Engineering Gram Selectivity of Mixed‐Charge Gold Nanoparticles by Tuning the Balance of Surface Charges

Nanoparticles covered with ligand shells comprising both positively and negatively charged ligands exhibit Gram‐selective antibacterial action controlled by a single experimental parameter, namely the proportion of [+] and [?] ligands tethered onto these particles. Gram selectivity is attributed to the interplay between polyvalent electrostatic and non‐covalent interactions that work in unison to disrupt the bacterial cell wall. The [+/?] nanoparticles are effective in low doses, are non‐toxic to mammalian cells, and are tolerated well in mice. These results constitute the first example of rational engineering of Gram selectivity at the (macro)molecular level.     

On a new type of distance Fibonacci numbers

In this paper, we define a new kind of Fibonacci numbers generalized in the distance sense. This generalization is related to distance Fibonacci numbers and distance Lucas numbers, introduced quite recently. We also study distinct properties of these numbers for negative integers. Their representations and interpretations in graphs are also studied.     

A three‐dimensional AlIII/NaI metal–organic framework resulting from dimethylformamide hydrolysis

The three‐dimensional metal–organic framework poly[bis(dimethylammonium) [hexa‐μ₂‐formato‐κ¹²O:O′‐aluminium(III)sodium(I)]], {(C₆H₈N)₂[AlNa(HCOO)₆]}_n, was obtained serendipitously and has been characterized by X‐ray diffraction. The product has arisen as a result of a hydrolysis reaction of dimethylformamide (DMF) and contains dimethylammonium (DMA) cations included in structural voids formed by a three‐dimensional [AlNa(HCOO)₆]⁻ network. This study provides evidence that, in the presence of traces of aluminium, DMF stored in a glass bottle can be hydrolysed to formate and dimethylamine with simultaneous extraction of Na⁺ cations from the glass. It also demonstrates that care must be taken regarding the metal and water content when DMF is not freshly distilled, since the hydrolysis of amide can occur.     

Spectroscopy and crystal structure of anabasine salts

The anabasinium hydrochloride, hydriodide and perchlorate were characterized by IR and NMR spectroscopy as well as by X-ray diffraction. Anabasinium hydrochloride crystallizes with three independent ionic pairs in the asymmetric part of the orthorhombic unit cell, while anabasinium hydriodide and perchlorate crystals, being isostructural, are hexagonal and contain only one symmetry independent ionic pair. Despite these differences in the crystal data, both types of crystals display very similar helical solid-state patterns. The reported results combined with the CSD searches indicate an inherent tendency of anabasinium salts to crystallize with multiple asymmetric units, and to form folded arrangements in crystals. In the solid state the anabasinium cations predominantly adopt either synperiplanar or antiperiplanar conformations with respect to the mutual orientation of C^*–H and pyridine C–C(N) bonds, with deformations towards, respectively, (+) synclinal or (+) anticlinal rotamers.     

Thermodynamics of organic mixtures containing amines. X. Phase equilibria for binary systems formed by imidazoles and hydrocarbons: Experimental data and modelling using DISQUAC

(Solid + liquid) equilibrium (SLE) temperatures have been determined using a dynamic method for the systems (1H-imidazole, + benzene, + toluene, + hexane, or + cyclohexane; 1-methylimidazole + benzene, or + toluene, 2-methyl-1H-imidazole + benzene, + toluene, or + cyclohexane, and benzimidazole + benzene). In addition (liquid + liquid) equilibrium (LLE) temperatures have been obtained using a cloud point method for (1H-imidazole, + hexane, or + cyclohexane; 1-methylimidazole + toluene, and 2-methyl-1H-imidazole + cyclohexane). The measured systems show positive deviations from the Raoult’s law, due to strong dipolar interactions between amine molecules related to the high dipole moment of imidazoles. On the other hand, DISQUAC interaction parameters for the contacts present in these solutions and for the amine/hydroxyl contacts in (1H-imidazole + 1-alkanol) mixtures have been determined. The model correctly represents the available data for the examined systems. Deviations between experimental and calculated SLE temperatures are similar to those obtained using the Wilson or NRTL equations, or the UNIQUAC association solution model. The quasichemical interaction parameters are the same for mixtures containing 1H-imidazole, 1-methylimidazole, or 2-methyl-1H-imidazole and hydrocarbons. This may be interpreted assuming that they are members of a homologous series. Benzimidazole behaves differently.     

Measurements of the density and viscosity of binary mixtures of (hyper-branched polymer,B-H2004 + 1-butanol,or 1-hexanol,or 1-octanol,or methyl tert-butyl ether)

Density and viscosity were determined for binary mixtures of {hyper-branched polymer, Boltorn H2004 (B-H2004) + 1-alcohol (1-butanol, 1-hexanol, and 1-octanol)} at T = (298.15, 308.15, 318.15, 328.15, and 338.15) K and of {B-H2004 + methyl tert-butyl ether (MTBE)} at T = (298.15, 308.15, and 318.15) K and ambient pressure. The temperature dependence of density and viscosity is described by linear regression and by the Vogel–Fucher–Tammann equation, respectively. Excess volumes for the system {B-H2004 + MTBE} are presented as a function of mass fraction. Viscosity deviations were calculated and correlated by the Redlich–Kister polynomial expansions using also the mass fractions. The polynomial correlations describe the variation of viscosity with composition. A qualitative discussion on these quantities in terms of molecular interactions is reported.