High resolution 15N NMR of the 225 K phase transition of ammonia borane (NH3BH3): mixed order-disorder and displacive behavior

We report high resolution 15N NMR probing of the solid-solid phase transition of 15N-labeled ammonia borane (NH3BH3) at 225 K. Both the 15N isotropic chemical shift (delta iso) and the spin-lattice relaxation rate (T1-1) exhibited strong anomalies around 225 K. The analysis of T1-1 using the Bloembergen, Purcell, and Pound model showed that the motional correlation time, tau, increased from about 1 to 100 ps and the corresponding Arrhenius activation energy increased from 6 to 14.5 kJ/mol on going through the transition toward lower temperatures. The temperature dependence of delta iso was interpreted by an extension of the Bayer model. The time scale of the underlying motion was found to be in a reasonable agreement with the T1-1 data. These results imply that the NH3 rotor motion plays a pivotal role in the transition mechanism and that the transition is of both order-disorder and displacive type.     

Theoretical study of the spectroscopically relevant parameters for the detection of HNP(q) and HPN(q) (q = 0, +1, -1) in the gas phase

High level ab initio electronic structure calculations at different levels of theory have been performed on HNP and HPN neutrals, anions, and cations. This includes standard coupled cluster CCSD(T) level with augmented correlation-consistent basis sets, internally contacted multi-reference configuration interaction, and the newly developed CCSD(T)-F12 methods in connection with the explicitly correlated basis sets. Core-valence correction and scalar relativistic effects were examined. We present optimized equilibrium geometries, harmonic vibrational frequencies, rotational constants, adiabatic ionization energies, electron affinities, vertical detachment energies, and relative energies. In addition, the three-dimensional potential energy surfaces of HNP(-1,0,+1) and of HPN(-1,0,+1) were generated at the (R)CCSD(T)-F12b∕cc-pVTZ-F12 level. The anharmonic terms and fundamentals were derived using second order perturbation theory. For HNP, our best estimate for the adiabatic ionization energy is 7.31 eV, for the adiabatic electron affinity is 0.47 eV. The higher energy isomer, HPN, is 23.23 kcal∕mol above HNP. HPN possesses a rather large adiabatic electron affinity of 1.62 eV. The intramolecular isomerization pathways were computed. Our calculations show that HNP(-) to HPN(-) reaction is subject to electron detachment.     

Quantum phase transition from superparamagnetic to quantum superparamagnetic state in ultrasmall Cd(1-x)Cr(II)(x)Se quantum dots?

Despite a long history of success in formation of transition-metal-doped quantum dots (QDs), the origin of magnetism in diluted magnetic semiconductors (DMSs) is yet a controversial issue. Cr(II)-doped II-VI DMSs are half-metallic, resulting in high-temperature ferromagnetism. The magnetic properties reflect a strong p-d exchange interaction between the spin-up Cr(II) t(2g) level and the Se 4p. In this study, ultrasmall (~3.1 nm) Cr(II)-doped CdSe DMSQDs are shown to exhibit room-temperature ferromagnetism, as expected from theoretical arguments. Surprisingly, a low-temperature phase transition is observed at 20 K that is believed to reflect the onset of long-range ordering of the single-domain DMSQD.     

Production decisions under joint price and production uncertainty

While production decisions in the presence of price uncertainty have been extensively studied, this is not so for the case in which the level of production is itself uncertain. In this paper,we provide a decision analysis under multiplicative production uncertainty, both with and without price uncertainty. We depict equilibrium and obtain comparative statics results with the aid of a diagram based on the difference between expected price and marginal cost. Comparative statics results are obtained for the model with production uncertainty alone and also for simultaneous price and production uncertainty (including two special cases). We first derive results based on the Arrow–Pratt coefficients of risk aversion, and then supplement these with the Ross measure of relative risk aversion, since this proves useful in the presence of multiple sources of uncertainty. We find that increases in risk (both price and production) or input prices reduce expected output. However, expected output supply is an increasing function of (expected) price only for “low” levels of risk aversion, and in general the relationship is ambiguous.     

Observation of a half step magnetization in the {Cu3}-type triangular spin ring

We report pulsed field magnetization and ESR experiments on a {Cu3} nanomagnet, where antiferromagnetically coupled Cu(2+) (S = 1/2) ions form a slightly distorted triangle. The remarkable feature is the observation of a half step magnetization, hysteresis loops, and an asymmetric magnetization between a positive and a negative field in a fast sweeping external field. This is attributed to an adiabatic change of magnetization. The energy levels determined by ESR unveil that the different mixing nature of a spin chirality of a total S = 1/2 Kramers doublet by virtue of Dzyaloshinskii-Moriya interactions is decisive for inducing half step magnetization.     

Solventless Mechanosynthesis Of Bis(Indolyl)Methanes

Ball-milling technique as a solvent-free and an alternative green process was investigated for the eco-benign synthesis of bis(indolyl)methanes (BIMs) from various aldehydes and selected ketones with indoles in high yields. The present methodology has several advantages such as simple procedure, good yields, mild conditions, and reduced environmental consequences. The silica gel acts both as a grinding medium and an acid catalyst. The utility of this technique was demonstrated by synthesizing library of 17 BIMs including two natural products trisindoline and tris(1H-indol-3-yl)methane.     

Load-Deformation Behavior of Nitinol Stents

The rate of fracture of Nitinol stents in the superficial femoral artery (SFA) is higher than desirable. Development of more fracture-resistant stents requires a better understanding of in-vivo loads, how stents deform under these loads, and the influence of the artery on stent deformation. In the work reported here, testing devices were designed and constructed to measure loads in stents undergoing tensile, bending, and torsional deformations. Tests to measure mechanical stiffnesses were performed on stents, mock arteries, and stents emplaced in mock arteries. Significant stent/artery interaction was observed under tension and bending; little interaction occurred under torsion loads. The results are explained by changes in stent geometry under load. The deformation, load, and stent/artery interaction information will be useful in validating finite element codes for designing and analyzing stents.     

Anti-Inflammatory Potential of Fucoidan for Atherosclerosis: In Silico and In Vitro Studies in THP-1 Cells

Several diseases, including atherosclerosis, are characterized by inflammation, which is initiated by leukocyte migration to the inflamed lesion. Hence, genes implicated in the early stages of inflammation are potential therapeutic targets to effectively reduce atherogenesis. Algal-derived polysaccharides are one of the most promising sources for pharmaceutical application, although their mechanism of action is still poorly understood. The present study uses a computational method to anticipate the effect of fucoidan and alginate on interactions with adhesion molecules and chemokine, followed by an assessment of the cytotoxicity of the best-predicted bioactive compound for human monocytic THP-1 macrophages by lactate dehydrogenase and crystal violet assay. Moreover, an in vitro pharmacodynamics evaluation was performed. Molecular docking results indicate that fucoidan has a greater affinity for L-and E-selectin, monocyte chemoattractant protein 1 (MCP-1), and intercellular adhesion molecule-1 (ICAM-1) as compared to alginate. Interestingly, there was no fucoidan cytotoxicity on THP-1 macrophages, even at 200 µg/mL for 24 h. The strong interaction between fucoidan and L-selectin in silico explained its ability to inhibit the THP-1 monocytes migration in vitro. MCP-1 and ICAM-1 expression levels in THP-1 macrophages treated with 50 µg/mL fucoidan for 24 h, followed by induction by IFN-γ, were shown to be significantly suppressed as eight- and four-fold changes, respectively, relative to cells treated only with IFN-γ. These results indicate that the electrostatic interaction of fucoidan improves its binding affinity to inflammatory markers in silico and reduces their expression in THP-1 cells in vitro, thus making fucoidan a good candidate to prevent inflammation.