Bound states and resonance states of the plasma-embedded tdμ and ddμ molecular ions

We have investigated the bound states and resonance states of plasma-embedded tdμ and ddμ molecular ions using accurate correlated basis functions. The plasma effect has been taken care of by considering the Debye shielding approach of plasma modeling which admits a variety of plasma conditions. The density of resonance states are calculated using the stabilization method. The ground and excited states energies, and the S-wave resonance energies of tdμ and ddμ molecular ions immersed in plasmas are reported for various shielding parameters, along with the 1S and 2S threshold energies of the tμ and dμ atoms.     

Unified reciprocity of dithiophosphate by dichalcogenophosph(in)ate ligands on copper hydride nanoclusters via ligand exchange reaction

A structural study of ligand exchange on chalcogen‐passivated copper nanoclusters is far less developed. Herein, we report the synthesis of polyhydrido copper nanoclusters [Cu₂₀H₁₁{Se₂P(O ⁱBu)₂}₉] ( 2 ) passivated by Se‐donor ligands via ligand replacement reaction on [Cu₂₀H₁₁{S₂P(O ⁱPr)₂}₉] ( 1 ) with NH₄[Se₂P(O ⁱBu)₂]. In parallel to the synthesis of 2 , cluster [Cu₂₀H₁₁{S₂P(CH₂CH₂Ph)₂}₉] ( 4 ) was produced by the ligand exchange reaction on a new derivative of 1 , that is [Cu₂₀H₁₁{S₂P(O ⁿPr)₂}₉] ( 3 ). Solid state structures of both clusters 2 and 4 were unequivocally established by single‐crystal X‐ray diffraction studies and cluster 4 epitomizes exceptional case to preserve both the shape and size of the nanocluster during the course of ligand exchange. Structurally precise cluster 2 is the second example where the copper hydride nanocluster is stabilized by Se‐donor ligands. The anatomy of 2 can be visualized as a twisted cuboctahedral Cu₁₃ core, two triangular faces of which are capped by a Cu₆ cupola and a single Cu atom along the C₃ rotational axis.     

Electronic Structure and Triplet–Triplet Energy Transfer in Artificial Photosynthetic Antennas

Three Pd(II) phthalocyanine–carotenoid dyads featuring chromophores linked by amide bonds were prepared in order to investigate the rate of triplet–triplet (T‐T) energy transfer from the tetrapyrrole to the covalently attached carotenoid as a function of the number of conjugated double bonds in the carotenoid. Carotenoids having 9, 10 and 11 conjugated double bonds were studied. Transient absorption measurements show that intersystem crossing in the Pd(II) phthalocyanine takes place in 10 ps in each case and that T‐T energy transfer occurs in 126, 81 and 132 ps in the dyads bearing 9, 10 and 11 double bond carotenoids, respectively. To identify the origin of this variation in T‐T energy transfer rates, density functional theory (DFT) was used to calculate the T‐T electronic coupling in the three dyads. According to the calculations, the primary reason for the observed T‐T energy transfer trend is larger T‐T electronic coupling between the tetrapyrrole and the 10‐double bond carotenoid. A methyl group adjacent to the amide linker that connects the Pd(II) phthalocyanine and the carotenoid in the 9 and 11‐double bond carotenoids is absent in the 10‐double bond carotenoid, and this difference alters its electronic structure to increase the coupling.     

Finely Controlled Circularly Polarized Luminescence of a Mechano‐Responsive Supramolecular Polymer

Finely controlled circularly polarized luminescence (CPL) supramolecular polymerization based on a tetraphenylethene core with four l ‐ or d ‐alanine branch side chains (l ‐ 1 and d ‐ 1 ) in the solution state is presented, resulting from the tuning of mechanical stimulus. Weak, green emissions of l ‐ 1 and d ‐ 1 in tetrahydrofuran (THF) were converted into strong blue emissions by tuning the mechanical stimulus. The strong blue emissions were caused by an aggregation‐induced emission (AIE) effect during the formation of a supramolecular polymer. Lag time in the supramolecular polymerization was drastically reduced by the mechanical stimulus, which was indicative of the acceleration of the supramolecular polymerization. A significant enhancement of circular dichroism (CD) and CPL signals of l ‐ 1 and d ‐ 1 was observed by tuning the rotational speed of the mechanical stimulus, implying that the chiral supramolecular polymerization was accelerated by the mechanical stimulus.     

Neutron activation analysis of carbonate reference materials: coral (JCp-1) and giant clam (JCt-1)

Journal of Radioanalytical and Nuclear Chemistry - Two kinds of carbonate reference materials, coral (JCp-1) and giant clam (JCt-1), were subjected to neutron activation analysis (NAA) using the...     

Nanoconfined heliconical structure of twist-bend nematic liquid crystal phase

We produced controlled heliconical structures of a twist-bend nematic (N_TB) liquid-crystal (LC) phase in nanoconfinement in a porous anodic aluminium oxide (AAO) film. The structural parameters of the N_TB phase such as conical angle and helical pitch can be modulated by varying the surface energy of the inner surface of the porous AAO film, done by using different self-assembled monolayers (SAMs). The LC molecules tend to be more freely packed, thus forming a larger conical angle, when placed on the tri-deca-fluoro-1,1,2,2-tetrahydrooctyl-trichlorosilane (FOTS)-treated substrate, which has a relatively low surface energy. In contrast, the molecules form a more tightly packed structure, and thus a smaller conical angle, when placed on the 2-(methoxy(polyethyleneoxy)-propyl)trimethoxysilane (PEG 6/9)-treated substrate, which has higher surface energy. This work improves our collective understanding of self-assembled heliconical structures in the N_TB phase.     

Optical measurement of neural activity using surface plasmon resonance

We demonstrate that surface plasmon resonance (SPR) is applicable to the optical detection of neural signals. A low-noise SPR sensor was developed as a label- and artifact-free method for the extracellular recording of neural activity. The optical responses obtained from a rat sciatic nerve were highly correlated with simultaneously recorded electrical responses. Additional studies with stimulation intensity and lidocaine further confirmed that the optically measured signals originated from neural activities.     

Sensitive and automated detection of iron-oxide-labeled cells using phase image cross-correlation analysis

Superparamagnetic iron oxide (SPIO) nanoparticles are increasingly being used to noninvasively track cells, target specific molecules and monitor gene expression in vivo. Contrast changes that are subtle relative to intrinsic sources of contrast present a significant detection challenge. Here, we describe a postprocessing algorithm, called Phase map cross-correlation Detection and Quantification (PDQ), with the purpose of automating identification and quantification of localized accumulations of SPIO agents. The method is designed to sacrifice little flexibility - it works on previously acquired data and allows the use of conventional high-SNR pulse sequences with no extra scan time. We first investigated the theoretical detection limits of PDQ using a simulated dipole field. This method was then applied to three-dimensional (3D) MRI data sets of agarose gel containing isolated dipoles and ex vivo transplanted allogenic rat hearts infiltrated by numerous iron-oxide-labeled macrophages as a result of organ rejection. A simulated dipole field showed this method to be robust in very low signal-to-noise ratio images. Analysis of agarose gel and allogenic rat heart shows that this method can automatically identify and count dipoles while visualizing their biodistribution in 3D renderings. In the heart, this information was used to calculate a quantitative index that may indicate its degree of cellular infiltration.     

Interfaces in perovskite heterostructures

Recent advances in film synthesis have made it possible to investigate the properties of well-controlled interfaces in perovskite metal-oxides. A review of published experimental data and computational results indicate that so far most interfaces that have been analyzed in ferroelectric materials—while necessary to impose large lattice strain on the polar material—contribute little to the ferroelectricity and may instead be detrimental to the desired properties. In contrast, a very different situation arises at interfaces that show changes in the electronic configuration as a consequence of a compositional discontinuity. Data is shown for LaMnO₃/SrTiO₃ superlattices as an example of electronic effects that produce enhanced properties, further illustrating the richness of interfacial properties that can be obtained at interfaces (as shown in numerous published results for different but related interfaces).