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.     

Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Eye-safe compact scanning LIDAR technology

A 1.5-μm eye-safe, 3-D scanning, and compact Mie LIght Detection and Ranging (LIDAR) is presented. The transmitter of the LIDAR is based on a KTA optical parameter oscillator (OPO) resonator. For detecting return signals, an InGaAs APD is used. The all solid-state OPO laser transmitter has the feature of small volume and lightweight, which allows a 165-lb compact eye-safe scanning LIDAR to be constructed. A system simulation using our own model was conducted to direct the system development. A method to solve the problem with small active area APD detectors was developed and described. The preliminary field-test measurement results indicated that the LIDAR has the capability to detect aerosols and clouds in lower atmospheres up to three dimensions.     

Cycle and circle tests of balance in gain graphs: Forbidden minors and their groups

We examine two criteria for balance of a gain graph, one based on binary cycles and one on circles. The graphs for which each criterion is valid depend on the set of allowed gain groups. The binary cycle test is invalid, except for forests, if any possible gain group has an element of odd order. Assuming all groups are allowed, or all abelian groups, or merely the cyclic group of order 3, we characterize, both constructively and by forbidden minors, the graphs for which the circle test is valid. It turns out that these three classes of groups have the same set of forbidden minors. The exact reason for the importance of the ternary cyclic group is not clear. © 2005 Wiley Periodicals, Inc. J Graph Theory     

Wechselnde Bindungen in einem Zweikörpersystem mit trockener Reibung

Übersicht Betrachtet wird ein zwangserregtes Zweikörpersystem mit wechselnden Bindungen infolge trockener Reibung. Stationäre Bewegungen werden als Grenzfall instationärer Einschwingvorgänge berechnet. Abhängig von den Systemparametern ergeben sich drei typische Bewegungsformen. Ihnen entsprechen dauernde Haftzustände, wechselnde Haft-Gleitzustände oder dauernde Gleitzustände an der Berührfläche beider Körper.

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Intermittant constraints in a two-body-system with dry friction

Summary An externally excited two-body-system with intermittant constraints due to dry friction is considered. Stationary motions are calculated as limit cases of instationary transients. Depending on the parameters of the system, three typical modes are of interest. These correspond to permanent sticking, slipstick behaviour, or to permanent slipping in the contact surface of the bodies, respectively.

     

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.     

Robust Speed Control of a Low Damped Electromechanical System Based on CRONE Control: Application to a Four Mass Experimental Test Bench

Robust speed control of a low damped electromechanical system with backlash is studied, controlled load angular speed being not measured. The proposed control strategy combines a Luenberger observer (load angular speed and load torque disturbance estimations) and a robust CRONE controller. The observer provides estimation of the load angular speed and of the disturbance torque applied on the load. Through the computation of only three independent parameters (as many as a PID controller), the CRONE controller permits to ensure the robust speed control of the load in spite of plant parametric variations and speed observation errors. The proposed control strategy is applied to a four mass experimental test bench.