Spin crossover transition of Fe(phen)2(NCS)2: periodic dispersion-corrected density-functional study

Periodic dispersion corrected DFT calculations have been performed to study the spin-crossover transition of Fe(phen)(2)(NCS)(2) in the molecular and in the crystalline state. We show that London dispersion interactions play a crucial role in the cohesion of the crystals. Based on calculations of vibrational eigenstates of the isolated molecule and of the crystalline phase in both the low- and high-spin states, the transition entropies and enthalpies have been calculated. We demonstrate that, due to the stabilization of the low-spin state by intermolecular dispersion forces, the transition enthalpy at the transition temperature is larger for the crystalline phase in comparison with an isolated molecule. The effective coordination number of the nitrogen atoms of the ligands around the iron atom has been identified as the order parameter driving the quasi-reversible low-spin to high-spin transition in the crystal. Finally, using constrained geometry relaxations at fixed values of the coordination number, we computed the energy barrier of the LS to HS transition and found it to be in a reasonable agreement with the experimental value.     

Does shape matter? Bioeffects of gold nanomaterials in a human skin cell model

Gold nanomaterials (AuNMs) have distinctive electronic and optical properties, making them ideal candidates for biological, medical, and defense applications. Therefore, it is imperative to evaluate the potential biological impact of AuNMs before employing them in any application. This study investigates two AuNMs with different aspect ratios (AR) on mediation of biological responses in the human keratinocyte cell line (HaCaT) to model potential skin exposure to these AuNMs. The cellular responses were evaluated by cell viability, reactive oxygen species (ROS) generation, alteration in gene and protein expression, and inflammatory response. Gold nanospheres, nominally 20 nm in diameter and coated with mercaptopropane sulfonate (AuNS-MPS), formed agglomerates when dispersed in cell culture media, had a large fractal dimension (D(f) = 2.57 ± 0.4) (i.e., tightly bound and densely packed) and were found to be nontoxic even at the highest dose of 100 μg/mL. Highly uniform, 16.7 nm diameter, and 43.8 nm long polyethylene glycol-capped gold nanorods (AuNR-PEG) also formed agglomerates when dispersed into the cell culture media. However, the agglomerates had a smaller fractal dimension (D(f) = 1.28 ± 0.08) (i.e., loosely bound) and were found to be cytotoxic to the HaCaT cells, with a significant decrease in cell viability occurring at 25 μg/mL and higher. Moreover, AuNR-PEG caused significant ROS production and up-regulated several genes involved in cellular stress and toxicity. These results, combined with increased levels of inflammatory and apoptotic proteins, demonstrated that the AuNR-PEG induced apoptosis. Exposure to AuNS-MPS, however, did not show any of the detrimental effects observed from the AuNR-PEG. Therefore, we conclude that shape appears to play a key role in mediating the cellular response to AuNMs.     

Status of uncertainty assessment in k 0-NAA measurement: anything still missing?

Several approaches to quantifying measurement uncertainty in k ₀-based neutron activation analysis (k ₀-NAA) are reviewed, comprising the original approach, the spreadsheet approach, the dedicated computer program involving analytical calculations and the two k ₀-NAA programs available on the market. Two imperfectness in the dedicated programs are identified, their impact assessed and possible improvements presented for a concrete experimental situation. The status of uncertainty assessment in k ₀-NAA is discussed and steps for improvement are recommended. It is concluded that the present magnitude of measurement uncertainty should further be improved by making additional efforts in reducing uncertainties of the relevant nuclear constants used.     

Recent Advances on Metal-Organic Frameworks in the Conversion of Carbon Dioxide

With the development of modern industry,global warming is becoming a challenging issue due to the emissions of large quantities of greenhouse gases,mainly carbon dioxide(CO₂).The conversion of CO₂to useful compounds is considered as an effective and economic way to solve such a climate problem.Metal-organic frameworks(MOFs)are an emerging class of porous crystalline materials that have shown great potential in the conversion of CO₂.The advantages of MOFs in CO 2 conversion lie in their high surface areas,adjustable pore size,and high porosity.More importantly,desirable functional sites can be easily designed and precisely installed to the pore wall of target MOFs by pre-assembly and/or post-synthetic modification(PSM)ways.This review summarizes the recent advances in constructing MOF catalysts for the application in CO₂conversion.We believe that the design and synthesis of MOF catalysts for CO₂conversion can be a promising way to solve the“greenhouse effect”.     

X-ray determination of thermal expansion of Na(ClO3)x(BrO3)1−x mixed crystals

Lattice constants of sodium chlorate and sodium bromate and their mixed crystals were determined over the temperature range from room temperature to 320 °C. The observed lattice constants for the various compositions show strong deviations from those expected from Vegard's rule. The lattice constants at various temperatures were fitted to polynomials of type a = a₀ + a₁t + a₂t². The linear coefficients of expansion for the Na(ClO₃)_x · (BrO₃)_1−x series varies non-linearly with composition showing negative deviations from linearity.     

Theory of modified thermally stimulated current and direct determination of trap level distribution

In order to investigate the trap level distribution in polymer films, a new method is proposed based on modified thermally stimulated current (TSC) theory and numerical calculation of the TSC measurement. In this method, a new function is defined to weight the contribution of every trap level to the external current. The demarcation energy is used to study the trap emptying process. The modified TSC theory shows that only the electrons with trap levels very close to the demarcation energy can significantly contribute to the external circuit at any instant temperature. Based on this method, the trap level distribution of the DuPont original polyimide film 100HN and nanocomposite polyimide film 100CR are investigated as an application example. The effectiveness of the method is confirmed by the experiments. The experimental results show that the trap level density in the 100CR PI films is about six times larger than that in the 100HN PI films through the investigated trap level ranges 06–1.3 eV. The increased traps in 100CR should be introduced by nanofillers, probably come from the interfaces formed between nanofillers and the polymer matrix.     

Ionization of hydrogen and deuterium atoms in thermal energy collisions with state-selected Ne(3s 3 P 2,3 P 0) metastable atoms

High resolution energy spectra of electrons and ions resulting from thermal energy collisions of hydrogen and deuterium atoms with state-selected metastable Ne(Ne(3s ³ P ₂,³ P ₀) atoms are reported. The electron spectra for Ne(³ P ₂)+H(D) are very broad: The high energy part due to formation of NeH⁺ (NeD⁺) bound states (associative ionization), amounts to about 30% of the ionizing events, whereas the dominant part of the spectrum including a prominent low-energy peak is due to Penning ionization out of a strongly-attractive entrance potential curve. Comparison of the spectra with quantum mechanical fit calculations yields fairly accurate information on this potential, in particular its well depthD _e [Ne(³ P ₂)?H,D]= 2.0(1) eV. The spectra for Ne(³ P ₀)+H, D are comparatively narrow with much lower cross sections than the one for the Ne(³ P ₂) state. The corresponding entrance channel is a weakly bound van der Waals molecule with a well depth below 0.1 eV. A perturbation calculation of the Ne(3s)+H(1s) potential energy curves at large distances explains the observed difference between the Ne(³ P ₂)+H(D) and Ne(³ P ₀)+H(D) systems. Symmetry arguments are given that the major contribution to the Ne(³ P ₂)+H(D) spectra is due to the² Σ potential.     

The effect of zinc ions on the fluorescence spectra of (La, Zn)OF:Sm powder phosphors

This paper reports the fluorescence properties of a new series of (La, Zn) OF:Sm³⁺ powder phosphors. The measured fluorescence spectra were analyzed by computing the color coordinates and relative fluorescence intensity ratios (ED/MD). A bright yellowish-orange color was observed from these powder phosphors under a UV-source due to the confirmation of the transitions ⁴G_5/2→⁶H_5/2, ⁴G_5/2→⁶H_7/2, and ⁴G_5/2→⁶H_9/2. Scanning electron microscopic studies were performed to understand the average grain size of the synthesized powder phosphors.