The Role of Radical Bridges in Polynuclear Single-Molecule Magnets

Employing radical bridges between anisotropic metal ions has been a viable route to achieve high-performance single-molecule magnets (SMMs). While the bridges have been mainly considered for their ability to promote exchange interactions, the crystal-field effect arising from them has not been taken into account explicitly. This lack of consideration may distort the understanding and limit the development of the entire family. To shed light on this aspect, herein we report a theoretical investigation of a series of N -radical-bridged diterbium complexes. It is found that while promoting strong exchange coupling between the terbium ions, the N -radical induces a crystal field that interferes destructively with that of the outer ligands, and thus reduces the overall SMM behavior. Based on the theoretical results, we conclude that the SMM behavior in this series could be further maximized if the crystal field of the outer ligands is designed to be collinear with that of the radical bridge. This conclusion can be generalized to all exchange-coupled SMMs.     

Notiz über Parachloraldehyd

Ohne Zusammenfassung     

Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Synthesis and Characterization of Silica@Copper Core–Shell Nanoparticles: Application for Conjugate Addition Reactions

Silica@copper (SiO₂@Cu) core–shell nanoparticles were synthesized and well characterized by XRD, TEM, AFM, XPS, UV/Vis, TGA–MS, and ICP–AES techniques. The synthesized SiO₂@Cu core–shell nanoparticles were employed as catalysts for the conjugate addition of amines to α,β‐unsaturated compounds in water to obtain β‐amino carbonyl compounds in excellent yields in shorter reaction times. Furthermore, the catalyst works well for hetero‐Michael addition reactions of heteroatom nucleophiles such as thiols to α,β‐unsaturated compounds. As the reaction is performed in water, it allows for easy recycling of the catalyst with consistent activity.     

An enrichment method of molybdenum on a cellulose nitrate resin for the determination by electrothermal atomic absorption spectrometry coupled with the resin suspension injection.

Cellulose derivative resin (CDR) suspensions containing resin particles of cellulose nitrate (CDR(CN)), cellulose acetate (CDR(CA)), or cellulose triacetate (CDR(CTA)) were prepared as the sorbent for resin suspension injection (RSI) electrothermal atomic absorption spectrometry (ETAAS), in which fine resin particles holding a desired trace element were directly injected into the graphite tube as the suspension. To compare the sorption ability, the distribution ratios of the Mo(VI)-phenylfluorone complex were measured between the aqueous phase and the sorbents, including the CDRs mentioned above and the finely divided anion exchange resin (AR). The results showed that the sorption ability decreases in the following order: CDR(CN) > or = AR > CDR(CA) > or = CDR(CTA). It was concluded that CDR(CN) was able to extract more than 98% of Mo(VI), and was suitable for RSI-ETAAS as well as AR. CDR(CN) was used for the determination of Mo in NIES certified reference materials, No. 10 Rice flour-unpolished; the results showed fairly good agreements between the analytical values and the certified values.     

Direct observation of chemical oscillation at a water/nitrobenzene interface with a sodium-alkyl-sulfate system.

The oscillation of the interfacial tension and electrical potential at a water/nitrobenzene interface was observed with homologous anionic surfactant molecules, sodium-alkyl-sulfates. Concerning small molecules with a short hydrophobic carbon chain, the oscillation period and amplitude decreased with a decrease of the length of the alkyl chain. On the other hand, when surfactant molecules with a long hydrophobic carbon chain were used, no remarkable periodic oscillation occurred after the first oscillation. In all systems, an interfacial flow by Marangoni convection was observed when the oscillation took place. By monitoring the movement of carbon powder scattered on the liquid/liquid interface with a CCD camera, we could observe that the liquid/liquid interface expanded outward from the area on which the surfactant molecules adsorbed when the oscillation occurred. When the small molecule was used, the speed of expansion of the interface (flow speed) was small and shrinkage followed by expansion of the interface repeatedly occurred. However, when the large molecule was used, the flow speed was large and expansion occurred only one time. These results show that hydrodynamic factors and surface activities are important in chemical oscillation systems.     

Validation of a method for predicting the precision, limit of detection and range of quantitation in competitive ELISA.

The mathematical model for predicting the precision, limit of detection (LOD) and range of quantitation (ROQ) in a competitive enzyme-linked immunosorbent assay (ELISA) proposed by Hayashi et al. (Anal. Chem., 2004, 76, 1295) was validated. The model describes the relative standard deviation (RSD) of concentration estimates by the RSDs of pipetting volumes of analyte, enzyme-conjugated antigen, antibody and substrate solutions, and the standard deviation (SD) of inherent absorbances between the wells in an ELISA plate. For 6 kinds of direct competitive ELISA kits, the LOD and ROQ predicted by the model agreed well with those obtained by experiments with real samples. It was also confirmed that the model is applicable to the prediction of uncertainty that depends on the pipetting error of the viscous antiserum solution. The model was demonstrated to be useful for estimating the LOD and ROQ of competitive ELISA.     

The absorptive pion-nucleus optical potential

We calculate s-wave and p-wave absorptive pion-nucleus optical potentials assuming that a pion is absorbed by a pair of nucleons. Employing a model which takes into account both a single nucleon absorption with nucleon-nucleon correlations and rescattering, we obtain simple analytic expressions for Im B₀ sid Im C₀ of the pion-nucleus optical potential. The off-shell effect on the s-wave pion absorption is examined and shown to be strongly modified by short range correlations. The result for the p-wave absorptive part Im C₀ clearly shows the importance of the tensor correlations. The enhanced nn emission after π^? absorption is shown to be related with a large p-wave πN scattering length a₃₃ via the tensor correlations.