Exposure of [MnIII6CrIII]3+ single-molecule magnets to soft X-rays: The effect of the counterions on radiation stability

X-ray absorption spectroscopy studies of the [Mn^III₆Cr^III]³⁺ single-molecule magnet deposited as a microcrystalline layer on gold substrates are presented. The oxidation state of the manganese centers changes from Mn^III to Mn^II due to irradiation with soft X-rays. The influence of the charge-neutralizing anions on the stability of [Mn^III₆Cr^III]³⁺ against soft X-ray exposure is investigated for the different anions tetraphenylborate (BPh₄^?), lactate (C₃H₅O₃^?) and perchlorate (ClO₄^?). The exposure dependence of the radiation-induced reduction process is compared for [Mn^III₆Cr^III]³⁺ with the three different anions.     

Hydrogen-bonding networks from first-principles: exploring the guanidine crystal

Hydrogen bonding is among the most important interactions in molecular crystals, and examples are abundant. As a consequence of such interactions, many molecules crystallize in complex but intriguing structures, in contrast to the relatively simple packing principles of metallic or ionic solids. In this work, we present a computational approach based on plane-wave density-functional theory (DFT) and supercell techniques, aiming to understand and quantify hydrogen-bonded networks in the solid state and in two-, one-, and zero-dimensional fragments derived from the molecular crystal. With such methodology at hand, we investigate guanidine, a fitting example of a molecular crystal and an important compound for inorganic and organic chemistry alike. On the basis of our computations, we discuss the initially proposed layered structure of guanidine and identify both stabilizing and destabilizing cooperative interactions in the three crystalline dimensions.     

Azaphthalocyanines with fused triazolo rings: formation of sterically stressed constitutional isomers

The presented work deals with synthesis and isolation of constitutional isomers of triazolo-fused azaphthalocyanines. Distribution of the isomers did not follow the statistical calculations due to steric effects of the substituents preferring the least sterically stressed C(4h) isomer.     

Isolation and Characterization of Novel Capsorubin‐Like Carotenoids from the Red Mamey (Pouteria sapota)

From the ripe fruits of red mamey (Pouteria sapota), two new carotenoids, 3′‐deoxycapsorubin and 3,3′‐dideoxycapsorubin, were isolated and identified based on their UV/VIS, CD, ¹H‐NMR, and mass spectral data.     

Magnesium azaphthalocyanines: an emerging family of excellent red-emitting fluorophores

Magnesium(II), zinc(II), and metal-free phthalocyanines (Pcs) and azaphthalocyanines (AzaPcs) containing alkylsulfanyl, aryloxy, and dialkylamino peripheral substituents have been synthesized. The complexation of magnesium(II) by metal-free Pcs and AzaPcs has been studied in detail to determine the optimal reaction conditions necessary to ensure a complete conversion. Photophysical and photochemical measurements in tetrahydrofuran showed that magnesium(II) AzaPcs with aryloxy and alkylsulfanyl substituents have excellent fluorescent properties (Φ(F) up to 0.73) and that the corresponding zinc(II) Pcs are efficient singlet oxygen producers (Φ(Δ) up to 0.68). The presence of dialkylamino substituents causes intramolecular charge transfer within the molecule that competes with fluorescence and singlet oxygen formation. Alkylsulfanyl MgAzaPc and ZnAzaPc were the most photostable compounds among the series of studied derivatives. In addition, high molar absorption coefficients (ε ～ 300,000 M(-1) cm(-1)), absorption (λ(max) ～ 650 nm), and emission (λ(em) ～ 660 nm, high Φ(F)) in the red region suggest that these molecules are potential fluorescent probes that are superior to the commercial red cyanine dye Cy5. MgAzaPc, when incorporated into lipidic bilayers of liposomes, maintains excellent fluorescence properties (Φ(F) = 0.64). Water-soluble MgAzaPc with quaternary ammonium peripheral substituents retained a high fluorescence quantum yield even in water (Φ(F) = 0.25). The described properties show that magnesium(II) AzaPcs are excellent red-emitting fluorophores with potential applications as fluorescent probes in sensing or in vitro imaging applications.     

Command surfaces, 20. Fixation of surface-assisted homogeneous alignment of nematic liquid crystals by cationic photopolymerization

The surface-assisted alignment of a nematic liquid crystal yields a persistent ordered structure upon cationic photopolymerization of liquid-crystalline epoxides. Linearly polarized light irradiation of a photocrosslinkable polymer containing azobenzene moieties played a crucial role in this procedure since the photoinduced alignment is not deteriorated by heating for polymerization.     

Electrochemical Analysis of Glycoprotein Samples Prepared on a Pneumatically‐controlled Microfluidic Device

In this work, we designed and manufactured a microfluidic device for isolation and purification of glycoprotein samples. The conceived sample preparation device was fabricated in polycarbonate by micro‐milling. The flow control and the fluid dosage into the micro‐channels was solved by equipping the device with integrated pneumatic valves. The biochemical functionality was provided by beaded support modified by molecules with affinity to glycoproteins which was stacked inside the micro‐channel reminiscent of packed affinity columns used in glycoprotein lectin assays. Unlabeled glycoproteins, namely fetuin, asialofetuin, and prostate‐specific antigen, were voltammetrically analyzed using catalytic peak H at silver amalgam electrode.     

Characterizing Polyoxovanadate-Alkoxide Clusters Using Vanadium K-Edge X-Ray Absorption Spectroscopy

A number of technologies would benefit from developing inorganic compounds and materials with specific electronic and magnetic exchange properties. Unfortunately, designing compounds with these properties is difficult because metal⋅⋅⋅metal coupling schemes are hard to predict and control. Fully characterizing communication between metals in existing compounds that exhibit interesting properties could provide valuable insight and advance those predictive capabilities. One such class of molecules are the series of Lindqvist iron-functionalized and hexavanadium polyoxovanadate-alkoxide clusters, which we characterized here using V K-edge X-ray absorption spectroscopy. Substantial changes in the pre-edge peak intensities were observed that tracked with the V 3d-electron count. The data also suggested substantial delocalization between the vanadium cations. Meanwhile, the Fe^III cations were electronically isolated from the polyoxovanadate core.     

Quadrupolar ordering of phospholipid molecules in narrow necks of phospholipid vesicles

Shapes of phospholipid vesicles that involve narrow neck(s) were studied theoretically. It is taken into account that phospholipid molecules are intrinsically anisotropic with respect to the membrane normal and that they exhibit quadrupolar orientational ordering according to the difference between the local principal membrane curvatures. Direct interactions between oriented molecules were considered within a linear approximation of the energy coupling with the deviatoric field. The equilibrium shapes of axisymmetric closed vesicles were studied by minimization of the free energy of the phospholipid bilayer membrane under relevant geometrical constraints. The variational problem was stated by a system of Euler-Lagrange differential equations that revealed a singularity in the derivative of the meridian curvature at points where the effect of the orientational ordering exactly counterbalances the effect of the isotropic bending. The system of Euler-Lagrange differential equations was solved numerically to yield consistently related equilibrium orientational distribution of the phospholipid molecules and vesicle shape. According to our estimation of the model constants the formation of the neck is promoted if direct interactions between the oriented molecules are taken into account. It was shown that the energy of the equilibrium shapes is considerably affected by the quadrupolar ordering of phospholipid molecules.