of calcium picolinate has been proposed.

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Zusammenfassung Die Dehydratisierung der hydratisierten Ca(II)-, Mn(II)-, Co(II)-, Ni(II)-, Cu(II)- und Zn(II)-Salze der Pyridin-2-carboxylsäure (Picolinsäure) in fester Phase und die nachfolgende Decarboxylierung der entsprechenden wasserfreien Salze wurden mittels simultaner TG, DTA und DTG untersucht. Aus den thermoanalytischen Kurven wurde die der thermischen Stabilität entsprechende Reihenfolge der hydratisierten und wasserfreien Verbindungen ermittelt. Thermische Parameter wie Aktivierungsenergie, Enthalpieänderung und Reaktionsordnung wurden für die einzelnen Schritte jedes Prozesses nach Standardmethoden berechnet. Es wurde ein Versuch unternommen, den Trend in der thermischen Stabilität der wasserfreien Salze gegenüber Decarboxylierung zu erklären. Ein Mechanismus der thermischen Decarboxylierung von Calciumpicolinat wird vorgeschlagen.

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Tripodal europium complex with triangulenium dye: a model bifunctional metallo-organic system

A new tripodal ligand has been designed by coupling pyridyldicarbonyl binding strands with a triazatriangulenium platform (TATA). The complexation reaction with europium provides a C(3)-symmetrical mononuclear compound that is characterized with NMR, ESMS and qualitatively with single-crystal X-ray crystallography. In addition, photophysical studies of this dual emissive system have been performed, since the combination of the TATA fluorophore with trivalent lanthanides is of potential interest for the further development of imaging applications.     

Role of spatial distortions on the quadratic nonlinear optical properties of octupolar organic and metallo-organic molecules

Following on the recent experimental demonstration of a discrepancy between the nonlinear optical (NLO) behavior of several pi-conjugated chromophores and their assumed octupolar symmetry, the authors investigate how geometrical distortions influence the NLO response of multipolar push-pull molecules. Their analytical model is set on a basis of valence-bond and charge-transfer states to estimate the hyperpolarizability of organic and metallo-organic chromophores using the lowest possible number of variables. Since symmetry breakdown changes the definition of the molecular Cartesian framework, tensorial spherical coordinates are implemented. The evolution of the nonlinear molecular anisotropy with possible rotational deviations is then evaluated for two recently studied chromophores. Zero-frequency calculations show that, outside optical resonance, weak geometrical distortions lead to strong anisotropy variations in agreement with experimental data. Their goal is to underscore which molecular engineering strategies should be applied when designing a photoisomerizable nonlinear octupole.     

Proline adducts of metallo-organic,sextuply-stranded lanterns as homogeneous catalysts for asymmetric catalysis

Two homochiral metal–organic, sextuply-stranded, lantern-like complexes, Ce-L-Pro1 and Ce-D-Pro1, were synthesized via self-assembly by incorporating a L or D-pyrrolidine moiety within the respective ligands. The Ce-Pro1 complexes are comprised of chiral pyrrolidine-containing ligands and have lantern-like cavities. They function as asymmetric catalysts that promote cyanosilylation reactions with good conversions and enantioselectivity.     

A Study of solid state thermal decomposition characteristics of some metallo-organic compounds. IV

Solid state dehydration of the hydrated Ca(II), Co(II), Ni(II) and Cu(II) salts of furan-2-carboxylic acid (furoic acid) and subsequent decarboxylation of the corresponding anhydrous salts have been studied by simultaneous TG, DTA and DTG techniques. The order of thermal stability of the hydrated and the anhydrous compounds have been determined from the analysis of the TG, DTA and DTG traces for the dehydration of the hydrated salts and for the decarboxylation of the anhydrous compounds. Thermal parameters such as activation energy, enthalpy change and order of reaction for the different stages of each process have been computed by standard methods. An attempt has been made to account for the observed trend in the thermal stability of the anhydrous salts towards decarboxylation. A mechanism of thermal decarboxylation of calcium furoate has also been proposed.

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Zusammenfassung Die Dehydratisierung in fester Phase der hydratisierten Salze von Ca(II), Co(II), Ni(II) und Cu(H) mit Furan-2-carboxylsäure und die darauffolgende Decarboxylierung der entsprechenden wasserfreien Salze wurde mittels simultan ausgeführter TG, DTA and DTG untersucht. Die Reihenfolge der thermischen Stabilität der hydratisierten und wasserfreien Verbindungen wurde aus dem Verlauf der TG-, DTA- und DTG-Kurven ermittelt. Die thermischen Parameter (Aktivierungsenergie, Enthalpieveränderung, Reaktionsordnung) wurden für die verschiedenen Schritte eines jeden Prozesses nach Standardmethoden berechnet. Es wurde ein Versuch zur Erklärung des beobachteten Trends in der Thermostabilität der wasserfreien Salze gegenüber Decarboxylierung unternommen und ein Mechanismus für die themische Decarboxylierung von Calciumfuorat in Vorschlag gebracht.

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Hydrophilic anchors for transmembrane anion–π slides

The concept of hydrophilic anchoring is introduced to activate rigid oligonaphthalenediimide (O-NDI) rods as anion–π slides for multi-ion hopping across lipid bilayers. We report that short peptide solubilizers suffice to reach the rare combination of high activity and high selectivity that is needed for anion pumping in vesicles.     

Biomimetic anchors for antifouling and antibacterial polymer brushes on stainless steel

Barnacle cement (BC) was beneficially applied on stainless steel (SS) to serve as the initiator anchor for surface-initiated polymerization. The amine and hydroxyl moieties of barnacle cement reacted with 2-bromoisobutyryl bromide to provide the alkyl halide initiator for the surface-initiated atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate (HEMA). The hydroxyl groups of HEMA polymer (PHEMA) were then converted to carboxyl groups for coupling of chitosan (CS) to impart the SS surface with both antifouling and antibacterial properties. The surface-functionalized SS reduced bovine serum albumin adsorption, bacterial adhesion, and exhibited antibacterial efficacy against Escherichia coli (E. coli). The effectiveness of barnacle cement as an initiator anchor was compared to that of dopamine, a marine mussel inspired biomimetic anchor previously used in surface-initiated polymerization. The results indicate that the barnacle cement is a stable and effective anchor for functional surface coatings and polymer brushes.     

Assessment of heavy metals leachability from metallo-organic sorbent-iron humate-with the aid of sequential extraction test

The sequential extraction test, known as a BCR procedure, was used to assess a leachability of heavy metals (Zn, Cd, Pb, Cu) from the metallo-organic sorbent—iron humate—loaded with these metals. The sequential test allowed to discriminate between various fractions of heavy metals, namely the acid-extractable fraction, the fraction bound to Fe oxides, and the fraction bound to organic matter. It was proven that the heavy metals are bound mainly to Fe oxides and organic matter, and thus they may be relatively hardly liberated into the environment. The BCR sequential extraction test exhibited a very good repeatability, when it was applied to the loaded sorbent—relative standard deviations were typically lower than 10%.     

Molecular gears with two-toothed and three-toothed wheels

Dynamic NMR studies of 9-arylmethyltriptycene derivatives revealed that the compounds exist in conformations which are regarded as static meshed gears with a two-toothed and a three-toothed wheels and that some of them behave as dynamic gears, rotation about the triptycyl-methylene and the aryl-methylene bonds being correlated. Similar behavior was observed in 9-aryloxytriptycenes as well.     

Low generation PEGylated phosphorus-containing dendrons with phosphonate anchors

We present a simple strategy to obtain non-symmetrical polyethylene glycols equipped with telechelic phosphorus-containing dendrimeric moieties having adhesive phosphonate surface functions. The dendronized PEG tails were characterized by means of multi-nucleus NMR. The grafting abilities of model symmetrical PEG compounds equipped with telechelic amino-bis(methylene-dimethylphosphonates) and amino-bis(methylenephosphonic acids) were rapidly screened on plasma treated silicon wafers and activated silica.     

Luminol anchors improve the electrochemical-tyrosine-click labelling of proteins

New methods for chemo-selective modifications of peptides and native proteins are important in chemical biology and for the development of therapeutic conjugates. Less abundant and uncharged amino-acid residues are interesting targets to form less heterogeneous conjugates and preserve biological functions. Phenylurazole (PhUr), N-methylphenylurazole (NMePhUr) and N-methylluminol (NMeLum) derivatives were described as tyrosine (Y) anchors after chemical or enzymatic oxidations. Recently, we developed the first electrochemical Y-bioconjugation method coined eY-click to activate PhUr in biocompatible media. In this work, we assessed the limitations, benefits and relative efficiencies of eY-click conjugations performed with a set of PhUr, NMePhUr and NMeLum derivatives. Results evidenced a high efficiency of NMeLum that showed a complete Y-chemoselectivity on polypeptides and biologically relevant proteins after soft electrochemical activation. Side reactions on nucleophilic or heteroaromatic amino-acids such as lysine or tryptophan were never observed during mass spectrometry analysis. Myoglobine, bovine serum albumin, a plant mannosidase, glucose oxidase and the therapeutically relevant antibody trastuzumab were efficiently labelled with a fluorescent probe in a two-step approach combining eY-click and strain-promoted azide–alkyne cyclization (SPAAC). The proteins conserved their structural integrity as observed by circular dichroism and the trastuzumab conjugate showed a similar binding affinity for the natural HER2 ligand as shown by bio-layer interferometry. Compared to our previously described protocol with PhUr, eY-click with NMeLum species showed faster reaction kinetics, higher (complete) Y-chemoselectivity and reactivity, and offers the interesting possibility of the double tagging of solvent-exposed Y.

We assessed the relative efficiencies of tyrosine anchors in the electrochemical conjugation of peptides and proteins. Luminol derivatives showed faster reaction kinetics, complete tyrosine-chemoselectivity, and possible double modification.     

Templated assembly of biomembranes on silica microspheres using bacteriorhodopsin conjugates as structural anchors

Membrane proteins are some of the most sophisticated molecules found in nature. These molecules have extraordinary recognition properties; hence, they represent a vast source of specialized materials with potential uses in sensing and screening applications. However, the strict requirement of the native lipid environment to preserve their structure and functionality presents an impediment in building biofunctional materials from these molecules. In general, the purification protocols remove the native lipid support structures found in the cellular environment that stabilize the membrane proteins. Furthermore, the membrane protein structure is often highly complex, typified by large, multisubunit complexes that not only span the lipid bilayer but also contain large (>2 nm) cytoplasmic and extracellular domains that protrude from the membrane. The present study is focused on using a biomimetic approach to build a stable, fluid microenvironment to be used to incorporate larger membrane proteins of interest into a tether-supported lipid bilayer membrane adequately spaced above a substrate passivated to liposome fusion and nonspecific adsorption. Our aim is to reintroduce the supporting structures of the native cell membrane using self-assembled supramolecular complexes constructed on microspheres in an artificial cytoskeleton motif. Central to our architecture is to utilize bacteriorhodopsin (bR), a transmembrane protein, as a biomembrane anchoring molecule to be tethered to surfaces of interest as a sparse structural element in the design. Compared to a typical lipid tether, which inserts into one leaflet of the lipid bilayer, bR anchoring provides an over 8-fold greater hydrophobic surface area in contact with the bilayer. In the work presented here, the silica microsphere surface was biofunctionalized with streptavidin to make it a suitable supporting interface. This was achieved by self-assembly of (p-aminophenyl)trimethoxysilane on the silica surface followed by subsequent conjugation of biotin-PEG3400 (PEG = poly(ethylene glycol) and PEG2000 for further passivation and the binding of streptavidin. We have conjugated bR with biotin-PEG3400 through amine-based coupling to use it as a tether. The biotin-PEG-bR conjugate was further labeled with Texas Red to facilitate localization via fluorescence imaging. Confocal microscopy was utilized to analyze the microsphere surface at different stages of surface modification by employing fluorescent staining techniques. Sparely tethered supported lipid bilayer membranes were constructed successfully on streptavidin-functionalized silica particles (5 mum) using a detergent-based method in which tethered bR nucleates self-assembly of the bilayer membrane. The fluidity of the supported membranes was analyzed using fluorescence recovery after photobleaching in confocal imaging detection mode. The phospholipid diffusion coefficients obtained from these studies indicated that nativelike fluidity was achieved in the tether-supported membranes, thus providing a prospective microenvironment for insertion of membrane proteins of interest.     

Dipolar and nonpolar altitudinal molecular rotors mounted on an Au(111) surface

We describe the preparation of a compound whose molecules consist of two metal sandwich stands carrying tentacles with affinity to metal surfaces and holding an axle that carries a dipolar or a nonpolar rotator. The dipolar rotor exists as three pairs of enantiomers, rapidly interconverting at room temperature. When mounted on a gold surface, each molecule represents a chiral altitudinal rotor, with the rotator axle parallel to the surface. The surface-mounted rotor molecules are characterized by several spectroscopic and imaging techniques. At any one time, in about one-third of the dipolar rotors the rotator is free to turn and the direction of its dipole can be flipped by the electric field applied by an STM tip, as revealed by differential barrier height imaging. Molecular dynamics calculations suggest that electric field normal to the surface causes members of one pair of enantiomers to rotate unidirectionally.     

Molecular spur gears comprising triptycene rotators and bibenzimidazole-based stators

Dynamic gearing of molecular spur gears, the most common type of mechanical gear, is elucidated. Molecular design and conformational analysis show that derivatives of 4,4-bis(triptycen-9-ylethynyl)bibenzimidazole represent suitable constructs to investigate gearing behavior of collateral triptycene (Tp) groups. To test this design, DFT calculations (B97-D/Def2-TZVP) were employed and the results suggest that these molecules undergo geared rotation preferentially to gear slippage. Synthesis of derivatives was carried out, providing a series of molecular spur gears, including the first desymmetrized spur gear molecules, which were subsequently subjected to stereochemical analysis.     

The use of electrospray ionization tandem mass spectrometry on the structural characterization of novel asymmetric metallo-organic supermolecules,based on pentafluorophenylporphyrins and ruthenium complexes

The novel asymmetric metallo-organic triads cis- and trans-[B(4-py)BPFPH₂{Ru₃O(Ac)₆(py)₂}{Ru(bpy)₂Cl}](PF₆)₂ (5a,b) for which cis- and trans-B(4-py)BPFPH₂ = 5,10-bis(pentafluorophenyl)-15,20-bis(4-pyridyl)porphyrin and 5,15-bis(pentafluorophenyl)-10,20-bis(4-pyridyl)porphyrin, respectively; Ac = acetate; py = pyridine and bpy = 2,2′-bipyridine, as well as their corresponding monosubstituted dyads cis- and trans-[B(4-py)BPFPH₂{Ru₃O(Ac)₆(py)₂}]PF₆ (4a,b) have been structurally characterized via electrospray ionization mass spectrometry (ESI-MS and ESI-MS/MS). The ESI-MS of dyads 4a,b display two characteristic Ru-multicomponent clusters of isotopologue ions corresponding to singly charged ions 4a,b⁺ of m/z 1629 and doubly charged ions [4a,b+H]²⁺ of m/z 815 and the triads 5a,b are detected by ESI-MS as the intact doubly charged cluster of isotopologue ions of m/z 1039 [5a,b]²⁺. The ESI-MS/MS of 4a,b⁺, [4a,b+H]²⁺ and [5a,b]²⁺ reveal characteristic dissociation pathways, which confirm the structural assignments providing additional information on the intrinsic binding strengths of the gaseous ions. Although the gas-phase behavior of each pair of isomers was rather similar, the less symmetric dyads 4a,b are distinguished via the ¹H NMR spectral profile of the pyrrolic signals. Exploratory photophysical assays have shown that both modifying motifs alter the porphyrinic core emission profile, opening the possibility to use these asymmetric systems as photophysical devices.