Towards rod-shaped molecules based on the twelve-vertex ferratricarbollides

The compounds with a single and double -CH₂C₆H₄CH₂- spacer, [CpFeC₃B₈H₁₀-NH-CH₂C₆H₄CH₂-NH-C₃B₈H₁₀FeCp] and [CpFeC₃B₈H₁₀-N-(CH₂C₆H₄CH₂)₂-N-C₃B₈H₁₀FeCp], represent the first example of designed shaping by extremely stable cyclopentadienyl-ferratricarbollide (CpFeTCB) cages into rigid molecular constructions approaching linear arrangement.     

An Improved HPLC Post-Column Methodology for the Identification of Free Radical Scavenging Phytochemicals in Complex Mixtures

The importance of natural antioxidants principally relates to their health-promoting properties. The discovery of new sources of established compounds or more potent compounds is a costly exercise and any technique capable of aiding this procedure would be highly significant. An approach combining chromatographic separation, component analysis and post-column identification of free radical scavenging has been reported. However, its effectiveness is dependent upon various factors and the number of samples analyzed without operator intervention is restricted. A more applicable technique using a 10% to 100% methanol with 2% acetic acid mobile phase and a citric acid-sodium citrate buffered methanolic 1,1-diphenyl-2-picrylhydrazyl free radical reagent is presented, whereby free radical scavengers can be detected within crude extracts of variable polarity without special considerations. As an illustration, acetone, 70% (aq.) methanol and acetonitrile-soluble extracts were prepared from sage (Salvia officinalis L.) for extraction of polar and non-polar radical scavengers and analyzed. Radical scavenging components were identified as carnosic, caffeic and rosmarinic acids and luteolin-7-O-glycoside. Others radical scavengers were tentatively identified as benzoic and hydroxycinnamic acid derivatives, flavonoids and diterpenoids. Through the application of this technique, carnosic acid and rosmarinic acid were identified as the principal free radical scavengers.     

Crystal structures and magnetic properties of two low-dimensional materials constructed from [Mn(III)(salen)H2O]+ and [M(CN)8](3-/4-) (M = Mo or W) precursors

The syntheses, X-ray structures, and magnetic behaviors of two new cyano-bridged assemblies, the molecular [Mn(III)(salen)H2O]3[W(V)(CN)8].H2O (1) and one-dimensional [Mn(salen)(H2O)2]2[[Mn(salen)(H2O)][Mn(salen)]2[Mo(CN)(8)]].0.5ClO4.0.5OH.4.5H2O (2), are presented. Compound 1 crystallizes in the monoclinic system, has space group P2(1)/c, and has unit cell constants a = 13.7210(2) A, b = 20.6840(4) A, c = 20.6370(2) A, and Z = 4. Compound 2 crystallizes in the triclinic system, has space group P, and has unit cell dimensions a = 18.428(4) A, b = 18.521(3) A, c = 18.567(4) A, and Z = 2. The structure of 1 consists of the asymmetric V-shaped Mn-NC-W-NC-Mn-O(phenolate)-Mn molecules, where W(V) coordinates with [Mn(salen)H2O] and singly phenolate-bridged [Mn(salen)H2O]2 moieties through the neighboring cyano bridges. The [W(V)(CN)8]3- ion displays distorted square-antiprism geometry. The structure of 2 consists of the cyano-bridged [Mn3(III)Mo(IV)]n- repeating units linked by double phenolate bridges into one-dimensional zigzag chains. The Mn(III) centers are bound to Mo(IV) of square-antiprism geometry through the neighboring cyano bridges. The magnetic studies of 1 reveal the antiferromagnetic intramolecular interactions through the CN and phenolate bridges and the relatively weak intermolecular interactions. Compound 1 becomes antiferromagnetically ordered below TN = 4.6 K. The presence of the magnetic anisotropy is documented with the MH measurements carried out for both polycrystalline and single-crystal samples. At T = 1.9 K, the spin-flop transition is observed in the field of 18 kOe applied parallel to the bc plane, which is the easy plane of magnetization. Field dependence of magnetization of 1 shows field-induced metamagnetic behavior from the antiferromagnetic ground state of ST = 3/2 to the state of ST = 5/2. The magnetic properties of 2 indicate a weak antiferromagnetic interaction between Mn(III) centers in double-phenolate-bridged [Mn(III)(salen)]2 dinuclear subunits and a very weak ferromagnetic interaction between them through the diamagnetic [Mo(IV)(CN)8]4- spacer.     

Stabilization of cobalt(II) chloro-complexes with the butanediammonium cation

Summary Cobalt(II) chlorocomplexes with empirical formulae (bnH₂)₂CoCl₆·2H₂O (1) and (bnH₂)₂CoCl₆ (2), where bnH ₂ ²⁺ represents the diprotonated species of putrescine (1,4-butanediamine), were prepared.The visible spectra in the solid state and measurement of the magnetic moments permit the assignation of an octahedral geometry for cobalt in (1) and a tetrahedral geometry for (2).     

Reversible binding of the HPLC6 isoform of type I antifreeze proteins to ice surfaces and the antifreeze mechanism studied by multiple quantum filtering-spin exchange NMR experiment

Antifreeze proteins (AFPs) protect organisms from freezing damage by inhibiting the growth of seed-ice crystals. It has long been hypothesized that irreversible binding of AFPs to ice surfaces is responsible for inhibiting the growth of seed-ice crystals as such a mechanism supports the popularly accepted Kelvin effect for the explanation of local freezing-point depression. However, whether the binding is reversible or irreversible is still under debate due to the lack of direct experimental evidence. Here, we report the first direct experimental result, by using the newly developed multiple quantum (MQ) filtering-spin exchange NMR experiment, that shows that the binding of HPLC6 peptides to ice surfaces is reversible. It was found that the reversible process can be explained by the model of monolayer adsorption. These results suggest that the Kelvin effect is not suitable for explaining the antifreeze mechanism, and direct interactions between the peptides and the ice-surface binding sites are the driving forces for the binding of AFPs to ice surfaces. We propose that there exists a concentration gradient of AFP from an ice-binding surface to the solution due to the affinity of ice surfaces to AFPs. This concentration gradient creates a dense layer of AFP in contact with the ice-binding surface, which depresses the local freezing point because of the colligative property, but not the Kelvin effect.     

On the strong almost convergence of double sequences

In this paper, necessary and sufficient conditions that the real doubly infinite matrixA sums every strongly almost convergent double sequence, leaving the limit invariant, have been determined.     

Individual extraction constants of some dicarbollylcobaltate anions in the water-nitrobenzene system

Individual extraction constants of nine dicarbollylcobaltate anions in the two-phase water-nitrobenzene system were determined radiometrically assuming that the changes of Gibbs energy of the transfer of the tetraphenylarsonium cation, Ph₄As⁺, and of the tetraphenylborate anion, BPh ₄ ^– , from the aqueous into the nitrobenzene phase are equal. The constants obtained by this method were correlated with Hansch's constants of hydrophobity.     

Labelings of two classes of plane graphs

The paper describes magic labelings of type (1,1,1) for two classes of graphs, which are obtained by a combination of vertex, edge and face labelings.     

Measurement of L&agr; and Lß X-ray fluorescence cross sections in Er, Ta, W and Au by 16.896–59.543 keV photons

La and Lb X-ray fluorescence cross sections in Er, Ta, W and Au at excitation energies of 16.896, 22.581, 25.770, 32.890, 38.184, 43.949, 50.214 and 59.5 keV were investigated. Measurements were made using a low energy Si(Li) detector coupled to a model 4096 computerized multi-channel analyser. The experimental results were compared with the theoretically calculated values of L X-rays fluorescence cross sections and other experimental results. Good agreement was observed between experimental and theoretical values.