Fe(III) coordination properties of a new saccharide-based exocyclic trihydroxamate analogue of ferrichrome

The coordination chemistry of a saccharide-based ferrichrome analogue, 1-O-methyl-2,3,4-tris-O-[4-(N-hydroxy-N-methylcarbamoyl)-n-butyrate]-alpha-d-glucopyranoside (H(3)L), is reported, along with its pK(a) values, Fe(III) and Fe(II) chelation constants, and aqueous-solution speciation as determined by spectrophotometric and potentiometric titration techniques. The use of a saccharide platform to synthesize a hexadentate trihydroxamic acid chelator provides some advantages over other approaches to ferrichrome models, including significant water solubility and hydrogen-bonding capability of the backbone that can potentially provide favorable receptor recognition and biological activity. The pK(a) values for the hydroxamate moieties were found to be similar to those of other trihydroxamates. Proton-dependent Fe(III)-H(3)L and Fe(II)-H(3)L equilibrium constants were determined using a model involving the sequential protonation of the iron(III)- and iron(II)-ligand complexes. These results were used to calculate the formation constants, log beta(110) = 31.86 for Fe(III)L and 12.1 for Fe(II)L(-). The calculated pFe value of 27.1 indicates that H(3)L possesses an Fe(III) affinity comparable to or greater than those of ferrichrome and other ferrichrome analogues and is thermodynamically capable of removing Fe(III) from transferrin. E(1/2) for the Fe(III)L/Fe(II)L(-) couple was determined to be -436 mV from quasi-reversible cyclic voltammograms at pH = 9, and the pH-dependent E(1/2) profile was used to determine the Fe(II)L(-) protonation constants.     

Pniktogenidostannate(IV) mit isolierten Tetraeder‐Anionen: Neue Vertreter (E1)4(E2)2[Sn(E15)4] (mit E1 = Na,K; E2 = Ca,Sr, Ba; E15 = P,As, Sb,Bi) vom Na6[ZnO4]‐Typ und die Überstrukturvariante von K4Sr2[SnAs4]

Pnictogenidostannates(IV) with Discrete Tetrahedral Anions: New Representatives (E1)₄(E2)₂[Sn(E15)₄] (with E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) of the Na₆[ZnO₄] Type and the Superstructure Variant of K₄Sr₂[SnAs₄] The silvery to dark metallic lustrous compounds (E1)₄(E2)₂[Sn(E15)₄] (E1 = Na, K; E2 = Ca, Sr, Ba; E15 = P, As, Sb, Bi) were prepared from melts of stoichiometric mixtures of the elements. They crystallize in the Na₆[ZnO₄]‐type structure (hexagonal, space group: P6₃mc, Z = 2; Na₄Ca₂[SnP₄]: a = 938.94(7), c = 710.09(8) pm; K₄Sr₂[SnAs₄]: a = 1045.0(2), c = 767.0(1) pm; K₄Ba₂[SnP₄]: a = 1029.1(6), c = 780.2(4) pm; K₄Ba₂[SnAs₄]: a = 1051.3(1), c = 795.79(7) pm; K₄Ba₂[SnSb₄]: a = 1116.9(2), c = 829.2(1) pm; K₄Ba₂[SnBi₄]: a = 1139.5(2), c = 832.0(2) pm). The anionic partial structure consists of tetrahedra [Sn(E15)₄]^8– orientated all in the same direction along [001]. In the cationic partial structure one of the two cation positions is occupied statistically by alkali and alkaline earth metal atoms. Up to now only for K₄Sr₂[SnAs₄] a second modification could be isolated, forming a superstructure type with three times the unit cell volume (hexagonal, space group: P6₃cm, Z = 6; a = 1801.3(2), c = 767.00(9) pm) and an ordered cationic partial structure.     

Tetracyanoquinodimethane Reduction by Complexed Guanidinyl‐Functionalized Aromatic Compounds

In this work, we report on the reduction of tetracyanoquinodimethane (TCNQ) with dicationic complexes of guanidinyl‐functionalized aromatic (GFA) electron donors. In contrast to reduction with free GFAs, milder reduction conditions were achieved, and this led to semiconducting materials with extended TCNQ π stacking. The charge on the TCNQ units was estimated from the structural data obtained by single‐crystal X‐ray diffraction analysis and from IR spectroscopic data. The electrical conductivity was studied and the activation energy of the semiconducting materials was estimated from the temperature dependence of the conductivity.     

Reactions of Polyarsenides with Acetylene: Synthesis and Characterization of [Cs([18]crown‐6)]2As7C14H11·6NH3 and As2C6H6

The reaction of Cs₃As₇ with diphenylacetylene in the presence of 18 crown‐6 in liquid ammonia results in the formation of the new compound [Cs( 18 crown‐6)]₂As₇C₁₄H₁₁ · 6NH₃, which crystallizes in black monoclinic crystals. It contains the first monosubstituated heptaarsenide anion with a hydrocarbon‐only substituent and theoretical calculations show a significant influence of the organic substituent on the electronic structure within the cage. The (Z)‐1, 2‐diphenylethenyl‐heptaarsenide di‐anion can be seen as the first step towards the formation of 1, 2,3‐triarsolides. Further experiments regarding the reaction of Rb₃As₁₁ and Cs₃As₁₁ with acetylene gas in liquid ammonia reveal the formation of the diarsabarrelene As₂C₆H₆, which crystallizes as colorless orthorhombic crystals. Calculations based on the structural data obtained by X‐ray crystallography show the electronically inert character of the arsenic lone pair.     

Capillary isoelectric focusing immunoassay as a new nanoscale approach for the detection of oligoclonal bands

The detection of oligoclonal bands (OCBs) in cerebrospinal fluid is an indicator of intrathecal synthesis of immunoglobulins which is a neurochemical sign of chronic inflammatory brain diseases. Intrathecally synthesized IgGs are typically observed in patients with multiple sclerosis. The current standard protocol for the detection of OCBs is IEF on agarose or polyacrylamide gels followed by immunoblotting or silver staining. These methods are time consuming, show substantial interlaboratory variation and cannot be used in a high throughput‐approach. We have developed a new nanoscale method for the detection of OCBs based on automated capillary IEF followed by immunological detection. Evidence for intrathecal IgG synthesis was found in all tested patients (n = 27) with multiple sclerosis, even in two subjects who did not have oligoclonal bands according to standard methods. The test specificity was at 97.5% (n = 19). Our findings indicate that the novel OCB‐CIEF‐immunoassay is suitable for the rapid and highly sensitive detection of OCBs in clinical samples. Furthermore, the method allows for a higher sample throughput than the current standard methods.     

One‐Step Synthesis of a [20]Silafullerane with an Endohedral Chloride Ion

Silicon analogues of the most prominent carbon nanostructures, namely, hollow spheroidals such as C₆₀ and the fullerene family, have been unknown to date. Herein we show that discrete Si₂₀ dodecahedra, stabilized by an endohedral guest and valence saturation, are accessible in preparative yields through a chloride‐induced disproportionation reaction of hexachlorodisilane in the presence of tri(n‐butyl)amine. X‐ray crystallography revealed that each silicon dodecahedron contains an endohedral chloride ion that imparts a net negative charge. Eight chloro substituents and twelve trichlorosilyl groups are attached to the surface of each cluster in a strictly regioregular arrangement, a thermodynamically preferred substitution pattern according to quantum‐chemical assessment. Our results demonstrate that the wet‐chemical self‐assembly of a complex, monodisperse Si nanostructure is possible under mild conditions starting from simple Si₂ building blocks.     

Studies into the Early Degradation Stages of Cellulose by Different Iron Gall Ink Components

Selective fluorescence labelling of oxidized cellulose functionalities followed by GPC-MALLS was used to get a deeper insight into ink-induced degradation processes. As the method is very sensitive towards oxidation and molecular weight changes, slight variations at the very beginning of aging processes, e.g. during ink corrosion of cellulose, can be studied. Five different ink modifications were applied on model papers and underwent mild accelerated aging at 55 °C and cycling humidity (7 days) followed by a short period of static humid aging at 80 °C (2 days). Pure ink constituents like tannic acid or iron sulphate do not result in the same degree of oxidation or chain scission as complete inks. Balanced ink degrades paper more than single compounds, but less than unbalanced inks. Interestingly, some degradation occurs already during or shortly after the application process of unbalanced inks on paper. It could be demonstrated that this oxidation proceeded in a rather high Mw area, while the subsequent aging steps affected predominantly regions of shorter cellulose chains.