Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine

The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)Fe^III₂] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex 1 at room temperature and the magnetic behavior of 1 in the temperature range of 2–300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively. The neutral character of dpp-BIAN in 1 was confirmed by IR and UV spectroscopy. The electrochemistry of 1 was studied in solution and solid state using cyclic voltammetry. The generation of the radical anion form of the dpp-BIAN ligand upon reduction of 1 in a CH₂Cl₂ solution was monitored by EPR spectroscopy.     

Single-electron coherence: Finite temperature versus pure dephasing

We analyze a coherent injection of single electrons on top of the Fermi sea in two situations, at finite-temperature and in the presence of pure dephasing. Both finite-temperature and pure dephasing change the property of the injected quantum states from pure to mixed. However, we show that the temperature-induced mixedness does not alter the coherence properties of these single-electron states. In particular two such mixed states exhibit perfect antibunching while colliding at an electronic wave splitter. This is in striking difference with the dephasing-induced mixedness which suppresses antibunching. On the contrary, a single-particle shot noise is suppressed at finite temperatures but is not affected by pure dephasing. This work therefore extends the investigation of the coherence properties of single-electron states to the case of mixed states and clarifies the difference between different types of mixedness.     

Reprint of : Single-electron coherence: Finite temperature versus pure dephasing

We analyze a coherent injection of single electrons on top of the Fermi sea in two situations, at finite-temperature and in the presence of pure dephasing. Both finite-temperature and pure dephasing change the property of the injected quantum states from pure to mixed. However, we show that the temperature-induced mixedness does not alter the coherence properties of these single-electron states. In particular two such mixed states exhibit perfect antibunching while colliding at an electronic wave splitter. This is in striking difference with the dephasing-induced mixedness which suppresses antibunching. On the contrary, a single-particle shot noise is suppressed at finite temperatures but is not affected by pure dephasing. This work therefore extends the investigation of the coherence properties of single-electron states to the case of mixed states and clarifies the difference between different types of mixedness.     

Generation of a four-qubit cluster state for atoms in a thermal cavity

We propose two schemes for generating a four-atom cluster state in a thermal cavity. With the assistant of a strong classical field the photon-number-dependent parts in the effective Hamiltonian are canceled. Thus the schemes are insensitive to the thermal field. The schemes can also be used to generate the cluster state for the trapped ions in thermal motion.     

Frequency combinations in the magnetoresistance oscillations spectrum of a linear chain of coupled orbits with a high scattering rate

The oscillatory magnetoresistance spectrum of the organic metal (BEDO)₅Ni(CN)₄. 3C₂H₄(OH)₂ has been studied up to 50 T, in the temperature range from 1.5 K to 4.2 K. In high magnetic field, its Fermi surface corresponds to a linear chain of quasi-two-dimensional orbits coupled by magnetic breakdown (MB). The scattering rate consistently deduced from the data relevant to the basic α and the MB-induced β orbits is very large which points to a significant reduction of the chemical potential oscillation. Despite of this feature, the oscillations spectrum exhibits many frequency combinations. Their effective masses and (or) Dingle temperature are not in agreement with either the predictions of the quantum interference model or the semiclassical model of Falicov and Stachowiak.     

Effects of Cd2+ substitution on elastic properties and step-like anomalies in Tl0.9Bi0.1Sr1.8Yb0.2Ca1−xCdxCu1.99Fe0.01o7−δ superconductors

Cd-doped Tl_0.9Bi_0.1Sr_1.8Yb_0.2Ca_1−xCd_xCu_1.99Fe_0.01O_7−δ (x=0–0.4) bulk superconductor samples were prepared by solid-state reaction method, to examine the effect of Cd on ultrasonic velocity and elastic behavior of the samples. The samples were characterized by X-ray diffraction, DC electrical resistivity and temperature dependent ultrasonic velocity measurements. DC electrical resistivity measurement showed all the samples exhibit metallic normal-state behavior with the highest T_{c zero} observed at around 76.4 K (x=0.3). Ultrasonic velocity measurements at 80 K showed a non-linear increase in both absolute longitudinal and shear velocities as well as elastic moduli with Cd substitution with the largest increase observed for the x=0.3 sample. Temperature dependant longitudinal modulus showed elastic anomaly characterized by a step-like slope change at around 230 K for x=0 & x=0.3 and at around 250 K for x=0.4 with the x=0.3 sample showing the sharpest slope change. A comparison between experimental data and calculated lattice anharmonicity curve based on the model proposed by Lakkad, showed large deviation of the experimental longitudinal modulus curves for (x=0.3) from the calculated anharmonicity curves indicating that the elastic behavior was strongly influenced by the existence of the step-like longitudinal anomaly. On the other hand, our analysis using the Landau free energy model found that the anomalous step-like elastic behavior fitted well with the equation derived from the model for regions below and above the elastic anomaly temperature, T_A. The fitting indicated that the anomaly is related to a phase transition that is suggested to involve ordering of oxygen which introduces strain in the system.     

Limitations on the performance of ‘field mill’ fieldmeters with alternating electric fields

The response of field mill type electrostatic fieldmeters to alternating electric fields is limited by the chopping frequency. Measurements reported here show that alternating frequencies at the chopping frequency, and related harmonics, can create confusing low frequency outputs. Hence care is needed for interpreting observations where such alternating electric fields may be present.     

Single-Carbon-Fiber-Powered Microsensor for In Vivo Neurochemical Sensing with High Neuronal Compatibility

The development of new principles and techniques with high neuronal compatibility for quantitatively monitoring the dynamics of neurochemicals is essential for deciphering brain chemistry and function but remains a great challenge. We herein report a neuron-compatible method for in vivo neurochemical sensing by powering a single carbon fiber through spontaneous bipolar electrochemistry as a new sensing platform. By using ascorbic acid as a model target to prove the concept, we found that the single-carbon-fiber-powered microsensor exhibited a good response, high stability and, more importantly, excellent neuronal compatibility. The microsensor was also highly compatible with electrophysiological recording, thus enabling the synchronous recording of both chemical and electrical signals. The sensing principle could be developed for in vivo monitoring of various neurochemicals in the future by rationally designing and tuning the electrochemical reactions at the two poles of the carbon fiber.     

Polymer Lamellae as Reaction Intermediates in the Formation of Copper Nanospheres as Evidenced by In Situ X‐ray Studies

The classical nucleation theory (CNT) is the most common theoretical framework used to explain particle formation. However, nucleation is a complex process with reaction pathways which are often not covered by the CNT. Herein, we study the formation mechanism of copper nanospheres using in situ X‐ray absorption and scattering measurements. We reveal that their nucleation involves coordination polymer lamellae as pre‐nucleation structures occupying a local minimum in the reaction energy landscape. Having learned this, we achieved a superior monodispersity for Cu nanospheres of different sizes. This report exemplifies the importance of developing a more realistic picture of the mechanism involved in the formation of inorganic nanoparticles to develop a rational approach to their synthesis.     

SLIM: A Short‐Linked,Highly Redox‐Stable Trityl Label for High‐Sensitivity In‐Cell EPR Distance Measurements

The understanding of biomolecular function is coupled to knowledge about the structure and dynamics of these biomolecules, preferably acquired under native conditions. In this regard, pulsed dipolar EPR spectroscopy (PDS) in conjunction with site‐directed spin labeling (SDSL) is an important method in the toolbox of biophysical chemistry. However, the currently available spin labels have diverse deficiencies for in‐cell applications, for example, low radical stability or long bioconjugation linkers. In this work, a synthesis strategy is introduced for the derivatization of trityl radicals with a maleimide‐functionalized methylene group. The resulting trityl spin label, called SLIM, yields narrow distance distributions, enables highly sensitive distance measurements down to concentrations of 90 nm , and shows high stability against reduction. Using this label, the guanine‐nucleotide dissociation inhibitor (GDI) domain of Yersinia outer protein O (YopO) is shown to change its conformation within eukaryotic cells.