Non-centrosymmetric tetrameric assemblies of tetramethylammonium halides with uranyl salophen complexes in the solid state

Ditopic salophen-UO(2) receptors 1-4 and 7 co-crystallize with tetramethylammonium (TMA) chloride and fluoride salts producing good quality crystals amenable for X-ray diffraction characterization. The arrangement of the receptor and salt units in the crystal lattice is such that tetrameric ball-shaped assemblies are formed, where an inner cluster of four TMA cations are surrounded by an outer shell of four UO(2)-bound anions. These elaborate architectures, which occur in all cases, regardless of a certain degree of structural modification on the receptors, lead to lattices that belong to non-centrosymmetric (NCS) space groups. Interestingly, the tetragonal symmetry of the tetrameric ball-shaped assemblies is either retained (I4?) or lost (R3c and I4?3d) at the lattice level, without compromising the NCS nature of the crystal lattices. The principal X-ray investigation on TMAX (X = Cl/F) co-crystals, that is, 1-(TMA)Cl, 2-(TMA)Cl, 3-(TMA)Cl, 4-(TMA)Cl, 7-(TMA)Cl, and 7-(TMA)F, is accompanied by NMR and electrospray ionization (ESI) mass spectrometry studies to gather additional insight on the modality of formation of the solid state structures observed. The important role of cation-π interactions in the receptor-salt recognition process is renewed and strengthened by comparison with NMR titration data with a novel reference compound, the salophen-UO(2) complex 8. Given the importance of NCS and polar crystalline solids in the development of functional materials, this study shows that this property can be introduced into elaborate host-guest systems, as those which assemble in the architectures described here, thus expanding its field of applicability.     

Synthesis and thermal behavior of Janus dendrimers,part 2

The thermal properties of twelve Janus-type dendrimers up to the second generation were evaluated by termogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Compounds consist of the dendritic bisMPA based polyester moieties, and either 3,4-bis-dodecyloxybenzoic acid, 3,5-bis-dodecyloxybenzoic acid or 3,4,5-tris-dodecyloxybenzoic acid moieties, attached to opposite sides of the pentaerythritol core. The thermal stability of the compounds was evaluated by TGA, displaying onset decomposition temperatures (T_d) at around 250 °C. DSC measurements upon heating and cooling confirmed that OH terminated Janus dendrimers featuring large polarity difference in opposite sides display liquid crystalline phases with exception of 3,5-type G1 dendrimer; while acetonide terminated dendrimers displayed merely melting transitions. Dendrimers having terminal alkyl chains at positions 3,4 or 3,4,5 in aromatic moieties exhibited enantiotropic mesophases. However, the thermal behavior of the dendrimers with 3,5-substitution pattern was different: the 3,5-type G1 dendrimer exhibit a lack of mesomorphic transition, and in the case of the 3,5-type G2 dendrimer, the mesophase was absent in the first heating scan but was observed during the subsequent cooling and heating scans at the rate of 10 °C/min.     

Avoiding eddy-current problems in ultra-low-field MRI with self-shielded polarizing coils

In ultra-low-field magnetic resonance imaging (ULF MRI), superconductive sensors are used to detect MRI signals typically in fields on the order of 10-100 μT. Despite the highly sensitive detectors, it is necessary to prepolarize the sample in a stronger magnetic field on the order of 10-100 mT, which has to be switched off rapidly in a few milliseconds before signal acquisition. In addition, external magnetic interference is commonly reduced by situating the ULF-MRI system inside a magnetically shielded room (MSR). With typical dipolar polarizing coil designs, the stray field induces strong eddy currents in the conductive layers of the MSR. These eddy currents cause significant secondary magnetic fields that may distort the spin dynamics of the sample, exceed the dynamic range of the sensors, and prevent simultaneous magnetoencephalography and MRI acquisitions. In this paper, we describe a method to design self-shielded polarizing coils for ULF MRI. The experimental results show that with a simple self-shielded polarizing coil, the magnetic fields caused by the eddy currents are largely reduced. With the presented shielding technique, ULF-MRI devices can utilize stronger and spatially broader polarizing fields than achievable with unshielded polarizing coils.     

On the resonant neutrinoless double-electron-capture decay of Ce

The double-electron-capture Q value for the ¹³⁶Ce decay to ¹³⁶Ba has been determined at JYFLTRAP. The measured value 2378.53(27) keV excludes the energy degeneracy with the ⁰⁺$0^{+}$ excited state of the decay daughter ¹³⁶Ba at 2315.32(7) keV in a resonant 0νECEC$0\nu \mathrm{ECEC}$ decay by 11.67 keV. The new Q value differs from the old adopted value 2419(13) keV (Atomic Mass Evaluation 2003) by 40 keV and is 50 times more precise. Our calculations show that the precise Q   value renders the resonant 0νECEC$0\nu \mathrm{ECEC}$ decay of ¹³⁶Ce undetectable by the future underground detectors. We measured also the double-β decay Q value of ¹³⁶Xe to be 2457.86(48) keV which agrees well with the value 2457.83(37) keV measured at the Florida State University.     

Effect of hydrogen doping in ZnO thin films by pulsed DC magnetron sputtering

This study examined the role of hydrogen impurities in highly oriented ZnO thin films. Hydrogen intentionally incorporated was found to play an important role as a donor in n-type conduction, improving the free carrier concentration. The increase in the conductivity of ZnO thin films was attributed to the two centers assigned to isolated hydrogen atoms in the anti-bonding sites as well as bond-centered interstitial hydrogen located between the Zn–O bonds and Zn vacancy passivated by one or two hydrogen atoms. Micro Raman spectroscopy showed two additional modes at approximately 501 and 573 cm⁻¹. These two peaks were attributed to damage to the crystal lattice, which could be explained by the optical-phonon branch at the zone boundary and host lattice defects, such as vacancy clusters, respectively.     

A Halogen‐Bonded Dimeric Resorcinarene Capsule

Iodine (I₂) acts as a bifunctional halogen‐bond donor connecting two macrocyclic molecules of the bowl‐shaped halogen‐bond acceptor, N‐cyclohexyl ammonium resorcinarene chloride 1 , to form the dimeric capsule [(1,4‐dioxane)₃@ 1 ₂(I₂)₂]. The dimeric capsule is constructed solely through halogen bonds and has a single cavity (V=511 ų) large enough to encapsulate three 1,4‐dioxane guest molecules.     

Phase diagram of the uniaxial and biaxial soft-core Gay-Berne model

Classical molecular dynamics simulations have been used to explore the phase diagrams for a family of attractive-repulsive soft-core Gay-Berne models [R. Berardi, C. Zannoni, J. S. Lintuvuori, and M. R. Wilson, J. Chem. Phys. 131, 174107 (2009)] and determine the effect of particle softness, i.e., of a moderately repulsive short-range interaction, on the order parameters and phase behaviour of model systems of uniaxial and biaxial ellipsoidal particles. We have found that isotropic, uniaxial, and biaxial nematic and smectic phases are obtained for the model. Extensive calculations of the nematic region of the phase diagram show that endowing mesogenic particles with such soft repulsive interactions affect the stability range of the nematic phases, and in the case of phase biaxiality it also shifts it to lower temperatures. For colloidal particles, stabilised by surface functionalisation, (e.g., with polymer chains), we suggest that it should be possible to tune liquid crystal behaviour to increase the range of stability of uniaxial and biaxial phases (by varying solvent quality). We calculate second virial coefficients and show that they are a useful means of characterising the change in effective softness for such systems. For thermotropic liquid crystals, the introduction of softness in the interactions between mesogens with overall biaxial shape (e.g., through appropriate conformational flexibility) could provide a pathway for the actual chemical synthesis of stable room-temperature biaxial nematics.